JP2013134321A - Photosensitive colored composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a red or yellow photosensitive colored composition for a color filter, the composition having high luminance, capable of suppressing decrease in luminance in a formation step of a color filter, excellent in heat resistance and giving a good pattern profile of a filter segment, and to provide a color filter with high luminance and high definition using the composition.SOLUTION: The photosensitive colored composition includes a red pigment and/or a yellow pigment, and as an antioxidant (C), a phenolic antioxidant (c1), with a sulfur antioxidant or a phosphorus antioxidant (c2). Thereby, with the composition, a red or yellow filter segment having high lightness and an excellent pattern profile can be formed. Therefore, a high-quality color filter can be obtained by using the photosensitive colored composition.

Description

  The present invention relates to a photosensitive liquid color composition used for manufacturing a color filter used in a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. is there.

In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. There is an increasing demand for contrast.
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 in a fixed arrangement. It is made up of arranged ones. The filter segments are as fine as several μm to several 100 μm, and are regularly arranged in a predetermined arrangement for each hue.

  The filter segments that make up the color filter are activated by proximity exposure (ultraviolet light source exposure) through a photomask for pixel formation after applying a photosensitive material on a glass substrate, drying and removing excess solvent. It is formed by irradiating energy rays, curing (negative type) or increasing alkali solubility (positive type), removing a portion that dissolves with an alkali solution, etc., and heating to 230 ° C. or more called post-baking. By repeating this for each color of red, green and blue, for example, a color filter is produced.

Conventionally, for red filter segments, diketopyrrolopyrrole pigments, anthraquinone pigments, perylene pigments or disazo pigments as colorants, and for yellow filter segments, the light resistance and heat resistance of azo pigments, etc. It is common to use excellent pigments alone or in combination.
Further, in order to realize high brightness and high contrast of the color filter, the pigment contained in the filter segment is refined. However, even if the pigment is refined by various refinement treatment methods, the pigment whose primary particles or secondary particles have been refined easily aggregates in the pigmentation or dispersion process. For this reason, there is a limit to just increasing the brightness by making the pigment finer.

  In recent years, reflecting the high quality of color image sensors and color liquid crystal televisions, not only high brightness of display panels but also high definition has been strongly demanded. In order to meet such demands, high-sensitivity materials are being studied for high definition. However, if the components such as the photopolymerization initiator and the photopolymerizable monomer are increased in order to increase the photocurability, yellowing occurs in the post-bake process at 230 ° C. or higher, and the brightness of the red and yellow filter segments. There is a problem that it becomes a factor of lowering.

  On the other hand, about the photosensitive resin composition used for formation of each color filter segment, using various antioxidants is examined (for example, refer patent document 1, 2). It is also known to suppress lightness yellowing by adding a hindered phenol-based antioxidant (see Patent Document 3). However, just using these antioxidants is not sufficient to suppress the yellowing of the post-baking process, and furthermore, when using the hindered phenol-based antioxidant, it suppresses photocuring. It becomes difficult to make a high-definition color filter.

  As described above, in the red and yellow filter segments, with the demand for higher brightness and higher definition of the color filter, there is no decrease in brightness in the color filter formation process, and the high definition of the filter segment pattern shape is excellent. Currently, it is very difficult to obtain a color filter.

JP 2000-214580 A JP 2002-022925 A JP 2002-22925 A

  An object of the present invention is a photosensitive coloring composition for a color filter which has high luminance, can suppress a decrease in brightness even in a color filter forming process, has excellent heat resistance, and has a good filter segment pattern shape. It is an object to provide a high-luminance and high-definition color filter using the object.

  The said subject contains a red antioxidant and / or a yellow pigment, a phenolic antioxidant (c1), a sulfur type antioxidant, or a phosphorus antioxidant (c2) as an antioxidant (C). Solved by the characteristic photosensitive coloring composition.

  That is, the present invention is a photosensitivity containing a pigment (A), a binder resin (B), an antioxidant (C), a photopolymerization initiator (D), and a photopolymerization monomer (E). A coloring composition, wherein the pigment (A) contains a red pigment and / or a yellow pigment, the antioxidant (C) is a phenol-based antioxidant (c1), a sulfur-based antioxidant or a phosphorus-based composition The present invention relates to a photosensitive coloring composition comprising an antioxidant (c2).

