TWI287694B - Photosensitive black-colored composition, and black matrix substrate and color filter, using the same - Google Patents

Abstract

There is provided a photosensitive black-colored composition, in which carbon black with specific surface area of 50 to 200 m<2>/g, pigment derivatives represented by the following formula (A) possessing alkali replacing groups with triazine rings, and ethylene unsaturated compounds are contained. Then there is provided a black matrix substrate with black matrix made from the black composition. And then there is provided a color filter made of filter segment including two colors at least but black. Formula (A): (In the formula, Q represents organic pigment residual group.)

Description

1287694 IX. Description of the invention: (I) Technical field to which the invention pertains: The present invention relates to a photosensitive black composition for manufacturing a black matrix which can be used for a color filter used in combination with a liquid crystal display device or a solid-state imaging member, Use its black matrix substrate and color filter. (2) Prior art: In the gap portion between the color filter segments of red, green and blue of the color filter, for the purpose of contrast enhancement, a lattice-like black pattern called a black matrix having a light-shielding property is generally formed. In the past, although the black matrix was formed of a metal film such as chromium or nickel, it was attempted to use a black pigment such as a black pigment such as carbon black or a mixture of several pigments to form a black coloring agent from the viewpoint of display quality and cost. The photosensitive black composition forms a black matrix. The black matrix formed by using the photosensitive black composition has a low surface light reflectance, can shorten the manufacturing process, and can produce a large color filter, and has a larger number of black matrices than metal materials such as chrome. advantage. However, when a black matrix is formed by photolithography using a photosensitive black composition, it is necessary to blend a large amount of black colorant such as carbon black in the composition in order to obtain high light-shielding property, but black colorant. The higher the content of the black coloring agent becomes, the more difficult it is to uniformly disperse the black coloring agent, and the problem that the dispersion stability of the long-term viscosity increase of the so-called photosensitive black composition is lowered. In addition, the light-shielding property is high and the sensitivity is remarkably low, and it is difficult to obtain a hardened coating film even when irradiated with an active energy ray. In order to obtain a sufficiently hardened coating film, a large amount of exposure is required, and there is a so-called production -7- 1287694 Problem of reduced sex or black matrix shape degradation. In order to solve such a problem, it is proposed to blend a dye derivative represented by the following formula (B) in a color filter forming composition containing a black matrix (for example, refer to Japanese Patent Laid-Open 3 - 1 5 3 7 8 Bulletin No. 0.). General formula (B):

Q DQj (b) wherein Q represents the residual functional group of the organic pigment,

Xi represents a hydrogen atom, a carboxyl group or a sulfonic acid group, and X2 represents a formula A-

The substituents represented by i and j each independently represent an integer of 1 to 4, and R: and 1 each independently represent a hydrogen atom or an alkyl, aryl or heterocyclic residual functional group which may have a substituent, