JP2007233230A - Photosensitive black composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive black composition having high sensitivity, high light shielding effect, excellent stability and low viscosity, and a color filter with a black matrix having high light shielding effect and adhesion. <P>SOLUTION: The photosensitive black composition contains carbon black, a photopolymerization initiator, a dye derivative, an ethylenically unsaturated compound and a resin, wherein the carbon black is produced by mixing and dry-grinding carbon black (a1) not containing particles of >40 nm and having an average primary particle diameter of 8-20 nm and carbon black (a2) having a larger average particle diameter than the carbon black (a1) by ≥5 nm and having an average primary particle diameter of 21-40 nm. The color filter has the black matrix formed of the photosensitive black composition on a transparent substrate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive black composition used for forming a black matrix constituting a color filter used in a liquid crystal display device, an imaging tube element, etc., and a color comprising a black matrix formed from the photosensitive black composition Regarding filters.

The color filter forms a grid-like black pattern called a black matrix (hereinafter sometimes abbreviated as “BM”) between red (R), green (G), and blue (B) filter segments. Is common. The function of this black matrix is to block the light from the backlight and improve the contrast, and to prevent color mixing of adjacent RGB pixels.
In the black matrix formation method, a metal thin film is formed on a transparent substrate using a metal compound such as chromium by vapor deposition or sputtering, and then a fine pattern is formed through a photolithography method and an etching process (metal) BM), and a method (resin BM) formed by a photolithography method using a photosensitive black composition in which a black component such as carbon black is dispersed in a photosensitive material has been developed.

However, the metal BM is not only very expensive to manufacture due to the complicated manufacturing process, but it is difficult to form it on a large substrate from the viewpoint of apparatus cost or from a technical point of view because it employs a vapor deposition method or a sputtering method. In addition, commonly used chromium is not preferred in terms of environmental issues.
In recent years, the resin BM has attracted attention in place of the metal BM from the viewpoint of the environmental problems described above and also from the viewpoint of cost reduction. However, the resin BM has a problem that the light shielding property (optical density = OD) is lower than that of the metal BM. That is, the metal BM can generally obtain a desired light-shielding property with a film thickness of 0.1 to 0.2 μm, while the resin BM has a film thickness of 1 to 1 in order to exhibit an equivalent light-shielding property. Must be set to 2 μm. When creating a color filter, in order to eliminate light leakage, the BM and the adjacent RGB layer are overlapped and formed, but in the resin BM, the step where the BM and the RGB layer overlap is increased. Causes a problem that the liquid crystal alignment is disturbed and the display quality is deteriorated. Against this background, the resin BM is required to have a high light shielding property, that is, a high OD value in a unit film thickness.

Therefore, attempts have been made to increase the content of light-shielding components such as carbon black contained in the composition in order to improve the light-shielding property of the black matrix and reduce the level difference. However, in the method of increasing the content of the light shielding component, sensitivity reduction, developability, resolution, black matrix pattern shape, composition stability (sensitivity change over time, developability change, resolution change, Not only is the pattern shape change) worsened, but the viscosity of the composition is increased, so that there is a problem that it cannot be satisfactorily applied to the substrate.
In addition, for the purpose of improving the light-shielding property of the black matrix, a method of increasing the OD value by using two kinds of light-shielding materials in combination, that is, using carbon black having a small average particle size and carbon black having a large average particle size in combination, It has been proposed to improve the light shielding property (OD value) by forming a close-packed structure in a black matrix (see Patent Documents 1 to 3).

  That is, Patent Document 1 preferably includes at least two kinds of carbon black having an average particle diameter of 40 to 130 nm and the other carbon black having an average particle diameter of 135 to 500 nm and having different average particle diameters. A photosensitive black resin composition comprising carbon black and a photosensitive resin is disclosed. Patent Document 2 contains a light-shielding material and a polymer material, and the light-shielding material preferably has a large particle size distribution with an average particle size of 50 nm or more, and a smaller particle size. A black paint composition which is a powder particle (for example, carbon black) having a double particle size distribution consisting of a small particle size distribution with an average particle size of is disclosed.

  Patent Document 3 discloses that two or more kinds of carbon blacks coated with a resin and having an average primary particle diameter different by at least 20 nm, preferably one carbon black having an average primary particle diameter of 10 to 40 nm and the other carbon black. There is disclosed a carbon black for forming a black resist pattern, which includes carbon black having an average primary particle diameter of 45 to 300 nm and a difference between the average primary particle diameters of both being 30 nm.

  However, when the black composition contains carbon black having an average primary particle diameter of more than 40 nm, in addition to being disadvantageous from the viewpoint of light shielding properties, the black matrix pattern shape has a particularly unevenness in linearity. There is a problem that the straight portion of the pattern shape of the black matrix is likely to be chipped because it tends to occur or has poor adhesion to the glass substrate.

As a method for applying the composition (paste) to the substrate, a spin coating method, a roll coating method, a bar coating method, a die coating method, and the like are known.
The spin coating method is a method widely used for applying a photoresist on a semiconductor wafer, and a coating film is formed by dropping a paste on the center of the surface of a rotating substrate. For color filter applications, for example, it is disclosed in JP-A-63-107769. The coating film obtained by the spin coating method is, for example, disclosed in Japanese Patent Application Laid-Open No. 6-348023 and Japanese Patent Application Laid-Open No. 7-261378. However, if the paste is non-Newtonian or has a high viscosity, a thick portion is formed at the center of rotation, resulting in a reduction in film thickness uniformity. In addition, the amount of paste used to obtain a predetermined film thickness is extremely large, which is uneconomical. In addition, the paste may adhere to the edge or back surface of the substrate, or the paste scattered in the apparatus may be gelled or solidified, resulting in poor process stability and cleanliness, and a decrease in yield.

