JP5151126B2 - Black composition and color filter using the same - Google Patents

Description

  The present invention relates to a black composition containing carbon black. The present invention also relates to a color filter formed using the black composition.

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

However, the metal BM method is not only very expensive due to the complicated manufacturing process, but also uses a vapor deposition method or a sputtering method, so that the metal BM is applied to a large substrate from the viewpoint of apparatus cost or from a technical viewpoint. Difficult to form. In addition, commonly used chromium can cause environmental problems during the disposal process.
In recent years, the resin BM has attracted attention in place of the metal BM from the viewpoints of cost reduction, technical viewpoint, and environmental problems.

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, in the metal BM, a desired light shielding property can be generally obtained with a film thickness of 0.1 to 0.2 μm, whereas in the resin BM, the film thickness is obtained in order to obtain a light shielding property equivalent to that of the metal BM. Must be set thicker. Furthermore, it is necessary to increase the film thickness as the light shielding property of the resin BM is lower. When creating a color filter, a BM and an adjacent RGB layer are overlaid to eliminate light leakage. In the case of the resin BM having a low light shielding property, there is a problem that the step where the BM and the RGB layer overlap becomes large, and this step portion disturbs the liquid crystal alignment and deteriorates the display quality.
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.

  As a method for forming the resin BM, as described above, for example, there are a printing method and a photolithography method. When forming a BM by a printing method, there are a method of forming a pattern on a substrate using a relief plate, or a method of forming a pattern on an intaglio plate and then transferring a plurality of patterns over the same substrate via a blanket. However, although these printing methods are short in process, stringing occurs in the process of transferring ink from the printing plate to the substrate, or from the printing plate to the blanket, or from the printing plate to the substrate, and the linearity of the pattern. May deteriorate the pattern shape. Therefore, in general, a photolithography method without such fear is employed.

Attempts have been made to increase the content of light-shielding components such as carbon black contained in the composition for the purpose of improving the light-shielding properties of the resin BM and reducing the level difference. However, the method of increasing the content of the light-shielding component has problems such as deterioration of the stability of the composition.
Further, for the purpose of improving the light shielding property of BM, a method for increasing the OD value by using two kinds of light shielding materials in combination has been proposed. That is, there is a method of improving the light shielding property (OD value) by using a carbon black having a small average particle size and a carbon black having a large average particle size together to form a close-packed structure in the BM (for example, patents). Reference 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 carbon black for forming a black resist pattern, which is coated with a resin and contains two or more kinds of carbon blacks having an average primary particle diameter different by at least 20 nm. In Patent Document 3, two or more kinds of carbon blacks preferably have one carbon black having an average primary particle diameter of 10 to 40 nm and the other carbon black having an average primary particle diameter of 45 to 300 nm. The difference in diameter is 30 nm.

However, when the black composition contains carbon black having an average primary particle diameter exceeding 40 nm, there is a problem that it is still disadvantageous from the viewpoint of light shielding properties.
On the other hand, Patent Document 4 and Patent Document 5 disclose a photosensitive black composition using a specific dye derivative or a specific initiator. However, in either case, the point that the stability and high light-shielding property of the photosensitive black composition are satisfied at the same time is still insufficient.
Japanese Patent Laid-Open No. 9-133806 Japanese Patent Laid-Open No. 9-279082 Japanese Patent Laid-Open No. 11-80584 JP 2005-10604 A JP 2005-99488 A

  An object of the present invention is to provide a black composition having high light shielding properties and excellent stability. Another object of the present invention is to provide a color filter including a black matrix having a high light shielding property.

The present invention includes (a1) carbon black having an average primary particle diameter of 8 to 20 nm, (a2) carbon black having an average primary particle diameter of 21 to 40 nm, (b) a dye derivative, (c) a resin, and (d ) A black composition containing a solvent, wherein the difference between the average primary particle sizes of (a1) carbon black and (a2) carbon black is 5 nm or more, and the average primary particle size exceeds 40 nm. Does not contain ,
(A1) The specific surface area of carbon black is 200 to 600 m ² / g,
(A2) It is related with the black composition characterized by the specific surface area of carbon black being 40-600 m < ² > / g .

The black composition of the present invention is preferably (a1) carbon black having an average primary particle diameter of 8 to 20 nm, (a2) carbon black having an average primary particle diameter of 21 to 40 nm, (b) a dye derivative, ( c) a black composition obtained by mixing a resin and (d) a solvent, wherein the difference in average primary particle size between the (a1) carbon black and the (a2) carbon black is 5 nm or more, and Carbon black having an average primary particle size exceeding 40 nm is not mixed , and (a1) the specific surface area of carbon black is 200 to 600 m ² / g,
(A2) A black composition having a specific surface area of carbon black of 40 to 600 m ² / g .
Another aspect of the present invention relates to a color filter comprising a transparent substrate and a black matrix formed on the transparent substrate using the black composition described above.

The black composition of the present invention contains carbon black having an average primary particle diameter of 8 to 20 nm with a difference in average primary particle diameter of 5 nm or more, and carbon black having an average primary particle diameter of 21 to 40 nm, In addition, since it does not contain carbon black exceeding 40 nm, it has high light-shielding properties and excellent stability.
By using the black composition of the present invention, a black matrix having high light shielding properties can be formed.

The black composition of the present invention has, as a light-shielding component, a difference in average primary particle diameter of 5 nm or more, (a1) carbon black having an average primary particle diameter of 8 to 20 nm, and (a2) an average primary particle diameter of 21 to 21. And carbon black having an average primary particle diameter of more than 40 nm.
In the black composition using each carbon black, there exists a tendency as shown below.

  (A1) In a black composition in which carbon black having an average primary particle diameter of 8 to 20 nm is used alone, compared to a black composition in which carbon black having the same average weight of primary particles is used alone. The number of carbon black particles per unit volume is large, which is advantageous from the viewpoint of light shielding properties. However, the photocurability is inferior because of the high light shielding properties. Furthermore, it is difficult to stably disperse carbon black, and a problem of causing a phenomenon of a residue (or also referred to as background stain) in which a part of the black composition remains on a glass substrate after development is likely to occur.

  On the other hand, (a2) a black composition in which carbon black having an average primary particle diameter of 21 to 40 nm is used alone, a black composition in which carbon black having the same average weight of smaller primary particles is used, In comparison, the number of carbon black particles per unit volume is small and photocurability is advantageous, but light shielding is insufficient. Moreover, a viscosity becomes high and it becomes difficult to prepare a black composition.

  In addition, in the black composition in which carbon black having an average primary particle diameter of more than 40 nm is used, compared with a black composition in which only carbon black having an average primary particle diameter of less than 40 nm is used, the weight per unit volume Although the number of carbon black particles is small and photocurability is advantageous, the light shielding property and the pattern shape of the black matrix, in particular, the linearity are insufficient.

As (a1) carbon black, carbon black having an average primary particle diameter of 10 to 18 nm is 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 of more than 600 m ² / g is used, carbon It tends to be difficult to stably disperse black. Carbon black having an average primary particle size of less than 8 nm is difficult to produce, and is not suitable as (a1) carbon black.

As (a2) carbon black, carbon black having an average primary particle diameter of 22 to 37 nm is preferable, and carbon black having a specific surface area of 40 to 600 m ² / g can be suitably used. 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, It tends to be difficult to stably disperse black.
Furthermore, when the difference between the average primary particle diameters of (a1) carbon black and (a2) carbon black is less than 5 nm, the high light-shielding property expressed when (a1) carbon black and (a2) carbon black are used together, When the black composition is stored for a predetermined period, it is not possible to expect the stability effect that almost no change in development speed or change in line width occurs before and after storage.

The average primary particle diameter of carbon black contained in the black composition can be determined by the following method.
First, the black composition is diluted about 100 times using a solvent contained in the black composition to obtain a diluted product. Next, the diluted product is air-dried on a sample stage, and several tens of thousands of photographs are taken with an electron microscope for the obtained carbon black. About 2000-3000 maximum particle diameters of carbon black are measured, and the measured values are simply averaged to determine the average primary particle diameter. For a black composition containing two or more types of carbon black, first, the number-based particle size distribution of the entire carbon black contained in the black composition is determined. Next, assuming that each particle size distribution of two or more types of carbon black follows a normal distribution, curve fitting is performed with the number of Gaussian functions expected from the shape of the particle size distribution and the number of peaks, and each distribution function is determined. . The average primary particle diameter of each carbon black is determined from the parameters of the obtained distribution function. The average primary particle diameter is usually expressed as a value (nm) rounded off to the first decimal place.

The black composition of the present invention comprises (a1) carbon black having an average primary particle diameter of 8 to 20 nm and (a2) carbon having an average primary particle diameter of 21 to 40 nm. It is characterized by not containing carbon black which contains black and whose average primary particle diameter exceeds 40 nm. Such a black composition preferably has a difference in average primary particle diameter of 5 nm or more, (a1) carbon black having an average primary particle diameter of 8 to 20 nm, and (a2) an average primary particle diameter of 21 to 40 nm. It can be obtained by mixing some carbon black. At this time, carbon black having an average primary particle diameter exceeding 40 nm is not mixed.
The average primary particle size of carbon black before mixing can also be measured by the same method using an electron microscope as described above. Commercially available carbon black can be used as (a1) carbon black having an average primary particle diameter of 8 to 20 nm and (a2) carbon black having an average primary particle diameter of 21 to 40 nm.

  (A1) Examples of carbon black having an average primary particle diameter of 8 to 20 nm include MONARCH manufactured by CABOT, or BLACK PERLS (1400, 1300, 1100, 1000, 900, 880, 800, 700), VULCAN (P 9A32), Mitsubishi Chemical # (2700B, 2650, 2600, 2450B, 2400B, 2350, 2300, 1000, 990, 980, 970, 960, 950, 900, 850), MCF88, MA600, Color Black made by DEGUSSA (FW2000, FW2, FW2V, FW1, FW18, S170, S160), Special Black (6, 5), Printex (95, 90, 85, 80, 75, 40, 60), Tokai Carbon's seast (9 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, RA (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), PrintX 95 manufactured by DEGUSSA, # 850 manufactured by Mitsubishi Chemical, particularly preferably MONARCH1100 manufactured by CABOT, and PrintX 95 manufactured by DEGUSSA are used. it can. (A1) Carbon black may be used individually by 1 type, or 2 or more types may be mixed and used for it.

  (A2) Examples of carbon black 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), Mitsubishi Chemical 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, S made by DEGUSSA special Black (4, 4A, 550, 350), PrintX (150T, U, V, 140U, 140V, 55, 45, P, L6, L, 300, 30, ES23, 3, ES22, 35, XE2), NIPex35 Tokai Carbon Co., Ltd. [6ISAF, 600ISAF-LS, 5H-IISAF-HS, KH (N339), 3H HAF-HS, NH (N351), 3 HAF, 3M, NLI-HAF, 300 HAF-LS, 116 MAF], Asahi Carbon 75 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, 8 0HPOWDER, 850,825BEADS), CONDUCTEX (975BEADS, 900BEADS) and the like. Preferably, REGAL (300R, 250R, 250, 99R, 99I) manufactured by CABOT, MA (7, 11, 100R), # (47, 45, 45L) manufactured by Mitsubishi Chemical, Printex55, NIPex35 manufactured by DEGUSSA, particularly preferably # 47 manufactured by Mitsubishi Chemical, REGAL 250R manufactured by CABOT, PrintX55 manufactured by DEGUSSA, and NIPex35 can be used. (A2) Carbon black may be used individually by 1 type, or 2 or more types may be mixed and used for it.

The weight ratio of (a1) carbon black and (a2) carbon black contained in the black composition is preferably (a1) / (a2) = 1/3 to 1/30, more preferably 1/3 to 1/10. It is. When (a1) / (a2) = 1/3 is exceeded, that is, when (a1) is large, stable dispersion of carbon black tends to be difficult. On the other hand, when (a1) / (a2) is less than 1/30, that is, when (a1) is reduced, the high light-shielding property expressed when (a1) carbon black and (a2) carbon black are used in combination. There is a tendency that the stability effect of the black composition cannot be expected.
Further, (a1) carbon black and (a2) carbon black are preferably 40 to 60% by weight in total, more preferably 45 in total, based on the total solid weight of the black composition (100% by weight). It can be used in an amount of ~ 55% by weight.

  The (b) pigment derivative contained in the black composition of the present invention is a compound in which a substituent is introduced into an organic pigment. Organic dyes include, in addition to compounds generally called dyes, light yellow aromatic polycyclic compounds such as naphthalene compounds that are not generally called dyes. 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 (2) to (11).

（式中、Ｑは有機色素残基を表し、Ｘは直接結合、−ＣＯＮＨ−Ｙ₂−、−ＳＯ₂ＮＨ−Ｙ₂−、または−ＣＨ₂ＮＨＣＯＣＨ₂ＮＨ−Ｙ₂−（但し、Ｙ₂は置換基を有してもよいアルキレン基または置換基を有してもよいアリーレン基を表す。）を表し、Ｙ₁は−ＮＨ−または−Ｏ−を表し、Ｚは、ｎが１の場合には水酸基、アルコキシ基、下記一般式で示される置換基、−ＮＨ−Ｘ−Ｑ（但し、Ｑ及びＸは前記のとおりである。）を表し、ｎが２〜４の場合には水酸基、アルコキシ基、下記一般式で示される置換基を表し、Ｒ₁およびＲ₂は、それぞれ独立に置換基を有してもよいアルキル基を表し、Ｒ₁とＲ₂とが互いに結合して少なくとも窒素原子を含むヘテロ環を形成してもよく、ｍは１から６の整数を表し、ｎは１から４の整数を表す。 General formula (1)