The present invention also relates to a photosensitive coloring composition, wherein the photopolymerization initiator (D) contains an oxime ester compound or an acetophenone compound.
The present invention also provides the photosensitive coloring composition, wherein the total amount of the antioxidant (C) is 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition. Related to things.

  The present invention also relates to a color filter comprising a filter segment formed from the red and / or yellow photosensitive coloring composition on a substrate.

  The photosensitive coloring composition of the present invention comprises a red and / or yellow pigment, an antioxidant (C), a phenol-based antioxidant (c1), a sulfur-based antioxidant or a phosphorus-based antioxidant (c2). In addition to high sensitivity, it is possible to suppress a decrease in lightness in a post-baking step of 230 ° C. or higher when forming the transparent electrode and the alignment film in the color filter forming step. Further, since the brightness does not decrease during the color filter forming process, the change in the white balance of the color filter is smaller than that before forming the transparent electrode and the alignment film. Furthermore, a high-luminance color filter can be formed by using this.

Hereinafter, the present invention will be described in detail.
The photosensitive composition of the present invention contains a pigment (A), a binder resin (B), an antioxidant (C), a photopolymerization initiator (D), and a photopolymerization monomer (E). A photosensitive coloring composition, wherein the pigment (A) contains a red and / or yellow pigment, the antioxidant (C) is a phenolic antioxidant (c1) and a sulfurous antioxidant or And a phosphorus-based antioxidant (c2).
“CI” means a color index (CI).

[Photosensitive coloring composition]
<Pigment (A)>
The photosensitive composition of the present invention contains a red pigment and / or a yellow pigment as the pigment (A).

  The red pigment and / or yellow pigment can be selected according to the characteristics of the color filter and may be either an organic pigment or an inorganic pigment, but an organic pigment is more commonly used.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like.
Among these, in order to exert an excellent effect of brightness and contrast ratio, C.I. I. Pigment Red 48: 1, 122, 168, 176, 177, 202, 206, 207, 209, 224, 242, or 254, more preferably C.I. I. Pigment Red 176, 177, 242, or 254.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, 213, 214 and the like.

  Other orange pigments that can be used in combination include C.I. I. And orange pigments such as CI Pigment Orange 5, 13, 14, 24, 34, 36, 38, 40, 43, 46, 49, 61, 64, 68, 70, 71, 72, 73, 74.

  When the photosensitive coloring composition of the present invention is used as a red photosensitive coloring composition, a yellow pigment or an orange pigment can be used in combination for toning. Among these yellow pigments, lightness and contrast can be used. In order to exert an excellent effect, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, or 180 is preferable. As an orange pigment, C.I. I. Pigment Orange 38 is preferable.

  When used as a yellow photosensitive coloring composition, among these yellow pigments, preferably C.I. I. Pigment Yellow 13, 83, 117, 129, 138, 139, 139, 150, 185, 213, or 214, and more preferably C.I. I. Pigment yellow 139 and 150. Further, an orange pigment can be used in combination for toning, and among these orange pigments, C.I. I. Pigment Orange 38 is preferable.

  The preferable content of the pigment (A) in all the non-volatile components of the photosensitive coloring composition according to the present invention is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of obtaining sufficient color reproducibility. And most preferably 20 to 80% by weight. When the content of the pigment (A) is less than 10% by weight, sufficient color reproducibility cannot be obtained, and when the content exceeds 90% by weight, the content of the pigment carrier decreases, and the stability of the coloring composition is improved. Deteriorate.

  The pigment used in the photosensitive coloring composition of the present invention is preferably refined by salt milling. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, with respect to 100 or more pigment particles, the volume of each particle is obtained by approximating it with a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment (A) from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment (A).

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment (A).

<Binder resin (B)>
The binder resin (B) 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. The binder resin (B) includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone or in admixture of two or more.

  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, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, 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.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and 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 obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer 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.

  The binder resin (B) can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, with respect to 100 parts by weight of the pigment (A) in the photosensitive coloring composition.

<Antioxidant (C)>
The antioxidant (C) contains a phenol-based antioxidant (c1) and a sulfur-based antioxidant or a phosphorus-based antioxidant (c2). The red or yellow photosensitive coloring composition has a large absorption of the dye during pattern exposure, and it is difficult for light to pass through the inside. Therefore, it is common to increase sensitivity by increasing the amount of photopolymerization initiator (D) or photopolymerization monomer (E), but at this time, excess components that were not used for pattern exposure. However, there is a problem that radicals are generated by heat during the post-bake process, or yellowing occurs due to the formation of peroxides, resulting in a decrease in brightness.
Since the antioxidant (C) of the present invention can suppress yellowing of the photopolymerization initiator (D) and the photopolymerization monomer (E) in such a post-baking step, the color filter forming step Therefore, it is possible to form a color filter with high brightness.
Antioxidant (C) includes a primary antioxidant that suppresses generation of radicals by heat and a secondary antioxidant that decomposes peroxides generated by radicals, and phenolic antioxidant (c1) is primary oxidized. Since the antioxidant, the sulfur-based antioxidant or the phosphorus-based antioxidant (c2) has the function of a secondary antioxidant, the yellowing of the coating film in the post-baking process can be achieved by using these antioxidants in combination. Therefore, it is possible to form a high brightness and high definition filter segment.

<< Phenolic antioxidant (c1) >>
The phenol-based antioxidant (c1) functions as a primary antioxidant that suppresses generation of radicals by heat.
Examples of the phenolic antioxidant (c1) contained in the photosensitive coloring composition of the present invention include 2,6-di-t-butyl-4-ethylphenol and 2,4-bis- (n-octylthio). ) -6- (4-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis {3- (3,5-di-t-butyl-) 4-hydroxyphenyl) propionate}, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzyl phosphate Nate-diethyl ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-creso 2,6-di-tert-butyl-4-methoxyphenol, triethylene glycol-bis {3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol -Bis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 -Hydroxyphenyl) benzene, etc., may be used alone or in combination of two or more.

  Among them, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate}, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t- A hindered phenolic antioxidant selected from the group consisting of butyl-4-hydroxybenzylphosphonate-diethyl ester and tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate is: It is preferable from the viewpoint of balance between photocurability and lightness.

<< Sulfur Antioxidant or Phosphorus Antioxidant (c2) >>
The sulfur-based antioxidant or the phosphorus-based antioxidant (c2) serves as a secondary antioxidant that decomposes peroxides generated by radicals.
(Sulfur-based antioxidant)
A sulfur-based antioxidant is an antioxidant containing sulfur in the molecule. As such a sulfur-containing antioxidant, commercially available ones can be used, but dioctadecyl 3,3′-thiodipropanoate, dimyristyl-3,3′-thiodipropionate, dipalmityl-3,3′- Thiodipropionate, distearyl-3,3′-thiodipropionate, 4,4′-thiobis-3-methyl-6-tert-butylphenol, thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], and is preferably at least one compound selected from the group consisting of these, and one or more of these may be used.

(Phosphorus antioxidant)
Although what is marketed can be used as phosphorus antioxidant, Tris [2,4-di- (tert) -butylphenyl] phosphinetris [2-[[2,4,8,10-tetrakis ( 1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11- Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl) oxy] ethyl] amine, ethylbisphosphite (2,4-ditert-butyl-6-) It is preferable that it is at least one compound selected from the group consisting of these, and these may be used alone or in combination of two or more.

  The content of the phenolic antioxidant (c1) is based on the total content of the phenolic antioxidant (c1) and the sulfurous antioxidant or phosphorus antioxidant (c2) (100% by weight), It is preferably 20 to 95% by weight, more preferably 45 to 95% by weight, and even more preferably 55 to 95% by weight. When the content of the phenolic antioxidant (c1) is less than 20% by weight, the effect of suppressing the decrease in lightness in the post-baking process is small, and when it is more than 95% by weight, the photocurability may be insufficient. is there.