  The roll coating method is a method of transferring a paste to a substrate through a rubber roll, and can be applied to a long coated material or a rolled coated material. However, because the paste is sequentially sent from the pan to the application roll and the substrate, the paste is exposed to air for a long time, and not only is the deterioration due to moisture absorption of the paste easy to occur, but also foreign matter is likely to be mixed. When foreign matter is mixed, if the paste is non-Newtonian or has a high viscosity, the leveling property is poor and streaks occur in the direction of substrate movement starting from the foreign matter.

  The bar coating method is a method in which a paste is applied to a substrate using a bar in which a thin wire is wound around a rod, and is disclosed in JP-A-2-258081. In this method, since the wire wound around the rod is in direct contact with the substrate, when the paste is non-Newtonian or the viscosity is high, the leveling property is poor and the wire trace remains.

  The die coating method is a method of forming a coating film on a substrate by moving a base for discharging paste from a slit relative to the substrate, and is disclosed in Japanese Patent Application Laid-Open No. 7-8894. This method is an excellent coating method that has the advantage that the usage rate of the discharged paste is extremely high, and the paste feeding path is sealed until it is discharged from the slit, so that the quality of the coating film can be kept high. is there. However, if the gap between the substrate and the tip of the die is not controlled as narrow as possible, when the relative speed between the die and the substrate is increased, the liquid pool between the tip of the die and the substrate is interrupted and the film is cut off. There is also a drawback that occurs. In particular, this phenomenon tends to occur when the viscosity of the paste is too high or when a thin wet film is to be formed. Therefore, the viscosity of the paste used in the die coating method is preferably as low as possible.

As described above, it is more preferable that the viscosity is low in any coating method.
Although Cited Document 4 discloses a technique that defines the solid component concentration and the shear rate of the composition, there is a problem that a required light shielding degree cannot be obtained if the viscosity is lowered.

  On the other hand, Patent Documents 5 and 6 disclose a photosensitive black composition using a specific dye derivative or a specific initiator. In this case, the stability (sensitivity with time) of the photosensitive black composition is disclosed. Change, pattern shape change) and high light-shielding properties at the same time are still insufficient.

Furthermore, the basic structure of the substrate used for the color liquid crystal display is provided with a transparent glass substrate, a black matrix and a color filter layer, an overcoat layer, and a transparent conductive film. Among these, the black matrix has a role of improving display characteristics by suppressing light leakage from other than the effective region. In recent years, resin-made black matrix materials have been frequently used, and in particular, patterning is generally performed by a photolithography process. However, when a resin material is used as the black matrix, the adhesion between the transparent glass substrate, which is an inorganic material, and the resin material is small, resulting in insufficient adhesion. As a result, the black matrix patterning process peels off the black matrix. There was a problem that it was easy to occur. That is, in the process of exposing and developing after coating the black matrix material, the black matrix may be locally peeled off due to variations in development conditions. This necessitates strict management of all process conditions, particularly in industrial production, and in some cases leads to a decrease in yield.
In order to solve the above problem, a technique for increasing the adhesion between glass and resin by coating a hydrophobic organic silicon compound film on a glass substrate has been disclosed (Patent Document 7). There was no improvement.

Japanese Patent Laid-Open No. 9-133806 Japanese Patent Laid-Open No. 9-279082 Japanese Patent Laid-Open No. 11-80584 JP 2000-056126 A JP 2005-10604 A JP 2005-99488 A Japanese Patent Laid-Open No. 2000-212485

An object of the present invention is to provide a photosensitive black composition excellent in high light-shielding property and stability and having a low viscosity, and a color filter including a black matrix having high light-shielding property and adhesion.

The photosensitive black composition of the present invention is a photosensitive black composition containing (a) carbon black, (b) a photopolymerization initiator, (c) a dye derivative, (d) an ethylenically unsaturated compound, and (e) a resin. In the composition, carbon black does not contain particles exceeding 40 nm, the average primary particle diameter is 8 to 20 nm, carbon black (a1), the average particle diameter is 5 nm or more larger than carbon black (a1), and the average primary A carbon black (a2) having a particle diameter of 21 to 40 nm is mixed and dry pulverized.
The weight ratio of carbon black (a2) to carbon black (a1) (weight of carbon black (a1) / weight of carbon black (a2)) is 1/3 to 1/20.
Carbon black (a1), carbon black (a2), and (c) a pigment derivative are mixed and dry pulverized.
The carbon black (a1) and the carbon black (a2) are dry-pulverized and then mixed with (c) a pigment derivative.

The photopolymerization initiator is at least one photopolymerization initiator selected from an oxime photopolymerization initiator, an imidazole photopolymerization initiator, and a borate photopolymerization initiator, and further contains a polyfunctional thiol. The dye derivative includes a dye derivative represented by the general formula (1).
The ratio (M / P) of the weight (P) of the resin and the weight (M) of the ethylenically unsaturated compound is 0.10 to 0.70.
The color filter of the present invention comprises a black matrix formed from the photosensitive black composition on a transparent substrate.