(Wherein Q represents an organic dye residue, X represents a direct bond, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH ₂ NHCOCH ₂ NH—Y ₂ — (where Y ₂ Represents an alkylene group which may have a substituent or an arylene group which may have a substituent.), Y ₁ represents —NH— or —O—, and Z represents a case where n is 1. Represents a hydroxyl group, an alkoxy group, a substituent represented by the following general formula, -NH-XQ (where Q and X are as defined above), and when n is 2 to 4, a hydroxyl group, An alkoxy group, which represents a substituent represented by the following general formula, R ₁ and R ₂ each independently represents an alkyl group which may have a substituent, and R ₁ and R ₂ are bonded to each other to form at least a nitrogen atom; A heterocycle containing an atom may be formed, m represents an integer of 1 to 6, and n represents an integer of 1 to 4. .

（式中、Ｙ₃は−ＮＨ−または−Ｏ−を表す。また、ｍ、Ｒ₁およびＲ₂は前記のとおりである。））
アルキレン基としては、メチレン基、エチレン基等が挙げられる。アリーレン基としては、フェニレン基等が挙げられる。アルコキシ基としては、メトキシ基、エトキシ基等が挙げられる。アルキル基としては、メチル基、エチル基等が挙げられる。また、これらの基が有する置換基としては、メチル基、エチル基等が挙げられる。

(Wherein Y ₃ represents —NH— or —O—, and m, R ₁ and R ₂ are as defined above.)
Examples of the alkylene group include a methylene group and an ethylene group. Examples of the arylene group include a phenylene group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the substituent that these groups have include a methyl group and an ethyl group.

  Examples of the organic dye constituting the dye derivative represented by the general formula (1) include phthalocyanine, quinacridone, quinacridonequinone, isoindolinone, quinophthalone, diketopyrrolopyrrole, perylene, perinone, Condensed polycyclic organic pigments such as indigo, thioindigo, dioxazine, anthraquinone, pyranthrone, anthanthrone, flavanthrone, indanthrone, metal complex, benzimidazolone, insoluble azo, condensation Examples thereof include organic pigments or dyes such as azo series and soluble azo series, and pale yellow aromatic polycyclic compounds such as naphthalene series.

(B) A pigment derivative may be used individually by 1 type, or 2 or more types may be mixed and used for it.
(B) The pigment derivative is preferably used in an amount of 0.05 to 20% by weight, more preferably 0.5 to 10% by weight, based on the total solid weight of the black composition (100% by weight). it can. When the content of the pigment derivative is less than 0.05% by weight, the effect of dispersing the carbon black tends not to be sufficiently exhibited, and when more than 20% by weight, the dispersion of the carbon black tends to become unstable. is there.

  Furthermore, examples of the resin (c) contained in the black composition of the present invention include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride-vinyl acetate. Thermoplastic resins such as polymers, polyvinyl acetate, polyurethane resins, polyester resins, acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, etc. Thermosetting resins such as epoxy resins, benzoguanamine resins, rosin-modified maleic resins, rosin-modified fumaric resins, melamine resins, urea resins, and phenol resins can be used.

Among the resins (c) contained in the black composition, the resin represented by the following general formula (12) is advantageous for high OD due to the large improvement in developability and film reduction. Preferably it is 0.1 to 30 weight%, More preferably, 1 to 20 weight% can be used.
Formula (12)

(Wherein R ₁ is a tetravalent aromatic tetracarboxylic acid compound residue, R ₂ is a monoalcohol residue, R ₃ is a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is Represents (4-m).)
Examples of the acid dianhydride that gives an aromatic tetracarboxylic acid residue include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 9,9-bis (3 , 4-dicarboxyphenyl) fluorene dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, ethylene glycol ditrimellitic anhydride ester. Examples of the monoalcohol include 1-dodecanol, n-stearyl alcohol, isostearyl alcohol, glycerin dimethacrylate, pentaerythritol triacrylate, and 2-ethylhexyl alcohol. Examples of the lactone include δ-valerolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone.

(C) The weight average molecular weight of the resin is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. If it is less than 1,000, the occurrence of tack and the coating strength may not be sufficiently obtained, and if it exceeds 100,000, the viscosity may increase and the coatability may decrease. In this invention, a weight average molecular weight means the weight average molecular weight of polystyrene conversion by gel permeation chromatography.
(C) Resin may be used individually by 1 type, or may mix and use 2 or more types. (C) The content of the resin is preferably 5 to 60% by weight, more preferably 10 to 50% by weight based on the total solid weight of the black composition (100% by weight). When the content is less than 5% by weight, the coating film tends to be brittle. When the content is more than 60% by weight, developability tends to be lowered in photolithography.

The black composition of the present invention contains (d) 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 -N amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like can be used, and these can be used alone or in combination.
(D) 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 black composition.

The black composition of the present invention may further contain (e) an ethylenically unsaturated compound. The (e) ethylenically unsaturated compound contained in the black composition of the present invention is a compound having one or more ethylenically unsaturated double bonds in one molecule, and examples thereof include monomers, oligomers, and photosensitive compounds. Can be used.
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 the photosensitive resin, a photosensitive resin in which an ethylenically unsaturated bond is introduced into the above-described resin by a 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 Or a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting with cinnamic acid. In addition, (meth) acrylic compounds having a hydroxyl group such as hydroxyalkyl (meth) acrylate as a linear polymer containing an acid anhydride group such as a styrene-maleic anhydride copolymer and an α-olefin-maleic anhydride copolymer A linear polymer that has been half-esterified with can be used.

(E) An ethylenically unsaturated compound is used individually by 1 type or in mixture of 2 or more types.
(E) The ethylenically unsaturated compound is preferably 5 to 30% by weight based on the total solid weight of the black composition (100% by weight), more preferably 7 to 28 from the viewpoint of photocurability and developability. It can be used in an amount of% by weight, particularly preferably 10 to 25% by weight. When the content of the ethylenically unsaturated compound is more than 30% by weight, the BM pattern shape tends to be poor in linearity or cross-sectional shape. Tend to be inadequate.

  In the black composition of the present invention, the ratio (M / P) of (c) the weight (P) of the resin and (e) the weight (M) of the ethylenically unsaturated compound is 0.10 to 0.70. Is more preferable, 0.15 to 0.65 is more preferable, and 0.20 to 0.60 is particularly preferable. If M / P is less than 0.10, the sensitivity may be low, and if M / P exceeds 0.70, the black matrix pattern shape may have poor linearity, cross-sectional shape failure, or tack. .

  The black composition of the present invention may further contain (f) a photopolymerization initiator. (F) Examples of the photopolymerization initiator include acetophenone photopolymerization initiators, benzoin photopolymerization initiators, benzophenone photopolymerization initiators, thioxanthone photopolymerization initiators, triazine photopolymerization initiators, and carbazole photopolymerization initiators. It is possible to use a polymerization initiator, an imidazole photopolymerization initiator, an oxime photopolymerization initiator, a borate photopolymerization initiator, a phosphine photopolymerization initiator, a quinone photopolymerization initiator, a titanocene photopolymerization initiator, or the like. it can. 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.

式（１３） Examples of the oxime photopolymerization initiator include etanone represented by the following formula (13), 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 (13)

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 (14) to (17).

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 (f) photopolymerization initiator is used alone or in combination of two or more. (F) The photopolymerization initiator is preferably used in an amount of 0.5 to 50% by weight, more preferably 2 to 20% by weight based on the total solid weight of the black composition (100% by weight). it can.
The ratio (I / M) of (f) the weight (I) of the photopolymerization initiator to (e) the weight (M) of the ethylenically unsaturated compound is preferably 0.10 to 1.00. 0.15 to 0.80 is more preferable, and 0.20 to 0.60 is particularly preferable. If the I / M is less than 0.10, the sensitivity may be low. If the I / M exceeds 1.00, the linearity of the BM pattern shape, the cross-sectional shape defect, and the mask pattern width after development In some cases, the pattern width becomes thick.

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

Of these (g) polyfunctional thiols, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate) can be preferably used. .
Moreover, these (g) polyfunctional thiols are preferable when combined with an imidazole-based photopolymerization initiator among the above (f) photopolymerization initiators because the sensitivity is increased and the photocurability is improved.
(G) 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 weight of the black composition (100% by weight). . If the amount is less than 0.1% by weight, the effect of adding a polyfunctional thiol may be insufficient. If the amount exceeds 30% by weight, the sensitivity is too high and the resolution is lowered, or the stability of the black composition is lowered. There is a case.

The 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 can be used in an amount of preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total solid weight of the black composition (100% by weight).
Further, the black composition of the present invention may contain other additives such as a surfactant and a silane coupling agent for the purpose of improving coatability, improving sensitivity, and improving adhesion. .

