KR20070057019A - Black composition and production method thereof - Google Patents

Abstract

Provided is a black composition, which shows excellent light-shielding property and stability, and is useful for forming a black pattern on a black matrix of a color filter. The black composition comprises: (a1) carbon black having an average primary particle diameter of 8-20 nm; (a2) carbon black having an average primary particle diameter of 21-40 nm; (b) a pigment derivative; (c) a resin; and (d) a solvent, wherein the carbon black(a1) and the carbon black(a2) show a difference in average primary particle diameter of at least 5 nm. Additionally, the black composition contains no carbon black having an average primary particle diameter of greater than 40 nm.

Description

Black composition and manufacturing method of black composition {BLACK COMPOSITION AND PRODUCTION METHOD THEREOF}

The present invention relates to a black composition containing carbon black. The present invention also relates to a method for producing a black composition containing carbon black. Furthermore, this invention relates to the color filter formed using the said black composition.

In the color filter, a lattice black pattern called a black matrix (hereinafter sometimes abbreviated as "BM") is formed between red (R), green (G), and blue (B) filter segments. have. The function of this BM is to block light in the backlight to 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 using a metal compound such as chromium by a deposition method, a sputtering method, or the like, followed by a photolithography process and an etching process to form a fine pattern (metal BM method), carbon black Using the black composition which disperse | distributed black components, such as these, to a resin material, the method (resin BM method) of forming by the printing method or the photolithographic method is developed.

However, in the metal BM method, the manufacturing process is not only very expensive due to the complex manufacturing process, but also the deposition method and the sputtering method are employed. Therefore, the metal BM method is formed on the metal BM large substrate from the viewpoint of the device cost or from the technical point of view. it's difficult. In addition, commonly used chromium has the potential to cause environmental problems during disposal.

In view of the above-described cost reduction, technical viewpoints, and further environmental problems, resin BM has been recently devised instead of metal BM.

However, in resin BM, there exists a problem that light shielding property (optical density = OD) is low compared with metal BM. In other words, in the metal BM, the desired light shielding property is generally obtained at a thickness of 0.1 to 0.2 µm, whereas in the resin BM, the film thickness must be set thicker in order to obtain the same light shielding property as the metal BM. Furthermore, the lower the light shielding property of the resin BM, the thicker the film needs to be. When creating a color filter, an RGB layer adjacent to the BM is formed by overlapping to eliminate light leakage. In the light-shielding resin BM, the level difference between the portions where the BM and the RGB layers overlap is large, and this step portion disperses the liquid crystal alignment, thereby degrading display quality.

Against this backdrop, resin BM has a high barrier property, that is, a high OD value in the unit film.

As a formation method of resin BM, there exist a printing method and the photolithographic method as mentioned above, for example. In the case of forming the BM by the printing method, there is a method of forming a pattern on a substrate by using a convex plate, or a method of forming a pattern by a concave plate, and then transferring a plurality of patterns onto the same substrate through a blanket. . However, these printing methods have a short process, and cobwebbing occurs in the process of transferring the ink from the plate to the substrate, or the process of transferring the ink from the plate to the blanket, or from the blanket to the substrate, and the pattern is straight. Deterioration of the pattern shape may be caused, such as poor sex. Therefore, generally, the photolithographic method which does not have such a concern is employ | adopted.

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 properties of the resin BM and to lower the level difference. However, in the method of increasing the content of the light shielding component, there have been problems such as deterioration of stability of the composition and the like.

Moreover, the method of raising OD value by using two types of light-shielding materials together for the purpose of improving the light-shielding property of BM is proposed. In other words, there is a method of improving the light shielding properties (OD value) by forming a closest filling structure in BM by using carbon black having a small average particle diameter and carbon black having a large average particle diameter (for example, Japanese Patent Laid-Open). Japanese Patent Application Laid-Open No. 9-133806, Japanese Patent Application Laid-Open No. 9-279082, Japanese Patent Application Laid-Open No. 11-80584).

That is, Japanese Patent Application Laid-open No. Hei 9-133806 preferably has at least two kinds of at least two kinds having an average particle diameter of one carbon black of 40 to 130 nm and an average particle diameter of the other carbon black of 135 to 500 nm. A photosensitive black resin composition composed of carbon black and photosensitive resin is disclosed. In addition, Japanese Patent Application Laid-Open No. 9-279082 contains a light-shielding material and a polymer material, and the light-shielding material preferably has a large particle size distribution having an average particle diameter of 50 nm or more, and a smaller particle size than that. The black coating composition which is a three-dimensional particle | grain (for example, carbon black) which has a particle size distribution which consists of a small particle size distribution made into a particle size is disclosed. Further, Japanese Patent Laid-Open No. Hei 11-80584 discloses carbon black for forming a black resist pattern comprising two or more kinds of carbon blacks having at least 20 nm in average primary particle diameter coated with a resin. In Japanese Patent Laid-Open No. 11-80584, the two or more kinds of carbon blacks preferably have an average primary particle diameter of 10 to 40 nm of one carbon black and an average primary particle diameter of 45 to 300 nm of the other carbon black. The difference in average primary particle diameter is 30 nm.

However, when the black composition contains carbon black having an average primary particle size of more than 40 nm, there is a problem that it is still disadvantageous from the viewpoint of light shielding properties.

On the other hand, Japanese Patent Laid-Open No. 2005-10604 and Japanese Patent Laid-Open No. 2005-99488 disclose a photosensitive black composition using a specific dye derivative or a specific initiator. However, none has yet been sufficient to satisfy both the stability and high light blocking property of the photosensitive black composition.

An object of the present invention is to provide a black composition having high breakthrough properties and excellent stability. Another object of the present invention is to provide a method for producing a black composition having high light shielding properties and excellent stability. Further, another object of the present invention is to form a color filter having a black matrix having high light blocking property.

The present invention comprises (al) 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 pigment composition, wherein the difference between the average primary particle diameter of the carbon black (a1) and the carbon black (a2) is 5 nm or more, and does not contain carbon black having an average primary particle diameter of more than 40 nm. To

The black composition of the present invention is preferably (al) 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) pigment derivative, (c) resin, and ( d) A black composition obtained by mixing a solvent, wherein the difference between the average primary particle diameter of the above (al) carbon black and the above (a2) carbon black is 5 nm or more, and the black of which the average primary particle diameter exceeds 40 nm is not mixed with black. Composition.

In another aspect of the present invention, (al) 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, and (b) a pigment derivative are mixed to obtain a mixture, and the obtained mixture is dried. It is related with the manufacturing method of the black composition which grind | pulverizes and dry-pulverizes, and (c) resin and (d) solvent are mixed.

In another aspect of the present invention, a mixture obtained by mixing (a1) carbon black having an average primary particle diameter of 8 to 20 nm and carbon black having (a2) average primary particle diameter of 21 to 40 nm is obtained to obtain a mixture, and the obtained mixture is subjected to dry grinding and dry grinding. And (b) a dye derivative, (c) resin and (d) solvent.

Yet another aspect of the present invention relates to a color filter comprising a transparent substrate and a black matrix formed on the transparent substrate by using the black composition.

The black composition of the present invention contains carbon black having a difference in average primary particle diameter of 5 nm or more and (a1) average primary particle diameter of 8 to 20 nm, and (a2) carbon black having an average primary particle diameter of 21 to 40 nm as a light shielding component. In addition, it is characterized by containing no carbon black whose average primary particle diameter exceeds 40 nm.

In the black composition using each carbon black, there exists a tendency as shown below.

(a1) In the black composition in which carbon black having an average primary particle diameter of 8 to 20 nm was used alone, the number of carbon black particles per unit volume was larger than that of the black composition in which carbon black having a larger average primary particle diameter of the same weight was used alone. It is advantageous from the viewpoint of blocking property, but photocurability is inferior because of high blocking light properties. Furthermore, it is difficult to stably disperse carbon black and cause problems such as residues (also called scumming) in which a part of the black composition remains on the glass substrate after development.

In one case, (a2) in the black composition in which carbon black having an average primary particle diameter of 21 to 40 nm was used alone, carbon black particles per unit volume were compared with the black composition in which carbon black having a smaller average weight of primary particle diameter was used alone. The number becomes minor and the photocurability is advantageous, but the light shielding property is insufficient. Moreover, a viscosity will become high and it will become difficult to prepare a black composition.

In addition, in the black composition using carbon black having an average primary particle diameter of more than 40 nm, the number of carbon black particles per unit volume is smaller than that of the black composition using only carbon black having an average primary particle diameter of less than 40 nm. Is liberated, but the shape of the light-shielding property and the black matrix, in particular, the linearity is insufficient.

As carbon black (a1), carbon black whose average primary particle diameter is 10-18 nm is preferable, and carbon black whose specific surface area is 200-600 m <^2> / g can be used suitably. When using carbon black with a specific surface area of less than 200 m ² / g, carbon black tends to cause deterioration of the pattern shape of the black matrix and deterioration of adhesion, and when carbon black larger than 600 m ² / g is used, carbon black is stable. Dispersion tends to be difficult. In addition, carbon black having an average primary particle diameter of less than 8 nm is difficult to manufacture, and therefore, it is not suitable as (a1) carbon black.

As the carbon black (a2), 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 can be suitably used. When using carbon black with a specific surface area of less than 40 m ² / g, carbon black tends to cause deterioration of the pattern shape of the black matrix and deterioration of adhesiveness, and when carbon black larger than 600 m ² / g is used, carbon black is stable. Dispersion tends to be difficult.

Furthermore, when the difference of the average primary particle diameter of (a1) carbon black and (a2) carbon black is less than 5 nm, the high light-shielding property which expresses when the (a1) carbon black and (a2) carbon black are used together is used. When stored for a predetermined period of time, it is possible to expect the effect of stability that hardly occurs development speed change or line width change before and after storage.

The average primary particle diameter of the carbon black contained in a black composition can be calculated | required by the following method.

First, the black composition is diluted about 100-fold using the solvent contained in the black composition, and a dilution is obtained. Next, the diluent is air-dried on a sample stage, and several thousand times of photographs are photographed several times by the electron microscope about the obtained carbon black. The maximum particle diameter of carbon black is measured about 2000-3000 pieces, and the average value of the primary particles is obtained by simply averaging the measured values. About the black composition which contains two or more types of carbon black, the particle size distribution based on the number-based distribution of the whole carbon black contained in a black composition is calculated | required first. Next, each particle diameter distribution of two or more types of carbon blacks is based on a normal distribution, and curve approximation is performed using the Gaussian function 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 which obtains the average primary particle diameter of each carbon black from the parameter of the obtained distribution function is normally shown as the value (nm) rounded off to a decimal place.

The black composition of the present invention contains carbon black having a difference in average primary particle diameter of 5 nm or more, (a1) average primary particle diameter of 8 to 20 nm, and carbon black having (a2) average primary particle diameter of 21 to 40 nm. It is characterized by not containing carbon black whose diameter exceeds 40 nm. Such a black composition can be obtained by mixing the carbon black whose average primary particle diameter is 5 nm or more (a1) average primary particle diameter of 8-20 nm, and (a2) average primary particle diameter of 21-40 nm preferably. At this time, carbon black whose average primary particle diameter exceeds 40 nm is not mixed.

The average primary particle diameter of carbon black before mixing can also be measured by the method of using the same electron microscope as mentioned above. Commercially available carbon black can be used as (a1) carbon black having an average primary particle diameter of 8 to 20 nm, and carbon black having (a2) average primary particle diameter of 21 to 40 nm.