  The content of the antioxidant (C) in the photosensitive coloring composition of the present invention is preferably 0.1 to 10% by weight in 100% by weight of the solid content of the photosensitive coloring composition. More preferably, it is ˜5% by weight. When the content of the antioxidant is less than 0.1% by weight, the effect of suppressing the decrease in lightness in the post-baking process is small, and when it is more than 10% by weight, the photocurability may be insufficient.

<Photopolymerization initiator (D)>
In the photosensitive coloring composition of the present invention, in order to cure the composition by ultraviolet irradiation and form a filter segment by a photolithography method, a photopolymerization initiator (D) is added and a solvent development type or an alkali development type. It can be prepared in the form of a photosensitive coloring composition.

As photopolymerization initiator (D), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Or benzoin compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-me Xylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -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, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 Yl]-, 1- (0-acetyloxime), 1,2-octadion-1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like; bis (2,4 , 6-trimethylbenzoyl) phenylphosphine oxide or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; Compounds: carbazole compounds; imidazole compounds; or titanocene compounds.
These photopolymerization initiators (D) can be used singly or as a mixture of two or more at any ratio as required.

  Among these, it is preferable to contain an acetophenone-based compound or an oxime ester-based compound as the sensitive photopolymerization initiator (D) in order to produce a color filter having good pattern shape and linearity.

  The oxime ester-based compound absorbs ultraviolet rays to cleave the N—O bond of the oxime to generate an iminyl radical and a benzoyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. As oxime ester photoinitiators, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), 1,2- Octadione-1- [4- (phenylthio)-, 2- (O-benzoyloxime)] is preferred.

  An acetophenone compound is cleaved to generate a radical having an amino group that becomes an active hydrogen donor, so that it is possible to reduce the influence of oxygen inhibition, which is a problem in UV curing, and to cure the surface of the coating film. . Examples of the acetophenone compound include α-aminoalkylacetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone is preferred.

  The content of the photopolymerization initiator (D) is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the pigment (A), and 10 to 150 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Sensitizer>
Furthermore, the red or yellow photosensitive composition of the present invention can contain a sensitizer.
Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives, and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (D) contained in the colored composition, and 5 to 5 from the viewpoint of photocurability and developability. More preferably, it is 50 parts by weight.

<Photopolymerizable monomer (E)>
The photopolymerizable monomer (E) used in the present invention includes a monomer or oligomer that forms a resin by being cured by ultraviolet rays or heat.

Examples of the photopolymerizable monomer (E) include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, β-carboxyethyl methacrylate, polyethylene glycol diester. Methacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 1,6- Hexanediol diglycidyl ether dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, neopenthi Glycol diglycidyl ether dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, tricyclodecanyl methacrylate, ester acrylate, methylolated melamine methacrylate, epoxy methacrylate, urethane acrylate, etc. Acrylic acid ester and methacrylic acid ester, acrylic acid, methacrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, methacrylamide, N-hydroxymethylmethacrylamide, N-vinylformamide, acrylonitrile However, it is not necessarily limited to these.
These photopolymerizable monomers (E) can be used singly or as a mixture of two or more at any ratio as required.

  The content of the photopolymerizable monomer (E) is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the pigment (A), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. More preferably.

In the photosensitive coloring composition, the ratio [I _a / M] of the weight [I _a ] of the photopolymerization initiator (D) and the weight [M] of the photopolymerization monomer (E) is 0.03 to 1 0.00 is preferable, and 0.04 to 0.95 is more preferable.
Further, when the photosensitive coloring composition contains a sensitizer, the total weight [I _b ] of the photopolymerization initiator (D) and the sensitizer and the weight [M] of the photopolymerization monomer (E). The ratio [I _b / M] is preferably 0.04 to 1.50, more preferably 0.05 to 1.45.

When [I _a / M] is 0.03 or more and [I _b / M] is 0.04 or more, the sensitivity is high and good. Moreover, when [I _a / M] is 1.00 or less and [I _b / M] is 1.50 or less, the linearity and resolution of the pattern shape are more excellent.

<Solvent>
In the photosensitive composition of the present invention, the pigment (A) is sufficiently dispersed in a dye carrier, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 10 μm. Is used to facilitate the formation.

  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, methylpropylene glycol, cyclohexyl acetate, xylene, ethyl cellosolve, methyl-n amyl ketone, Examples include propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, isopentyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents. These may be used alone or in combination of two or more. it can.

<Method for producing photosensitive coloring composition>
In the photosensitive composition of the present invention, first, a pigment (A) containing a red pigment and / or a yellow pigment is mixed with a three-roll mill, a two-roll mill, a sand mill, a dye carrier such as a binder resin (B) and / or a solvent. A finely dispersed pigment dispersion is produced using various dispersing means such as a kneader and an attritor, and the antioxidant (C), photopolymerization initiator (D), and photopolymerizable monomer are prepared in the pigment dispersion. (E) In some cases, other binder resins (B), sensitizers, polyfunctional thiols, ultraviolet absorbers, polymerization inhibitors, storage stabilizers, solvents, and other components can be mixed and stirred to produce. . In addition, the photosensitive coloring composition containing two or more kinds of pigments is prepared by mixing each pigment dispersion separately in a dye carrier and / or a solvent, and further mixing a photopolymerization initiator or a photopolymerizable compound. Etc. can be mixed and stirred.

  When the pigment (A) is dispersed in the binder resin (B) and / or the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment 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 photosensitivity formed by dispersing the pigment in the binder resin (B) and / or solvent using the dispersion aid. In the case of using a coloring property composition, a color filter having excellent transparency can be obtained.

  The photosensitive composition of the present invention can be prepared in the form of a solvent development type or alkali development type colored resist material by using a solvent-soluble or alkali-soluble resin as the binder resin (B) as a part of the dye carrier. it can. That is, the colored resist material comprises a pigment (A) containing a red and / or yellow pigment, a photopolymerizable monomer (E), a solvent-soluble or alkali-soluble resin, a photopolymerization initiator (D), an oxidation A photosensitive composition of the present invention comprising an inhibitor (C) is dispersed in a solvent.

《Dispersing aid》
The dispersing aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.

(Resin type pigment dispersant)
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 adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works.

Examples of resin type pigment dispersants include polyvinyl, polyurethane, polyester, polyether, formalin condensation, silicone, and composite polymers thereof.
Examples of the pigment affinity site include carboxyl groups, hydroxyl groups, phosphate groups, phosphate ester groups, sulfonate groups, hydroxyl groups, amino groups, quaternary ammonium bases, amide groups, and other polar groups, as well as polyethylene oxide and polypropylene oxide. , And hydrophilic polymer chains of these composite systems, etc.
Examples of the site compatible with the dye carrier include a long-chain alkyl chain, a polyvinyl chain, and a polyester chain.

Specifically, as a resin-type pigment dispersant,
Styrene-maleic anhydride cocondensate, olefin-maleic anhydride copolymer, poly (meth) acrylate, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester Copolymer, (meth) acrylic acid-polyvinyl-based macromer copolymer, phosphoric ester group-containing acrylic resin, aromatic carboxyl group-containing acrylic resin, polystyrene sulfonate, acrylamide- (meth) acrylic acid copolymer, carboxymethylcellulose An anionic resin type pigment dispersant such as a polyurethane prepolymer having a carboxyl group, a formalin condensate of naphthalene sulfonate, and sodium alginate;
Nonionic resin-type pigment dispersants such as polyvinyl alcohol, polyalkylene polyamine, polyacrylamide, and polymer starch; and polyethyleneimine, aminoalkyl (meth) acrylate copolymer, polyvinyl imidazoline, polyurethane prepolymer having amino groups, and Examples thereof include cationic resin type pigment dispersants such as Satokinsan, and these can be used alone or in admixture of two or more.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc. are mentioned, these are used alone or in combination of two or more. Can be used.

(Surfactant)
As surfactant,
Polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, lauryl Anionic surfactants such as ammonium sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; and
Examples include alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline, and these can be used alone or in admixture of two or more.

(Dye derivative)
The dye derivative is a compound in which a substituent is introduced into an organic dye, and the organic dye includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivative 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.

<Other additive components>
In the photosensitive composition of the present invention, an amine compound having a function of reducing dissolved oxygen, a storage stabilizer for stabilizing the time-dependent viscosity of the composition, or an adhesion with a transparent substrate is improved. It is also possible to contain an adhesion improver such as a silane coupling agent.

Examples of amine compounds include:
Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

Examples of storage stabilizers include:
Quaternary ammonium chlorides such as benzyltrimethylammonium chloride and diethylhydroxyamine;
Organic acids such as lactic acid and oxalic acid;
Methyl esters of the organic acids;
catechols such as t-butylpyrocatechol;
And organic phosphines such as triphenylphosphine, tetraethylphosphine, and tetraphenylphosphine; and phosphites.
The content of the storage stabilizer can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, with respect to 100 parts by weight of the pigment (A) in the photosensitive coloring composition. .
By using 0.01 parts by weight or more of the storage stabilizer, the temporal stability of the color filter coloring composition is improved.

As a silane coupling agent,
Vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane;
(meth) acryloylsilanes such as γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, and γ- (meth) acryloxypropyldimethoxymethylsilane;
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3, Epoxy silanes such as 4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane;
N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Aminosilanes such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane; and
and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane;

  The content of the silane coupling agent is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the pigment (A) in the photosensitive coloring composition. it can.

<Removal of coarse particles>
The photosensitive composition of the present invention may be mixed with a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably 0.5 μm or more by using means such as centrifugation, sintered filter, membrane filter and the like. It is preferable to remove the dust.

[Color filter]
Next, the color filter of the present invention will be described.
The color filter of the present invention comprises a filter segment or a black matrix formed from the photosensitive composition of the present invention on a transparent substrate, and a general color filter has at least one red filter segment, at least one. One green filter segment and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

  The green filter segment can be formed using a conventional green coloring composition comprising a green pigment and a colorant carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used.

  A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213,214,218,219,220, or it can be mentioned yellow pigment 221, and the like. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. As the blue pigment, a phthalocyanine pigment and / or a triarylmethane lake pigment or the like is used. As the phthalocyanine pigment, it is preferable to use a copper phthalocyanine blue pigment. Examples of the copper phthalocyanine blue pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and the like. Among them, a copper phthalocyanine blue pigment having an ε-type or α-type structure is preferable. Such preferred pigments are specifically C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Blue 15: 1. Examples of triarylmethane lake pigments include C.I. I. Pigment Blue 1, 1: 2, 1: 3, C.I. I. Pigment Blue 2, 2: 1, 2: 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 8, C.I. I. Pigment blue 9, C.I. I. Pigment Blue 10, 10: 1, C.I. I. Pigment blue 11, C.I. I. Pigment blue 12, C.I. I. Pigment blue 18, C.I. I. Pigment blue 19, C.I. I. Pigment blue 24, 24: 1, C.I. I. Pigment blue 53, C.I. I. Pigment blue 56, 56: 1, C.I. I. Pigment blue 57, C.I. I. Pigment blue 58, C.I. I. Pigment blue 59, C.I. I. Pigment blue 61, C.I. I. Pigment Blue 62 and the like. Among these, C.I. I. It is preferable to use pigment blue 15: 6.

  In addition to the blue pigment, it is preferable to use a dioxazine pigment, an anthraquinone pigment, an azo pigment, or a quinacridone pigment exhibiting purple or red. Among them, it is preferable to use a dioxazine pigment in combination. Examples of the dioxazine pigment include C.I. I. Pigment violet 23 is preferably used. By using a dioxazine pigment in combination with the blue coloring composition of the present invention, it is possible to obtain a stable and high-quality blue coloring composition which is further excellent in heat resistance, light resistance and solvent resistance.

  The magenta color filter segment can be formed using a normal magenta color coloring composition containing a magenta color pigment and a colorant carrier. Examples of the magenta coloring composition include C.I. I. Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 192, 202, 207, 209, C.I. I. Pigment Violet 19 or the like is used.

  The cyan filter segment can be formed using a normal cyan coloring composition comprising a cyan pigment and a colorant carrier. Examples of the cyan coloring composition include C.I. I. Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 80, etc., preferably C.I. I. Pigment Blue 15: 3, 15: 4 can be used.

Moreover, the green pigment used for a green coloring composition can be used together with a cyan coloring composition.

