JP5861171B2 - Red coloring composition for color filter and color filter - Google Patents

Description

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

  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. Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  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. Increasing demands are being made.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or 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.

Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, when light must be transmitted (ON state), the brightness decreases due to the attenuation of transmitted light, or when light must be blocked (OFF state), light must leak or be transmitted. Since the transmitted light attenuates when it does not become (ON state), there is a problem that the ratio of luminance (contrast ratio) on the display device in the ON state and the OFF state is low.

Until now, in order to realize high brightness and high contrast of the color filter, the pigment contained in the filter segment has been refined. However, various pigments (similarly called crudes having a particle size of 10 to 100 μm produced by chemical reaction, which are made into a mixture of primary particles and aggregated secondary particles by pigmentation treatment) Even if the particles are refined by the refinement treatment method, the pigments whose primary particles or secondary particles have been refined generally tend to agglomerate. When the refinement is too advanced, a huge lump of pigment solid is formed. End up. Furthermore, even if the finely-divided pigment is dispersed in a pigment carrier containing a resin or the like and the secondary particles of the pigment are stabilized as close as possible to the primary particles, a stable coloring composition is obtained. It is very difficult.

  In general, two or more kinds of pigments are used in combination in the red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate. I. Pigment red 254 and C.I. I. Pigment Red 177 is also a yellow pigment for toning. I. Pigment yellow 150, C.I. I. Pigment yellow 138, or C.I. I. Pigment Yellow 139 or the like is used.

  Here, C.I. I. Pigment Red 254 is a pigment that is particularly excellent in luminance when used as a colored composition. Further, since the coloring power is high, it is advantageous when adjusting the chromaticity and film thickness of the color filter. However, C.I. I. Pigment Red 254 has a problem in heat resistance when used in a refined form, and has a drawback that the contrast ratio is lowered when a refined product is used as a colored coating film.

  As a method for obtaining a color filter having a high contrast ratio, C.I. I. Pigment Red 254, C.I. I. A technique for producing a colored composition by adding Pigment Red 177 is used. However, C.I. I. Pigment Red 177 itself has low luminance and coloring power, so it cannot be used at a high content rate. I. Pigment Red 254 and C.I. I. When Pigment Red 177 is contained, the luminance, coloring power, and contrast are lowered in terms of arithmetic average, and as long as the combination of these conventionally used red pigments and yellow pigments can be used, the high contrast ratio and the high brightness are the limits. This is the current situation.

  Therefore, C.I. I. Pigment red 177 and C.I. I. Coloring for color filters that has a clearer color tone, a wider color display area, and higher coloring power than pigments that use Pigment Red 254, and that has a pigment with high brightness and contrast ratio Development of the composition is calculated | required and the benzimidazolone pigment is proposed as such a pigment (patent document 1). Patent Document 1 discloses C.I. which is a benzimidazolone pigment. I. A coloring composition using Pigment Red 176 as a main pigment is described. However, C.I. I. The use of CI Pigment Red 176 is not only insufficient for higher contrast as required in recent years, but also has a problem of fluidity when it contains finer pigments. In addition, a great amount of energy is required to disperse until high gloss and transparency are obtained when loosely aggregated fine pigment particles are loosened.

  A benzimidazolone pigment with a large specific surface area has some effects of improving the sharpness, brightness, and contrast ratio of the coating film, but the dispersibility and dispersion stability of the pigment are poor. When the liquid is prepared, reaggregation of the pigment particles occurs, resulting in an unstable state with high viscosity, and there is a problem that fluidity and storage stability are insufficient. The color filter red pixel portion using the pigment dispersion has a defect that the coating film has low sharpness, brightness, contrast ratio, and heat resistance.

JP 2009-237462 A JP 2002-121420 A JP 2005-234007 A JP 2009-191244 A

  The present invention is a stable red coloring composition for color filters having high brightness and contrast ratio and excellent fluidity, and has good color characteristics and heat resistance formed using the red coloring composition for color filters. It is to provide a color filter having excellent properties.

As a result of intensive studies to solve the above problems, the present inventors have found that the colorant (a) has a general formula (1) having a BET specific surface area of 10 m ² / g or more and 50 m ² / g or less by a nitrogen adsorption method. It has been found that the above-mentioned problems can be solved by a coloring composition containing a benzimidazolone pigment (a1) represented by

一般式（１）：
[一般式（１）中、Ｒ1、Ｒ2、Ｒ₃は、それぞれ独立に−Ｈ、−ＣＨ₃、−ＯＣＨ₃、−ＣＯＯＣＨ₃、−ＣＯＯＣ₄Ｈ₉、−Ｃｌ、−ＮＯ₂、−ＳＯ₂ＮＨＣＨ₃、または−ＣＯＮＨＣ₆Ｈ₅である。] That is, in the coloring composition containing the colorant (a), the resin (b), and the solvent (c), the colorant (a) has a BET specific surface area of 10 m ² / g or more and 50 m by a nitrogen adsorption method. ^{The present} invention relates to a red coloring composition for a color filter comprising a benzimidazolone pigment (a1) represented by the following general formula (1) of ² / g or less.

General formula (1):
[In General Formula (1), R 1, R 2 and R ₃ are each independently —H, —CH ₃ , —OCH ₃ , —COOCH ₃ , —COOC ₄ H ₉ , —Cl, —NO ₂ , —SO _2. NHCH ₃ or —CONHC ₆ H ₅ . ]

  The present invention also relates to the red coloring composition for a color filter, wherein the benzimidazolone pigment (a1) has an average primary particle diameter of 10 to 50 nm.

  The present invention also relates to the red coloring composition for a color filter, wherein the benzimidazolone pigment (a1) is a pigment obtained by a salt milling treatment in the presence of the dye derivative (e).

  The present invention further includes a resin-type dispersant (d1) having an acidic substituent, and the resin-type dispersant (d1) is a resin-type dispersant having two or more carboxyl groups in one molecule. It is related with the said red coloring composition for color filters characterized by the above-mentioned.

  In the present invention, the pigment derivative (e) is at least one selected from the group consisting of a pigment derivative having a basic substituent, a β-naphthol derivative having a basic substituent, and a triazine compound having a basic substituent. The present invention relates to the above-mentioned red coloring composition for a color filter, which contains a pigment derivative having at least two types of basic substituents.

  In the present invention, the colorant (a) further comprises C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment yellow 139 and C.I. I. The present invention relates to the red coloring composition for a color filter, comprising at least one pigment selected from the group consisting of CI Pigment Yellow 150.

  The present invention further relates to the red coloring composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also relates to a color filter comprising a red filter segment formed on the substrate from the red coloring composition for a color filter.

According to the present invention, as the colorant (a), a benzimidazolone pigment (a1) represented by the following general formula (1) having a BET specific surface area of 10 m ² / g or more and 50 m ² / g or less by a nitrogen adsorption method is used. Color composition for color filters with high brightness and contrast ratio, high fluidity and good stability, and by using this, color filters with good color characteristics, high brightness and high contrast ratio can be formed It becomes possible to do.