(a1) As carbon black having an average primary particle diameter of 8 to 20 nm, for example, MONARCH or BLACK PERLS (1400, 1300, 1100, 1000, 900, 880, 800, 700) of CABOT product, VULCAN (P, 9A32), # (2700B, 2650, 2600, 2450B, 2400B, 2350, 2300, 1000, 990, 980, 970, 960, 950, 900, 850) from Mitsubishi Chemical, Color Black (FW2000, FW2 from MCF88, MA600, DEGUSSA) , FW2V, FW1, FW18, S170, S160), Special Black (6, 5), Printex (95, 90, 85, 80, 75, 40, 60), SEAST from Tokai Carbon (9H SAF-HS, 9 SAF ), Asashi # 80 from Asashi Carbon, ROYAL SPECTRA, NEO SPECTRA MARK (I and II) from Columian Carbon, 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, etc. are mentioned. Preferably MONARCH (1100, 800) of CABOT product, BLACK PERLS (1100, 800), PrinteX 95 of DEGUSSA product, # 850 of Mitsubishi Chemical, particularly preferably MONARCH 1100 of CABOT product, PrinteX 95 of DEGUSSA product Can be. (a1) Carbon black may be used individually by 1 type, or may mix and use 2 or more types.

(a2) As carbon black having an average primary particle diameter of 21 to 40 nm, for example, VULCAN (XC72R, XC72), MOGUL L, BLACK PEARLS (L, 570, 520, 490, 480, 470, 460, 450, 430, manufactured by CABOT) , 420, 410), REGAL (660R, 660, 500R, 330R, 330, 300R, 250R, 250, 99I, 991), ELFTEX (5, 8, 12, PELLETS 115), MA (77, 7) from Mitsubishi Chemical , 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 from DEGUSSA (4, 4A, 550, 350), PrinteX (150T, U, V, 140U, 140V, 55, P, L6, L, 300, 30, ES23, 3, ES22, 35, XE2), NIPex35, 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 # 75 from Asahi Carbon, ASAHI # 70 (-IH, -IN, -L), ASAHI HS-500, ASAHI F-200, RAVEN from Columbian Carcon (1255) , 1250, 1200, 1170, 1040, 1035, 1030, BEADS, 1020, 1000, 890POWDWE, 890HPOWDER, 850, 825BEADS), and CONDUCTEX (975DEADS, 900BEADS). Preferably REGAL (300R, 250R, 250, 99R, 99I) from CABOT, MA (7, 11, 100R) from Mitsubishi Chemical, # (47, 45, 45L), Printex55, NIPex35 from DEGUSSA, particularly preferred For example, # 47 from Mitsubishi Chemical, REGAL 250R from CABOT, PrinteX55 from DEGUSSA, and NIPex35 may be used. (a2) Carbon black may be used individually by 1 type, or may mix and use 2 or more types.

As for the weight ratio of (a1) carbon black and (a2) carbon black contained in a black composition, (a1 / a2) = 1 / 3-1 / 30 are preferable, More preferably, it is 1 / 3-1 / 10, ( When a1) / (a2) = 1/3 is exceeded, that is, when (a1) is large, there exists a tendency for stable dispersion of carbon black to become difficult. When (a1) / (a2) = 1/30 is less than one, that is, when (a1) becomes less, when the (a1) carbon black and the (a2) carbon black are used together, The effect of stability tends not to be expected.

In addition, the total solid weight of the black composition of (a1) carbon black and (a2) carbon black is based on 100 weight%, Preferably it is 40 to 60 weight% in total, More preferably, 45 to 55 weight in total Can be used in an amount of%.

Carbon black usually exists as aggregates in which primary particles are aggregated, and the aggregates are conceptually likened to tears of grapes. The extent of this aggregate's development is called a structure, and the height of the structure may affect dispersibility, coloration, viscosity, and so on.

In the present invention, by dry pulverizing carbon black, the aggregate of high structure in which primary particles of carbon black are agglomerated is separated or pulverized to disintegrate the aggregate to obtain a low structure agglomerate.

As an apparatus used for the dry grinding of carbon black, the apparatus which uses media, such as a pulverizer, a ball mill, a vibration mill, the apparatus which does not use media, such as a pin mill, a hammer mill, and micros, etc. are mentioned. Moreover, the temperature at the time of dry grinding is not specifically limited, 60-110 degreeC is preferable from a safety point at the time of exercise. The grinding time can be arbitrarily set according to the type of the grinding apparatus of the grinding apparatus.

Although (a1) carbon black and (a2) carbon black may be mixed beforehand after dry grinding respectively, it is preferable to dry-grind after mixing (a1) carbon black and (a2) carbon black from a viewpoint of production efficiency.

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. In addition to the compound generally called a pigment | dye, organic pigment | dye contains aromatic polycyclic compounds, such as naphthalene system which is not generally called a pigment | dye. As a dye derivative, what is represented by following General formula (1) can be used preferably. As a pigment derivative represented by General formula (1), the pigment derivative represented by following General formula (2)-(11) is mentioned, for example.

General formula (1)

Wherein Q represents an organic pigment 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 Or 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 hydroxyl group, an alkoxy group, or the following general formula The substituent represented by-, -NH-XQ- (however, Q and X are the same as the above), and when n is 2-4, represent a hydroxyl group, an alkoxy group, the substituent represented by the following general formula, R <_1> and R ₂ each independently represents an alkyl group which may have a substituent, R ₁ and R ₂ may be bonded to each other to form a heterocycle including at least a nitrogen atom, m represents an integer of 1 to 6, and n represents 1 The integer of 4 is shown.

(Wherein Y ₃ represents -NH- or -O-. M, R ₁ and R ₂ are the same as above).

Methylene group, ethylene group, etc. are mentioned as an alkylene group. A phenylene group etc. are mentioned as an arylene group. As an alkoxy group, a methoxy group, an epoxy group, etc. are mentioned. A methyl group, an ethyl group, etc. are mentioned as an alkyl group. Moreover, a methyl group, an ethyl group, etc. are mentioned as a substituent which has these groups.