The black composition is composed of carbon black, a pigment derivative, a resin, a solvent, and, if necessary, an ethylenically unsaturated compound, a photopolymerization initiator, other additives, a three roll mill, a two roll mill, a sand mill, It can manufacture by disperse | distributing using various dispersion apparatuses, such as a kneader, an attritor, and a micros.
The black composition removes coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, more preferably 0.5 μm or larger and mixed dust by means of centrifugation, sintered filter, membrane filter, etc. It is preferable to carry out.

Next, the color filter of the present invention will be described. Here, a method for producing a color filter by photolithography using a black composition containing an ethylenically unsaturated compound and a photopolymerization initiator in addition to carbon black, a pigment derivative, a resin and a solvent will be described. The invention is not limited to this.
The color filter of the present invention preferably comprises a BM formed from the black composition of the present invention and a filter segment of at least two colors other than black on a transparent substrate such as a glass plate. The color of the filter segment is selected from about 2 to 6 colors from blue, green, red, cyan, yellow, magenta, orange and purple. Filter segments having the same color system and different densities may be formed.

After applying the black composition of the present invention on a transparent substrate by a coating method such as spin coating, slit coating, roll coating, etc., the BM is irradiated with active energy rays from the composition coating surface side through a photomask. The film can be formed by immersing in a solvent or an alkali 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 black composition is preferably in the range of 0.2 to 5 μm (when dry), more preferably in the range of 0.5 to 2 μm, which makes it easy to balance coating properties and light shielding properties. preferable.

In addition, the optical density (OD) per 1 μm dry film thickness of BM 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. is there. 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 with active energy rays, the black composition is coated and dried, and then coated with a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin and dried to prevent polymerization inhibition due to oxygen. After the film to be formed 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. 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 light 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 application surface side can be appropriately set in the range of 5 to 1000 mJ, but is preferably in the 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 previously formed on the surface of a transfer base sheet is transferred onto a BM 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 on a transparent substrate on which BM is formed by a coating method such as spin coating, slit coating or roll coating, and then through a photomask. This is a method for producing a color filter by performing ultraviolet exposure, washing the unexposed area with a solvent or an alkali developer to form a desired pattern, and then repeating the same operation for other colors. 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 having a desired color instead of carbon black contained in the black composition of the present invention, but does not necessarily contain the dye derivative represented by the general formula (1). Also good. 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.

  The method for producing a color filter in which BM is formed by the photolithography method has been described above. In addition to this, the black composition containing the carbon black, the pigment derivative, the resin, and the solvent of the present invention is used, and conventionally known. The BM can be formed by a printing method, an electrodeposition method combined with a photolithography method, a dry film transfer method, or the like.

  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 (1)]
370 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, and heated to 80 ° C. while injecting nitrogen gas into the vessel. Subsequently, the mixture of the following monomer and thermal polymerization initiator was dripped in reaction container over 1 hour at the same temperature, and the polymerization reaction was performed.
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. Then, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added to the reaction vessel, and the mixture was further heated at 80 ° C. The mixture was reacted for 1 hour to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 40,000. After cooling the acrylic resin solution to room temperature, about 2 g of the solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Thereafter, propylene glycol monomethyl ether acetate was added to the synthesized acrylic resin solution so as to have a nonvolatile content of 30% by weight to prepare a resin solution (1).

[Preparation of resin solution (2)]
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst to obtain a mixture. Then, the mixture was heated and stirred at 120 ° C. for 4 hours while injecting nitrogen gas into the container. After confirming that 98% by weight of the raw material had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added to the reaction vessel, and the mixture was reacted at 120 ° C. for 2 hours. After confirming that 98% by weight or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated to obtain a resin. The obtained resin was white solid at room temperature, the weight average molecular weight was about 3,600, and the acid value was 49 mgKOH / g. Cyclohexanone was added to the resin so that the nonvolatile content was 30% by weight, thereby preparing a resin solution (2).

[Preparation of carbon black dispersions A to I]
A carbon black dispersion was prepared using the carbon black described in Table 1. 100 parts of carbon black having the blending composition and blending ratio shown in Table 2, 4 parts of the dye derivative represented by the following formula (18), and 70 parts of the resin solution (1) are mixed and diluted with cyclohexanone to obtain a final solid content of 20% by weight. A mixture of was obtained. Carbon black dispersions A to I were prepared by dispersing the obtained mixture with a glass shaker having a diameter of 0.8 mm for 2 hours using a paint shaker. Except for the dispersion F, a dispersion having a viscosity of 40 mPa · s or less could be obtained. Dispersion F had an extremely high viscosity after dispersion of 200 mPa · s or more, and was a gel at room temperature, so a black composition could not be prepared. Carbon Black Dispersion I was prepared by performing the same operation as Dispersion G except that 56 parts of resin solution (1) and 14 parts of resin solution (2) were used instead of 70 parts of resin solution (1). .