  As the substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate are used. Further, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a photolithography method. The formation of each color filter segment by photolithography is performed by the following method. That is, the red photosensitive composition prepared as a solvent development type or alkali development type colored resist material is dried on a substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, or the like. It is applied so as to be 10 to 10 μm, preferably 0.2 to 5 μm. If necessary, the coating film dried using a vacuum dryer, convection oven, IR oven, hot plate, etc. is exposed to ultraviolet rays through a mask having a predetermined pattern in contact or non-contact with the coating film. Do. Thereafter, the filter segment can be formed by immersing in a solvent or an alkaline developer, or spraying the developer by spraying or the like to remove the uncured portion and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a filter segment with higher accuracy than the printing method can be formed.

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. An antifoaming agent or a surfactant can also be added to the developer.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkali-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.

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
Moreover, the measuring method of the weight average molecular weight (Mw) of resin and the average primary particle diameter of a pigment is as follows.

<Weight average molecular weight (Mw) of resin>
The weight average molecular weight (Mw) of the resin is a polystyrene equivalent measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a mass average molecular weight (Mw).

<Average primary particle diameter of pigment>
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

  First, a method for producing an acrylic resin solution, a method for producing a micronized pigment solution, a method for adjusting a pigment dispersant solution, and a method for producing a pigment dispersion used in Examples and Comparative Examples will be described.

<Manufacture of acrylic resin solution>
70.0 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer, the temperature was raised to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. Then, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.) 7.4 from the dropping tube. And a mixture of 0.4 parts of 2,2′-azobisisobutyronitrile were added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26,000.
After cooling to room temperature, about 2 g of the acrylic resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the solid content was measured. Based on the measurement results, propylene glycol monomethyl ether acetate was added to the previously synthesized acrylic resin solution so that the solid content was 30% to obtain an acrylic resin solution.

<Manufacture of refined pigments>
(Preparation of red fine pigment 1)
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment 1 were obtained.

(Preparation of red fine pigment 2)
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“Chromophthaled A2B” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment 2 were obtained.

(Preparation of red fine pigment 3)
Benzimidazolone red pigment C.I. I. 200 parts of Pigment Red 176 (“Novoperm Carmine HF3C” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of benzimidazolone pigment refined pigment 3 were obtained.

(Preparation of red fine pigment 4)
Red pigment C.I. I. 200 parts of Pigment Red 242 (“NOVOPERM SCARLET 4RF” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment 4 were obtained.

(Preparation of orange fine pigment 1)
Orange pigment C.I. I. 200 parts of CI Pigment Orange 38 (“NOVOPERM RED HFG” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of orange fine pigment 1 were obtained.

(Preparation of yellow fine pigment 1)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a yellow fine pigment 1 were obtained.

(Preparation of yellow fine pigment 2)
Isoindolinone yellow pigment 1C. I. 200 parts of Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by Ciba Japan Co., Ltd.), 1400 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow fine pigment 2 were obtained.

<Manufacture of pigment dispersion>
(Preparation of pigment dispersion (DP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion (PR-1) was produced by filtration using a filter.
Red fine pigment 1 (CI Pigment Red 254: 11.0 parts acrylic resin solution: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts resin type dispersant (“EFKA4300 manufactured by Ciba Japan Co., Ltd.) : 1.0 part

Hereinafter, pigment dispersions (DP-2 to 7) were produced in the same manner as the pigment dispersion (DP-1) except that the pigments were changed to the pigments shown in Table 1.

[Examples 1 to 24 and Comparative Examples 1 to 17]
(Manufacture of red or yellow photosensitive coloring composition (colored resist material))
With compositions and blending amounts (parts by weight) as shown in Tables 2 to 5, the pigment dispersion, the acrylic resin solution, the photopolymerizable monomer, the photopolymerization initiator, the antioxidant, and the solvent The mixture was stirred and mixed to be uniform and then filtered through a 1 μm filter to obtain each colored resist material.