As organic pigments constituting the dye derivative represented by the general formula (1), for example, phthalocyanine-based, quinacridone-based, quinacridonequinone, isoindolinone-based, quinophthalone-based, diketopyrrolopyrrole-based, and peryl Condensed polycyclic organic pigments such as len, perinone, indigo, thioindigo, dioxadine, anthraquinone, pyrantrone, ananthrone, flavansrone, indanthrone and metal complexes, benzimi Organic pigments such as dazolone, insoluble azo, condensed azo and soluble azo, or light yellow aromatic polycyclic compounds such as dyes and naphthalenes.

(b) A pigment derivative may be used individually by 1 type, or may mix and use 2 or more types.

(b) As for the pigment derivative, the total solid weight of the black composition is based on 100% by weight, preferably 0.05 to 20% by weight, and more preferably 0.5 to 10% by weight. When the content of the dye derivative is less than 0.05% by weight, the effect of dispersing the carbon black tends not to be sufficiently exhibited, and when it is more than 20% by weight, the dispersion of the carbon black tends to be unstable.

When dry grinding (a1) carbon black and (a2) carbon black, (b) a pigment derivative may be added after dry grinding of (a1) carbon black and (a2) carbon black. Or (a) a carbon black and (a2) a carbon black, and (b) a pigment derivative may be dried and then pulverized. (A1) a carbon black and (a2) a carbon black may be added at the time of dry grinding. You may also It is preferable to add (b) a pigment derivative after dry grinding of (a1) carbon black and (a2) carbon black from a viewpoint that carbon black is disperse | distributed better and low viscosity and adhesiveness increase.

Furthermore, as the (c) resin contained in the black composition of the present invention, for example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate , Polyurethane resins, polyester resins, acrylic acid resins, alkyd resins, polystyrenes, polyamide resins, rubber resins, cyclized rubber resins, celluloses, thermoplastic resins such as polyethylene, polybutadiene, polyimide resins, epoxy resins, benzogua Thermosetting resins, such as a namin resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, a melamine resin, urine resin, and a phenol resin, can be used.

Among the (c) resins contained in the black composition, the resins represented by the following general formula (12) are advantageous in terms of high OD due to the high developability improvement and the large film reduction, so that the total amount of resin is preferably 0.1 to 30. % By weight, more preferably 1 to 20% by weight can be used.

(Wherein R ₁ is a tetravalent aromatic tetracarboxylic acid residue, R ₂ is a monoalcohol residue, R ₃ is a lactone residue, m is 2 or 3, n is an integer from 1 to 50, t is (4-m) Indicates

As an acid dianhydride which gives an aromatic tetracarboxylic acid residue, a pyromellitic dianhydride, 3,3'4,4'-biphenyl tetracarboxylic dianhydride, 9,9-bis (3,4- dicarboxyphenyl, for example) Fluorene dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, and ethylene glycol dianhydride trimellitic acid ester. Examples of the monoalcohol include 1-dodecanol, n-stearyl alcohol, isostealyl alcohol, glycerin dimethacrylate, pentaerythritol triacrylate, and 2-ethylhexyl alcohol. Examples of lactones include δ-valerolactone, ε-caprolactone, and alkyl substituted ε-caprolactone.

(c) It is preferable that it is 1,000-100,000, and, as for the weight average molecular weight of resin, it is more preferable that it is 2,000-50,000. If it is less than 1,000, the occurrence of tuck and coating film strength may not be sufficiently obtained. If it exceeds 100,000, the viscosity may increase and the coatability may decrease. In the present invention, the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene by gel permeation chromatography.

(c) Resin may be used individually by 1 type, or may mix and use 2 or more types. The content of the resin (c) 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 content is less than 5 weight%, there exists a tendency for a coating film to become weak, and when more than 60 weight%, developability tends to fall in photolithography.

The black composition of this invention contains a (d) solvent in order to fully disperse | distribute carbon black and to form the desired black matrix of a film | membrane. As a solvent, for example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylbenzene, and ethylene glycol di Ethyl ether, propyl 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 Ketones, petroleum solvents, and the like, and these may be used alone or in combination. The solvent (d) may be used in an amount of preferably 150 to 3500 parts by weight, more preferably 250 to 2000 parts by weight based on 100 parts by weight of the total solid of the black composition.

The black composition of this invention may further have (e) ethylenically unsaturated compound. The (e) ethylenically unsaturated compound contained in the black composition of this invention is a compound which has 1 or 2 or more ethylenically unsaturated double bonds in 1 molecule, For example, a monomer, an oligomer, and photosensitive resin can be used.

As a monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethyleneglycol di (meth) acrylate, trimethylolpropane tri (meth), for example ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. Moreover, an epoxy (meth) acrylate, urethane (meth) acrylate, ester (meth) acrylate, etc. are mentioned as an oligomer.

As photosensitive resin, the photosensitive resin which introduce | transduced ethylenically unsaturated bond into the above-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, an epoxy group, or cinnamic acid is reacted with a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group present in the resin, and a (meth) acryl Resin which introduce | transduced photocrosslinkable groups, such as a diary and a styryl group, into the said linear polymer is used. Moreover, the linear polymer containing acid anhydride groups, such as a styrene maleic anhydride copolymer and an alpha olefin maleic anhydride copolymer, is half-esterified by the (meth) acryl compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate. The linearized linear polymer 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, more preferably 7 to 28% by weight, particularly preferably from the viewpoint of photocurability and developability, based on the total solids weight of the black composition (100% by weight). May be used in an amount of 10 to 25% by weight. When the content of the ethylenically unsaturated compound is more than 30% by weight, there is a tendency to produce linearity defects and cross-sectional defects in the pattern shape of the BM, and when the content is less than 5% by weight, the photocurability tends to be insufficient. There is this.