The photosensitive black composition of the present invention comprises (a) carbon black containing no particles exceeding 40 nm and having an average primary particle diameter of 8 to 20 nm and an average primary from carbon black (a1). Since carbon black (a2) having a particle size of 5 nm or more and an average primary particle size of 21 to 40 nm is mixed and dry-pulverized, (a) the carbon black has good dispersion even at a high concentration, High light-shielding property, excellent stability, and low viscosity.
In addition, (a) carbon black is mixed with a pigment derivative and then dry-pulverized, whereby a light-sensitive black composition having higher light-shielding properties, excellent stability, and low viscosity can be obtained.
By using the photosensitive black composition, it is possible to form a color filter including a black matrix having high light blocking properties and high adhesion.

First, the photosensitive black composition of the present invention will be described.
The photosensitive black composition of the present invention contains (a) carbon black as a light shielding component. (a) does not include particles exceeding 40 nm, the average primary particle diameter is 8 to 20 nm, carbon black (a1), the average particle diameter is 5 nm or more larger than carbon black (a1), and the average primary particle diameter is Carbon black (a2) having a diameter of 21 to 40 nm is mixed and dry pulverized.
A photosensitive black composition using carbon black (a1) having an average primary particle size of 8 to 20 nm alone is advantageous in terms of light shielding properties because it has a large number of carbon black particles per unit volume, but has high light shielding properties. Therefore, the photocurability is inferior. In addition, it is difficult to stably disperse carbon black, and there is a problem that a phenomenon of a residue (or also referred to as background stain) is caused in which a part of the black composition remains on the glass substrate after development.

On the other hand, in the photosensitive black composition using carbon black (a2) having an average primary particle diameter of 21 to 40 nm alone, the number of carbon black particles per unit volume is small and the photocurability is advantageous, but the light shielding property. Is insufficient.
Further, in the photosensitive black composition containing carbon black having an average primary particle diameter exceeding 40 nm, the number of carbon black particles per unit volume is small and photocurability is advantageous, but the light shielding property and the pattern shape of the black matrix, In particular, the linearity is insufficient.

As the carbon black (a1), those having an average primary particle diameter of 10 to 18 nm are preferable, and carbon black having a specific surface area of 200 to 600 m ² / g can be suitably used. When carbon black with a specific surface area of less than 200 m ² / g is used, it tends to cause deterioration of the pattern shape and adhesion of the black matrix, and when carbon black greater than 600 m ² / g is used, the stability of the carbon black Dispersion tends to be difficult. Carbon black having an average primary particle diameter of less than 8 nm is difficult to produce, and is not suitable as carbon black (a1).

Moreover, as carbon black (a2), that whose average primary particle diameter is 22-37 nm is preferable, and also the carbon black whose specific surface area is 40-600 m < ² > / g can be used conveniently. When carbon black with a specific surface area of less than 40 m ² / g is used, it tends to cause deterioration of the pattern shape and adhesion of the black matrix, and when carbon black greater than 600 m ² / g is used, the stability of the carbon black Dispersion tends to be difficult.
Furthermore, when the difference in average primary particle size between the carbon black (a1) and the carbon black (a2) is less than 5 nm, the high light-shielding property that is manifested when the carbon black (a1) and the carbon black (a2) are used together, When the photosensitive black composition is stored for a predetermined period, it is not possible to expect a stability effect that almost no change in development speed or change in line width occurs before and after storage.

  Examples of carbon black (a1) having an average primary particle diameter of 8 to 20 nm include, for example, MONARCH or BLACK PEARLS (1400, 1300, 1100, 1000, 900, 880, 800, 700) manufactured by CABOT, VULCAN (P, 9A32). ), Mitsubishi Chemical # (2700B, 2650, 2600, 2450B, 2400B, 2350, 2300, 1000, 990, 980, 970, 960, 950, 900, 850), MCF88, MA600, Color Black (FW2000 made by DEGUSSA) , FW2, FW2V, FW1, FW18, S170, S160), Special Black (6, 5), Printex (95, 90, 85, 80, 75, 40, 60), Tokai Carbon Seast (9H SAF-HS, 9 SAF), Asahi Carbon's Asahi # 80, Colombian Carbon's ROYAL SPECTRA, NEO SPECTRA MARK (I and II), NEO SPECTRA AG, SUPERBA (NEO MK III), NEO SPECTRA MARK IV, RAVEN (5000, 7000, 5750, 5250, 3500, 3200, 2000, 1500), CONDUCTEX (40-220, SC), RAVEN C BEADS, and the like. Preferably, MONARCH (1100, 800) manufactured by CABOT, BLACK PERLS (1100, 800), # 850 manufactured by Mitsubishi Chemical, particularly preferably MONARCH 1100 manufactured by CABOT can be used.

  Examples of carbon black (a2) having an average primary particle size of 21 to 40 nm include, for example, VULCAN (XC72R, XC72), MOGUL L, BLACK PEARLS (L, 570, 520, 490, 480, 470, 460, manufactured by CABOT) 450, 430, 420, 410), REGAL (660R, 660, 500R, 330R, 330, 300R, 250R, 250, 99R, 99I), ELFTEX (5, 8, 12, PELLETS115), MA (77) , 7, 8, 11, 100, 100R, 100S, 230, 200RB, 14), # (750B, 650B, 52, 50, 47, 45, 45L, 44, 40, 33, 32, 30, 95, 85, 260, 3230B, 3350B), CF9, Special Black (4, 4A, 550, 350) manufactured by DEGUSSA, Printex (150T, U, V, 140U, 140V, 55, 45, P, L6, L, 300, 30, ES23, 3, ES22, 35, XE2), Tokai carbon seast {6ISAF, 600ISAF-LS, 5H-IISAF-HS, KH (N339), 3H HAF-HS , NH (N351), 3 HAF, 3M, N LI-HAF, 300 HAF-LS, 116 MAF}, Asahi Carbon made Asahi # 75, Asahi # 70 (-IH, -IN, -L), Asahi HS- 500, Asahi F-200, Colombian Carbon RAVEN (1255, 1250, 1200, 1170, 1040, 1035, 1030 BEADS, 1020, 1000, 890POWDWE, 890HPOWDER, 850, 825BEADS), CONDUCTEX (975BEADS, 900BEADS), etc. Can be mentioned. Preferably, REGAL (300R, 250R, 250, 99R, 99I) manufactured by CABOT, MA (7, 11, 100R), # (47, 45, 45L) manufactured by Mitsubishi Chemical, Printex55 manufactured by DEGUSSA, particularly preferably Mitsubishi Chemical # 47 manufactured by CABOT, and REGAL 250R manufactured by CABOT can be used.

