KR101904761B1 - Red colored composition for color filter, and color filter - Google Patents

Abstract

A coloring composition for a color filter which is excellent in fluidity and a color filter formed by using a red coloring composition having a high brightness and contrast ratio and which is excellent in color characteristics and excellent in heat resistance, (A), a resin (b), a resinous dispersant (c) having an acidic substituent, and a solvent (d), each of which contains a benzimidazolone pigment represented by the following general formula (1)
[Chemical Formula 1]

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a red coloring composition and a color filter for a color filter,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube device and the like, and a color filter having a filter segment formed by using the same.

The liquid crystal display device is a display device which performs display by controlling the amount of light passing through the second polarizer plate by controlling the degree of polarization of light passing through the first polarizer plate and the liquid crystal layer interposed between the two polarizers, And a type using a 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 are provided on one substrate to apply an electric field in a direction parallel to the substrate, a nematic liquid crystal having negative dielectric anisotropy Vertical alignment (VA) system for vertically aligning and Optical Convensend Bend (OCB) system for optically compensating optical axes of a uniaxial retardation film by mutually orthogonalizing each other are put to practical use.

In the liquid crystal display device, color display can be achieved by providing a color filter between two polarizing plates. Recently, since the liquid crystal display device is used for a television or a monitor of a computer, the demand for high contrast and high definition for a color filter is increasing.

The color filter is formed by arranging filter strips of a fine band (stripe) shape having two or more different colors on the surface of a transparent substrate such as glass in parallel or crossing, or arranging fine filter segments in a horizontal arrangement . The filter segments are not only fine from several microns to several hundreds of microns, but also arranged in a predetermined arrangement in a regular manner for each color.

In general, 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 orienting the liquid crystal in a predetermined direction is formed thereon. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is generally necessary to carry out the formation at a high temperature of 200 DEG C or higher, preferably 230 DEG C or higher. For this reason, at present, as a method of producing a color filter, a method called a pigment dispersion method using a pigment excellent in light resistance and heat resistance as a coloring agent is mainstream.

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

Here C.I. Pigment Red 254 is a pigment that is particularly excellent in luminance when used as a coloring composition. Further, since the coloring power is high, it is advantageous in adjusting the chromaticity of the color filter and adjusting the film thickness. However, C.I. Pigment Red 254 is disadvantageous in that it has a problem in heat resistance when it is used in a finely divided state, and the contrast ratio is lowered when a colored coating film is formed using a fine powder.

Further, as a method of obtaining a color filter having a high contrast ratio, C.I. Pigment Red 254, C.I. Pigment Red 177 is added to prepare a coloring composition. However, C.I. Since Pigment Red 177 itself is low in luminance and coloring power, it can not be used at a high content, and consequently C.I. Pigment Red 254 to C.I. When Pigment Red 177 is contained, the luminance, coloring power and contrast are lowered on average, and therefore there is a limit to the high contrast ratio and high definition as long as the combination of these conventionally used red and yellow pigments can be used .

Thus, C.I. Pigment Red 177 or C.I. Development of a coloring composition for a color filter having a pigment having a high luminance and a high contrast ratio as a coloring material exhibiting a higher coloring power and exhibiting a clearer color tone and a wider color display region than a color filter using Pigment Red 254 is required. Benzimidazolone pigments have been proposed as pigments (Patent Document 1). Patent Document 1 discloses that benzimidazolone pigment C.I. Pigment Red 176 as a main pigment. However, C.I. The use of Pigment Red 176 alone is insufficient for realizing a further higher high contrast as required in recent years, and in the case of including a finely divided pigment, fluidity also becomes a problem. Furthermore, when the strongly agglomerated fine pigment particles are unwound, much energy is required to disperse until high gloss and transparency are obtained.

Since the affinity of the pigment itself to the solvent and the acidity of the pigment surface are different from those of CI Pigment Red 254 and CI Pigment Red 177 and the like, the benzimidazolone pigment has excellent dispersibility, fluidity and storage stability , But a coloring composition having a high brightness and a high contrast ratio has not yet been obtained.

Japanese Patent Application Laid-Open No. 2009-237462

An embodiment of the present invention is to provide a coloring composition for a stable color filter having high brightness and a high contrast ratio and excellent fluidity and a color filter formed using the coloring composition for color filter and excellent in color characteristics and excellent in heat resistance .

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a colorant (a) comprising a benzimidazolone pigment (a1) represented by the formula (1) and a resinous dispersant having an acidic substituent It has been found that the above problems can be solved by a coloring composition comprising a resinous dispersant (c).

The present invention relates to the following embodiments.

That is, an embodiment of the present invention is a coloring composition containing a colorant, a resin, a resinous dispersant and a solvent, wherein the colorant comprises a benzimidazolone pigment represented by the following formula (1) Wherein the dispersing agent is a resinous dispersant having an acidic substituent.

[Chemical Formula 1]

Here, the formula (1) of, R _1, R _2, 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 BET specific surface area of the benzimidazolone pigment represented by the formula (1) by the nitrogen adsorption method may be 10 m ² / g or more and 50 m ² / g or less.

The benzimidazolone pigment represented by the formula (1) may be CI Pigment Red 176. [

The resinous dispersant having an acidic substituent may be a resinous dispersant having two or more carboxyl groups in one molecule.

The dye derivative (e) comprises at least one dye selected from the group consisting of a pigment derivative having a basic substituent, a? -Naphthol derivative having a basic substituent, and a triazine derivative having a basic substituent Or may contain a pigment derivative having a basic substituent group or more.

The colorant may further contain at least one pigment selected from the group consisting of CI Pigment Red 254, CI Pigment Red 177, CI Pigment Yellow 139 and CI Pigment Yellow 150.

It may also contain a photopolymerizable monomer and / or a photopolymerization initiator.

An embodiment of the present invention also relates to a color filter characterized by comprising a red filter segment formed from any one of the red coloring compositions for a color filter.

(A) is a coloring composition containing a colorant (a), a resin (b) and a solvent (d), wherein the colorant (a) has a BET specific surface area of 10 m ² / and a benzimidazolone pigment (a2) represented by the general formula (1), wherein the benzimidazolone pigment (a2) is at least 50 m ² / g.

According to the embodiment described above, not only is it possible to provide a coloring composition for a color filter having high brightness and high contrast ratio and high stability due to its high flowability, and by using it, it is possible to provide a color filter having good color characteristics, Can be formed.

Hereinafter, embodiments of the present invention will be described in detail.

The red coloring composition for a color filter comprises a colorant (a) containing a benzimidazolone pigment (a1) represented by the formula (1), a resin (b), a resinous dispersant (c), a resinous dispersant having an acidic substituent, And a solvent (d).

≪ Colorant (a) >

The colorant (a) in the coloring composition for a color filter contains the benzimidazolone pigment (a1) represented by the formula (1).

[Chemical Formula 1]

In the equation (1) of, R _1, R _2, 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 a solvent and to light. By using this pigment, a coloring composition for a color filter having excellent brightness and contrast ratio can be obtained.

Examples of the benzimidazolone pigment (a1) include CI Pigment Red 171, 175, 176, 185, 208 and the like as represented by color index (CI) numbers. Among them, CI Pigment Red 176 is preferable because it has a high contrast ratio and high brightness.

The benzimidazolone pigment (a1) has a BET specific surface area of not less than 10 m ² / g and not more than 50 m ² / g (hereinafter referred to as benzimidazolone pigment (a2)) by a nitrogen adsorption method, More preferably 10 m ² / g or more and less than 40 m ² / g. Particularly preferably, the specific surface area is 15 m ² / g or more and less than 35 m ² / g.

When the specific surface area of the benzimidazolone pigment is 10 m ² / g or more, the luminance and the contrast ratio of the color filter are higher, which is preferable. When the specific surface area is 50 m ² / g or less, the dispersibility and the dispersion stability of the pigment are good in addition to the effect of improving the sharpness, brightness and contrast ratio of the coating film, and when the pigment dispersion is prepared using the pigment, Is not re-agglomerated and has a stable viscosity. Therefore, it has excellent fluidity and storage stability, and has excellent luminance and contrast ratio characteristics of a color filter. In addition, since a small amount of the polymer dispersant necessary for dispersion stabilization can be obtained, it is excellent in resolution and developability.

On the other hand, the specific surface area of the pigment is the specific surface area of the dried pigment when measured according to an automatic vapor adsorption amount measuring apparatus (BELSORP 18 manufactured by BEL Japan, Inc.) according to the BET method of nitrogen adsorption. Since the benzimidazolone pigment has a specific surface area of 10 m ² / g or more and 50 m ² / g or less, it can be more suitably used as a red pigment for a color filter. The method for obtaining such a fine pigment is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation described below can be used. By these methods, a method of obtaining a fine pigment with a density of 10 m ² / g to 50 m ² / g The following fine pigment can be suitably obtained.

As the coloring agent (a) in the coloring composition for a color filter, benzimidazolone pigments may be used singly or in combination of two or more kinds.

Further, in order to facilitate color adjustment, other red pigment, yellow pigment, or the like may be used in combination.

For example, CI Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48 81, 81: 3, 81: 4, 122, 146, 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 them, CI Pigment Red 254 or CI Pigment Red 177 is preferably used from the viewpoint of obtaining a high contrast ratio and high brightness, and both of them may be used.

Examples of yellow pigments that can be used in combination include CI 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, , 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, 182, 185, 187, 188, 193, 194, 198, 199, 213 and 214.

Of these, CI Pigment Yellow 138, 139 and 150 are preferable and CI Pigment Yellow 139 and 150 are more preferable in that the chromaticity region can be widened.

When the red pigment or the yellow pigment is used in combination, the content of the benzimidazolone pigment (a1) is preferably 10 to 100% by weight, preferably 20 to 90% by weight, more preferably 10 to 100% by weight, Preferably 30 to 60% by weight. Within this range of content, the chromaticity region can be widened.

The benzimidazolone pigment (a1) has a blue color as compared with the CI Pigment Red 254, a yellow color as compared with the CI Pigment Red 177, and a rise wavelength of the transmission spectrum of 560 to 580 nm, The bright line of the backlight which is generally used in the backlight can be effectively used, and high brightness can be obtained. Further, when the benzimidazolone pigment and the resinous dispersant (c) are used together, the pigment can stably exist in the primary particle state, and a high contrast ratio can be obtained at the same time.

[Minification of Pigment]

The pigment can be used by making it finer. It is preferable that the benzimidazolone pigment (a1) be finely used. However, the finizing method is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution deposition may be used. A salt milling treatment by a kneader method which is one type of wet milling can be performed as illustrated. Any commercially available benzimidazolone pigment (a1) to be micronized may be used, and a product prepared by a coupling reaction of a diazo compound and a coupler compound corresponding to the benzimidazolone pigment (a1) may be used .

The primary particle diameter of the finely divided pigment is preferably 10 nm or more, more preferably 20 nm or more, from the viewpoint of good dispersion into the colorant carrier. Further, from the viewpoint of forming a filter segment having a high contrast ratio, it is preferable that the thickness is 100 nm or less. A particularly preferable range is from 25 to 85 nm from the viewpoint of " viscosity ". From the viewpoint of "balance of brightness and CR", 10 to 50 nm is particularly preferable, and the most preferable range is 15 to 35 nm.

Among them, the benzimidazolone pigment (a2), as conventionally used, has an average primary particle diameter of not more than 100 nm as fine as the average primary particle diameter, and unlike the pigment having a larger specific surface area However, it can be finely colored by setting the specific surface area to 10 m ² / g or more and 50 m ² / g or less, so that a coloring composition having excellent brightness and contrast ratio as well as excellent fluidity, stability and heat resistance can be obtained.