In the black composition of the present invention, the ratio (M / P) of the weight (P) of the resin (c) and the weight (M) of the (e) ethylenically unsaturated compound is preferably 0.10 to 0.70, and preferably 0.15 to 0.65. It is more preferable that it is, and it is especially preferable that it is 0.20-0.60. If M / P is less than 0.10, it may become a reduction degree, and if M / P exceeds 0.70, the linearity defect, cross-sectional defect, or tack of a black matrix may be produced.

The black composition of this invention may further contain the (f) photoinitiator. (f) As a photoinitiator, an acetophenone type photoinitiator, a benzoin type superpolymer initiator, a benzophenone type photoinitiator, a thioxanthone type photoinitiator, a triazine type photoinitiator, a carbazole type photoinitiator, an imidazole type photoinitiator, for example , Oxime photopolymerization initiator, borate photopolymerization initiator, phosphine photopolymerization initiator, quinone photopolymerization initiator, titanocene photopolymerization initiator and the like can be used. Especially, at least 1 type of photoinitiator selected from an oxime system photoinitiator, an amidazole type photoinitiator, and a borate type photoinitiator is preferable, and an oxime system photoinitiator is especially preferable from a photocurable viewpoint.

Examples of the oxime photoinitiator include ethanone represented by the following formula (13), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl]-, and 1- (0-acetyloxime ), 1,2-octanedione, 1- [4-phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- ( 4'-methoxy-naphthyl) ethylidene) hydroxylamine etc. are mentioned.

2,2'-bis (o-chlorophenyl) -4 and 5,4 ', 5'- tetraphenyl- 1,2'-biimidazole are mentioned as an imidazole series photoinitiator.

As a borate type photoinitiator, the compound represented by following formula (14)-(17) is mentioned.

As an acetophenone type photoinitiator, 4-phenoxydicycloloacetophenone, 4-t-butyl- dichloroacetophenone, diethoxy acetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.

As a benzoin type photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, etc. are mentioned.

Examples of the benzophenone photopolymerization initiators include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoic acid, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl-4'-methyldiphenylsulfide.

As a thioxanthone type photoinitiator, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc. are mentioned.

As a triazine photoinitiator, 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-tril) -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 (trichloro Rhomethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- ( Piperonyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine, and the like.

Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine oxide, etc. are mentioned as a phosphine type photoinitiator.

9,10-phenanthrene quinone, a camphor quinone, ethyl anthraquinone etc. are mentioned as a quinone system photoinitiator.

Said (f) photoinitiator is used individually by 1 type or in mixture of 2 or more types. The photopolymerization initiator (f) may 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 weight of the black composition (100% by weight).

Moreover, it is preferable that ratio (I / M) of the weight (I) of (f) photoinitiator and the weight (M) of (e) ethylenically unsaturated compound is 0.10-1.00, It is more preferable that it is 0.15-0.80 It is especially preferable that they are 0.20-0.60. If I / M is less than 0.10, it may be reduced. If I / M exceeds 1.00, the linearity of the pattern of BM is poor, the cross-sectional shape of defect, or the pattern width after development is thicker with respect to the mask pattern width. Problems may arise.

The black composition of this invention can contain (g) polyfunctional thiol which acts as a chain transfer agent.

(g) The polyfunctional thiol may be a compound having two or more thiol groups, for example, hexanedithiol, decandithiol, 1,4-butanediolbisthiopropionate, 1,4-butanediolbisthioglycolate, ethylene glycol Bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhioglycolate, trimethylolpropane tris (3-mercaptobutylate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetraquistiopionopionate, trimercaptopropionate tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, trimethylolpropane tris (3-methcaptoisobutyrate), etc. are mentioned. These (g) polyfunctional thiols can be used 1 type or in mixture of 2 or more types.

Among these (g) polyfunctional thiols, trimethylolpropane tristyropropionate, trimethylolpropane tris (3-methylcaptobutylate) and trimethylolpropane tris (3-mercaptoisobutylate) are preferable. Can be used.

Moreover, these (g) polyfunctional thiols are preferable in the said (f) photoinitiator, especially when it combines with an imidazole series photoinitiator, since a sensitivity increases and photocurability improves.

(g) As for the polyfunctional thiol, the total solid weight of a black composition is based on 100 weight%, Preferably it is 0.1-30 weight%, More preferably, it can be used in the quantity of 1-20 weight%. If it is less than 0.1 weight%, the effect of adding polyfunctional thiol may become inadequate, and if it exceeds 30 weight%, sensitivity may be too high and resolution may fall or stability of a black composition may fall.

The black composition of the present invention may contain a sensitizer. Examples of the sensitizer include α-acyloxyester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone And 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. As a sensitizer, the black composition may 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 solids weight (100% by weight).

Moreover, you may add other additives, such as surfactant, a silane coupling agent, etc. to the black composition of this invention for the purpose of an improvement of coating property, an improvement of a sensitivity, adhesiveness, etc.

The black composition is a mixture of carbon black, a dye derivative, a resin, a solvent, and an ethylenically unsaturated compound, a photopolymerization initiator, and other additives, if necessary, and three roll mills, two roll mills, sand mills, kneaders, pulverizers, and micros. It can manufacture by disperse | distributing using various dispersion apparatuses, such as these.

The black composition preferably removes 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 the mixed dust by means of centrifugation, sintering filter, membrane filter, or the like. Do.

Next, the color filter of this invention is demonstrated. Here, a method for producing a color filter by a photolithography method using a black composition to which carbon black, a dye derivative, a resin, and a solvent are added to contain an ethylenically unsaturated compound and a photopolymerization initiator, but the present invention is limited thereto. It doesn't work.

The color filter of the present invention is preferably provided with a BM formed from the 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 of blue, green, red, cyan, yellow, magenta, orange, and purple. Filter segments having different concentrations may be formed with the same color.