Hereinafter, the present invention will be described in detail.
For color filters red colored composition of the present invention, BET specific surface area by nitrogen adsorption method comprises a pigment (a1) benzimidazolone represented by 10 m ² / g or more 50 m ² / g or less of the following general formula (1) Coloring It is a coloring composition containing an agent (a), resin (b), and a solvent (c).

[一般式（１）中、Ｒ1、Ｒ2、Ｒ₃は、それぞれ独立に−Ｈ、−ＣＨ₃、−ＯＣＨ₃、−ＣＯＯＣＨ₃、−ＣＯＯＣ₄Ｈ₉、−Ｃｌ、−ＮＯ₂、−ＳＯ₂ＮＨＣＨ₃、または−ＣＯＮＨＣ₆Ｈ₅である。] <Colorant (a)>
The colorant (a) in the color filter coloring composition of the present invention is a benzimidazolone pigment represented by the following general formula (1) having a BET specific surface area of 10 m ² / g or more and 50 m ² / g or less by a nitrogen adsorption method ( a1) Including.
General formula (1):

[In General Formula (1), R 1, R 2 and R ₃ are each independently —H, —CH ₃ , —OCH ₃ , —COOCH ₃ , —COOC ₄ H ₉ , —Cl, —NO ₂ , —SO _2. NHCH ₃ or —CONHC ₆ H ₅ . ]

  The benzimidazolone pigment (a1) is a water-insoluble pigment having excellent fastness to solvents and light, and by using this pigment, it has excellent brightness and contrast ratio. A colored composition can be obtained.

  As the benzimidazolone pigment (a1), the color index (CI) number indicates C.I. I. Pigment red 171, 175, 176, 185, 208 and the like. Among these, C.I. I. Pigment Red 176 is preferable because it has a high contrast ratio and higher brightness.

  Benzimidazolone pigments are C.I. I. Bluish than C.I. I. Since it is yellowish than CI Pigment Red 177 and the rising wavelength of the transmission spectrum is in the range of 560 to 580 nm, it effectively acts on the bright line of the backlight generally used in liquid crystal display devices, and high brightness is obtained. . Further, by using a benzimidazolone pigment and a resin-type dispersant in combination, the pigment can be stably present in a primary particle state, and a high contrast ratio can be obtained at the same time.

Further, benzimidazolone pigments (a1) is the BET specific surface area by nitrogen adsorption method be at 10 m ² / g or more 50 m ² / g or less, more preferably less than 10 m ² / g or more 40 m ² / g More preferred. The specific surface area is particularly preferably 15 m ² / g or more and less than 35 m ² / g.
When the specific surface area of the benzimidazolone pigment (a1) is smaller than 10 m ² / g, the luminance and contrast ratio of the color filter are lowered, which is not preferable. When the specific surface area exceeds 50 m ² / g, although the effect of improving the sharpness, brightness, and contrast ratio of the coating film can be seen to some extent, the dispersibility and dispersion stability of the pigment are low. When the pigment dispersion is prepared, reaggregation of the pigment particles occurs, resulting in an unstable state with high viscosity, insufficient fluidity and storage stability, and extreme characteristics of color filter brightness and contrast ratio. Getting worse. In addition, a large amount of a polymer dispersant necessary for stabilizing the dispersion may be required, and the polymer dispersant is insoluble in the developer, so that there is a problem that resolution and developability are likely to deteriorate. There is.

In addition, the measurement of the specific surface area of a pigment is a specific surface area of the dried pigment when it measures according to the automatic vapor | steam adsorption amount measuring apparatus ("BELSORP18" by Nippon Bell Co., Ltd.) by nitrogen adsorption BET method. The benzimidazolone pigment (a1) of the present invention has a specific surface area of 10 m ² / g or more and less than 50 m ² / g, so that it can be suitably used as a red pigment for a color filter. A method for obtaining such a fine pigment is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation methods described later can be used. However, by these methods, 10 m ² / g or more and 50 m ² / A fine pigment of g or less can be suitably obtained.

[Miniaturization of pigment]
The benzimidazolone pigment (a1) used in the present invention is preferably obtained by refining, but the refining method is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution precipitation methods can be used. As illustrated in the present invention, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed. As the benzimidazolone pigment to be refined, any commercially available product may be used, or a benzimidazolone pigment produced by a coupling reaction of a diazo compound corresponding to the benzimidazolone pigment and a coupler compound may be used.

The average primary particle size of the refined pigment is preferably 10 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. More preferably, it is 10-50 nm, and the most preferable range is 15-35 nm.
The benzimidazolone pigment (a1) of the present invention is different from a pigment in which the specific surface area is increased as the average primary particle diameter is small as in the prior art, and the average primary particle diameter of the pigment is 100 nm or less. Although it is fine, the specific surface area has a characteristic of 10 m ² / g or more and 50 m ² / g or less, so it is fine, so it not only has excellent brightness and contrast ratio but also fluidity, stability, and heat resistance. In addition, an excellent coloring composition can be obtained.

  As a method for obtaining the benzimidazolone pigment (a1) having such a unique property, it is possible to control the conditions of the miniaturization treatment, and in particular, to perform a salt milling treatment in the presence of the dye derivative (e). Can be obtained at

  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, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor or sand mill. Then, after mechanically 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 obtained by obtaining a red pigment composition for a color filter containing a benzimidazolone pigment (a1) having a specific BET specific surface area as defined in the present invention, and 100 parts by weight of the pigment from both aspects of processing efficiency and production efficiency. On the other hand, it is preferable to use 50 to 1500 parts by weight, and most preferably 300 to 1000 parts by weight.

  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.

  When the pigment is subjected to a salt milling treatment, a dye derivative (e) described later may be added as necessary. These dye derivatives (e) may be the same as the dye derivatives used when the pigment dispersion is produced. The benzimidazolone pigment (a1) is subjected to a solvent salt milling treatment in the presence of the dye derivative (e) (where the crude pigment is subjected to a solvent salt milling treatment in the presence of the dye derivative (e). Therefore, it is easy to obtain a benzimidazolone pigment (a1) having a specific specific surface area, which is a feature of the present application, which is preferable. Further, the benzimidazolone pigment (a1) having a specific surface area within the range specified in the present invention can be obtained in a shorter time than when the dye derivative (e) is not used, and the amount of inorganic salt used can be reduced. This is preferable because it can be further reduced.

  As the pigment derivative (e), a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, β-naphthol compound, acridone compound or triazine compound. And the like.

  Among these, a pigment derivative having a basic substituent, a β-naphthol derivative having a basic substituent, and a triazine compound having a basic substituent are preferable. In particular, the triazine-based compound having a basic substituent can easily control the specific particle surface area and the average particle diameter of primary particles, improve the dispersibility of the benzimidazolone pigment (a1), and the pigment after dispersion. It is preferable because it has the greatest effect of preventing reaggregation.

  In the present invention, the amount of the pigment derivative (e) in the solvent salt milling treatment is 100 parts by weight of the benzimidazolone pigment (a1) from the viewpoint of easy control of the specific surface area and resistance of the coloring composition. , Preferably 5-30 parts by weight or less, preferably 5-20 parts by weight or less, most preferably 5-10 parts by weight or more.

  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.

  The temperature during the salt milling treatment of the pigment is preferably 30 to 150 ° C, and more preferably 50 to 80 ° C. The salt milling time is preferably 3 hours to 20 hours, and more preferably 5 to 15 hours.

Thus, the benzimidazolone pigment (a1) having a BET specific surface area of 10 m ² / g or more and 50 m ² / g or less in the nitrogen adsorption method is obtained by controlling the conditions such as temperature or time during the salt milling treatment. Is possible.

  Furthermore, the red pigment composition of the present invention containing the benzimidazolone pigment (a1) having such a specific surface area has high dispersion and dispersion stability of the pigment in the liquid medium, and low viscosity of the pigment dispersion ( Excellent fluidity), stable, and high viscosity stability over time (storage stability). When a color filter red filter segment is produced using the pigment composition, a uniform coating film is formed. It is possible to obtain a color filter that is excellent in contrast and excellent in heat resistance while maintaining initial sharpness and brightness.

  Furthermore, by using a finer pigment having an average primary particle size of 10 to 50 nm of pigment particles, when used for forming a red filter segment for a color filter, it has a higher brightness, a higher contrast ratio, and an excellent stability. It becomes a coloring composition.

[Other pigments]
As the colorant (a) in the color filter coloring composition of the present invention, the benzimidazolone pigment (a1) can be used alone or in combination with other pigments.
These other pigments are also preferably used after being refined by the above-described refinement treatment.

In order to facilitate color adjustment, other red pigments or yellow pigments may be used in combination.
Examples of red pigments that can be used in combination include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, Red pigments such as 166, 168, 177, 178, 179, 184, 187, 200, 202, 210, 221, 242, 246, 254, 255, 264, 270, 272, and 279 can be used in combination. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment red 254 or C.I. I. Pigment Red 177 is preferably used, and these may be used together.

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, and 214, and the like.
Among these, C.I. can be expanded in that the chromaticity region can be expanded. I. Pigment Yellow 138, 139 and 150 are preferable. I. Pigment Yellow 139 and 150 are more preferable.

  When used in combination with the above red pigment or yellow pigment, the content of the benzimidazolone pigment (a1) represented by the general formula (1) is preferably 10 to 100% by weight in the total 100% by weight of the colorant (a), preferably Is 20 to 90% by weight, more preferably 30 to 60% by weight. By being in this content range, the chromaticity region can be expanded.

<Resin (b)>
The resin (b) contained in the coloring composition for a color filter of the present invention disperses the colorant (a), and examples thereof include a thermoplastic resin and a thermosetting resin. The resin (b) is preferably a transparent resin having a spectral 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. Moreover, when using with the form of an alkali image development type photosensitive coloring composition, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic substituent containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  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 vinyl-based alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. It may be used in combination. In addition, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

  In order to disperse the colorant (a) preferably, the weight average molecular weight (Mw) of the resin (b) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. is there. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  In addition, from the viewpoint of dispersibility, stability, developability, and heat resistance of the colorant (a), as a colorant adsorption group and a carboxyl group that acts as an alkali-soluble group during development, an affinity group for the colorant carrier and the solvent The balance between the working aliphatic group and the aromatic group is important for the dispersibility of the pigment, the developer permeability in the coating film, the developer solubility of the uncured part, and the durability. The acid value is 20 to 300 mgKOH / g. It is preferable to use this resin. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The resin (b) is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant (a) because the film formability and various resistances are good, and the colorant concentration is high. From the viewpoint that good color characteristics can be expressed, it is preferably used in an amount of 500 parts by weight or less. More preferably, it is 100-400 weight part. More preferably, it is 160-320 weight part. The chromaticity region can be expanded by such a composition ratio of the pigment.

<Solvent (c)>
The solvent (c) is a filter segment in which a colorant is sufficiently dispersed in a resin, and the colored composition of the present invention is applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. Is used to facilitate the formation.
As the solvent (c), 1,2,3-trichloropropane, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3- Propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy- 3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N- Dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, P-chlorotoluene, P-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, Isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene Glycol monopropyl ether, ethylene glycol monohexyl ether, ethyl Lenglycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol Acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol Nopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate , Propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, vinegar n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used singly or in combination of two or more at any ratio as required.

  Among them, since the dispersibility of the colorant (a) of the present invention is good, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, It is preferable to use aromatic alcohols such as benzyl alcohol and ketones such as cyclohexanone.

  Since the solvent (c) can adjust the colored composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, the amount of the solvent (c) is 800 to 4000 parts by weight with respect to 100 parts by weight of the colorant (a). It is preferable to use in.

<Resin type dispersant (d)>
When dispersing the pigment in the pigment carrier, a resin-type pigment dispersant can be appropriately used. The resin-type dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, a red coloring composition obtained by dispersing a pigment in a pigment carrier using a dispersion aid was used. In this case, a color filter having a high spectral transmittance can be obtained.

  The resin-type dispersant has a pigment affinity unit containing an acidic substituent adsorbed on the benzimidazolone pigment (a1) represented by the general formula (1), and a unit compatible with the pigment carrier. It functions to stabilize the dispersion of the benzimidazolone pigment (a1) represented by the formula (1) in the pigment carrier.

Among the resin type dispersants that are acidic, the resin type dispersant (d1) having an acidic substituent is preferable.
In particular, when the benzimidazolone pigment (a1) represented by the general formula (1), the resin-type dispersant (d1) having an acidic substituent, and a dye derivative having a basic substituent are used, fluidity is obtained. This is preferable in order to exhibit excellent effects such as compatibility of the dispersion and dispersibility.

  The basic structure of the resin-type dispersant is not particularly limited, and examples thereof include general resins such as acrylic resins, polyester resins, polyether resins, urethane resins, silicone resins, epoxy resins, and vinyl acetate resins.

  Examples of the acidic substituent include a phosphoric acid group, a sulfonic acid group, and a carboxyl group. Further, trimellitic acid and / or pyromellitic acid partially esterified are preferably used. In some cases, an aromatic ring having two or more acidic substituents may be a unit having one acidic substituent by a plurality of direct bonds and / or linking groups. Especially, it is preferable to have two or more carboxyl groups in one molecule. A dispersant having two or more carboxyl groups in one molecule has more adsorbing groups to the colorant than a resin-type dispersant having zero or one carboxyl group in one molecule. This is preferable because it has a strong function of stabilizing the dispersion on the carrier, the polarity of the dispersant is increased, and higher dispersion stability can be secured.