The method for obtaining the benzimidazolone pigment (a2) having such a peculiar property can be obtained by controlling the condition of the finely divided treatment, and among them, it can be obtained by a salt milling treatment in the presence of the pigment derivative (e).

On the other hand, the primary particle size of the pigment was measured by direct measurement of the size of the primary particle from the electron microscope photograph of the pigment by TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was determined as the particle diameter of the pigment particles. Subsequently, for each of 100 or more pigment particles, the average particle size of each particle volume is obtained by approximating the cubic particle of the obtained particle size, and the length of one side of the cubic particle having this average volume is defined as the average primary particle size.

The salt milling treatment is a treatment in which a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is mechanically heated with a kneader such as a kneader, a trimmix, a 2 roll mill, a 3 roll mill, a ball mill, an atrito, After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt functions as a crushing aid, and at the time of salt milling, the pigment is crushed using the height of the hardness of the inorganic salt. By optimizing the conditions under which the pigment is subjected to the salt milling treatment, it is possible to obtain a pigment having a very fine primary particle size, narrow distribution width, and sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate And the like can be used, but it is preferable to use sodium chloride (salt) in terms of cost. The water-soluble inorganic salt is preferably used in an amount of from 50 to 2000 parts by weight, and most preferably from 300 to 1000 parts by weight, based on 100 parts by weight of the pigment from both the treatment efficiency and the production efficiency.

The water-soluble organic solvent is not particularly limited so long as it dissolves (mixes) with water and does not substantially dissolve the inorganic salt used, which acts to wet the pigment and the water-soluble inorganic salt. However, since the temperature rises at the time of the salt milling and the solvent tends to evaporate, a high boiling point solvent having a boiling point of 120 ° C or higher is preferable from the viewpoint of safety. For example, there can be mentioned 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl Diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, Monoethyl ether, and liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, more preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

When the pigment is subjected to the salt milling treatment, a resin may be added as needed. 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 to be used is preferably a solid at room temperature, preferably water-insoluble, and further preferably partially soluble in the organic solvent. The amount of the resin to be used is preferably in the range of 5 to 200 parts by weight based on 100 parts by weight of the pigment.

When the pigment is subjected to the salt milling treatment, the dye derivative (e) described later may be added as necessary. These dye derivative (e) may be the same as the dye derivative used in producing the pigment dispersion. The benzimidazolone pigment (a1) is subjected to a solvent salt milling treatment in the presence of a pigment derivative (e), wherein the crude pigment is subjected to solvent salt milling treatment in the presence of the pigment derivative (e) It is preferable that the benzimidazolone pigment (a2) having a specific surface area, which is a feature of the present invention, is easily formed. In addition, the benzimidazolone pigment (a2) having a specific specific surface area can be obtained in a shorter time, while the use amount of the inorganic salt can be further reduced, as compared with the case where the pigment derivative (e) is not used.

Examples of the pigment derivative (e) include a compound in which a phthalimide methyl group, which may have a basic substituent, an acidic substituent or a substituent, is introduced into an organic pigment, a? -Naphthol compound, an acridone compound or a triazine compound .

Among them, a pigment derivative having a basic substituent, a? -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 surface area and the average particle diameter of the primary particles, and improves the dispersibility of the benzimidazolone pigment, so that the pigment aggregation after dispersion It is preferable from the point of view of the greatest effect of prevention.

The blending amount of the pigment derivative (e) in the solvent salt milling treatment is preferably 5 to 30 parts by weight per 100 parts by weight of the benzimidazolone pigment (a2) from the viewpoint of easiness of control of the specific surface area and resistance of the coloring composition Preferably 5 to 20 parts by weight, and most preferably 5 to 10 parts by weight or more.

The temperature at which the pigment is subjected to the salt milling treatment is preferably 30 to 150 占 폚, more preferably 50 to 80 占 폚. The salt milling treatment time is preferably 3 hours to 20 hours, more preferably 5 to 15 hours.

Thus, by controlling the conditions such as temperature or time during the salt milling treatment, 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 can be obtained.

The red pigment composition containing the benzimidazolone pigment (a2) having such a specific surface area has a high dispersion and dispersion stability of the pigment in the liquid medium, a low viscosity of the pigment dispersion (excellent fluidity) It is possible to form a homogeneous coating film when the color filter red filter segment is manufactured by using the pigment composition from the viewpoint that the pigment composition is stable and has a high viscosity stability over time (storage stability) It is possible to obtain a color filter excellent in heat resistance while maintaining brightness.

In addition, when the pigment particles are made into a finely divided pigment having an average primary particle diameter of 10 to 50 nm, the pigment composition becomes a coloring composition having high definition, high contrast ratio, and excellent stability when used for forming a red filter segment for a color filter .

≪ Resin (b) >

The resin (b) 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, and more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region. In the case of using in the form of an alkali developing photosensitive coloring composition, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic substituent. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond may 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, polyurethane- (HDPE, LDPE), polybutadiene, and polyimide resin, and the like can be given as examples of the resin composition of the present invention. Examples of the resin include a polyester resin, a vinyl resin, an alkyd resin, a polystyrene resin, a polyamide resin,

Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin and a phenol resin.

Examples of the vinyl-based alkali-soluble resin in which an ethylenically unsaturated monomer containing an acidic substituent group is copolymerized include a resin having an acidic substituent such as a carboxyl group or a sulfonic group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an? -Olefin / (maleic anhydride) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer or an isobutylene / Maleic anhydride copolymer, and the like. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic substituent group, is suitably used because it has high heat resistance and transparency.

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

[Method (i)]

As the method (i), for example, a method in which a carboxyl group of an unsaturated monobasic acid having an etheric unsaturated double bond is added to a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers And then reacting the resultant hydroxyl group with a polybasic acid anhydride to introduce an unsaturated unsaturated double bond and a carboxyl group.

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

Examples of the unsaturated monobasic acid include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of alkenyl (meth) acrylate, alkoxyl, halogen, nitro, And the like. These may be used alone, or two or more of them may be used in combination.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. A tricarboxylic acid anhydride such as trimellitic acid anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride may be used to increase the number of carboxyl groups and to hydrolyze the remaining anhydride group And so on. The use of tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond as the polybasic acid anhydride can further increase the ethene unsaturated double bond.

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

[Method (ii)]

As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group can be used to copolymerize a monomer of an unsaturated monobasic acid having another carboxyl group or a monomer obtained by copolymerizing another monomer with an ethylenically unsaturated monomer having an isocyanate group There is a method of reacting an isocyanate group.

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) acrylates such as glycerol (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, etc. These may be used alone or in combination of two or more kinds. . Further, polyether mono (meth) acrylates obtained by addition polymerization of the above-mentioned hydroxyalkyl (meth) acrylates with ethylene oxide, propylene oxide and / or butylene oxide, poly (? - valerolactone) And polyester mono (meth) acrylate to which lactone and / or poly 12-hydroxystearic acid and the like are added can also be used. 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred from the standpoint of coating inhibition.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [methacryloyloxy] ethyl isocyanate. Or more.

To preferably disperse the colorant (a), the weight average molecular weight (Mw) of the resin (b) is preferably in the range of 10,000 to 100,000, more preferably 10,000 to 80,000. 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.

From the viewpoints of dispersibility, stability, developability and heat resistance of the colorant (a), a colorant adsorbent and a carboxyl group functioning as an alkali-soluble group at the time of development, an aliphatic group and an aromatic group which function as affinity groups for a colorant carrier and a solvent Is important for the dispersibility of the pigment, the penetration of the developer into the coating film, the solubility of the developer in the uncured portion, and further the durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. If the acid value is 20 mgKOH / g or more, the solubility in a developing solution is excellent, so that a fine pattern can be formed. Further, when it is 300 mgKOH / g or less, the fine pattern is not excessively dissolved.

The resin (b) is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant (a) from the viewpoint of good film formability and various resistance properties. It is preferably used in an amount of 500 parts by weight or less. More preferably 100 to 400 parts by weight, and still more preferably 160 to 320 parts by weight. The chromaticity region can be broadened according to the composition ratio of such pigments.

≪ Resin type dispersant (c) >

The resinous dispersant (c) is a resinous dispersant having an acidic substituent. The resinous dispersant (c) has a pigment affinity unit comprising an acidic substituent group adsorbed on the benzimidazolone pigment (a1) and a unit compatible with the pigment carrier, wherein the benzimidazolone pigment (a1) And functions to stabilize the dispersion in the pigment carrier.

Among the resinous dispersants, a resinous dispersant having an acidic substituent is preferable.

In particular, use of a benzimidazolone pigment (a1), a resinous dispersant (c) having an acidic substituent, and a pigment derivative having a basic substituent, are preferred because they exhibit excellent effects of both fluidity and dispersibility .

The basic structure of the resinous dispersant (c) is not particularly limited, and general resins such as an acrylic resin, a polyester resin, a polyether resin, a urethane resin, a silicone resin, an epoxy resin, have.

The acidic substituent includes, for example, 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, the aromatic ring having two or more acidic substituents may be a unit having one acidic substituent group depending on plural, direct bond and / or linkage group. Among them, it is preferable to have two or more carboxyl groups in one molecule. The dispersing agent having two or more carboxyl groups in one molecule has a strong function of stabilizing the dispersion of the coloring agent in the coloring agent carrier because the adsorbing agent to the coloring agent is larger than that of the resinous dispersing agent having one or two carboxyl groups in one molecule. The polarity is increased, and a higher dispersion stability can be ensured.

The resinous dispersant preferably has an acidic substituent group, an aromatic group, or the like in a block or random manner in the main chain or side chain of the main chain or terminal of the linear chain resin, or the comb chain (comb chain) resin. Specific examples thereof include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, Amide or a salt thereof formed by the reaction of a poly (lower alkyleneimine) with a polyester having a free carboxyl group is used. Further, water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, Ester type, modified poly (meth) acrylate, ethylene oxide / propylene oxide adduct, phosphoric ester and the like. These may be used alone or in combination of two or more, but the present invention is not limited thereto.

At least one kind of polymer unit selected from polyester, polyether, and poly (meth) acrylate is preferable as a site of the resinous dispersant (c) having high affinity for the dispersion medium.

Examples of the polyester include polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, Diol, 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, hydroxy pivaloyl hydroxy pivalate, trimethylol ethane, trimethylol propane, 2,2,4- Hexanetriol, hexahydrophthalic acid, maleic acid, fumaric acid, fumaric acid, maleic acid, fumaric acid, maleic acid, maleic acid, 1,4-cyclohexanedicarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, or 2,5,7-naphthalenetricarboxylic acid. And polyester polyols obtained by summing.

Examples of the polyether include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, Diol, 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxy pivalate, trimethylol ethane, trimethylol propane, 2,2,4- - alcohols such as pentanediol, glycerol or hexanetriol and alcohols such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether And modified polyether polyols obtained by ring-opening polymerization with various (cyclic) ether bond-containing compounds such as cidyl ether.

Examples of the poly (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethyleneglycol ( (Meth) acrylates such as methoxypolyethylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate, (meth) acrylates such as methoxypolyethylene glycol ) Arc Amide and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone Containing (meth) acrylates such as N-substituted (meth) acrylamides, N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl And homopolymers and copolymers such as nitriles such as acrylonitrile. These may be used alone, mixed, or in the form of a block polymer, a graft polymer or a random polymer.