BM is applied to the black composition of the present invention by a coating method such as spin coat, slit coat, roll coat or the like on a transparent substrate, and then irradiates active energy rays from the composition-coated surface side through a photomask, and then a solvent or an alkali developer. The developer can be formed by spraying a developer by immersion in a spray or by spraying to remove the unilluminated portion, that is, the uncured portion, and perform development.

It is preferable that it is the range of 0.2-5 micrometers (at the time of drying) after the coating film of a black composition, and it is more preferable that it is the range which is 0.5-2 micrometers which is easy to balance coatability and inviolability.

In addition, the optical density (0D) per 1 탆 after the dry film of BM is preferably 3.0 or more, particularly preferably 3.5 or more, and more preferably 3.8 or more from the viewpoint of high light shielding properties. The higher the optical density, the more preferable. However, when the active energy ray is ultraviolet light or visible light, it is preferable that the cured coating film is less than about 4.7 because it is difficult to obtain.

As the alkali developer, aqueous solutions such as sodium carbonate and sodium hydroxide are used, and organic alkalis such as dimethyl benzylamine and triethanolamine may be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

In addition, in order to increase the exposure sensitivity by the active energy ray, the black composition is applied and dried, followed by drying after coating with a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin, and preventing polymerization inhibition by oxygen. After forming a film, you may irradiate an active energy ray from the composition application surface side.

As an active energy ray, an electron beam, an ultraviolet-ray, and visible light of 400-500 nm can be used. As the source of the electron beam to be irradiated from the composition-coated surface side, a thermal electron radiation gun, an electric field radiation gun, or the like can be used. In addition, for example, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, gallium lamps, xenon lamps, carbon arc lamps, and the like can be used as the sources of ultraviolet rays and visible light of 400 to 500 nm. Specifically, since the point light source and the brightness are stable, an ultra high pressure mercury lamp and a xenon mercury lamp are often used. Although active energy dose irradiated from the surface of a composition application surface can be set timely in the range of 5-1000mJ, it is preferable that it is the range of 20-300mJ which is easy to manage on a process.

The color filter segment is formed by gravure offset printing, anhydrous offset printing, silkscreen printing, photolithography using a solvent developer or alkali developing colored resist, or electrophoresis of colloidal particles. The electrodeposition method of electrodeposition-forming on the upper surface, the transcription | transfer method of transferring the filter segment layer previously formed on the surface of the transfer base sheet on a BM board | substrate, etc. are mentioned.

Since the printing method can be patterned only by repeating printing and drying, it is excellent in mass productivity at low cost as a manufacturing method of a color filter. Further, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. When manufacturing a color filter by the printing method, control of the fluidity | liquidity of the ink on a printing machine is important, and the ink viscosity by a dispersing agent or a extender pigment can be adjusted.

In the photolithography method using a solvent developing type or an alkali developing type colored resist, a colored resist is coated on a transparent substrate on which BM is formed by a coating method such as spin coat, slit coat, roll coat, and the like. Ultraviolet exposure is performed through, the unexposed part is wash | cleaned with a solvent or alkaline developing solution, and a desired pattern is formed, and the same operation is repeated about a different color and a color filter is manufactured. This manufacturing method can manufacture a color filter with high precision by the said printing method.

The colored resist is a resist containing a colorant of a desired color instead of the carbon black contained in the black composition of the present invention, but the dye derivative represented by the general formula (1) does not necessarily need to be contained. As a coloring agent, the coloring agent excellent in various tolerances is used, It is preferable to use a pigment from a viewpoint of light resistance, heat resistance, or solvent resistance, and it is especially preferable to use organic pigment in the magnitude | size of light absorption ability. Specific examples of representative pigments are indicated by color index (CI) numbers.

Pigment Yellow 12, 13, 14, 20, 24, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, 166, 173 Etc. can be mentioned.

Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 etc. are mentioned as orange coloring agent.

Pigment red 9, 97, 122, 123, 144, 149, 166, 168, 177, 190, 192, 215, 216, 224, 254, 255 etc. are mentioned as a coloring agent of red and magenta.

Pigment violet 19, 23, 29, 32, 33, 36, 37, 38 etc. are mentioned as a purple coloring agent.

As a coloring agent of blue and cyan, peakment blue 15 (15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 etc.), 21, 22, 60, 64, etc. are mentioned.

Pigment green 7, 10, 36, 47 etc. are mentioned as a green coloring agent. You may use these coloring agents combining 2 or more types in order to obtain a desired color.

Although the method of manufacturing the color filter which formed BM by the photolithographic method was demonstrated above, the conventionally well-known printing method using the black composition containing the carbon black of this invention, a pigment derivative, resin, and a solvent is also used. , BM can be formed by an electrodeposition method, a dry film transfer method, or the like combined with a photolithography method.

<Example>

Hereinafter, although it demonstrates based on this invention and an Example, this invention is not limited by this. In addition, in an Example and a comparative example, "part" and "%" represent a "weight part" and "weight%", respectively.

[Preparation of Resin Solution (1)]

370 parts of propylene glycol momomethyl ether acetate were put into the reaction container provided with a gas introduction tube, a thermometer, a condenser, and a stirrer, and it heated at 80 degreeC, injecting nitrogen gas into a container. Next, at the same temperature, a mixture of the following monomers and a thermal polymerization initiator was added dropwise into the reaction vessel over 1 hour to conduct a polymerization reaction.

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

Paracumyl phenol ethylene oxide modified acrylate 20.0part

("ARONIX M-110" made by Toagosei company)

After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 3 hours, and then, 1.0 parts of azobisisobutylonitrile dissolved in 50 parts of cyclohexanone was added to the reaction vessel, and the mixture was allowed to react at 80 ° C for 1 hour to acryl A solution of the resin was obtained. The weight average molecular weight of the acrylic resin was about 40000. After cooling the solution of acrylic resin to room temperature, about 2 g of solution was sampled, it heat-dried for 20 minutes at 180 degreeC, and the non volatile matter was measured. Then, propylene glycol monomethyl ether acetate was added to the solution of the synthesize | combined acrylic resin so that a non volatile matter might be 30 weight%, and the resin solution (1) was prepared.