  As the resin-type dispersant, those having an acidic substituent, an aromatic group or the like in the main chain or terminal of the linear resin, or in the main chain or side chain of the comb-like resin, in a block or randomly are preferable. Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, poly ( An amide formed by a reaction between a lower alkyleneimine) and a polyester having a free carboxyl group, a salt thereof, or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble High molecular compounds, polyesters, modified poly (meth) acrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are used. These may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  As a site | part with high affinity to a dispersion medium of the resin type dispersing agent of this invention, the at least 1 sort (s) of polymer unit chosen from polyester, polyether, and poly (meth) acrylate is preferable.

  For example, as polyester, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, One or more alcohols such as glycerin or hexanetriol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid ,Guru Conic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexa And polyester polyols obtained by cocondensation with one or more carboxylic acids such as tricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid.

  For example, as the polyether, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane Diol, 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol , Alcohols such as glycerin or hexanetriol, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether Others include modified polyether polyols and the like obtained by ring-opening polymerization of various (cyclic) ether bond-containing compounds such as allyl glycidyl ether.

  For example, as poly (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, etc. Alkoxypolyalkylene glycol (meth) acrylates such as xypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta) ) N-substituted (meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( Examples include homopolymers and copolymers such as amino group-containing (meth) acrylates such as (meth) acrylate and nitriles such as (meth) acrylonitrile. These may be used alone or in combination, or may be in the form of a block polymer, graft polymer or random polymer.

  Examples of commercially available resin-type pigment dispersants having acidic functional groups include Solsperse 3000, Solsperse 21000, Solsperse 26000, Solsperse 36600, Solsperse 41000, Solsperse 44000, Solsperse 46000, Solsperse 55000 (manufactured by Abyssia); Disper Bic 108, Disperbic 110, Disperbic 111, Disperbic 112, Disperbic 116, Disperbic 142, Disperbic 180, Disperbic 2000, Disperbic 2001, (manufactured by BYK Chemie); Disparon 3600N, Disparon 1850 PA111 (Ajinomoto Fine Techno Co.); EFKA4 401, EFKA4550 (Efka) But not limited to these.

  As the resin-type dispersant, an acidic resin-type dispersant having an aromatic carboxyl group is particularly preferable, a polymer having a hydroxyl group at one end, an aromatic tricarboxylic acid anhydride and / or an aromatic tetracarboxylic acid dianhydride. Most preferably, the dispersant is obtained by reacting with. Examples of such resin-type dispersants include Japanese Patent No. 40201050, Japanese Patent Application Laid-Open No. 2007-140487, International Publication No. 2008/007776, Japanese Patent Application Laid-Open No. 2010-163500, and Japanese Patent Application Laid-Open No. 2010-223888. And exhibits excellent effects such as compatibility between fluidity and dispersibility.

  Among these, a preferable resin-type dispersant is a radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule described in WO2008 / 007776 pamphlet. A polyester dispersant produced by reacting a hydroxyl group in a vinyl copolymer having two hydroxyl groups in one terminal region with an acid anhydride group in tetracarboxylic dianhydride is preferable. More preferably, the polyester dispersant is characterized in that the tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride. Color filter coloring compositions using these polyester dispersants are preferable because they are excellent in pigment dispersion stability, and are synthesized using the method described in WO2008 / 007776 pamphlet or the like. be able to.

A more preferable resin type dispersant includes a resin type dispersant represented by the following formula described in JP-A No. 2007-140487.
_{(HOOC-) m -R 4 - (} - COO - [- R 6 -COO-] q -R 5) t
[Wherein R ₄ is a tetravalent tetracarboxylic acid compound residue, R ₅ is a monoalcohol residue, R ₆ is a lactone residue, m is 2 or 3, q is an integer of 1 to 50, and t is (4 -M). ]

  A coloring composition for a color filter using an acidic resin type dispersant having an aromatic carboxyl group has very excellent pigment dispersion stability.

  The acid value of the resin-type dispersant (d) is preferably 200 mgKOH / g or less, more preferably 40 to 200 mgKOH / g, and most preferably 40 to 150 mgKOH / g from the viewpoint of dispersion stability. The weight average molecular weight (Mw) of the resin-type dispersant is preferably in the range of 1000 to 50000, more preferably 1000 to 30000.

  The content of the resin-type dispersant (d) is preferably 10 to 70 parts by weight, more preferably 20 to 55 parts by weight with respect to 100 parts by weight of the benzimidazolone pigment (a1) represented by the general formula (1). It is. When the blending amount of the resin-type dispersant (c) is less than 10 parts by weight, it is difficult to obtain the pigment dispersibility effect. On the other hand, when the amount exceeds 70 parts by weight, alkali developability may be lowered when a pixel dispersion pattern containing the pigment dispersion composition is used and a pixel pattern of a color filter is formed by a photolithography method.

<Dye derivative (e)>
The coloring composition for a color filter of the present invention can preferably use a pigment derivative (e). The dye derivative is excellent in dispersion of the benzimidazolone pigment and has a large effect of preventing reaggregation of the benzimidazolone pigment after dispersion.
As the pigment derivative (e), a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, β-naphthol compound, acridone compound or triazine compound. And the like.

That is, the structure of the pigment derivative (e) that can be used in the present invention is a compound represented by the following general formula (2).
P-Ln Formula (2)
[In general formula (2),
P: Organic pigment residue, β-naphthol residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: 1-4 It is an integer. ]

  Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; benzoisoindole pigments; copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine Phthalocyanine pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, etc .; quinacridone pigment; dioxazine pigment; perinone pigment; perylene pigment; Examples thereof include thiaindigo pigments; isoindoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

  Triazines constituting the triazine residue of P are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro groups, hydroxyl groups, Alkoxy group (methoxy group, ethoxy group, butoxy group etc.), halogen (chlorine, bromine etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen etc.) And a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) 3,5-triazine.

Especially, the pigment derivative which has a basic substituent whose L in General formula (2) is a basic substituent can be used preferably.
By including a dye derivative having a basic substituent, a pigment composition having excellent dispersibility, fluidity, and storage stability can be obtained even in the case of a pigment that is difficult to disperse without a dye derivative having a basic substituent. This is preferable. The pigment can be effectively dispersed by the synergistic effect of the acidic resin type dispersant and the dye derivative having a basic substituent, and a pigment composition having excellent fluidity and storage stability can be obtained.
Among the basic substituents, L is preferably a substituent selected from the group represented by the general formulas (3), (4), and (5).