Examples of the resinous pigment dispersing agent having an acidic functional group on the market include SOLSPERSE 3000, SOLSPERSE 21000, SOLSPERSE 26000, SOLSPERSE 36600, SOLSPERSE 41000, SOLSPERSE 44000, SOLSPERSE 46000, SOLSPERSE 55000 (manufactured by Avecia); DISPER BYK 110, DISPER BYK 111, DISPER BYK 112, DISPER BYK 116, DISPER BYK 142, DISPER BYK 180, DISPER BYK 2000, DISPER BYK 2001, (BYK-Chemie); DISPARLON 3600 N, DISPARLON 1850 (manufactured by Kusumoto Chemicals); PA 111 (manufactured by Ajinomoto Fine-Techno Co., Ltd.); EFKA4401, and EFKA4550 (manufactured by EFKA ADDITIVES), but are not limited thereto.

As the resinous dispersant (c), an acidic resinous dispersant having an aromatic carboxyl group is preferable, and a polymer having a hydroxyl group at one end is reacted with an aromatic tricarboxylic acid anhydride and / or an aromatic tetracarboxylic acid dianhydride And most preferably a dispersant. As such a resinous dispersing agent, for example, Japanese Patent No. 4020150, Japanese Patent Application Laid-Open No. 2007-140487, International Publication No. 2008/007776, Japanese Patent Application Laid-Open No. 2010-163500, Japanese Patent Publication No. 2010-223988 And the like, and exerts excellent effects such as compatibility between fluidity and dispersibility.

Among these, the resinous dispersant is preferably produced by radical polymerization of an ethene-like unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in a molecule described in WO 2008/0077776, etc., and two hydroxyl groups Is reacted with an acid anhydride group in a tetracarboxylic acid dianhydride. More preferably, the polyester dispersant is characterized in that the tetracarboxylic dianhydride contains an aromatic tetracarboxylic acid dianhydride. The coloring composition for a color filter using such a polyester dispersant is preferable because of excellent dispersion stability of the pigment. As the synthesis method, it can be synthesized by a method described in WO2008 / 007776 pamphlet and the like.

A more preferred resinous dispersing agent is a resinous dispersing agent represented by the following formula described in JP-A-2007-140487.

(HOOC-) _m --R ₄ - (- COO - [- R ₆ --COO--] _q --R ₅ ) _t

[Wherein, R ₄ is is tetra tetravalent carboxylic acid compound residue, R ₅ is mono alcohol residue, R ₆ is a lactone moiety, m is 2 or 3, q is an integer of 1 ~ 50, t (4- m) .]

The coloring composition for a color filter using the acidic resin type dispersant having an aromatic carboxyl group is excellent in dispersion stability of the pigment.

As the constituent unit of the side chain portion of the resinous dispersant, for example,

An unsaturated unsaturated monomer having a carboxyl group such as acrylic acid, methacrylic acid and maleic acid;

Examples of the ethylenically unsaturated monomer having no acidic group include, for example,

Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate and lauryl (meth) acrylate;

Alicyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and dicyclopentanyl (meth) acrylate;

(Meth) acrylates having an aromatic substituent such as phenyl (meth) acrylate, benzyl (meth) acrylate and para-cumylphenoxyethylene oxide-modified (meth) acrylate;

Alkoxypolyalkylene glycol (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate; And mixtures thereof.

Among them, from the viewpoint of developability, it is preferable to include an unsaturated unsaturated monomer having a carboxyl group. These ethylenically unsaturated monomers having an acidic functional group may be used singly or in combination of two or more. In addition, since it has high hydrophilicity, it preferably contains alkoxypolyalkylene glycol (meth) acrylates having good stability and dispersibility.

The number of hydroxyl groups in one molecule of the other polyol is not particularly limited as long as the intended dispersant can be synthesized, but diol is preferable. Particularly, by reacting with the tetracarboxylic dianhydride (d1), carboxyl groups serving as pigment adsorbers can be regularly arranged in the main chain, which is advantageous for pigment dispersion. When a polyol having a hydroxyl group of more than 2 is used in a large amount, the main chain of the polyester tends to branch and become complicated, resulting in an increase in viscosity, which makes it difficult to obtain a dispersion effect. From the viewpoint of the pigment adsorption property, the tetracarboxylic acid dianhydride having two or more aromatic rings is preferable as a skeleton suitable for pigment adsorption because of the highest heat resistance.

The acid value of the resinous dispersant (c) 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. In consideration of the dispersibility and the viscosity, the acid value of the polyester dispersant is preferably 5 to 200 mgKOH / g. More preferably 10 to 150 mgKOH / g, and still more preferably 15 to 100 mgKOH / g.

The weight average molecular weight (Mw) of the resinous dispersant (c) is preferably in the range of 1,000 to 50,000, and more preferably in the range of 1,000 to 30,000. In consideration of the dispersibility and viscosity, the weight average molecular weight of the polyester dispersant is preferably 2,000 to 35,000, more preferably 4,000 to 25,000, even more preferably 6,000 to 15,000, and particularly preferably 7,000 to 12,000 .

The content of the resinous dispersant (c) is preferably 10 to 70 parts by weight, more preferably 20 to 55 parts by weight, based on 100 parts by weight of the benzimidazolone pigment (a1). When the blending amount of the resinous dispersant (c) is 10 parts by weight or more, the effect of pigment dispersibility can be sufficiently obtained. When the amount is 70 parts by weight or less, a pigment dispersion resist containing the pigment dispersion composition is used. Therefore, when a pixel pattern of a color filter is formed by a photolithography method, the alkali developability is excellent.

≪ Solvent (d) >

The solvent (d) is used in order to facilitate the formation of the filter segment by dispersing the colorant sufficiently in the resin and applying the colored composition on the transparent substrate such as a glass substrate so that the dry film thickness becomes 0.2 to 5 μm.

Examples of the solvent (d) include 1,2,3-trichloropropane, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, Methoxybutyl acetate, 4-heptanone, m-xylene, m-xylylene, m-xylylene, 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,? -butyrolactone, isobutyl alcohol, , Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono tert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl 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 mono Ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene Propylene glycol monomethyl ether acetate, propylene glycol monomethyl 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, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester.

These solvents may be used singly or as a mixture of two or more kinds in an optional ratio as required.

Among them, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate and the like, benzyl alcohol And ketones such as cyclohexanone are preferably used.

The solvent (d) is preferably used in an amount of 800 to 4000 parts by weight per 100 parts by weight of the colorant (a) in that the coloring composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness Is preferably used.

<Coloring matter derivative (e)>

The coloring composition for a color filter is preferably a coloring matter derivative (e). The pigment derivative is excellent in the dispersion of the benzimidazolone pigment and has a great effect of preventing the re-aggregation of the benzimidazolone pigment after dispersion.

Examples of the pigment derivative (e) include a compound in which a phthalimide methyl group, which may have a basic substituent, an acidic substituent or a substituent, is introduced into an organic pigment, a? -Naphthol compound, an acridone compound or a triazine compound .

That is, the structure of the dye derivative (e) is a compound represented by the following formula (2).

(2)

P-Ln Equation (2)

[In the formula (2)

P is an organic pigment residue,? -Naphthol residue, acridone residue or triazine residue

L: a basic substituent, an acidic substituent, or a phthalimide methyl group which may have a substituent

n is an integer of 1 to 4.]

Examples of the organic pigments constituting the organic pigment residue of P include diketopyrrolopyrrole pigments; Azo pigments such as azo, disazo and polyazo; Phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and non-metal phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and violanthrone; Quinacridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thioindigo pigments; Isoindoline pigments; Isoindolinone pigments; Quinophthalone pigments; Threne pigments; Metal complex system pigments, and the like.

The triazine which constitutes the triazine residue of P may be substituted with an alkyl group (methyl group, ethyl group, butyl group, etc.), an amino group, an alkylamino group (dimethylamino group, (Which may be substituted with an alkyl group, an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen or the like) and a phenylamino group (an alkyl group, An amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen, etc.).

Among them, a dye derivative having a basic substituent, in which L in the formula (2) is a basic substituent, can be preferably used.

By including a pigment derivative having a basic substituent, a pigment which is difficult to disperse without a pigment derivative having a basic substituent is preferable because it can be made into a pigment composition excellent in dispersibility, fluidity and storage stability. The synergistic effect of the acidic resinous dispersant and the pigment derivative having a basic substituent allows the pigment to be effectively dispersed to provide a pigment composition excellent in fluidity and storage stability.

Among the basic substituents, L is preferably a substituent selected from the group represented by the formulas (3), (4) and (5).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[In the 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 alkyl group having 1 to 36 carbon atoms which may have a substituent, an alkenyl group having 2 to 36 carbon atoms which may have a substituent, 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 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, or R ⁵⁰ and R ⁵¹ , Is a heterocycle which may have a substituent, including nitrogen, oxygen, or a sulfur atom,

R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, An arylene group having 6 to 20 carbon atoms,

R ⁵⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent,

R ⁵⁷ is a substituent represented by the formula (3) or a substituent represented by the formula (4)

Q is a hydroxyl group, an alkoxyl group, a substituent represented by the formula (3), or a substituent represented by the formula (4).

Examples of the amine component used for forming the substituent represented by the formulas (3) to (5) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N N, N-dimethylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N Butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisooamylamine, dihexylamine, diisobutylamine, N, N-dimethyloctylamine, N, N-dimethyloctylamine, dicyclohexylamine, diallyl amine, N, , N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, Amine, N, N-diethylaminoethylamine, N, N-di N, N-diethylaminobutylamine, N, N-diethylaminobutylamine, N, N-diethylaminobutylamine, N, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N- But are not limited to, N, N-diethylaminoethylamine, N, N-diethylaminoethylamine, N, N-diethylaminoethylamine, N, N-distearylaminobutylamine, Pipecoline), 3-Pipecolin, 4-Pipecolin, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidine Methanol, , Isonipecotic acid, isonipecotic acid methyl, isonipecotic acid ethyl, 2-piperidine ethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N- 4-piperolin, N-aminoethylmorpholine, N-aminopropylpiperidine , N-aminopropyl-4-piperolin, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methyl homopiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, and the like.

Pigment derivatives having a basic substituent,? -Naphthol derivatives and acridone derivatives can be synthesized by various synthetic routes. For example, it is possible to introduce a substituent represented by the formulas (6) to (9) into an organic dye,? -Naphthol or acridone and then react with the substituent to form a substituent represented by the formula (3) N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazin-2-ylamino] aniline, and the like.

[Chemical Formula 6]

Equation (6): -SO ₂ Cl

(7)

Equation (7): -COCl

[Chemical Formula 8]

Equation _{(8): -CH 2 NHCOCH 2} Cl

[Chemical Formula 9]

(9): -CH ₂ Cl

The substituents in the formulas (6) to (9) and the amine component may be partially hydrolyzed to replace the hydroxyl groups in the substituents of the formulas (6) to (9). In this case, the formulas (6) and (7) are respectively a sulfonic acid group and a carboxylic acid group, but they may be in the form of a free acid or may be a salt of a mono-trivalent metal or a salt thereof with the monoamine .

When the organic dye is an azo dye, the substituents represented by the formulas (3) to (5) are introduced into the diazo component or the coupling component in advance and then the coupling reaction is carried out to obtain the azo pigment derivative .

The triazine derivative having a basic substituent can be synthesized by various synthetic routes. For example, an amine component having, as a starting raw material, cyanuric chloride and forming a substituent represented by formulas (3) to (5) in at least one of chlorine atoms in cyanuric chloride, for example, N, N-dimethylamino Propylamine or N-methylpiperazine, and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

The parent skeleton is preferably a pigment derivative in which P in the formula (2) is an organic pigment residue, a? -Naphthol residue or a triazine residue, and among these, a thioindigo pigment, a diketopyrrolopyrrole pigment or An organic pigment residue or triazine residue, which is an anthraquinone pigment, is preferred.