The weight ratio of carbon black (a2) to carbon black (a1) is preferably (a1) / (a2) = 1/3 to 1/20, more preferably 1/3 to 1/10. When (a1) / (a2) = 1/3, that is, when (a1) is large, stable dispersion of carbon black becomes difficult. On the other hand, when (a1) / (a2) is more than 1/20, that is, when (a1) is reduced, a high light-shielding property and a photosensitive black composition that are manifested when carbon black (a1) and (a2) are used in combination. The effect of the stability of things cannot be expected.
Further, carbon black (a1) and carbon black (a2) are preferably added in a total amount of 40 to 60% by weight, more preferably in total, based on the total solid weight of the photosensitive black composition (100% by weight). In an amount of 45 to 60% by weight.

Carbon black is called an aggregate in which primary particles are aggregated (aggregate), and is conceptually compared to a bunch of grapes. The degree of development of this aggregate is called a structure, and the height of this structure has a great influence on dispersibility, coloring power, viscosity and the like.
By dry pulverization of carbon black in the present invention, a high structure aggregate formed by agglomerating primary particles of carbon black is broken or crushed to loosen the aggregate, and a low structure aggregate is obtained.
Examples of dry pulverization of carbon black include an apparatus using a medium such as an attritor, a ball mill, and a vibration mill, and an apparatus not using a medium such as a pin mill, a hammer mill, and a micros. Moreover, the temperature at the time of dry pulverization is not particularly limited, but 60 to 110 ° C. is preferable from the viewpoint of safety during operation.

  Carbon black (a1) and carbon black (a2) may be mixed after dry pulverization in advance, respectively, but from the viewpoint of production efficiency, it is preferable to mix (a1) and (a2) and then dry pulverize. .

  Examples of the (b) photopolymerization initiator contained in the photosensitive composition of the present invention include, for example, an acetophenone photopolymerization initiator, a benzoin photopolymerization initiator, a benzophenone photopolymerization initiator, and a thioxanthone photopolymerization initiator. , Triazine photopolymerization initiator, carbazole photopolymerization initiator, imidazole photopolymerization initiator, oxime photopolymerization initiator, borate photopolymerization initiator, phosphine photopolymerization initiator, quinone photopolymerization initiator, A titanocene photopolymerization initiator or the like can be used. Among these, from the viewpoint of photocurability, at least one photopolymerization initiator selected from an oxime photopolymerization initiator, an imidazole photopolymerization initiator, and a borate photopolymerization initiator is preferable, and an oxime photopolymerization initiator is used. Particularly preferred.

Examples of the oxime-based photopolymerization initiator include ethanone represented by the following formula (2), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O— Acetyloxime), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2) -(4'-methoxy-naphthyl) ethylidene) hydroxylamine and the like.
Formula (2)

Examples of the imidazole photopolymerization initiator include 2,2′bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole.
Examples of the borate photopolymerization initiator include compounds represented by the following formulas (3) to (6).

As the acetophenone-based photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like.
Examples of the benzoin photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal.
Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like.

Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and the like.
Examples of the triazine photopolymerization initiator include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s -Triazine, 2,4-bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxy styryl) -6-triazine.

Examples of the phosphine photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of the quinone photopolymerization initiator include 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.
The said photoinitiator is used individually by 1 type or in mixture of 2 or more types. The photopolymerization initiator can be used in an amount of preferably 0.5 to 50% by weight, more preferably 2 to 20% by weight, based on the total solid content weight of the photosensitive black composition (100% by weight). .

  The ratio (I / M) of (b) the weight (I) of the photopolymerization initiator to (d) the weight (M) of the ethylenically unsaturated compound is preferably 0.10 to 1.0. 0.15-0.8 is more preferable, and 0.20-0.6 is particularly preferable. If the I / M is less than 0.10, the sensitivity is low, and if the I / M exceeds 1.00, the pattern width after development with respect to the black matrix pattern shape poor linearity, cross-sectional shape failure or mask pattern width. Problems such as fatness occur.

  The photosensitive black composition of the present invention may contain a sensitizer. Examples of the sensitizer include α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethyliso Examples include phthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like. The said sensitizer can be used individually by 1 type or in mixture of 2 or more types. The sensitizer is preferably used in an amount of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total solid weight of the photosensitive black composition (100% by weight). it can.