[Preparation of Resin Solution (2)]

Into a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst were obtained to obtain a mixture. The mixture was heated and stirred at 120 ° C. for 4 hours while injecting nitrogen gas. After confirming that 98 weight% of raw materials reacted by solid content measurement, 36.6 parts of pyromellitic anhydrides were added to the reaction container, and the mixture was made to react at 120 degreeC for 2 hours. After confirming that 98 weight% or more of acid anhydrides semi-esterified by the measurement of acid value, reaction was complete | finished and resin was obtained. Obtained resin was white solid at normal temperature, the weight average molecular weight was about 3,600 and the acid value was 49 mgKOH / g. Cyclohexanone was added to this resin so that a non volatile matter might be 30 weight%, and the resin solution 2 was prepared.

[Preparation of Carbon Black Dispersion A ~ K]

The carbon black dispersion was prepared using the carbon black shown in Table 1. 100 parts of carbon black of the blending composition and blending ratio shown in Table 2, 4 parts of the dye derivative shown in the following formula (18), and 70 parts of the resin solution (1) were mixed, diluted with cyclohexanone, and the final solid content was 20% by weight. A mixture was obtained. Carbon black dispersions A to K were prepared by dispersing the obtained mixture in a paint shaker using glass beads having a diameter of 0.8 nm for 2 hours. Except dispersion F, the dispersion whose viscosity is 40 mPa * s or less was obtained. Dispersion F could not prepare a black composition because the viscosity after dispersion was extremely high at 200 mPa · s or more and gelled at room temperature. Carbon black dispersion I was prepared in the same manner as in dispersion B except that dry black grinding (apparatus: micros, grinding time: 10 min, grinding temperature: 70 ° C.) was used in the blending composition and blending ratio shown in Table 2. . The carbon black dispersion K was prepared in the same manner as in the dispersion G except that 56 parts of the resin solution (1) and 14 parts of the resin solution (2) were used instead of 70 parts of the resin solution (1).

[Examples 1-13 and Comparative Examples 1-4]

(Preparation of black composition)

After mixing and mixing a mixture so that it might become uniform at the mixing | blending composition and blending ratio shown in Table 3, it filtered with a 2 micrometer filter and obtained the black composition. About the obtained black composition, the sensitivity, stability, light-shielding property (OD value per unit film thickness), and the pattern shape of BM were evaluated by the following method.

The obtained results are shown in Table 4.

Monomer (ethylenically unsaturated compound): dipentaerythritol hexaacrylate (DPHA)

Copolymerization initiator A: Oxime type photoinitiator represented by Formula (13) (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazolyl-3-yl]-, 1- (0 -Acetyl oxime), "IRGACURE OXE02" manufactured by Chiba Specialty Chemical Co., Ltd.)

Photoinitiator B: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole

Photoinitiator C: The borate type photoinitiator represented by Formula (14).

Photoinitiator D: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ("IRGACURE 369" manufactured by Chiba Specialty Chemical)

Multifunctional thiol: trimethylolpropane tris (3-mercaptobutylate)

Solvent: Cyclohexanone

[Sensitivity]

The black composition was coated on a 10 cm x 10 cm glass substrate by spin coating, and then dried at 70 ° C. for 15 minutes to form a coating film of about 1 μm after the dry film, and the film thickness was measured. Then, the ultra-high pressure mercury lamp was used, and the coating film was exposed by the ultraviolet-ray of various exposure amount (mJ / cm <^2> ) through a photomask. After the coating film was developed using an aqueous sodium carbonate solution, the unexposed portion was removed by washing with ion-exchanged water. The film thickness of the exposed part after development / cleaning was measured, and the minimum exposure amount (mJ / cm <^2> ) by which 95% or more of film thickness is obtained with respect to the film thickness before image development was made into the sensitivity. A case in which the sensitivity ○ 10 ~ 50mJ / cm ² (good), greater than the 50mJ / cm ² was evaluated as × (poor). A mask pattern having a line width of 10 µm was used for the photomask, and a stripe-like black matrix pattern was formed.

[stability]

About the black composition immediately after preparation, and the black composition after 7 days storage at 40 degreeC, developing speed and line width were compared and stability was evaluated.

(Development speed) After coating a black composition on the glass substrate of 10 cm x 10 cm by the spin coat method, the coating film of about 1 micrometer was formed after the dry film by drying for 15 minutes at 70 degreeC, and the film thickness was measured. The coating film was spray-developed using the sodium carbonate aqueous solution, and time to lose a coating film was measured. The measurement time was removed to the thickness of the measurement film, and the time per second film thickness (sec / µm) was defined as the development speed.

The case where the development speed after storage was a change within 15% of the plasma relative to the development speed before storage was evaluated as (circle) (good), and a case where the high speed change or the low speed change exceeded the plasma minus 15% as x (defect).

(Line width) Using the black composition before and after storage, the stripe-shaped BM pattern was formed in the exposure amount of 70 mJ / cm <^2> in the same method as [sensitivity] evaluation, and the line width was measured with the optical microscope. However, since the black composition of Example 10 had low sensitivity, it exposed at 300mJ / cm <^2> . For the line width of the stripe-shaped BM pattern formed using the black composition before storage, the case where the change in the line diameter or the line thickness exceeded the case where the change was within 15% of the positive (good), and the 15% of the plasma negative was changed. It evaluated as (defect).

In addition, in the case of developing speed evaluation of X, it judged that stability was inferior, and the line width evaluation was not performed.