That is, in the coloring composition, P in the formula (2) is an organic pigment residue, a? -Naphthol residue, or a triazine residue, and L in the formula (2) is a pigment derivative having a basic substituent , A β-naphthol derivative having a basic substituent, and a triazine derivative having a basic substituent are preferable from the viewpoint of dispersion stability. Among them, a triazine derivative having a basic substituent has an excellent effect of dispersing the benzimidazolone pigment and preventing the re-aggregation of the benzimidazolone pigment after dispersion.

The blending amount of the pigment derivative (e) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and most preferably 10 parts by weight or more, based on 100 parts by weight of the benzimidazolone pigment (a1) Is at least 15 parts by weight. From the viewpoints of heat resistance and light resistance, it is preferably 30 parts by weight or less, and most preferably 25 parts by weight or less, based on 100 parts by weight of the benzimidazolone pigment.

The coloring composition for a color filter 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 includes a monomer or an oligomer which is cured by ultraviolet rays or heat to produce a resin. These may be used singly 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,? -Carboxyethyl methacrylate , Polyethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, Pentaerythritol tetramethacrylate, 1,6-hexanediol diglycidyl ether dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, neopentyl glycol diglycidyl ether dimethacrylate, dipenta Erythritol hexamethacrylate, dipentaerythritol penta methacrylate, tricyclotecanyl methacrylate, ester Acrylate, methacrylic acid, methacrylic acid, methacrylic acid ester of methylol melamine, epoxy methacrylate, urethane acrylate and the like, acrylic acid, methacrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol But are not limited to, divinyl ether, pentaerythritol trivinyl ether, methacrylamide, N-hydroxymethyl methacrylamide, N-vinyl formamide, acrylonitrile and the like.

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

<Photopolymerization initiator>

When the composition is cured by irradiation of ultraviolet rays and the filter segment is formed by photolithography, the coloring composition for a color filter may be prepared by adding a photopolymerization initiator or the like so as to form a photosensitive coloring composition in the form of a solvent developing type or an alkali developing type photosensitive coloring composition can do.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2 - [(4 (4-morpholinophenyl) -1-butanone, or 2-benzyl-2-dimethylamino-1- -Acetophenone-based compounds; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzyl dimethyl ketal; Benzophenone, benzoyl benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4,4'- benzophenone-based compounds such as t-butylperoxycarbonyl) benzophenone; Such as thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- A tonic compound; (Trichloromethyl) -s-triazine, 2- (p-methoxyphenylacetate) -4,6-bis (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl- ) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -s-triazine, 2- (4-methoxy- Triazine-based compounds such as 6-triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 2-oxo-2- (4 ' -methoxyphenyl) -1- [4- (phenylthio) -2- Methoxy-naphthyl) ethylidene) hydroxylamine; Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethyl anthraquinone;

Borate-based compounds; Carbazole-based compounds; Imidazole-based compounds; Or a titanocene compound.

These photopolymerization initiators may be used singly or as a mixture of two or more kinds in an optional ratio as required.

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

<Increase / decrease>

Further, the coloring composition for a color filter may contain a sensitizer.

Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, Anthracene derivatives, azine derivatives such as xanthene derivatives, thioxantene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanide derivatives, merocyanine derivatives and oxolin derivatives, A tetrabenzoporphine derivative, a tetrabenzoporphine derivative, a tetrabenzoporphyrin derivative, a thiazine derivative, an oxazine derivative, an indoline derivative, an azulene derivative, an azulenium derivative, a squarylium derivative, a porphyrin derivative, Pyrazine derivatives, phthalocyanine derivatives, tetraazapolpyrazine derivatives, tetraquinazolinopolpyrazine derivatives, naphthaloxy derivatives A thiopyrimidine derivative, a tetrapyrin derivative, an indene derivative, a spiropyran derivative, a spirooxazine derivative, a thiospyropyran derivative, a metal arene complex, an organic ruthenium complex or a Michler's ketone derivative , acyloxyester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ' , Or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone, and the like.

These sensitizers may be used singly or as a mixture of two or more kinds in an optional ratio as required.

More specifically, it is described in OKAWARA Makoto et al., "Coloring Handbook" (Kodansha Ltd., 1986), OKAWARA Makoto et al., "Functional dye chemistry" (CMC Publishing Co., Ltd., 1981), IKEMORI Chuzaburo et al. And "Special Functional Materials" (CMC Publishing Co., Ltd., 1986), but are not limited thereto. In addition, it is also possible to add a sensitizer that exhibits absorption of light from ultraviolet to near infrared.

The content of the sensitizer is preferably 3 to 60 parts by weight based on 100 parts by weight of the photopolymerization initiator contained in the coloring composition, more preferably 5 to 50 parts by weight from the viewpoint of photocurability and developability.

<Amine compound>

In addition, the coloring composition for a color filter may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl paratoluidine, and the like.

<Leveling agent>

In the coloring composition for a color filter, it is preferable to add a leveling agent in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray, BYK-333 manufactured by BYK-Chemie, and the like. Specific examples of the 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 its main chain and dimethylsiloxane having a polyester structure in its main chain may be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight based on 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 hydrophobic group in the molecule. The surfactant has a low hydrophilicity and low solubility in water and low surface tension lowering ability when added to a coloring composition. Desirably, the wettability to the glass plate is good even though the surface tension lowering ability is low, and that the chargeability can be suppressed sufficiently at the addition amount at which defects of the coating film due to bubbling do not appear. 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. The dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The mode of bonding of the polyalkylene oxide units to the dimethylpolysiloxane may be a pendant in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a terminal modification in which the terminal is bonded to the terminal of the dimethylpolysiloxane, alternating with the dimethylpolysiloxane And may be any of the straight-chain block copolymer type combined therewith. FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2110, FZ-2122, FZ-2130, FZ-2166 and FZ-2193 are commercially available from Dow Corning Toray. -2207, but are not limited thereto.

Depending on the leveling, anionic, cationic, nonionic, or amphoteric surfactants may be added additionally. The surfactants may be used in combination of two or more.

Examples of the anionic surfactant to be added to the leveling aid as auxiliary substances include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate , Monoethanolamine laurylsulfate, triethanolamine laurylsulfate, ammonium laurylsulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkylether phosphate ester. .

Examples of the cationic surfactant to be supplemented by leveling include alkyl quaternary ammonium salts and adducts of these ethene oxides. Examples of the nonionic surfactant to be supplementarily added by leveling include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate , Polyethylene glycol monolaurate and the like; Alkyl betaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based or silicone-based surfactants.

<Curing agent, hardening accelerator>

In addition, the coloring composition for a color filter may contain a curing agent, a curing accelerator, and the like, if necessary, to assist curing of the thermosetting resin. As the curing agent, a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but not limited thereto, and any of them may be used as long as it can react with a thermosetting resin Can be used. Among them, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably used. Examples of the curing accelerator include amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, Benzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (such as triethylbenzylammonium chloride), block isocyanate compounds (such as dimethylamine) (Such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine And the like), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyl Oxyethyl-S-tri Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino- Methacryloyloxyethyl-S-triazine isocyanuric acid adduct, etc.) and the like can be used. These may be used alone, or two or more of them may be used in combination. 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).

&Lt; Other additive components >

The coloring composition for a color filter may contain a storage stabilizer to stabilize the viscosity of the composition over time. Further, in order to improve the adhesion with the transparent substrate, an adhesion improving agent such as a silane coupling agent may be contained.

Examples of the storage stabilizer include organic acids such as quaternary ammonium chloride, lactic acid and oxalic acid such as benzyltrimethyl chloride and diethylhydroxyamine, and their methyl ethers, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl Organic phosphine such as phosphine, phosphite, and the like. The storage stabilizer may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the colorant (a).

Examples of the adhesion improver include vinylsilanes such as vinyltris (? -Methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilane such as? -Methacryloxypropyltrimethoxysilane (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as? - (3,4-epoxycyclohexyl) methyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane and? -Glycidoxypropyltriethoxysilane, N-? (Aminoethyl)? -Aminopropyltrimethoxysilane, N-? (Aminoethyl)? -Aminopropyltriethoxysilane, N-? (Aminoethyl)? -Aminopropylmethyldiethoxysilane,? -Aminopropyltri Aminopropyltrimethoxysilane, N-phenyl-gamma -aminopropyltrimethoxysilane, N-phenyl-gamma -aminopropyltriethoxysilane, etc. Amino silanes, may be mentioned silane coupling agents such as γ- mercaptopropyltrimethoxysilane, γ- mercapto thio silanes, such as the propyl triethoxysilane. The adhesion-promoting agent may 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).

&Lt; Production method of colored composition >

The coloring composition for a color filter is obtained by mixing a coloring agent (a) containing a benzimidazolone pigment (a1), a resinous dispersant (c), a resin (b), a solvent (d) The other components can be finely dispersed together using various dispersing means such as three roll mills, two roll mills, sand mill, kneader, tri-mix, or atrito (pigment dispersion). In addition, the coloring composition for a color filter may be prepared by dispersing the benzimidazolone pigment (a1) together with other coloring agents such as a red pigment and a yellow pigment, which are used together, and dispersing each other.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or an alkali-developing type coloring composition. The solvent-developing type or alkali-developing type coloring composition can be adjusted by mixing the pigment dispersion, the photopolymerizable monomer and / or the photopolymerization initiator and, if necessary, a solvent, other dispersant and additives. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

The particles contained in the red coloring composition for a color filter are preferably substantially less than 0.5 mu m, (The particle size measurement by SEM). The average dispersed particle diameter of the color filter red coloring composition is preferably 0.05 to 0.2 占 퐉 in order to increase the brightness or contrast ratio, and more preferably 0.06 to 0.15 占 m in order to further increase the brightness and contrast ratio.

<Removal of Coarse Particles>

The coloring composition for a color filter can be removed by removing the coarse particles of 5 占 퐉 or larger, preferably coarse particles of 1 占 퐉 or larger, more preferably 0.5 占 퐉 or larger coarse particles and entrained dust by means of centrifugal separation, sintering filter, . As described above, it is preferable that the coloring composition for a color filter does not contain particles substantially 0.5 mu m or more. More preferably 0.3 mu m or less.

<Color filter>

The color filter is characterized by comprising at least one filter segment formed by a coloring composition for a color filter.

The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one red filter segment is formed using a red coloring composition for a color filter desirable.

The green filter segment can be formed using a conventional green coloring composition. The green coloring composition is, for example, a composition obtained by using a green pigment such as CI Pigment Green 7, 10, 36, 37, 58 or the like. The green coloring composition includes CI 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, 37, 37, 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, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213 and 214 can be used in combination.

Further, the blue filter segment can be formed using a conventional blue coloring composition. The blue coloring composition is a composition obtained by using a blue pigment such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, . Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 may be used in combination with the blue coloring composition.

<Manufacturing Method of Color Filter>

The color filter 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 only by repeating printing and drying of the coloring composition prepared as the printing ink, so that the production method of the color filter is low cost and excellent in mass productivity. Further, by the development of the printing technique, it is possible to perform printing of a fine pattern having a high dimensional accuracy and smoothness. In order to perform the printing, it is preferable that the composition is such that the ink does not dry and solidify on the printing plate or on the blanket. Further, since control of the fluidity of the ink on the printing machine is also important, it is also possible to adjust the viscosity of the ink by the dispersing agent and the extender pigment.