（式中、Ｑは有機色素残基、Ｘは直接結合、−ＣＯＮＨ−Ｙ_２−、−ＳＯ_２ＮＨ−Ｙ_２−、または−ＣＨ_２ＮＨＣＯＣＨ_２ＮＨ−Ｙ_２−（但し、Ｙ_２は置換基を有してもよいアルキレン基またはアリール基を表す。）、Ｙ_１は−ＮＨ−または−Ｏ−、Ｚは水酸基、アルコキシ基、下記一般式で示される置換基、またはｎが１の場合には−ＮＨ−Ｘ−Ｑ、

（式中、Ｙ_３は−ＮＨ−または−Ｏ−）、
Ｒ_１およびＲ_２は、それぞれ独立に置換もしくは無置換のアルキル基、またはＲ_１とＲ_２とで形成される少なくとも窒素原子を含むヘテロ環、ｍは１から６の整数、ｎは１から４の整数を表す。） The (c) dye derivative contained in the photosensitive black composition of the present invention is a compound in which a substituent is introduced into an organic dye, and the organic dye includes naphthalene series, anthraquinone series, etc., which are not generally called dyes. The light yellow aromatic polycyclic compound is also included. As the pigment derivative, those represented by the following general formula (1) can be preferably used. Examples of the dye derivative represented by the general formula (1) include dye derivatives represented by the following general formulas (7) to (16).
General formula (1)

(Wherein Q is an organic dye residue, X is a direct bond, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH ₂ NHCOCH ₂ NH—Y ₂ — (where Y ₂ is a substituent) Represents an alkylene group or an aryl group which may have a group.), Y ₁ is —NH— or —O—, Z is a hydroxyl group, an alkoxy group, a substituent represented by the following general formula, or n is 1. -NH-XQ,

(Wherein Y ₃ is —NH— or —O—),
R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, or a heterocycle containing at least a nitrogen atom formed by R ₁ and R ₂ , m is an integer of 1 to 6, and n is 1 to 4 Represents an integer. )

Examples of the organic dye constituting the dye derivative represented by the general formula (1) include phthalocyanine, quinacridone, quinacridonequinone, isoindolinone, quinophthalone, diketopyrrolopyrrole, perylene, perinone, Indigo, thioindigo, dioxazine, anthraquinone, pyranthrone, anthanthrone, flavanthrone, indanthrone, metal complex, etc. condensed polycyclic organic pigments, benzimidazolone, insoluble azo, condensation Other organic pigments or dyes such as azo-based and soluble azo-based are listed.

  The pigment derivative represented by the general formula (1) may be used alone or in combination of two or more. The dye derivative represented by the general formula (1) is preferably 0.05 to 20% by weight, more preferably 0.5 to 10% by weight, based on the total solid content weight of the photosensitive black composition (100% by weight). % Can be used. When the content of the pigment derivative is less than 0.05% by weight, the effect of dispersing the carbon black is not sufficiently exhibited. When the content is more than 20% by weight, the dispersion of the carbon black becomes unstable, which is not preferable.

  (c) The pigment derivative may be added after dry pulverization of carbon black (a1) and carbon black (a2). Alternatively, (c) may be mixed with (a1) and (a2) and then dry pulverized, or (c) may be added during dry pulverization of (a1) and (a2). From the viewpoint of better dispersion of carbon black, low viscosity and increased adhesion, it is preferable to add a dye derivative after dry pulverization of (a1) and (a2).

The (d) ethylenically unsaturated compound contained in the photosensitive black composition of the present invention is a compound having one or more ethylenically unsaturated double bonds, and uses a monomer, oligomer, or photosensitive resin. be able to.
Examples of the monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tris. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. Examples of the oligomer include epoxy (meth) acrylate, urethane (meth) acrylate, and ester (meth) acrylate.

As photosensitive resin, the photosensitive resin which introduce | transduced the ethylenically unsaturated bond to the below-mentioned resin by a well-known method can be used. For example, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group present in the resin, A resin obtained by reacting cinnamic acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A half-esterified product can be used.

An ethylenically unsaturated compound is used individually by 1 type or in mixture of 2 or more types.
The ethylenically unsaturated compound is preferably 5 to 30% by weight based on the total solid weight of the photosensitive black composition (100% by weight), more preferably 7 to 28% from the viewpoint of photocurability and developability. %, Particularly preferably in an amount of 10 to 25% by weight. When the content of the ethylenically unsaturated compound is more than 30% by weight, it is not preferable because the black matrix pattern shape is poor in linearity and cross-sectional shape. Since curability is insufficient, it is not preferable.

The photosensitive black composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimerca DOO -s- triazine, 2-(N, N-dibutylamino) -4,6-dimercapto -s- triazine, trimethylolpropane tris (3-mercapto isobutyrate), and the like. These polyfunctional thiols can be used alone or in combination.

Among these polyfunctional thiols, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), and trimethylolpropane tris (3-mercaptoisobutyrate) can be preferably used.
Moreover, these polyfunctional thiols are preferable when combined with an imidazole-based photopolymerization initiator among the photopolymerization initiators, because the sensitivity is increased and the photocurability is improved.
The polyfunctional thiol can be used in an amount of preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the total solid content weight of the photosensitive black composition (100% by weight). If it is less than 0.1% by mass, the effect of adding a polyfunctional thiol is insufficient. If it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered, or the stability of the photosensitive black composition is lowered.

  Further, as the (e) resin contained in the photosensitive black composition of the present invention, for example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-acetic acid Heat of vinyl copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene, polybutadiene, polyimide resin, etc. Thermosetting resins such as plastic resins, epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins can be used.