[Blocking property (optical density (OD))]

The black composition was coated on 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 by a Macbeth densitometer (GRETAG D200-II), the measured optical concentration (OD) was removed after the measurement film, and the optical concentration per unit film thickness (OD / Μm) was obtained.

[shape]

In the same manner as in [Sensitivity] evaluation, a stripe-shaped BM pattern was formed at an exposure dose of 70 mJ / cm ² , and the pattern shape of the prepared stripe-shaped BM was observed with an exposure microscope or an electron beam scanning microscope, and linearity and cross-sectional shape were observed. . However, the black composition of Example 10 was exposed to 300mJ / cm ² because the sensitivity was low.

(Straightness) Straightness (good) when no flaw or protrusion is seen on the straight part, straightness △ (slightly poor) when a part or straight part is seen in the straight part, and a protrusion or When many defects were seen, it evaluated as linearity (defect).

(Cross-sectional shape) When the cross-sectional shape is perpendicular to the forward taper (the bottom of the surface in contact with the glass from the bottom), the cross-sectional shape ○ (good), and the cross-sectional shape overhangs (from the bottom of the surface where the top side is in contact). Wide)) was evaluated as x (defect).

[Viscosity]

The viscosity of the black composition was measured at 25 ° C and 20 rmp using a TVE-20L type viscometer (manufactured by Toki Sangyo).

[Adhesiveness]

The black composition was coated on a glass substrate in the same manner as in the [sensitivity] evaluation, and 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 grid adhesion test method based on JISK5400. Peeling is performed by attaching a high performance epoxy rapid curing adhesive (cured at room temperature for 1 hour) to the head of the M6 bolt, attaching (self-weighting) to a grid-shaped coating film, heating at 90 ° C. for 5 minutes, and then removing the bolt from the coating film by hand. It was. Since the bolt is smaller than the grid of 1mm × 1mm × 100, the adhesion is shown by the ratio of the peeling area of the coating film to the adhesive area of the bolt.

In addition, adhesiveness computed adhesiveness (%) in the following formula (19), and evaluated the calculated result by four steps of (circle) to (x). In addition, the decimal point of the value calculated | required by Formula (19) rounded off, and made it the adhesive value.

◎: 80% ≤Adhesive≤100%

○: 60% ≤ adhesion <80%

△: 30% ≤ adhesiveness <60%

X: 20% <adhesive <30

As is apparent from Table 4, Examples 1 to 13 of the present invention are superior to Comparative Examples 1 to 4 in terms of high light shielding properties and stability, and Examples 11 and 12 in which dry treatment of carbon black have low viscosity and Better in terms of adhesion

The black composition of the present invention contains carbon black having an average primary particle diameter of 5 nm or more and an average primary particle diameter of 8-20 nm, carbon black having an average primary particle diameter of 21-40 nm, and no carbon black exceeding 40 nm. Since it is not, the light-shielding property is high and it is excellent in stability. Furthermore, the black composition which has good dispersibility and low viscosity can be obtained by dry-pulverizing the said carbon black, or even when the density | concentration of the said carbon black is high.

By using the black composition of this invention, a black matrix with high light-shielding property can be formed.

Claims (11)

(a1) A black composition containing 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 color derivative, (c) a resin, and (d) a solvent. The black composition, wherein the difference between the average primary particle diameter of the (a1) carbon black and the (a2) carbon black is 5 nm or more, and the average primary particle diameter does not contain carbon black of more than 40 nm. (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) Color derivative, (c) resin, and (d) solvent A black composition obtained by mixing the above, wherein the average primary particle diameter of the carbon black (a1) and the carbon black (a2) is 5 nm or more, and carbon black having an average primary particle diameter of more than 40 nm is not mixed. Black composition. The black composition according to claim 1 or 2, wherein the dry milled (a1) carbon black and (a2) carbon black are used. The black composition according to claim 1 or 2, comprising (e) an ethylenically unsaturated compound and (f) a photopolymerization initiator. The black composition according to claim 4, wherein the photopolymerization initiator (f) comprises at least one photopolymerization initiator selected from an oxime photopolymerization initiator, an imidazole photopolymerization initiator, and a borate photopolymerization initiator. (G) The black composition of Claim 1 or 2 containing a polyfunctional thiol group. The black composition according to claim 1 or 2, wherein the (b) dye derivative comprises a dye derivative represented by the following General Formula (1). [Formula 1]

Wherein Q represents an organic pigment 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 Or 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 hydroxyl group, an alkoxy group, or the following general formula as substituents, -NH-XQ- shown represents (where, Q and X are as defined above), n the case of 2 to 4 represents a substituent represented by a hydroxyl group, an alkoxy group, the general formula, R ₁ and R ₂ Each independently represents an alkyl group which may have a substituent, R ₁ and R ₂ may be bonded to each other to form a heterocycle including at least a nitrogen atom, m represents an integer of 1 to 6, and n represents 1 to 4 Represents an integer. [Formula 2]

(Wherein Y ₃ represents —NH— or —O—. M, R ₁ and R ₂ are the same as above). The ratio (M / P) of the weight (P) of (c) resin contained in black composition, and the weight (M) of (e) ethylenically unsaturated compound contained in black composition is 0.10- Black composition, characterized in that 0.70. (a1) a 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, and (b) a pigment derivative are mixed to obtain a mixture, and the obtained mixture is subjected to dry grinding and dry grinding. A process for producing a black composition, comprising mixing a mixture with (c) a resin and (d) a solvent. (a1) carbon black having an average primary particle diameter of 8 to 20 nm and carbon black having an average primary particle diameter of 21 to 40 nm were mixed to obtain a mixture, and the obtained mixture was pulverized by dry grinding, and (b) pigment. A method for producing a black composition, comprising mixing a derivative, (c) resin and (d) solvent. A color filter comprising a transparent substrate and a black matrix formed on the transparent substrate using the black composition according to claim 1 or 2.