［一般式（３）〜（５）中、
Ｘは、−ＳＯ₂−、−ＣＯ−、−ＣＨ₂−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂ＮＨＳＯ₂ＣＨ₂−、又は直接結合であり、
Ｙは、−ＮＨ−、−Ｏ−、又は直接結合であり、
ｎは、１〜１０の整数であり、
Ｙ¹は、−ＮＨ−、−ＮＲ⁵⁸−Ｚ−ＮＲ⁵⁹−、又は直接結合であり、
Ｒ⁵⁸、及びＲ⁵⁹は、それぞれ独立に、水素結合、置換基を有しても良い炭素数１〜３６のアルキル基、置換基を有しても良い炭素数２〜３６のアルケニル基、又は置換基を有しても良いフェニル基であり、
Ｚは、置換基を有しても良いアルキレン基、又は置換基を有しても良いアリーレン基であり、
Ｒ⁵⁰、Ｒ⁵¹は、それぞれ独立に、水素原子、置換基を有しても良い炭素数１〜３０のアルキル基、置換基を有しても良い炭素数２〜３０のアルケニル基、又はＲ⁵⁰とＲ⁵¹とが一体となって更なる窒素、酸素、若しくは硫黄原子を含む、置換基を有しても良い複素環であり、
Ｒ⁵²、Ｒ⁵³、Ｒ⁵⁴、及びＲ⁵⁵は、それぞれ独立に、水素原子、置換基を有しても良い炭素数１〜２０のアルキル基、置換基を有しても良い炭素数２〜２０のアルケニル基、置換基を有しても良い炭素数６〜２０のアリーレン基であり、
Ｒ⁵⁶は、水素原子、置換基を有しても良い炭素数１〜２０のアルキル基、置換基を有しても良い炭素数２〜２０のアルケニル基であり、
Ｒ⁵⁷は、上記一般式（３）で示される置換基、又は上記一般式（４）で示される置換基であり、
Ｑは、水酸基、アルコキシル基、上記一般式（３）で示される置換基、又は上記一般式（４）で示される置換基である。］

[In the general formulas (3) to (5),
X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁵⁸ —Z—NR ⁵⁹ —, or a direct bond;
R ⁵⁸ and R ⁵⁹ are each independently a hydrogen bond, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or A phenyl group which may have a substituent,
Z is an alkylene group which may have a substituent, or an arylene group which may have a substituent,
R ⁵⁰ and R ⁵¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R ⁵⁰ and R ⁵¹ together are a heterocyclic ring which may further have a substituent containing a further nitrogen, oxygen or sulfur atom,
R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. 20 alkenyl group, an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ⁵⁶ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms,
R ⁵⁷ is a substituent represented by the general formula (3) or a substituent represented by the general formula (4);
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the above general formula (3), or a substituent represented by the above general formula (4). ]

  Examples of the amine component used to form the substituents represented by the general formulas (3) to (5) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadeci Amine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopen Ruamine, N, N-methyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonipecotate, Isonipecotic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, -Aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. Can be mentioned.

  The pigment derivative, β-naphthol derivative, and acridone derivative having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, after introducing the substituents represented by the formulas (6) to (9) into the organic dye, β-naphthol or acridone, the substituents represented by the formulas (3) to (5) are reacted with the above substituents. The amine component to be formed, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5 -Triazin-2-ylamino] aniline and the like are obtained by reaction.

Formula (6): —SO ₂ Cl
Formula (7): -COCl
Equation _{(8): -CH 2 NHCOCH 2} Cl
Formula (9): —CH ₂ Cl

  When the substituents of the formulas (6) to (9) and the amine component are reacted, a part of the substituents of the formulas (6) to (9) are hydrolyzed and chlorine is substituted with a hydroxyl group. It may be. In that case, the formula (6) and the formula (7) respectively become a sulfonic acid group and a carboxylic acid group, but both may be a free acid, or a 1-3 valent metal or the above monoamine. Or a salt thereof.

  When the organic dye is an azo dye, the substituent represented by the general formulas (3) to (5) is previously introduced into the diazo component or the coupling component, and then a coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The triazine derivative having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by general formulas (3) to (5) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  Further, the matrix skeleton is preferably a dye derivative in which P in the general formula (2) is an organic pigment residue, β-naphthol residue, or triazine residue. Among them, thiaindigo pigments, benzoisoindole pigments, diesters Organic pigment residues that are ketopyrrolopyrrole pigments or anthraquinone pigments, or triazine residues are preferred.

  That is, in the colored composition of the present invention, P in the general formula (2) is an organic pigment residue, β-naphthol residue, or triazine residue, and L in the general formula (2) is a basic substitution. From the viewpoint of dispersion stability, a dye derivative having a basic substituent, a β-naphthol derivative having a basic substituent, and a triazine derivative having a basic substituent are preferable. Among them, the triazine derivative having a basic substituent is excellent in dispersion of the benzimidazolone pigment and has the greatest effect of preventing reaggregation of the benzimidazolone pigment after dispersion.

  In the present invention, the blending amount of the dye derivative (e) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, most preferably 100 parts by weight or more with respect to 100 parts by weight of the benzimidazolone pigment (a1), from the viewpoint of improving dispersibility. Preferably it is 15 parts by weight or more. Further, from the viewpoint of heat resistance and light resistance, it is preferably 30 parts by weight or less, and most preferably 25 parts by weight or less with respect to 100 parts by weight of the benzimidazolone pigment.

  The coloring composition for a color filter of the present invention can be used as a photosensitive coloring composition (resist material) for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer used in the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to form a resin, and these can be used alone or in combination of two or more.

Examples of the photopolymerizable monomer include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, β-carboxyethyl methacrylate, polyethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 1,6-hexanediol di Glycidyl ether dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, neopentyl grease 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 compounds can be used singly or in combination of two or more at any ratio as required.

  The content of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant (a), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Photopolymerization initiator>
In the coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithography method, a photopolymerization initiator or the like is added to add a solvent development type or an alkali development type photosensitive. Can be prepared in the form of an ionic coloring composition.

Examples of the photopolymerization initiator include 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] -1 Acetophenone compounds such as-[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 ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -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, or 2,4-trichloromethyl- (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O Oxime ester compounds such as (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; 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; borate compounds; carbazole compounds; imidazole compounds Or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

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

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as 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, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori 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 also 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 contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Amine compound>
Moreover, the coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. 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.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in 100% by weight of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, 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 Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight based on the total weight of the thermosetting resin (100 parts by weight).

<Other additive components>
The coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight relative to 100 parts by weight of the total weight of the colorant (a).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total weight of the colorant (a).

<Method for producing colored composition>
The coloring composition for a color filter of the present invention includes a colorant (a) containing a benzimidazolone pigment (a1) represented by the general formula (1), a resin-type dispersant, and a resin (b) as necessary. The solvent (c) and the pigment derivative (e) can be produced by finely dispersing together using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, a trimix, or an attritor. (Pigment dispersion). Moreover, the coloring composition for a color filter of the present invention may be obtained by dispersing together the benzimidazolone pigment (a1) represented by the general formula (1) and other colorants such as a red pigment and a yellow pigment used together. Well, it can be manufactured by mixing separately dispersed ones

It is preferable that the coloring composition for a color filter does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less. It is preferable that the color filter red coloring composition of the present invention does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less. (Measurement of particle size by SEM)
In addition, the average dispersed particle size of the color filter red coloring composition of the present invention is preferably 0.05 to 0.2 μm to increase the brightness and contrast ratio, and is 0.06 to 0.15 μm. Since brightness and contrast ratio can be made high, it is more preferable.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition comprises the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other dispersants, and additives. Can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Removal of coarse particles>
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that the coloring composition for color filters substantially does not contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
The color filter of the present invention is a color filter comprising at least one filter segment formed from the coloring composition for a color filter of the present invention.
The color filter comprises 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 a red coloring composition for a color filter of the present invention. It is preferable to use a product.