In the photosensitive black composition of the present invention, the ratio (M / P) of the weight (P) of the resin and the weight (M) of the ethylenically unsaturated compound is preferably 0.10 to 0.70, It is more preferably 0.15 to 0.65, and particularly preferably 0.20 to 0.60. When M / P is less than 0.10, the sensitivity is low, and when M / P exceeds 0.70, the black matrix pattern shape is poor in linearity, cross-sectional shape, or tack.

The photosensitive black composition of the present invention may contain a solvent in order to sufficiently disperse carbon black and form a black matrix having a desired film thickness. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylbenzene, ethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, xylene, ethyl cellosolve, methyl- Examples include n-amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents, and these can be used alone or in combination.
The solvent can be used in an amount of preferably 150 to 3500 parts by weight, more preferably 250 to 2000 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive black composition.

The photosensitive black composition of the present invention may be added with a surfactant, a silane coupling agent, other additives, etc. for the purpose of improving coating properties, improving sensitivity, and improving adhesion. good.
The photosensitive black composition is composed of carbon black, pigment derivative, ethylenically unsaturated compound, photopolymerization initiator, resin, solvent, and other additives as necessary, and is a three roll mill, two roll mill, sand mill. It can be produced by dispersing using various dispersing devices such as a kneader, attritor, and micros.
The photosensitive black composition is prepared by means of centrifugal separation, sintering filter, membrane filter, or the like, with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

Next, the color filter of the present invention will be described.
The color filter of the present invention comprises a black matrix formed from the photosensitive black composition of the present invention on a transparent substrate such as a glass plate and at least two color filter segments other than black. The color of the filter segment is selected from about 2 to 6 colors from blue, green, red, cyan, yellow, magenta, orange, purple and the like. Filter segments having the same color system and different densities may be formed.
The black matrix is formed by applying the photosensitive black composition of the present invention on a transparent substrate by a coating method such as spin coating, slit coating, roll coating, etc., and then active energy rays from the composition coating surface side through a photomask. Can be formed by soaking in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove an unirradiated portion, that is, an uncured portion and developing.

The coating thickness of the photosensitive black composition is preferably in the range of 0.2 to 5 μm (when dry), and is in the range of 0.5 to 2 μm, which makes it easy to balance coating properties and light shielding properties. Is more preferable.
Further, the optical density (OD) per 1 μm of the dry thickness of the black matrix is preferably 3.0 or more, particularly preferably 3.5 or more, more preferably 3.8 or more, from the viewpoint of high light shielding properties. It is. The higher the optical density, the better. However, when the active energy ray is ultraviolet light or visible light, it is difficult to obtain a cured coating film.

As the alkali developer, an aqueous solution such as sodium carbonate or sodium hydroxide is used, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the exposure sensitivity by active energy rays, after coating and drying the photosensitive black composition, 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. After the film is formed, active energy rays can be irradiated from the composition application surface side.

  As the active energy ray, an electron beam, ultraviolet rays, or visible light of 400 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source irradiated from the composition application surface side. Moreover, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) of ultraviolet rays and visible light of 400 to 500 nm. Specifically, since it is a point light source and the luminance is stable, an ultrahigh pressure mercury lamp or a xenon mercury lamp is often used. The active energy dose irradiated from the composition coated surface side can be set in a timely manner within a range of 5 to 1000 mJ, but is preferably within a range of 20 to 300 mJ that can be easily managed in the process.

Each color filter segment can be formed using a gravure offset printing method, a waterless offset printing method, a silk screen printing method, a photolithography method using a solvent developing type or an alkali developing type colored resist, and transparent coloring material by electrophoresis of colloidal particles. Examples thereof include an electrodeposition method in which electrodeposition is formed on a conductive film, and a transfer method in which a filter segment layer formed in advance on the surface of a transfer base sheet is transferred onto a black matrix substrate.
Since the printing method can be patterned simply by repeating printing and drying, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In the case of producing a color filter by a printing method, it is important to control the fluidity of the ink on the printing press, and the ink viscosity can be adjusted with a dispersant or extender pigment.

  The photolithography method using a solvent development type or alkali development type colored resist is a method in which a colored resist is applied to a transparent substrate on which a black matrix is formed by a coating method such as spin coating, slit coating or roll coating, and then through a photomask. In this method, a UV light exposure is performed, the unexposed portion is washed away with a solvent or an alkali developer to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. This manufacturing method can manufacture a color filter with higher accuracy than the above printing method.

The colored resist is a resist containing a colorant of a desired color instead of carbon black contained in the photosensitive black composition of the present invention, but it does not necessarily contain the dye derivative represented by the general formula (1). It does not have to be. As the colorant, various colorants having excellent resistance are used. However, it is preferable to use a pigment from the viewpoint of light resistance, heat resistance and solvent resistance, and an organic pigment is used because of its light absorption ability. It is particularly preferable to do this. Specific examples of typical pigments are indicated by color index (CI) numbers.
Examples of yellow colorants include Pigment Yellow 12, 13, 14, 20, 24, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, and 166. 173 and the like.
Examples of the orange colorant include Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and the like.