[Photolithography]

In the case of forming the filter segment by the photolithography method, the photosensitive coloring composition prepared as the solvent-developing type or alkali-developing type coloring composition is applied onto the transparent substrate by a coating method such as spray coating, spin coating, slit coating, To a dry film thickness of 0.2 to 5 占 퐉. If necessary, ultraviolet exposure as an active energy ray is performed on a dried film through a mask having a predetermined pattern provided in contact with or in contact with the film. Thereafter, the color filter can be manufactured by dipping in a solvent or an alkaline developing solution, or spraying a developing solution to remove un-hardened portions to form a desired pattern, and repeating the same operation for different colors. In order to accelerate the polymerization of the coloring composition, heating may be carried out if necessary. According to the photolithography method, it is possible to manufacture a color filter having a precision (accuracy) higher than that of the printing method.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide, or the like is used as an alkaline developer, and organic alkalis such as dimethylbenzylamine and triethanolamine may be used. Further, a defoaming agent or a surfactant may be added to the developing solution. On the other hand, in order to increase the ultraviolet exposure sensitivity, a coating film is formed which is applied and dried after the coloring composition is applied, and a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen , And ultraviolet exposure may be performed.

The color filter can be produced by an electrodeposition method, a transfer method, etc. in addition to the above method, but the coloring composition can be used in any method. On the other hand, the electrodeposition method is a method of manufacturing a color filter by electrodepositing colloidal particles on a transparent conductive film formed on a substrate to electrodeposit each color filter segment on a transparent conductive film. The transfer method is a method in which a filter segment is previously formed on the surface of a releasable transfer base sheet and the filter segment is transferred to a desired substrate.

The coloring composition can be used in any of the methods described above, but it is most suitable for photolithography.

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

The color filter is adhered to the counter substrate by using a sealant, the liquid crystal is injected from the injection port provided in the seal portion, the injection port is sealed, and the polarizing film or the retardation film is adhered to the outside of the substrate, .

Such a liquid crystal display panel has been widely used in various fields such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical converbend bend In the liquid crystal display mode in which coloring is performed by using the color filter of FIG.

Example

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it should be understood that the present invention is not limited to the following Examples unless the gist thereof is exceeded. In the Examples and Reference Examples, "part" and "%" mean "part by weight" and "% by weight", respectively.

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

<Acid value of resin and resin type dispersant>

The acid value of the resin and the resinous dispersant was determined by a potentiometric titration method using a 0.1N potassium hydroxide-ethanol solution. The acid value of the resin and the resinous dispersant indicates the acid value of the solid content.

&Lt; Weight average molecular weight (Mw) of resin >

The weight average molecular weight (Mw) of the resin was measured by GPC (Tosoh Corporation, HLC-8120 GPC) equipped with a RI detector using a TSKgel column (manufactured by Tosoh Corporation), and the polystyrene- Weight average molecular weight (Mw).

&Lt; Amine value of resinous dispersant >

The amine value of the resinous dispersant was determined by the potentiometric titration method using 0.1 N hydrochloric acid aqueous solution and then converted to the equivalent amount of potassium hydroxide. The amine value of the resinous dispersant indicates the amine value of the solid content.

&Lt; Quaternary ammonium salt value of resinous dispersant >

The quaternary ammonium salt value of the resinous dispersant was determined by titration with a 0.1 N aqueous solution of silver nitrate, using 5% aqueous solution of potassium chromate as an indicator, and then converted to the equivalent weight of potassium hydroxide. The quaternary ammonium salt value of the following resinous dispersant indicates the quaternary ammonium salt value of the solid content.

<Specific Surface Area of Pigment>

The specific surface area of the pigment was measured by an automatic vapor adsorption amount measuring device (BELSORP 18, manufactured by BEL Japan, Inc.) by the BET method of nitrogen adsorption.

&Lt; Measurement method of contrast ratio of coating film >

Light emitted from a backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a dried coating film of a coloring composition applied on a glass substrate, and reaches a polarizing plate. When the polarizing planes of the polarizing plate and the polarizing plate are parallel, light passes through the polarizing plate, but when the polarizing plane is straight, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the dried coating film of the coloring composition, scattering due to the pigment particles occurs, and when a deviation occurs in a part of the polarizing plane, the amount of light transmitted through the polarizing plate is reduced when the polarizing plate is parallel , And when the polarizing plate is straight, some light is transmitted through the polarizing plate. The transmitted light was measured as the luminance on the polarizing plate, and the ratio of the luminance when the polarizing plate was parallel to the luminance when the polarizing plate was parallel (contrast ratio) was calculated.

(Contrast ratio) = (luminance in parallel) / (luminance in non-direct)

("BM-5A" manufactured by TOPCON Co., Ltd.) was used as the sum of the luminance, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko) was used as the polarizing plate. In addition, in order to block unnecessary light, a black mask having a hole of 1 cm in width and 1 cm in length was placed in the measurement area.

<Average primary particle size of pigment>

The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron microscope photograph of a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was determined as the particle diameter of the pigment particles. Subsequently, the volume (weight) of each particle was determined with respect to 100 or more pigment particles to approximate the cubic of the obtained particle diameter, and the volume average particle diameter was determined as the average primary particle diameter.

&Lt; Embodiment I &gt;

First, the dye derivative used is described.

<Structural Formula of Pigment Derivative>

Table 1 summarizes the basic skeletons of the derivatives used to describe the derivative structure.

[Table 1]

Next, a method for producing an acrylic resin solution, a resinous dispersant solution, a finely divided pigment, a pigment dispersion, a green photosensitive coloring composition and a blue photosensitive coloring composition used in Examples and Reference Examples will be described.

&Lt; Process for producing acrylic resin solution >

(Adjustment of acrylic resin solution 1)

70.0 parts of cyclohexanone was charged into a separable four-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirrer, and the temperature was raised to 80 DEG C, 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, and 10 parts of para-cumylphenol-ethylene oxide-modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) ), And 0.4 part of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 DEG C for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl ether acetate was added to the resin solution so that the nonvolatile content was 20 wt% To prepare Resin Solution 1.

(Adjustment of acrylic resin solution 2)

A separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, and the temperature was raised to 80 ° C. After the inside of the flask was replaced with nitrogen, 18 parts of cumylphenol-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, -Azobisisobutyronitrile (2.0 parts) was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Subsequently, 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the vessel, and the reaction was continued at 120 ° C for 6 hours to change the solid content When the acid value became 0.5, the reaction was terminated to obtain a solution of the acrylic resin. Subsequently, 19.5 parts of the tetrahydrophthalic anhydride phthalic acid (100% of the produced hydroxyl group) and 0.5 part 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. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 캜 for 20 minutes to measure the non-volatile content. Cyclohexanone was added to the resin solution so that the non-volatile content became 20% by weight, To prepare an acrylic resin solution 2 as a curable resin.

&Lt; Process for producing resinous dispersant >

(Resinous dispersant A solution)

62.6 parts of 1-dodecanol, 287.4 parts of epsilon -caprolactone and 0.1 part of monobutyltin (IV) oxide as a catalyst were fed into a reaction tank equipped with a gas introduction pipe, a condenser, a stirring blade and a thermometer, , And the mixture was heated and stirred at 120 ° C for 4 hours. After confirming that 98% of the reaction was carried out by measuring the solid content, 36.6 parts of pyromellitic anhydride was added thereto, and the reaction was carried out at 120 ° C for 2 hours. The reaction was terminated by confirming that at least 98% of the acid anhydride was half-esterified by measurement of the acid value. Thus, a solution of a resinous dispersant A having an aromatic carboxyl group was obtained as a polycaprolactone skeleton having an acid value per solid part of 49 mgKOH / g and a nonvolatile content of 40% by weight.

(Resinous dispersant B solution)

As a first synthesis, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 100 parts of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAC) were added to a reaction vessel equipped with a gas introduction pipe, a condenser, a stirring blade and a thermometer ) Were charged and substituted with nitrogen gas. The inside of the reaction vessel was heated to 80 캜, 12 parts of 3-mercapto-1,2-propanediol was added, and then 0.2 part of 2,2'-azobisisobutyronitrile was added in 20 divided portions every 30 minutes, And reacted for 12 hours. It was confirmed that 95% of the reaction was carried out by the solid content measurement. Then, as a second synthesis, 30 parts of pyromellitic anhydride, 190 parts of PGMAC and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, Lt; / RTI &gt; It was appropriately confirmed that at least 98% of the acid anhydride was half-esterified, and the reaction was terminated. Thus, a solution of a resinous dispersant B having an aromatic carboxyl group was obtained as a poly (meth) acrylate skeleton having an acid value of 42 mgKOH / g and a nonvolatile content of 40 wt% per solid content.

(Resinous dispersant D solution)

To a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 80 parts of methyl ethyl ketone, 92.0 parts of butyl acrylate, 2.8 parts of sparte, and 1.9 parts of ethyl isobutyrate were added. &Lt; / RTI &gt; 1.1 parts of cuprous chloride was added, and the temperature was raised to 75 캜 to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled, and it was confirmed from the nonvolatile matter of the polymerization solution that the polymerization yield was 95% or more and the weight average molecular weight (Mw) was 6860. Then, 8.0 parts of dimethylaminoethyl methacrylate, 20.0 parts were added, and polymerization was carried out again. After 2 hours, it was confirmed from the nonvolatile matter of the polymerization solution that the polymerization yield was 97% or more, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone and 60 parts of cation exchange resin &quot; DIAION PK228LH (manufactured by Mitsubishi Chemical Corp.) &quot; was added thereto. The mixture was stirred at room temperature for 1 hour, and "KYOWORD 500SN Ltd.) was added, and the mixture was stirred for 30 minutes. The cation exchange resin and the adsorbent were removed by filtration to remove the residue of the polymerization catalyst. Further, the resin solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resinous dispersant D solution having a nonvolatile content of 40% by weight (amine value: 29 mgKOH / g, quaternary ammonium salt value: 0 mgKOH / g).

(Resinous dispersant E solution)

45.0 parts of methyl methacrylate, 15.0 parts of methacrylic acid and 40.0 parts of ethyl acrylate were charged into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a gas introducing tube, as a first synthesis, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 占 폚, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile in 45.3 parts of cyclohexanone was added to 6.0 parts of 3-mercapto-1,2-propanediol, And reacted for 10 hours. It was confirmed by the solid content measurement that 95% was reacted. At this time, the weight average molecular weight was 4,000. Next, as a second synthesis, 8.8 parts of RIKACID BT-100 (manufactured by New Japan Chemical Co., Ltd.), 69.2 parts of cyclohexanone, and 1,8-diazabicyclo- [5.4.0] And 0.2 part of 7-undecene were added, and the mixture was reacted at 120 DEG C for 7 hours. The reaction was terminated by confirming that at least 98% of the acid anhydride was half-esterified by measurement of the acid value. After completion of the reaction, cyclohexanone was added so as to have a nonvolatile content of 50% by weight to obtain a solution of a resinous dispersant E having an acid value of 129 mgKOH / g and a weight average molecular weight of 8,100.

(Resinous dispersant F, G solution)

The same procedure as in the case of the resinous dispersant E was carried out except that the type and weight of the acrylic monomer shown in Table 11 were changed to pyromellitic acid dianhydride (manufactured by Daicel Chemical Industries, Ltd.) instead of RIKACID BT- And G were prepared.