  The green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. Pigment Green 7, 10, 36, 37, 58, and the like. Green coloring compositions 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 It can be used in combination with the yellow pigments such as 181,182,185,187,188,193,194,198,199,213,214.

  Moreover, a blue filter segment can be formed using a normal blue coloring composition. Examples of the blue coloring composition include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.
[Printing method]
The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. 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.

[Photolithography]
When forming a filter segment by a photolithography method, the photosensitive coloring composition prepared as the solvent development type or alkali development type coloring composition is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays, which are active energy rays, 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 | stimulate superposition | polymerization of a coloring composition, it can also heat as needed. 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 composition, 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, etc. 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 substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  The colored composition of the present invention can be used in any of the methods described above, but is most suitable for the photolithography method.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  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.

  Also, the acid value and weight average molecular weight (Mw) of the resin and resin type dispersant, the amine value and quaternary ammonium salt value of the resin type dispersant, the average primary particle diameter and specific surface area of the pigment, and the contrast ratio of the coating film The measuring method is as follows.

<Acid value of resin and resin type dispersant>
The acid values of the resin and the resin-type dispersant were determined by potentiometric titration using a 0.1N potassium hydroxide / ethanol solution. The acid value of the resin and the resin-type dispersant indicates the acid value of the solid content.

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

<Amine value of resin-type dispersant>
The amine value of the resin-type dispersant was determined by potentiometric titration using a 0.1N hydrochloric acid aqueous solution, and then converted to an equivalent of potassium hydroxide. The amine value of the resin-type dispersant indicates the amine value of the solid content.

<Quaternary ammonium salt value of resin-type dispersant>
The quaternary ammonium salt value of the resin-type dispersant was determined by titrating with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into an equivalent of potassium hydroxide. The quaternary ammonium salt value of the following resin type dispersant indicates the quaternary ammonium salt value of the solid content.

<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 the primary particles from an electron micrograph of a transmission electron microscope (TEM). 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, 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.

<Specific surface area of pigment>
The specific surface area of the pigment was measured by an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the nitrogen adsorption BET method.

<Contrast ratio of coating film>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

First, the used pigment derivative (e) will be described.
<Structural formula of dye derivative (e)>
Table 1 summarizes the basic skeleton and substituents of the dye derivative (e) used, and then shows the structural formula of the dye derivative.

  Then, the manufacturing method of the acrylic resin solution used for the Example and the comparative example, the resin-type dispersant solution, the refinement | purification pigment, the pigment dispersion, the green photosensitive coloring composition, and the blue photosensitive coloring composition is demonstrated.

<Method for producing acrylic resin solution>
(Adjustment of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acrylic resin solution 1 was prepared by adding ether acetate.

(Adjustment of acrylic resin solution 2)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 19000. Obtained. 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. Then, an acrylic resin solution 2 which is an active energy ray curable resin was prepared.

<Method for producing resin-type dispersant>
(Resin type dispersant A solution)
A reaction vessel equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added here, and it was made to react at 120 degreeC for 2 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. In this way, a resin type dispersant A solution having a polycaprolactone skeleton having an acid value of 49 mgKOH / g per solid content and a nonvolatile content of 40% by weight and having an aromatic carboxyl group was obtained.

<Production method of fine pigment>
(Preparation of refined pigment 1 (PC-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 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 diketopyrrolopyrrole-based refined pigment 1 (PC-1) was obtained. The average particle diameter of primary particles of the micronized pigment 1 was 24.8 nm, and the BET specific surface area determined by the nitrogen adsorption method was 70 m ² / g.

(Preparation of refined pigment 2 (PC-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 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 anthraquinone-based micronized pigment 2 (PC-2) were obtained. The average particle diameter of the primary particles of the micronized pigment 2 was 27.6 nm, and the BET specific surface area determined by the nitrogen adsorption method was 80 m ² / g.

(Preparation of fine pigment 3 (PC-3))
Isoindoline yellow pigment C.I. I. 200 parts of Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by Ciba Geigy Co.), 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. did. 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 refined pigment 3 (PC-3) was obtained. The average particle diameter of primary particles of the micronized pigment 3 was 36.0 nm, and the BET specific surface area determined by the nitrogen adsorption method was 75 m ² / g.

(Preparation of refined pigment 4 (PC-4))
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 yellow refined pigment 4 (PC-4) was obtained. The average particle diameter of the primary particles of the micronized pigment 4 was 39.2 nm, and the BET specific surface area determined by the nitrogen adsorption method was 90 m ² / g.

(Preparation of refined pigment 5 (P-1))
Benzimidazolone pigment C.I. I. 200 parts of Pigment Red 176 (“Novoperm Carmine HF3C” manufactured by Clariant), 10 parts of derivative A, 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 60 ° 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 5 (P-1) were obtained. The average particle diameter of the primary particles of the micronized pigment 5 was 30.0 nm, and the BET specific surface area determined by the nitrogen adsorption method was 30 m ² / g.

(Preparation of refined pigment 6 (P-2))
Benzimidazolone pigment C.I. I. 200 parts of Pigment Red 176 (“Novoperm Carmine HF3C” manufactured by Clariant), 10 parts of derivative A, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° 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 6 (P-2) were obtained. The average particle diameter of primary particles of the micronized pigment 6 was 20.0 nm, and the BET specific surface area determined by the nitrogen adsorption method was 10 m ² / g.

(Preparation of refined pigment 7 (P-3))
Benzimidazolone pigment C.I. I. 200 parts of Pigment Red 176 (“Novoperm Carmine HF3C” manufactured by Clariant), 10 parts of derivative A, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 7 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 7 (P-3). The average particle diameter of the primary particles of the micronized pigment 7 was 40.0 nm, and the BET specific surface area determined by the nitrogen adsorption method was 50 m ² / g.

(Preparation of refined pigment 8 (P-4))
Benzimidazolone pigment C.I. I. 200 parts of Pigment Red 176 ("Novoperm Carmine HF3C" manufactured by Clariant), 20 parts of derivative A, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 10 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 8 (P-4) were obtained. The average particle diameter of primary particles of the micronized pigment 8 was 30.0 nm, and the BET specific surface area measured by the nitrogen adsorption method was 120 m ² / g.

(Preparation of refined pigment 9 (P-5))
Benzimidazolone pigment C.I. I. 200 parts of Pigment Red 176 (“Novoperm Carmine HF3C” manufactured by Clariant), 20 parts of derivative A, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 5 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 9 (P-5) were obtained. The average particle diameter of primary particles of the micronized pigment 9 was 30.0 nm, and the BET specific surface area determined by the nitrogen adsorption method was 65 m ² / g.