[Examples 1 to 11 and Comparative Examples 1 to 4]
(Preparation of black composition)
The mixture was stirred and mixed so as to be uniform at the blending composition and blending ratio shown in Table 3, and then filtered through a 2 μm filter to obtain a black composition. About the obtained black composition, a sensitivity, stability, light-shielding property (OD value per unit film thickness), and the pattern shape of BM were evaluated by the following method. Table 4 shows the obtained results.

Monomer (ethylenically unsaturated compound): dipentaerythritol hexaacrylate (DPHA)
Photopolymerization initiator A: an oxime photopolymerization initiator represented by the formula (13) (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), “Irgacure OXE02” manufactured by Ciba Specialty Chemicals)
Photopolymerization initiator B: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole photopolymerization initiator C: represented by formula (14) Borate-based photopolymerization initiator Photopolymerization initiator D: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“Irgacure 369” manufactured by Ciba Specialty Chemicals)
Multifunctional thiol: trimethylolpropane tris (3-mercaptobutyrate)
Solvent: cyclohexanone

[sensitivity]
After coating the 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, the coating film was exposed to ultraviolet rays of various exposure amounts (mJ / cm ² ) through a photomask using an ultrahigh pressure mercury lamp. The coating film was developed using an aqueous sodium carbonate solution, and then washed with ion-exchanged water to remove unexposed portions. 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 defined as sensitivity. Sensitivity to 10~50mJ / cm ² ○ (good), were evaluated if more than 50 mJ / cm ² as × (poor). Note that a mask pattern having a line width of 10 μm was used as the photomask, and a striped black matrix pattern was formed.

[Stability]
About the black composition immediately after preparation and the black composition after a 7 day preservation | save at 40 degreeC, the development speed and the line | wire width were compared, and stability was evaluated.
(Developing speed) After coating the black composition on a 10 cm x 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. The coating film was spray-developed using an aqueous sodium carbonate solution, and the time for the coating film to disappear was measured. The measurement time was divided by the measured film thickness, and the time per unit film thickness (second / μm) was taken as the development speed.
○ (good) when the development speed after storage is within ± 15% of the development speed before storage, x (bad) when the speed changes more than ± 15% ).

(Line width) Using the black composition before and after storage, a striped BM pattern was formed at an exposure amount of 70 mJ / cm ² in the same manner as in the [sensitivity] evaluation, and the line width was measured with an optical microscope. However, the black composition of Example 10 was exposed at 300 mJ / cm ² because of its low sensitivity. When the line width of the striped BM pattern formed using the black composition before storage is within plus or minus 15%, the mark is good (good), and the line width exceeds ± 15%. The case where the line weight changed was evaluated as x (defect).
When the development speed evaluation was x, it was determined that the stability was poor, and the line width evaluation was not performed.

[Shading (optical density (OD))]
The black composition was applied to a glass substrate in the same manner as in the [sensitivity] evaluation, and the film thickness was measured after heating at 230 ° C. for 1 hour without performing the exposure step. The optical density (OD) of the black composition coated substrate thus obtained was measured with a Macbeth densitometer (GRETAG D200-II), the measured optical density (OD) was divided by the measured film thickness, and the unit film The optical density per thickness (OD / μm) was determined.

[shape]
[Sensitivity] A striped BM pattern is formed at an exposure amount of 70 mJ / cm ² in the same manner as the evaluation, and the resulting striped BM pattern shape is observed with an optical microscope or an electron beam scanning microscope. -The cross-sectional shape was observed. However, the black composition of Example 10 was exposed at 300 mJ / cm ² because of its low sensitivity.
(Linearity) Linearity ○ (good) when no chipping or jaggedness is found in the straight line portion, linearity △ (slightly bad) when jaggedness or chipping is found in part of the straight line portion, the entire straight line portion When a lot of jaggedness or chipping was observed over the whole area, it was evaluated as linearity x (bad).
(Cross-sectional shape) If the cross-sectional shape is normal taper (the bottom that is the surface in contact with the glass is wider than the upper base) to the vertical, the cross-sectional shape ○ (good), the cross-sectional shape is overhanging (the upper bottom contacts the glass) In the case of a surface wider than the bottom), it was evaluated as x (defect).
[viscosity]
The viscosity of the black composition was measured at 25 ° C. and 20 rpm using a TVE-20L viscometer (manufactured by Toki Sangyo Co., Ltd.).