Examples of red and magenta colorants include Pigment Red 9, 97, 122, 123, 144, 149, 166, 168, 177, 190, 192, 215, 216, 224, 254, 255, and the like.
Examples of the purple colorant include pigment violet 19, 23, 29, 32, 33, 36, 37, and 38.
Examples of blue and cyan colorants include Pigment Blue 15 (15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, etc.), 21, 22, 60, 64, and the like.
Examples of the green colorant include Pigment Green 7, 10, 36, and 47.
These colorants may be used in combination of two or more in order to obtain a desired color.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

[Preparation of resin solution]
370 parts of propylene glycol monomethyl ether acetate is put into a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomers and a thermal polymerization initiator is added dropwise over 1 hour at the same temperature to conduct a polymerization reaction Went.
Methacrylic acid 20.0 parts Methyl methacrylate 10.0 parts n-Butyl methacrylate 35.0 parts 2-Hydroxyethyl methacrylate 15.0 parts 2,2'-azobisisobutyronitrile 4.0 parts Paracmylphenol ethylene oxide modification Acrylate 20.0 parts (“Aronix M-110” manufactured by Toagosei Co., Ltd.)
After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained. The weight average molecular weight of the acrylic resin was about 40,000. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate so that the non-volatile content was 30% in the previously synthesized resin solution. Was added to prepare a resin solution.

[Preparation of carbon black dispersions A to C]
A carbon black dispersion was prepared using the carbon black described in Table 1.
(Carbon black dispersion A)
320 parts of carbon black dry-pulverized in the composition and proportion shown in Table 2, 13 parts of a pigment derivative represented by the following formula (17), 224 parts of a resin solution, and 443 parts of cyclohexanone are mixed, and 862 parts of these are granulated. Circulation dispersion was performed for 104 minutes with DISPERMAT SL-0251C1-EX (produced by Eihiro Seiki Co., Ltd.) into which 720 parts of zirconia beads having a diameter of 0.5 mm were charged, and a carbon black dispersion A was obtained. The integrated power required for this dispersion was 1200 Wh. After completion of the dispersion, the final solid content was adjusted to 20% by diluting with cyclohexanone.
(Carbon black dispersion B)
320 parts of carbon black having a blending composition and blending ratio shown in Table 2 and 13 parts of a pigment derivative represented by the following formula (17) were mixed and dry-pulverized. 224 parts of the resin solution and 443 parts of cyclohexanone are mixed with this, and 800 parts of this is circulated for 150 minutes in DISPERMAT SL-0251C1-EX (manufactured by Eiko Seiki Co., Ltd.) into which 720 parts of zirconia beads having a particle diameter of 0.5 mm are charged. Dispersion was performed to obtain a carbon black dispersion liquid B. The integrated power required for this dispersion was 1200 Wh. After completion of the dispersion, the final solid content was adjusted to 20% by diluting with cyclohexanone.
(Carbon black dispersion C)
320 parts of carbon black having the blending composition and blending ratio shown in Table 2, 13 parts of a pigment derivative represented by the following formula (17), and 224 parts of a resin solution are mixed, of which 904 parts are zirconia beads 720 having a particle diameter of 0.5 mm. Circulating dispersion was performed for 135 minutes using DISPERMAT SL-0251C1-EX (manufactured by Eihiro Seiki Co., Ltd.) into which parts were added, and a carbon black dispersion C was obtained. The integrated power required for this dispersion was 1200 Wh. After completion of the dispersion, the final solid content was adjusted to 20% by diluting with cyclohexanone.

(Formula 17)

[Examples 1 and 2 and Comparative Example 1]
(Adjustment of photosensitive black composition)
The mixture having the blending composition and blending ratio shown in Table 3 was stirred and mixed to be uniform, and then filtered through a 2 μm filter to obtain a photosensitive black composition. About the obtained photosensitive black composition, sensitivity, stability, light-shielding property (OD value per unit film thickness), black matrix pattern shape, viscosity, and adhesion were evaluated by the following methods. Table 4 shows the obtained results.

[sensitivity]
After coating the photosensitive black composition on a 10 cm × 10 cm glass substrate by spin coating, a coating film having a dry film thickness of about 1 μm was prepared by drying at 70 ° C. for 15 minutes, and the film thickness was measured. Thereafter, ultraviolet rays of various exposure amounts (mJ / cm ² ) were exposed through a photomask using an ultrahigh pressure mercury lamp. After developing with an aqueous sodium carbonate solution, the unexposed portion was removed by washing with ion exchange water. The film thickness of the exposed part after development and washing with water was measured, and the minimum exposure amount (mJ / cm ² ) at which a film thickness of 95% or more with respect to the film thickness before development was obtained was taken as sensitivity. The case sensitivity is 10~50mJ / cm ² ○, was evaluated as × a case where more than 50 mJ / cm ^2. In addition, a 10 micrometer mask pattern was used for the photomask, and a striped black matrix pattern was formed.

[Stability]
The stability was evaluated by comparing the development speed and line width immediately after preparation of the photosensitive black composition and after storage at 40 ° C. for 7 days.
(Development speed) After coating the photosensitive black composition on a 10 cm × 10 cm glass substrate by spin coating, a coating film having a dry film thickness of about 1 μm was prepared by drying at 70 ° C. for 15 minutes, and the film thickness was measured. did. This was spray-developed using an aqueous sodium carbonate solution, and the time for the photosensitive black composition to disappear was measured. The measurement time was divided by the measured film thickness, and the time per unit film thickness (seconds / μm) was taken as the development speed.
A case where the development speed after storage was within ± 15% of the development speed before storage was evaluated as “◯”, and a case where the speed changed more than ± 15% at high speed or low speed was evaluated as “X”.

(Line Width) Using a photosensitive black composition before and after storage, a striped black matrix pattern was formed at an exposure amount of 70 mJ / cm ² in the same manner as in [Sensitivity] evaluation, and the line width was measured with an optical microscope. .
When the change is within ± 15% with respect to the line width of the striped black matrix pattern formed using the photosensitive black composition before storage, the change is within ± 15%; The case where the line weight changed was evaluated as x.