(Preparation of refined pigment 10 (P-6))
Benzimidazolone pigment C.I. I. Pigment Red 176 (Clariant “Novoperm Carmine HF3C”) 200 parts, derivative A 5 parts, sodium chloride 3000 parts, and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (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 10 (P-6) were obtained. The average particle diameter of primary particles of the micronized pigment 10 was 120 nm, and the BET specific surface area by nitrogen adsorption method was 5 m ² / g.

(Preparation of refined pigment 11 (P-7))
Benzimidazolone pigment C.I. I. 200 parts of Pigment Red 176 (“Novoperm Carmine HF3C” manufactured by Clariant), 5 parts of derivative A, 3000 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 8 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 11 (P-7) were obtained. The average particle diameter of the primary particles of the micronized pigment 11 was 80.0 nm, and the BET specific surface area determined by the nitrogen adsorption method was 5 m ² / g.

(Preparation of green fine pigment 1)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by Dainippon Ink & Chemicals, Inc.), 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 was put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. As a result, 190 parts of green refined pigment 1 were obtained, the average particle diameter of primary particles of green refined pigment 1 was 28.2 nm, and the BET specific surface area by nitrogen adsorption method was 75 m ² / g.

(Preparation of blue refined pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyo Ink Mfg. Co., Ltd. “LIONOL BLUE ES”, specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) It knead | mixed at 80 degreeC 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 blue refined pigment 1 were obtained. The average particle diameter of the primary particles of the blue refined pigment 1 was 28.3 nm, and the BET specific surface area by the nitrogen adsorption method was 80 m ² / g.

(Preparation of purple fine pigment 1)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Ink Manufacturing Co., Ltd.), 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 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 purple refined pigment 1 was obtained. The average particle diameter of the primary particles of the purple refined pigment 1 was 26.4 nm, and the BET specific surface area determined by the nitrogen adsorption method was 95 m ² / g.

<Method for producing pigment dispersion>
(Pigment dispersion (DC-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. The pigment dispersion (DC-1) whose non-volatile component is 20 weight% was produced.
Fine pigment 1 (PC-1): 11.0 parts (CI Pigment Red 254)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin type dispersant solution (dispersant A): 5.0 parts

(Pigment dispersion (DC-2))
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. The pigment dispersion (DC-2) whose non-volatile component is 20 weight% was produced.
Fine pigment 2 (PC-2): 11.0 parts (CI Pigment Red 177)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin type dispersant solution (dispersant A): 5.0 parts

(Pigment dispersion (DC-3))
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. The pigment dispersion (DC-3) whose non-volatile component is 20 weight% was produced.
Fine pigment 3 (PC-3): 11.0 parts (CI Pigment Yellow 139)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin type dispersant solution (dispersant A): 5.0 parts

(Preparation of pigment dispersion (DC-4))
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. The pigment dispersion (DC-4) whose non-volatile component is 20 weight% was produced.
Fine pigment 4 (PC-4): 11.0 parts (CI Pigment Yellow 150)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin-type dispersant solution (“EFKA4300” manufactured by Ciba Japan): 5.0 parts

<Method for producing green and blue photosensitive coloring composition>
(Green photosensitive coloring composition 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. The green pigment dispersion 1 having a nonvolatile content of 20% by weight was prepared.
Green refined pigment 1 (CI Pigment Green 58): 11.0 parts acrylic resin solution 1: 35.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts resin-type dispersant solution (Ciba Japan) "EFKA4300"): 5.0 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition 1.
Green pigment dispersion: 32.0 parts Pigment dispersion (DC-4): 18.0 parts Acrylic resin solution 2: 7.5 parts Photopolymerizable monomer (“Aronix M-402” manufactured by Toagosei Co., Ltd.): 2.0 parts dipentaerythritol hexaacrylate photopolymerization initiator (“OXE-02” manufactured by Ciba Japan): 1.5 parts ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition 1)
A non-volatile content of 20 was obtained in the same manner as the green pigment dispersion except that the green refined pigment 1 (CI Pigment Green 58) was changed to the blue refined pigment 1 (CI Pigment Blue 15: 6). A weight percent blue pigment dispersion was obtained.

  The non-volatile content is 20% by weight in the same manner as the green pigment dispersion except that the green fine pigment 1 (CI Pigment Green 58) is changed to the purple fine pigment 1 (CI Pigment Violet 23). A purple pigment dispersion was obtained.

  Subsequently, 50.0 parts in total of 32.0 parts of the green pigment dispersion and 18.0 parts of the pigment dispersion (DC-4) were converted to 46.0 parts in the blue dispersion and 4.0 parts in total of the purple dispersion 50. A blue photosensitive coloring composition 1 was obtained in the same manner as the green photosensitive coloring composition 1 except that 0 part was replaced.

[Example 1]
(Pigment dispersion (D-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. The pigment dispersion (D-1) whose non-volatile component is 20 weight% was produced.
Fine pigment 5 (P-1): 10.0 parts (CI Pigment Red 176)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin type dispersant solution (dispersant A): 5.0 parts Dye derivative (derivative A): 1.0 part

[Examples 2 to 10]
Hereinafter, a pigment dispersion (D-2 to 10) was prepared in the same manner as the pigment dispersion (D-1) except that the pigment, resin-type dispersant, and dye derivative were changed to the compositions shown in Table 2.

[Comparative Examples 1-4]
Hereinafter, a pigment dispersion (D11-14) was prepared in the same manner as the pigment dispersion (D-1) except that the pigment, resin-type dispersant, and derivative were changed to the compositions shown in Table 2.

[Evaluation of coloring composition (pigment dispersion) for color filter]
The viscosity of the pigment dispersions (D-1 to 14) obtained in Examples and Comparative Examples, the contrast ratio, and the heat resistance of the coating film were evaluated by the following methods. The results are shown in Table 3.

<Viscosity characteristics>
As for the viscosity of the pigment dispersion, an initial viscosity at 25 ° C. was measured using an E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the pigment dispersion was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the time-dependent viscosity.

<Contrast ratio (CR)>
Using the obtained pigment dispersion, a spin coater was used to produce three coated substrates so that the dry film thickness was about 1 μm by changing the number of rotations. After coating, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and the film thickness and the contrast ratio were measured. The contrast ratio (CR) at a film thickness of 1 μm was determined from the three points of data by the primary correlation method.

<Evaluation of heat resistance of coating film>
The coloring composition was applied on the transparent substrate so that the dried coating film was about 1.0 μm, and dried at 70 ° C. for 20 minutes. Then, after heating and cooling in an oven at 230 ° C. for 1 hour, the obtained coating film was subjected to L * a * b * color system using a C light source with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The color measurement (L * (1), a * (1), b * (1)) was performed. After that, as a heat resistance test, it was heated in an oven at 250 ° C. for 1 hour, and the color measurement (L * (2), a * (2), b * (2)) was performed in the same manner, and the color difference ΔEab * was calculated by the following formula. It calculated and the heat resistance of the coating film was evaluated in the following four steps.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
◎: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 Δ: ΔEab * is 3.0 or more and less than 5.0 x: ΔEab * is 5.0 or more

In Examples 1 to 10, a colorant (a) containing a benzimidazolone pigment (a1) represented by the general formula (1) having a BET specific surface area of 10 m ² / g or more and 50 m ² / g or less by a nitrogen adsorption method is used. When it was, the viscosity was low, the CR was high, and the heat resistance was good.