[Adhesion]
The black composition was coated on a glass substrate in the same manner as in the [sensitivity] evaluation, and was heated at 230 ° C. for 1 hour without performing the exposure step. About the obtained black composition coating film, glass adhesiveness was evaluated by the cross-cut adhesion test method according to JISK5400. To peel off, attach a high-performance epoxy rapid-curing adhesive (curing type at room temperature for 1 hour) to the head of M6 bolt, adhere (self-weight) on a grid-like film, heat at 90 ° C for 5 minutes, and apply by hand. This was done by removing the bolts from the membrane. Since the bolt was smaller than the 1 mm × 1 mm × 100 grid, the adhesion was represented by the non-peeled area ratio of the coating film with respect to the bolt bonding area.
For the adhesion, the adhesion (%) was calculated from the following calculation formula (19), and the calculated results were evaluated in four stages from A to X. In addition, the decimal part of the value calculated | required from Formula (19) was rounded off, and it was set as the value of adhesiveness.

◎：８０％≦密着性≦１００％
○：６０％≦密着性＜８０％
△：３０％≦密着性＜６０％
×：２０％＜密着性＜３０％ Formula (19)

A: 80% ≦ adhesion ≦ 100%
○: 60% ≦ adhesiveness <80%
Δ: 30% ≦ adhesiveness <60%
×: 20% <adhesion <30%

表４より明らかなとおり、本発明の実施例１〜１１は、高い遮光性、かつ、安定性の点で比較例１〜４よりも優れている。

As is apparent from Table 4, Examples 1 to 11 of the present invention are superior to Comparative Examples 1 to 4 in terms of high light shielding properties and stability.

Claims (8)

(A1) carbon black having an average primary particle diameter of 8 to 20 nm, (a2) carbon black having an average primary particle diameter of 21 to 40 nm, (b) a pigment derivative, (c) a resin, and (d) a solvent A black composition having a difference in average primary particle diameter between (a1) carbon black and (a2) carbon black of 5 nm or more and containing no carbon black having an average primary particle diameter exceeding 40 nm. ,
(A1) The specific surface area of carbon black is 200 to 600 m ² / g,
(A2) A black composition having a specific surface area of carbon black of 40 to 600 m ² / g .
(A1) Carbon black having an average primary particle diameter of 8 to 20 nm, (a2) Carbon black having an average primary particle diameter of 21 to 40 nm, (b) a pigment derivative, (c) a resin, and (d) a solvent A black composition having a difference in average primary particle size between (a1) carbon black and (a2) carbon black of 5 nm or more and an average primary particle size exceeding 40 nm. Do not mix
(A1) The specific surface area of carbon black is 200 to 600 m ² / g,
^2. The black composition according to claim 1 , wherein the specific surface area of (a2) carbon black is 40 to 600 m < ² > / g .
  The black composition according to claim 1 or 2, further comprising (e) an ethylenically unsaturated compound and (f) a photopolymerization initiator.   (F) The black composition according to claim 3, wherein the photopolymerization initiator contains at least one photopolymerization initiator selected from an oxime photopolymerization initiator, an imidazole photopolymerization initiator, and a borate photopolymerization initiator. .   Furthermore, the black composition in any one of Claims 1-3 containing (g) polyfunctional thiol. (B) The black composition in any one of Claims 1-5 in which a pigment derivative contains the pigment derivative shown by following General formula (1).
General formula (1)

(Wherein Q represents an organic dye residue, X represents a direct bond, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH ₂ NHCOCH ₂ NH—Y ₂ — (where Y ₂ Represents an alkylene group which may have a substituent or an arylene group which may have a substituent.), Y ₁ represents —NH— or —O—, and Z represents a case where n is 1. Represents a hydroxyl group, an alkoxy group, a substituent represented by the following general formula, -NH-XQ (where Q and X are as defined above), and when n is 2 to 4, a hydroxyl group, An alkoxy group, which represents a substituent represented by the following general formula, R ₁ and R ₂ each independently represents an alkyl group which may have a substituent, and R ₁ and R ₂ are bonded to each other to form at least a nitrogen atom; A heterocycle containing an atom may be formed, m represents an integer of 1 to 6, and n represents an integer of 1 to 4. .

(Wherein Y ₃ represents —NH— or —O—, and m, R ₁ and R ₂ are as defined above.)   The ratio (M / P) of the weight (P) of the resin (c) contained in the black composition and the weight (M) of the (e) ethylenically unsaturated compound contained in the black composition is 0.10 to 0.10. The black composition according to claim 3, which is 0.70.   A color filter comprising: a transparent substrate; and a black matrix formed using the black composition according to claim 1 on the transparent substrate.