(Resinous dispersant H)

A reaction vessel equipped with a thermometer, a condenser and a stirrer was charged with 15.0 parts of methyl methacrylate, 5.0 parts of methacrylic acid, 20.0 parts of t-butyl methacrylate, 2 parts of 2-methoxyethyl acrylic acid 60.0 parts were introduced and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 占 폚, and a solution prepared by dissolving 0.1 parts of 2,2'-azobisisobutyronitrile in 45.3 parts of PGMAC in 6.0 parts of 3-mercapto-1,2-propanediol was added, Respectively. It was confirmed that 95% was reacted by the measurement of the solid content. At this time, the weight average molecular weight was 4,000. Then, as a second synthesis, 9.69 parts of pyromellitic dianhydride, 31.7 parts of PGMAC, and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, And reacted for 7 hours. The reaction was terminated by confirming that at least 98% of the acid anhydride was half-esterified by measurement of the acid value. After completion of the reaction, PGMAC was added so as to have a nonvolatile content of 50% by weight to obtain a resinous dispersant H solution having an acid value of 71 mgKOH / g and a weight average molecular weight of 9,500.

(Resinous dispersant I solution)

20.0 parts of methyl methacrylate, 20.0 parts of ethyl acrylate, 10.0 parts of benzyl methacrylate, and 50.0 parts of 2-methoxyethyl acrylic acid were added to a reaction vessel equipped with a thermometer, a thermometer, a condenser and a stirrer as the first synthesis And the mixture was purged with nitrogen gas. The inside of the reaction vessel was heated to 80 占 폚, and a solution prepared by dissolving 0.1 parts of 2,2'-azobisisobutyronitrile in 45.3 parts of PGMAC in 6.0 parts of 3-mercapto-1,2-propanediol was added, Respectively. It was confirmed by the solid content measurement that 95% was reacted. At this time, the weight average molecular weight was 13,000. Next, as a second synthesis, 3.20 parts of pyromellitic dianhydride, 26.4 parts of PGMAC, and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added thereto, Lt; / RTI &gt; The reaction was terminated by confirming that at least 98% of the acid anhydride was half-esterified by measurement of the acid value. After completion of the reaction, PGMAC was added so as to have a nonvolatile content of 50% by weight to prepare a solution of a resinous dispersant I having an acid value of 16 mgKOH / g and a weight average molecular weight of 25,000.

The compositions of the dispersants B and E to I are shown in the following table.

[Table 11]

The names of the compounds in the table are as follows.

MMA: methyl methacrylate

EA: Ethyl acrylate

· MAA: methacrylic acid

N-BA: n-butyl acrylate

BzMA: benzyl methacrylate

T-BMA: t-butyl methacrylate

2-MTA: 2-methoxyethyl acrylic acid

MEDOH: 3-Mercapto-1,2-propanediol

AIBN: 2,2'-azobisisobutyronitrile

PGMAC: Propylene glycol monomethyl ether acetate

PMA: pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.)

RIKACID BT-100: 1,2,3,4-butanetetracarboxylic acid dianhydride (manufactured by New Japan Chemical Co., Ltd.)

DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene (available from San-Apro Ltd.)

&Lt; Production method of micronized pigment >

(Preparation of finely divided pigment 1 (PC-1)) [

200 parts of diketopyrrolopyrrole-based red pigment CI Pigment Red 254 (IRGAZIN RED 2030, manufactured by Ciba, Japan), 1400 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd. ) And kneaded at 80 DEG C for 6 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while being heated to 80 DEG C to form a slurry. After filtration and washing were repeated to remove sodium chloride and diethylene glycol, the mixture was dried at 85 DEG C for one day and one night , 190 parts of diketopyrrolopyrrole finely divided pigment 1 (PC-1) was obtained. The specific surface area of the finely divided pigment 1 was 70 m ² / g.

(Preparation of finely divided pigment 2 (PC-2)

Except that an anthraquinone-based red pigment CI Pigment Red 177 ("Cromophtal Red A2B" manufactured by Ciba Japan Ltd.) was used in place of the CI Pigment Red 254, To obtain 190 parts of finely divided pigment 2 (PC-2) of the anthraquinone system. The specific surface area of the finely divided pigment 2 was 80 m ² / g.

(Preparation of finely divided pigment 3 (PC-3)) [

(PC-1) except that the isoindoline yellow pigment CI Pigment Yellow 139 ("Irgaphor Yellow 2 R-CF" manufactured by Ciba-Geigy) was used instead of CI Pigment Red 254 , And 190 parts of finely divided pigment 3 (PC-3) was obtained. The specific surface area of the finely divided pigment 3 was 75 m ² / g.

(Preparation of finely divided pigment 4 (PC-4)

Except that CI Pigment Red 254 was replaced by nickel complex yellow pigment CI Pigment Yellow 150 ("E-4 GN" manufactured by Lanxess), the respective steps were performed under the same conditions as the finely divided pigment 1 (PC-1) Thus, 190 parts of yellow finely divided pigment 4 (PC-4) was obtained. The specific surface area of the finely divided pigment 4 was 90 m ² / g.

(Preparation of finely divided pigment 5 (P-1)

Each step was carried out under the same conditions as the finely divided pigment 1 (PC-1), except that benzimidazolone pigment CI Pigment Red 176 ("Novoperm Carmine HF3C" manufactured by Clariant) was used instead of CI Pigment Red 254 To obtain finely divided pigment 5 (P-1) of 190 parts of benzimidazolone pigment. The specific surface area of the finely divided pigment 5 was 75 m ² / g.

(Preparation of finely divided pigment 6 (P-2)) [

Each step was carried out under the same conditions as the finely divided pigment 1 (PC-1) except that benzimidazolone pigment CI Pigment Red 171 ("Novoperm Maroon HFM" manufactured by Clariant) was used instead of CI Pigment Red 254 To obtain finely divided pigment 6 (P-2) of 190 parts of benzimidazolone pigment. The specific surface area of the finely divided pigment 6 was 55 m ² / g.

(Preparation of finely divided pigment 7 (P-3)

Each step was carried out under the same conditions as the finely divided pigment 1 (PC-1) except that benzimidazolone pigment CI Pigment Red 175 ("Novoperm Red HFT" manufactured by Clariant) was used instead of CI Pigment Red 254 To obtain finely divided pigment 7 (P-3) of 190 parts of benzimidazolone pigment. The specific surface area of the finely divided pigment 7 was 72 m ² / g.

(Preparation of finely divided pigment 8 (P-4)

Each step was carried out under the same conditions as the finely divided pigment 1 (PC-1) except that benzimidazolone pigment CI Pigment Red 185 ("Novoperm Carmine HF4C" manufactured by Clariant) was used instead of CI Pigment Red 254 To obtain finely divided pigment 8 (P-4) of 190 parts of benzimidazolone pigment. The specific surface area of the finely divided pigment 8 was 55 m ² / g.

(Preparation of finely divided pigment 9 (P-5)) [

Each step was carried out under the same conditions as the finely divided pigment 1 (PC-1), except that benzimidazolone pigment CI Pigment Red 208 ("Novoperm Red HF2B" manufactured by Clariant) was used instead of CI Pigment Red 254 To obtain finely divided pigment 9 (P-5) of 190 parts of benzimidazolone pigment. The specific surface area of the finely divided pigment 9 was 76 m ² / g.

(Preparation of finely divided pigment 10 (P-6)

Each step was carried out under the same conditions as the finely divided pigment 5 (P-1) except that the kneading was carried out at 80 ° C for 8 hours instead of kneading at 80 ° C for 6 hours to obtain a finely divided pigment 10 of 190 parts of benzimidazolone pigment (P-6). The specific surface area of the finely divided pigment 10 was 100 m ² / g.

(Preparation of finely divided pigment 11 (P-7)

Each step was carried out under the same conditions as the finely divided pigment 5 (P-1) except that kneading was carried out at 80 DEG C for 5 hours instead of kneading at 80 DEG C for 6 hours to obtain a finely divided pigment 11 of 190 parts of benzimidazolone pigment (P-7). The specific surface area of the finely divided pigment 11 was 65 m ² / g.

(Preparation of finely divided pigment 12 (P-8)) [

Each step was carried out under the same conditions as the finely divided pigment 5 (P-1) except that the kneading was carried out at 80 DEG C for 4.5 hours instead of kneading at 80 DEG C for 6 hours to obtain 190 parts of the finely divided pigment 12 of the benzimidazolone pigment (P-8). The specific surface area of the finely divided pigment 12 was 55 m ² / g.

(Preparation of green finely-ground pigment 1)

200 parts of Phthalocyanine Green Pigment CI Pigment Green 58 (FASTOGEN GREENA 110 from Dainippon Ink & Chemicals, Inc.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were mixed in a stainless steel first gallon kneader (Inoue Manufacturing Co., Ltd.). And kneaded at 80 DEG C for 6 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while heating at 80 DEG C to obtain a slurry, followed by filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 DEG C , 190 parts of green finely divided pigment 1 was obtained. The specific surface area of the green finely-ground pigment 1 was 75 m ² / g.

(Preparation of blue finely divided pigment 1)

Except that the phthalocyanine blue pigment CI Pigment Blue 15: 6 ("LIONOL BLUE ES" manufactured by Toyo Ink Manufacturing Company, specific surface area 60 m ² / g) was used instead of CI Pigment Green 58, Each step was carried out under the same conditions to obtain 190 parts of blue finely divided pigment 1. The specific surface area of the blue finely divided pigment 1 was 80 m ² / g.

(Preparation of Purple Fine Pigment 1)

Each step was carried out under the same conditions as the green finely divided pigment 1, except that the dioxazine pigment CI Pigment Violet 23 ("LIONOGEN VIOLETRL" manufactured by Toyo Ink Manufacturing Company) was used instead of the CI Pigment Green 58, and 190 parts A purple finely divided pigment 1 was obtained. The specific surface area of the purple finely-ground pigment 1 was 95 m ² / g.

&Lt; Production method of pigment dispersion >

(Pigment dispersion (DC-1))

The following mixture was stirred and mixed, and then dispersed for 3 hours with Eigermill ("mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm and then filtered with a 5.0 μm filter , And a pigment dispersion (DC-1) having a non-volatile component of 20% by weight.

Mineralized pigment 1 (PC-1): 11.0 parts

(C.I. 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 mixture was stirred to homogeneity, and then dispersed for 3 hours using Eigermill ("mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, followed by filtration with a 5.0 μm filter To prepare a pigment dispersion (DC-2) having a non-volatile component of 20 wt%.

Mineralized pigment 2 (PC-2): 11.0 parts

(C.I. 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, and then dispersed for 3 hours with Eigermill ("mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm and then filtered with a 5.0 μm filter , And a pigment dispersion (DC-3) having a non-volatile component of 20 wt%.

Mineralized pigment 3 (PC-3): 11.0 parts

(C.I. 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

(Adjustment of pigment dispersion (DC-4)

The following mixture was stirred and mixed, and then dispersed for 3 hours with Eigermill ("mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm and then filtered with a 5.0 μm filter , And a pigment dispersion (DC-4) having a non-volatile component of 20 wt%.

Mineralized pigment 4 (PC-4): 11.0 parts

(C.I. 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 Co., Ltd.): 5.0 parts

&Lt; Green photosensitive coloring composition, production method of blue photosensitive coloring composition >

(Green photosensitive coloring composition 1)

The following mixture was stirred and mixed, and then dispersed for 5 hours with Eigermill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, And a non-volatile content of 20% by weight.

Green finely-ground pigment 1 (C. I. 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 ("EFKA4300" manufactured by Ciba Japan Co., Ltd.): 5.0 parts

Subsequently, the mixture of the following composition was stirred and mixed so as to be uniform, and then filtered with a filter of 1 m 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

(9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime) cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition 1)

A green pigment dispersion was prepared in the same manner as in the case of the green pigment dispersion except that the green finely divided pigment 1 (CI Pigment Green 58) was changed to blue finely divided pigment 1 (CI Pigment Blue 15: 6) To obtain a pigment dispersion.