  In particular, in the pigment compositions of Examples 1, 9, and 10, when an acidic resin type dispersant having an aromatic carboxylic acid group as an acidic substituent and a triazine derivative having a basic substituent are used, the viscosity is lower. , Higher CR and better heat resistance were obtained.

Further, in Comparative Examples 1, 2, 3, and 4, when the specific surface area exceeds 50 m ² / g, although the effect of improving the contrast is seen, the dispersibility and dispersion stability of the pigment are low, so the viscosity is not high. It became a stable state, and fluidity and storage stability were insufficient. When the specific surface area was lower than 10 m ² / g, the contrast ratio was low.

[Example 11]
(Photosensitive coloring composition (R-1))
The following mixture (100 parts in total) was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a photosensitive colored composition (R-1).
(Pigment dispersion) (Total 50 parts)
Pigment dispersion (D-1): 16.0 parts Pigment dispersion (DC-2): 26.5 parts Pigment dispersion (DC-3): 7.5 parts Acrylic resin solution 2: 7.5 parts Photopolymerization Monomer ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Dipentaerythritol hexaacrylate photopolymerization initiator ("OXE-02" manufactured by Ciba Japan): 1.5 parts Ethanone, 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

[Examples 12 to 23, Comparative Examples 5 to 11]
(Photosensitive coloring composition (R-2 to 20))
A photosensitive colored composition (R-2 to 18) was obtained in the same manner as the photosensitive colored composition (R-1) except that the pigment dispersion was changed to the type and blending amount of the pigment dispersion shown in Table 4. . In each photosensitive coloring composition adjustment, it added so that the sum total of a pigment dispersion might be 50 parts, and adjusted 100 parts of photosensitive coloring compositions.

[Evaluation of Color Filter Coloring Composition (Photosensitive Coloring Composition)]
The color characteristics of the photosensitive coloring compositions (R-1 to 20) obtained in Examples and Comparative Examples (R-1 to 20), the contrast ratio, and the heat resistance of the coating film were evaluated by the following methods. The results are shown in Table 5.

<Color characteristic evaluation>
The obtained photosensitive coloring composition is applied onto a glass substrate, dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes, so that the chromaticity of the substrate is x = 0. 658, y = 0.325 was obtained. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

<Contrast ratio (CR)>
Using the spin coater, the photosensitive coloring composition thus obtained was changed to 3 points so that the chromaticity x with a C light source in the CIE color system was 0.650, 0.658, and 0.665 by changing the rotation speed. A coated substrate was prepared. After coating and drying in a hot air oven at 80 ° C. for 30 minutes, the chromaticity and contrast ratio were measured, respectively, and the contrast ratio (CR) at a chromaticity x of 0.658 was determined from the three points by the primary correlation method. .
<Viscosity characteristics>
The viscosity of the photosensitive coloring composition was determined by measuring the initial viscosity at 25 ° C. using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the pigment dispersion was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the time-dependent viscosity.

<Evaluation of heat resistance of coating film>
The photosensitive coloring composition was applied on a transparent substrate so that the dried coating film was about 2.0 μm, and dried at 70 ° C. for 20 minutes. After performing ultraviolet exposure through a mask having a predetermined pattern, an alkali developer was sprayed by spraying to remove the uncured portion, thereby forming a desired pattern. Then, after heating and cooling in an oven at 230 ° C. for 1 hour, the obtained coating film was subjected to L * a * b * color system using a C light source with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The color measurement (L * (1), a * (1), b * (1)) was performed. After that, as a heat resistance test, it was heated in an oven at 250 ° C. for 1 hour, and the color measurement (L * (2), a * (2), b * (2)) was performed in the same manner, and the color difference ΔEab * was calculated by the following formula. It calculated and the heat resistance of the coating film was evaluated in the following four steps.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
：: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more, Table 6 shows Results are shown.

In Examples 11 to 23, a colorant (a) containing a benzimidazolone pigment (a1) represented by the general formula (1) having a BET specific surface area of 10 m ² / g or more and 50 m ² / g or less by a nitrogen adsorption method is used. The colored compositions for color filters of the present invention had high brightness and CR, low viscosity and good heat resistance.

In contrast, in Comparative Examples 5 and 6, the photosensitive coloring composition containing a benzimidazolone pigment having a BET specific surface area of more than 50 m ² / g by the nitrogen adsorption method has low dispersibility and dispersion stability of the pigment. When the pigment dispersion is prepared using the pigment, reaggregation of the pigment particles occurs, the viscosity becomes unstable and the fluidity and storage stability are insufficient, and the brightness and CR are low. And the viscosity was high.

In Comparative Examples 7 and 8, when the specific surface area of the benzimidazolone pigment was lower than 10 m ² / g, the brightness and CR were low.

  The photosensitive coloring composition containing no benzimidazolone pigment had a low CR in Comparative Example 9, and a low brightness in Comparative Examples 10 and 11.

[Example of color filter production]
Using the red photosensitive coloring composition 1, the green photosensitive coloring composition 1 and the blue photosensitive coloring composition 1 of the present invention, the dry film thickness is 1.7 μm by spin coating on the substrate. It is applied, dried, and exposed to UV light through a mask having a predetermined pattern provided in a non-contact state with the coating film. After that, an alkaline developer is sprayed to remove the uncured portion and form a desired pattern. After that, it was heated at 230 ° C. for 1 hour. By repeating the same operation for green and blue to produce a color filter, an RGB three-color filter having high brightness and excellent heat resistance could be produced.

Claims (6)

In a coloring composition containing a coloring agent (a), a resin (b), a solvent (c) , an acidic resin-type dispersant having an aromatic carboxyl group, and a pigment derivative having a basic substituent , The colorant (a) is a C.I. having a BET specific surface area of 10 m ² / g or more and 50 m ² / g or less by a nitrogen adsorption method. I. A red coloring composition for a color filter, comprising Pigment Red 176. C. above. I. The red colored composition for a color filter according to claim 1, wherein an average primary particle size of CI Pigment Red 176 is 10 to 50 nm. C. above. I. The red coloring composition for a color filter according to claim 1 or 2, wherein Pigment Red 176 is a pigment obtained by a salt milling treatment in the presence of a pigment derivative having a basic substituent . The colorant (a) further contains C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment yellow 139 and C.I. I. For color filters red coloring composition according to claim 1 to 3 any one which is characterized by containing at least one kind of pigment selected from the group consisting of CI Pigment Yellow 150. The red colored composition for a color filter according to any one of claims 1 to 4, further comprising a photopolymerizable monomer and / or a photopolymerization initiator. A color filter comprising a red filter segment formed from the red coloring composition for a color filter according to any one of claims 1 to 5 on a substrate.