Abbreviations in Tables 2 to 5 are shown below.
Photopolymerizable monomer: Dipentaerythritol hexaacrylate / pentaacrylate mixture (“Aronix M402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator A: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)
("Irgacure OXE02" manufactured by Ciba Japan)
Photopolymerization initiator B: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“Irga” manufactured by Ciba Japan) Cure 379 ")
Sensitizer: 4,4′-diethylaminobenzophenone (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.)
)
Antioxidant A: Phenolic antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Antioxidant B: Phosphorous antioxidant Tris [2, 4 -Di- (tert) -butylphenyl] phosphine, antioxidant C: sulfur-based antioxidant 3,3'-thiodipropanoic acid dioctadecyl, organic solvent: propylene glycol monomethyl ether acetate

  About the obtained photosensitive coloring composition, the following method evaluated the brightness, the sensitivity, the linearity, the pattern shape, and the resolution. The results are shown in Tables 2-5.

[Method for producing coated substrate]
The obtained photosensitive coloring composition was applied to a 10 cm × 10 cm glass substrate by spin coating, and then the solvent was removed by heating at 70 ° C. for 15 minutes in a clean oven to obtain a coating film of about 2 μm. . Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 30 minutes in a clean oven.

[Brightness difference evaluation]
The chromaticity (Y, x, y) of the C light source before and after the baking process of the coating film obtained by the above method was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), and the brightness difference The rank of the evaluation is as follows.
○: Less than 0.2 Δ: 0.2 or more and less than 0.6 ×: 0.6 or more

[Sensitivity evaluation]
The pattern film thickness in the 100 μm photomask portion of the filter segment formed by the above method was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was evaluated. The smaller the minimum exposure, the higher the sensitivity and the better the photosensitive coloring composition.
The rank of evaluation is as follows.
○: Less than 50 mJ / cm ² Δ: 50 mJ / cm ² or more and less than 100 mJ / cm ² ×: 100 mJ / cm ² or more

[Linearity evaluation]
The pattern in the 100 μm photomask portion of the filter segment formed by the above method was evaluated by observation using an optical microscope. The rank of evaluation is as follows.
○: Good linearity △: Partially poor linearity ×: Poor linearity

[Pattern shape evaluation]
The cross section of the pattern at the 100 μm photomask portion of the filter segment formed by the above method was evaluated by observation using an electron microscope. The pattern cross section has good forward taper. The rank of evaluation is as follows.
○: Cross section is forward tapered △: Partially forward tapered shape is poor ×: Cross section is reverse tapered

[Resolution evaluation]
The pattern in the 25 μm photomask portion of the filter segment formed by the above method was evaluated by observing with an optical microscope. The rank of evaluation is as follows. The poor resolution means that adjacent stripe patterns are connected or chipped. The rank of evaluation is as follows.
◯: Good resolution and linearity △: Slightly inferior in linearity but good resolution ×: Partially poor resolution

  As shown in Tables 2 to 5, as a red pigment and / or a yellow pigment and an antioxidant (C), a phenol-based antioxidant (c1) and a sulfur-based antioxidant or a phosphorus-based antioxidant (c2) The filter segment formed using the photosensitive coloring composition of the present invention containing) has good brightness difference, linearity, pattern shape, and resolution.

  In the case where the antioxidant (C) is not included as in Comparative Examples 1 to 17 and only in the case of the antioxidant (c2), since the yellowing in the heating process cannot be suppressed, the brightness is greatly reduced. As a result. When the antioxidant (c1) was used alone, the sensitivity characteristics, the linearity of the filter segment, and the resolution were poor.

Claims (4)

  A photosensitive coloring composition containing a pigment (A), a binder resin (B), an antioxidant (C), a photopolymerization initiator (D), and a photopolymerizable monomer (E). The pigment (A) contains a red pigment and / or a yellow pigment, and the antioxidant (C) is a phenol-based antioxidant (c1) and a sulfur-based antioxidant or a phosphorus-based antioxidant (c2). And a photosensitive coloring composition.   The photosensitive coloring composition according to claim 1, wherein the photopolymerization initiator (D) contains an oxime ester compound or an acetophenone compound.   3. The photosensitive property according to claim 1, wherein the total amount of the antioxidant (C) is 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition. Coloring composition.   A color filter comprising a filter segment formed from the photosensitive coloring composition according to claim 1 on a substrate.