A violet pigment dispersion having a nonvolatile content of 20% by weight was obtained in the same manner as in the case of the green pigment dispersion except that the green finely divided pigment 1 (CI Pigment Green 58) was changed to purple finely divided pigment 1 (CI Pigment Violet 23) I got a sieve.

Subsequently, the same procedure as in the case of the green photosensitive coloring composition 1 was carried out except that the total of 50.0 parts of the green pigment dispersion (32.0 parts) and the pigment dispersion (DC-4) (50.0 parts) in total was replaced by 46.0 parts of the blue dispersion and 4.0 parts of the purple dispersion To obtain a blue photosensitive coloring composition 1.

[Example 1]

(Pigment dispersion (D-1))

The following mixture was stirred and mixed, and then dispersed for 3 hours with Eigermill ("mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm and then filtered with a 5.0 μm filter , And a pigment dispersion (D-1) having a non-volatile component of 20 wt%.

Finely divided pigment 5 (P-1): 10.0 parts

(C.I. Pigment Red 176)

Acrylic resin solution 1: 35.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

Resin type dispersant A (referred to as dispersant A in the table): 5.0 parts

Dye derivative (derivative A): 1.0 part

[Examples 2 to 12 and Examples 14 to 18]

The pigment dispersions (D-2 to 12, 14 to 18) were adjusted in the same manner as in the pigment dispersion (D-1) except that the pigment, the resinous dispersant and the derivative were changed to the compositions shown in Table 2 Respectively.

[Example 13]

The following mixture was stirred and mixed, and then dispersed for 3 hours with Eigermill ("mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm and then filtered with a 5.0 μm filter Thereby preparing a pigment dispersion (D-13).

Finely divided pigment 5 (P-1): 11.0 parts

(C.I. Pigment Red 176)

Acrylic resin solution 1: 35.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

Resin Type Dispersant (Dispersant A): 5.0 parts

[Examples 111 to 115]

The pigment dispersions (D-111 to D-115) were prepared in the same manner as in the pigment dispersion (D-17) except that the resinous dispersant was changed to the composition shown in Table 2 below.

[Referential Example 1]

The pigment dispersion (D-19) was prepared in the same manner as in the pigment dispersion (D-13) except that the pigment, the resinous dispersant and the derivative were changed to the compositions shown in Table 2.

[Referential Example 2, 3]

The pigment dispersions (D-20 to D-21) were prepared in the same manner as in the pigment dispersion (D-1) except that the pigment, the resinous dispersant and the derivative were changed to the compositions shown in Table 2.

[Table 2]

Dispersant C: SP55000 (manufactured by Lubrizol) Non-volatile matter 40 wt%

[Evaluation of coloring composition (pigment dispersion) for color filter]

The viscosity, contrast ratio and heat resistance of the pigment dispersions (D-1 to D-21 and D-111 to D-115) obtained in Examples and Reference Examples were evaluated in the following manner.

<Viscosity characteristics>

The viscosity of the pigment dispersion was measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. Separately, 25 g of the pigment dispersion was allowed to stand in a glass container in a closed state at 40 DEG C for 24 hours, and then the viscosity was measured in the same manner as described above to obtain a viscosity with time.

<Contrast ratio (CR)>

Using the spin coater, the obtained pigment dispersion was changed in the number of revolutions to prepare three coated substrates so that the dried film thickness was about 1 탆. After coating, the film was dried in a hot-air oven at 80 DEG C for 30 minutes, and then the film thickness and the contrast ratio were measured. From the data of the three points, the contrast ratio (CR) at a film thickness of 1 mu m was determined by a first correlation method.

&Lt; Evaluation of coating film heat resistance &

The coloring composition was applied on the transparent substrate so that the dry coating film was about 1.0 mu m, and dried at 70 DEG C for 20 minutes. Thereafter, the coated film was heated in an oven at 230 deg. C for 1 hour and then cooled, and the resulting coating film was exposed to light in a L * a * b * color space using a brown light spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.) (L * (1), a * (1), b * (1)). Thereafter, as a heat resistance test, the color difference DELTA Eab * was calculated from the following equation by performing color measurement (L * (2), a * (2), b * (2) And the heat resistance of the coating film was evaluated in the following four stages.

ΔEab * = √ ((L * (2) - L * (1)) 2 + (a * (2) - a * (1)) 2 + (b * (2) - b * (1)) 2)

&Amp; cir &amp;: DELTA Eab * is less than 1.5

?:? Eab * is not less than 1.5 and less than 3.0

DELTA: Eab * was 3.0 or more and less than 5.0

×: ΔEab * is 5.0 or more

The results are shown in Table 3 below.

[Table 3]

The coloring composition for a color filter comprising the colorant (a) comprising the benzimidazolone pigment (a1) represented by the formula (1) and the resinous dispersant (c), which is a resinous dispersant having an acidic substituent, It was found that the coloring composition had a low viscosity, a high CR, and a good heat resistance.

In particular, when an acidic resinous dispersant having an aromatic carboxylic acid group as an acidic substituent and a colorant derivative having a basic substituent were included in the polyester skeleton, the viscosity was lower and the CR was higher.

In addition, among the benzimidazolone pigments (a1), the coloring composition containing CI Pigment Red 176 had higher CR and better CR.

Further, when comparing Examples 1 and 14 to 16 in which the specific surface area of the pigment is different, the larger the specific surface area, the higher the CR result.

[Example 19]

(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 filter of 1.0 mu m to obtain a photosensitive coloring 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

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

1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]

Cyclohexanone: 39.0 parts

[Examples 20 to 39, Reference Examples 4 to 9]

(Photosensitive coloring composition (R-2 to 28))

The photosensitive coloring compositions (R-2 to R-28) were obtained in the same manner as in the photosensitive coloring composition (R-1) except that the pigment dispersions were changed to the kinds and blending amounts of the pigment dispersions shown in Table 4. In the preparation of each photosensitive coloring composition, 100 parts of the photosensitive coloring composition was adjusted by adding such that the total of the pigment dispersions was 50 parts.

[Examples 121 to 125]

(Photosensitive coloring composition (R-121 to 125))

Photosensitive coloring compositions (R-121 to 125) were obtained in the same manner as in Photosensitive coloring composition (R-17) except that the pigment dispersion was changed to the kind of pigment dispersion shown in Table 4. In the preparation of each photosensitive coloring composition, 100 parts of the photosensitive coloring composition was adjusted by adding such that the total of the pigment dispersions was 50 parts.

[Table 4]

[Evaluation of coloring composition (photosensitive coloring composition) for color filter]

The color characteristics, contrast ratio and heat resistance of the photosensitive coloring compositions (R-1 to 28) obtained in Examples and Reference Examples were evaluated in the following manner.

&Lt; Evaluation of color characteristics &

The obtained photosensitive coloring composition was coated on the glass substrate and dried at 70 캜 for 20 minutes and heated again at 230 캜 for 60 minutes to obtain a substrate having chromaticity of x = 0.658 and y = 0.325 in the C light source To obtain a substrate. The brightness (Y) of the obtained substrate was measured with a micro spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

<Contrast ratio (CR)>

The obtained photosensitive coloring composition was changed in the number of revolutions using a spin coater to prepare three coated substrates so that the chromaticity x in the C light source in the CIE color system was 0.650, 0.658 and 0.665. After drying, the coating film was dried in a hot air oven at 80 DEG C for 30 minutes, and chromaticity and contrast ratio were measured. From the data of the three points, the contrast ratio (CR) at the chromaticity x of 0.658 was determined by the first correlation method.

&Lt; Evaluation of coating film heat resistance &

The photosensitive coloring composition was applied on the transparent substrate so as to have a dry film thickness of about 2.0 占 퐉, dried at 70 占 폚 for 20 minutes, exposed to ultraviolet rays through a mask having a predetermined pattern, sprayed with an alkaline developing solution, To form a desired pattern. Thereafter, the coated film was heated in an oven at 230 占 폚 for 1 hour, and then the coated film was exposed to light in an L * a * b * color space using a C light source by a fine spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.) (L * (1), a * (1), b * (1)). Thereafter, as a heat resistance test, the color difference DELTA Eab * was calculated from the following equation by performing color measurement (L * (2), a * (2), b * (2) And the heat resistance of the coating film was evaluated by the following four steps.

ΔEab * = √ ((L * (2) - L * (1)) 2 + (a * (2) - a * (1)) 2 + (b * (2) - b * (1)) 2)

&Amp; cir &amp;: DELTA Eab * is less than 1.5

○: Eab * is at least 1.5, less than 3.0

DELTA: Eab * was 3.0 or more and less than 5.0

×: ΔEab * is 5.0 or more

The results are shown in Table 5 below.

[Table 5]

The coloring composition for a color filter comprising the colorant (a) comprising the benzimidazolone pigment (a1) represented by the formula (1) and the resinous dispersant (c) which is a resinous dispersant having an acidic substituent, CR was high and heat resistance was good.

In addition, the photosensitive coloring composition further comprising a pigment derivative having a basic substituent group had CR better than the photosensitive coloring composition containing no pigment derivative.

On the other hand, the photosensitive coloring composition containing no benzimidazolone pigment (a1) had poor heat resistance and low brightness.

[Production Example of Color Filter]

The red photosensitive coloring composition 1, the green photosensitive coloring composition 1 and the blue photosensitive coloring composition 1 were applied on a substrate by spin coating to a dry film thickness of 1.7 μm and dried to obtain a Ultraviolet exposure was carried out through a mask having a predetermined pattern, and then an alkali developing solution was sprayed by spraying to remove un-hardened portions to form a desired pattern, followed by heating at 230 DEG C for 1 hour. By performing the same operation repeatedly for green and blue to manufacture a color filter, it was possible to produce an RGB three-color filter having high brightness and excellent heat resistance.

&Lt; Embodiment II &gt;

First, the dye derivative (e) used is described.

&Lt; Structural formula of coloring matter derivative (e) >

As in Embodiment I, the derivatives A to H were used.

Next, a method for producing an acrylic resin solution, a resinous dispersant solution, a finely divided pigment, a pigment dispersion, a green photosensitive coloring composition and a blue photosensitive coloring composition used in Examples and Reference Examples will be described.

&Lt; Process for producing acrylic resin solution >

(Adjustment of acrylic resin solution 1)

As in Embodiment I, an acrylic resin solution 1 was prepared.

(Adjustment of acrylic resin solution 2)

As in Embodiment I, an acrylic resin solution 2 was prepared.

&Lt; Process for producing resinous dispersant >

(Resinous dispersant A solution)

62.6 parts of 1-dodecanol, 287.4 parts of epsilon -caprolactone and 0.1 part of monobutyltin (IV) oxide as a catalyst were fed into a reaction tank equipped with a gas introduction pipe, a condenser, a stirring blade and a thermometer, , And the mixture was heated and stirred at 120 ° C for 4 hours. After confirming that 98% of the reaction was carried out by measuring the solid content, 36.6 parts of pyromellitic anhydride was added thereto, and the reaction was carried out at 120 ° C for 2 hours. The reaction was terminated by confirming that at least 98% of the acid anhydride was half-esterified by measurement of the acid value. Thus, a solution of a resinous dispersant A having an aromatic carboxyl group and having an acid value of 49 mgKOH / g per solid content and a non-volatile content of 40% by weight was obtained.

&Lt; Production method of micronized pigment >

(Preparation of finely divided pigment 1 (PC-1)) [

As in Embodiment I, finely divided pigment 1 (PC-1) was prepared.