[Shading (optical density (OD))]
The photosensitive black composition was applied to a glass substrate in the same manner as in the [sensitivity] evaluation, and after heating at 230 ° C. for 1 hour without performing an exposure step, the film thickness was measured. The optical density (OD) of the photosensitive black composition coated substrate thus obtained was measured with a Macbeth densitometer (GRETAGD200-II), the measured optical density (OD) was divided by the measured film thickness, and the unit The optical density per film thickness (OD / μm) was determined.

[shape]
The black matrix pattern shape was evaluated by forming a striped black matrix pattern with an exposure amount of 70 mJ / cm ² in the same manner as the [Sensitivity] evaluation, and the created black matrix pattern shape was measured with an optical microscope. Or it observed with the electron beam scanning microscope and observed linearity and cross-sectional shape.
(Linearity) ◯ when there is no chipping or jaggedness in the straight line part, △ when there are jagged or chipping in a part of the straight line part, and × when there are many jaggedness or chipping over the entire straight line part evaluated.
(Cross-sectional shape) ○ when the cross-sectional shape is perpendicular from the forward taper (the bottom side that is in contact with the glass is wider than the upper base), the cross-sectional shape is overhang (wider than the bottom side where the upper base is in contact with the glass) ) Was evaluated as x.

[viscosity]
The viscosity of the photosensitive black composition was measured at 25 ° C. and 20 rpm using a TVE-20L viscometer (manufactured by Toki Sangyo Co., Ltd.).

[Adhesion]
The photosensitive black composition was applied to a glass substrate in the same manner as in the [sensitivity] evaluation, and heated at 230 ° C. for 1 hour without performing an exposure step. The photosensitive black composition coated surface of the obtained photosensitive black composition coated substrate was bonded to a glass plate (Corning # 1737) using a sealing material (XN-21S manufactured by Mitsui Chemicals, Inc.). It was. Affixing a tensile test fitting with adhesive to the two pieces of glass that have been bonded together, peeling off the fitting with a tensile tester (RTE-1210, manufactured by Orientec Co., Ltd.), and bonding the sealant to the tensile strength when it is peeled off The value (g / mm ² ) divided by the area was evaluated as the adhesion.

表４より明らかなとおり、実施例１及び２は高い感度、安定性、形状が良好なだけでなく、低粘度かつ密着性も良好である点において比較例１より優れていた。
乾式粉砕した２種のカーボンブラックを色素誘導体と混合した分散体Ａを用いた実施例１の方が、２種のカーボンブラックと色素誘導体とを同時に乾式粉砕した分散体Ｂを用いた実施例２よりも低粘度であり、かつ密着性が良好であった。

As is apparent from Table 4, Examples 1 and 2 were superior to Comparative Example 1 in that not only high sensitivity, stability and shape were good, but also low viscosity and good adhesion.
Example 2 using dispersion A in which two types of dry-pulverized carbon blacks were mixed with a pigment derivative was used in Example 2 using dispersion B in which two types of carbon black and a pigment derivative were simultaneously dry-pulverized. In addition, the viscosity was lower and the adhesion was good.

Claims (9)

In a photosensitive black composition containing (a) carbon black, (b) a photopolymerization initiator, (c) a dye derivative, (d) an ethylenically unsaturated compound, and (e) a resin,
Carbon black does not contain particles over 40nm,
Carbon black (a1) having an average primary particle size of 8 to 20 nm,
A photosensitive black composition characterized by being mixed and dry-pulverized with carbon black (a2) having an average particle size of 5 nm or more larger than that of carbon black (a1) and an average primary particle size of 21 to 40 nm. .   The photosensitive black according to claim 1, wherein the weight ratio of carbon black (a2) to carbon black (a1) (weight of carbon black (a1) / weight of carbon black (a2)) is 1/3 to 1/20. Composition.   The photosensitive black composition according to claim 1 or 2, wherein carbon black (a1), carbon black (a2), and (c) a pigment derivative are mixed and dry-pulverized.   The photosensitive black composition according to claim 1 or 2, wherein the carbon black (a1) and the carbon black (a2) are dry-pulverized, and then the (c) pigment derivative is mixed.   The photopolymerization initiator is at least one photopolymerization initiator selected from oxime photopolymerization initiators, imidazole photopolymerization initiators, and borate photopolymerization initiators. 2. The photosensitive black composition according to item 1.   Furthermore, polyfunctional thiol is contained, The photosensitive black composition of any one of Claims 1-5 characterized by the above-mentioned. The photosensitive black composition according to any one of claims 1 to 6, wherein the pigment derivative contains a pigment derivative represented by the following general formula (1).
General formula (1)

(Wherein Q is an organic dye residue, X is a direct bond, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH ₂ NHCOCH ₂ NH—Y ₂ — (where Y ₂ is a substituent) Represents an alkylene group or an aryl group which may have a group.), Y ₁ is —NH— or —O—, Z is a hydroxyl group, an alkoxy group, a substituent represented by the following general formula, or n is 1. -NH-XQ,

(Wherein Y ₃ is —NH— or —O—),
R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, or a heterocycle containing at least a nitrogen atom formed by R ₁ and R ₂ , m is an integer of 1 to 6, and n is 1 to 4 Represents an integer. )   8. The ratio (M / P) of the weight (P) of the resin and the weight (M) of the ethylenically unsaturated compound is 0.10 to 0.70. 8. The photosensitive black composition described in 1.   A color filter comprising a black matrix formed from the photosensitive black composition according to claim 1 on a transparent substrate.