(Preparation of finely divided pigment 2 (PC-2)

As in Embodiment I, finely divided pigment 2 (PC-2) was prepared.

(Preparation of finely divided pigment 3 (PC-3)) [

As in Embodiment I, finely divided pigment 3 (PC-3) was prepared.

(Preparation of finely divided pigment 4 (PC-4)

As in Embodiment I, finely divided pigment 4 (PC-4) was prepared.

(Preparation of finely divided pigment 5 (P-1)

200 parts of benzimidazolone pigment CI Pigment Red 176 ("Novoperm Carmine HF3C" manufactured by Clariant), 10 parts of the derivative A, 1400 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel first gallon kneader (Inoue Manufacturing Co., Ltd. The mixture was kneaded at 60 DEG C for 6 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while being heated to 80 DEG C to form a slurry. After filtration and washing were repeated to remove sodium chloride and diethylene glycol, the mixture was dried at 85 DEG C for one day and one night , Finely divided pigment 5 (P-1) of 190 parts of benzimidazolone pigment was obtained. The average particle size of the primary particles of the finely divided pigment 5 was 30.0 nm and the BET specific surface area by the nitrogen adsorption method was 30 m ² / g.

(Preparation of finely divided pigment 6 (P-2)) [

A finely divided pigment 6 (P-2) of 190 parts of benzimidazolone pigment was obtained through the same process as that of finely divided pigment 5 (P-1) except that 1400 parts of sodium chloride was changed to 2000 parts. The mean particle diameter of the primary particles of the finely divided pigment 6 was 20.0 nm and the BET specific surface area by the nitrogen adsorption method was 10 m ² / g.

(Preparation of finely divided pigment 7 (P-3)

(P-3) of 190 parts of the benzimidazolone pigment was obtained through the same process as that of the finely divided pigment 5 (P-1), except that the kneaded mixture was kneaded at 70 DEG C for 7 hours instead of kneading at 60 DEG C for 6 hours. ). The average particle diameter of the primary particles of the finely divided pigment 7 was 40.0 nm, and the BET specific surface area by the nitrogen adsorption method was 50 m ² / g.

(Preparation of finely divided pigment 8 (P-4)

200 parts of benzimidazolone pigment CI Pigment Red 176 ("Novoperm Carmine HF3C" manufactured by Clariant), 20 parts of the derivative A, 2000 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded at 80 DEG C for 10 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while being heated to 80 DEG C to form a slurry. After filtration and washing were repeated to remove sodium chloride and diethylene glycol, the mixture was dried at 85 DEG C for one day and one night , Finely divided pigment 8 (P-4) of 190 parts of benzimidazolone pigment was obtained. The mean particle diameter of the primary particles of the finely divided pigment 8 was 30.0 nm and the BET specific surface area by the nitrogen adsorption method was 120 m ² / g.

(Preparation of finely divided pigment 9 (P-5)) [

Each step was carried out under the same conditions as the finely divided pigment 8 (P-4) except that the kneading was carried out at 80 DEG C for 10 hours instead of the kneading at 80 DEG C for 5 hours to obtain 190 parts of the finely divided pigment 9 of the benzimidazolone pigment (P-5). The mean particle size of the primary particles of the finely divided pigment 9 was 30.0 nm and the BET specific surface area by the nitrogen adsorption method was 65 m ² / g.

(Preparation of finely divided pigment 10 (P-6)

200 parts of benzimidazolone pigment CI Pigment Red 176 ("Novoperm Carmine HF3C" manufactured by Clariant), 5 parts of the derivative A, 3000 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel first gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded at 80 DEG C for 6 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while being heated to 80 DEG C to obtain a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 DEG C To obtain a finely divided pigment 10 (P-6) of 190 parts of benzimidazolone pigment. The average particle size of the primary particles of the finely divided pigment 10 was 120 nm, and the BET specific surface area by the nitrogen adsorption method was 5 m ² / g.

(Preparation of finely divided pigment 11 (P-7)

Each step was carried out under the same conditions as the finely divided pigment 10 (P-6), except that the kneaded mixture was blended at 80 ° C for 6 hours instead of at 80 ° C to obtain finely divided pigment 11 (190 parts) of benzimidazolone pigment P-7). The mean particle diameter of the primary particles of the finely divided pigment 11 was 80.0 nm and the BET specific surface area by the nitrogen adsorption method was 5 m ² / g.

(Preparation of green finely-ground pigment 1)

A green finely-ground pigment 1 was produced in the same manner as in Embodiment I.

(Preparation of blue finely divided pigment 1)

As in Embodiment I, a blue finely divided pigment 1 was prepared.

(Preparation of Purple Fine Pigment 1)

A purple finely divided pigment 1 was prepared in the same manner as in Embodiment I.

&Lt; Production method of pigment dispersion >

(Pigment dispersion (DC-1))

A pigment dispersion (DC-1) having a nonvolatile component of 20 wt% was prepared similarly to Embodiment I.

(Pigment dispersion (DC-2))

Similarly to Embodiment I, a pigment dispersion (DC-2) having a nonvolatile component of 20 wt% was prepared.

(Pigment dispersion (DC-3))

Similarly to Embodiment I, a pigment dispersion (DC-3) having a nonvolatile component of 20 wt% was prepared.

(Adjustment of pigment dispersion (DC-4)

Similarly to Embodiment I, a pigment dispersion (DC-4) having a nonvolatile component of 20 wt% was prepared.

&Lt; Preparation method of green and blue photosensitive coloring composition >

(Green photosensitive coloring composition 1)

A green pigment dispersion 1 having a nonvolatile content of 20% by weight was prepared in the same manner as in Embodiment I.

Subsequently, a green photosensitive coloring composition 1 was prepared in the same manner as in Embodiment I.

(Blue photosensitive coloring composition 1)

Similarly to Embodiment I, a blue pigment dispersion having a non-volatile content of 20% by weight was obtained.

A purple pigment dispersion having a nonvolatile content of 20% by weight was obtained.

Subsequently, a blue photosensitive coloring composition 1 was obtained in the same manner as in Embodiment I.

[Example 1]

(Pigment dispersion (D-1))

The following mixture was stirred and mixed, and then dispersed for 3 hours with Eigermill ("mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm and then filtered with a 5.0 μm filter , And a pigment dispersion (D-1) having a non-volatile component of 20 wt%.

Finely divided pigment 5 (P-1): 10.0 parts

(C.I. Pigment Red 176)

Acrylic resin solution 1: 35.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

Resin type dispersant A (referred to as dispersant A in the table): 5.0 parts

Dye derivative (derivative A): 1.0 part

[Examples 2 to 10]

The pigment dispersions (D-2 to D-10) were prepared in the same manner as in the pigment dispersion (D-1) except that the pigment, the resinous dispersant and the pigment derivative were changed to the compositions shown in Table 2.

[Reference Examples 1 to 4]

The pigment dispersions (D11 to D14) were prepared in the same manner as in the pigment dispersion (D-1) except that the pigment, the resinous dispersant and the derivative were changed to the compositions shown in Table 2 below.

[Table 2]

[Evaluation of coloring composition (pigment dispersion) for color filter]

The viscosity, the contrast ratio, and the heat resistance of the coating film of the pigment dispersions (D-1 to 14) obtained in the Examples and Reference Examples were evaluated in the same manner as in Embodiment I. The results are shown in Table 3.

[Table 3]

(A) comprising a benzimidazolone pigment (a2) represented by the formula (1) having a BET specific surface area of 10 m ² / g or more and 50 m ² / g or less according to a nitrogen adsorption method, , The result was that the viscosity was low, the CR was high, and the heat resistance was good.

Particularly, in the pigment compositions of Examples 1, 9 and 10, when an acidic resinous 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, the CR is higher, Good heat resistance was obtained.

In contrast, in Reference Examples 1, 2, 3 and 4, when the specific surface area exceeds 50 m ² / g, the effect of improving the contrast is exhibited. However, since the dispersibility and dispersion stability of the pigment are low, And the storage stability was 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 filter of 1.0 mu m to obtain a photosensitive coloring 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

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

(9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime) cyclohexanone: 39.0 parts

[Examples 12 to 23, Reference Examples 5 to 11]

(Photosensitive coloring composition (R-2 to 20))

The photosensitive coloring compositions (R-2 to R-20) were obtained in the same manner as in the photosensitive coloring composition (R-1) except that the pigment dispersion was changed to the kind and amount of the pigment dispersion shown in Table 4. In the preparation of each photosensitive coloring composition, 100 parts of the photosensitive coloring composition was adjusted by adding such that the total of the pigment dispersions was 50 parts.

[Table 4]

[Evaluation of coloring composition (photosensitive coloring composition) for color filter]

The color characteristics, contrast ratio and heat resistance of the photosensitive coloring compositions (R-1 to R-20) obtained from Examples and Reference Examples were evaluated in the same manner as in Embodiment I. The results are shown in Table 5.

The results are shown in Table 5 below.

[Table 5]

(A) comprising a benzimidazolone pigment (a2) represented by the formula (1) having a BET specific surface area of 10 m ² / g or more and 50 m ² / g or less according to a nitrogen adsorption method in Examples 11 to 23, The coloring composition for a color filter used had a high lightness and CR, a low viscosity, and a good heat resistance.

On the other hand, in Reference Examples 5 and 6, since the photosensitive coloring composition comprising a benzimidazolone pigment having a BET specific surface area of more than 50 m ² / g as measured by the nitrogen adsorption method is low in dispersibility and dispersion stability of the pigment, When the pigment dispersion was prepared using the pigment, re-aggregation of the pigment particles occurred, resulting in an unstable state with a high viscosity, resulting in insufficient fluidity and storage stability, and low lightness and CR and high viscosity.

Further, in Reference Examples 7 and 8, when the specific surface area of the benzimidazolone pigment was lower than 10 m ² / g, the lightness and CR were low.

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

[Production Example of Color Filter]

As a result of preparing a color filter in the same manner as in Embodiment I, an RGB three-color filter having high brightness and excellent heat resistance could be produced.

Claims (8)

A coloring composition comprising a colorant, a resin, a resinous dispersant and a solvent,
Wherein the colorant comprises a benzimidazolone pigment represented by the following formula (1) and CI Pigment Yellow 139,
Wherein the resinous dispersant is a resinous dispersant having an acidic substituent and the resinous dispersant having an acidic substituent is a resinous dispersant having an aromatic ring having two or more carboxyl groups in one molecule. .

[Here, Formula (1) of R _1, R _2, 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 method according to claim 1,
Wherein the BET specific surface area of the benzimidazolone pigment represented by the formula (1) by the nitrogen adsorption method is 10 m ² / g or more and 50 m ² / g or less.
The method according to claim 1,
A red coloring composition for a color filter, wherein the benzimidazolone pigment represented by the formula (1) is CI Pigment Red 176.
delete The method according to claim 1,
And at least one or more kinds selected from the group consisting of a pigment derivative having a basic substituent group, a? -Naphthol derivative having a basic substituent group and a triazine derivative having a basic substituent (e) A red coloring composition for a color filter, comprising a coloring matter derivative having a basic substituent.
The method according to claim 1,
Wherein the colorant further contains at least one kind of pigment selected from the group consisting of CI Pigment Red 254, CI Pigment Red 177 and CI Pigment Yellow 150.
The method according to claim 1,
Wherein the coloring composition further contains one or both of a photopolymerizable monomer and a photopolymerization initiator.
A color filter comprising a red filter segment formed on a substrate from the red coloring composition for a color filter according to any one of claims 1 to 3 and 5 to 7.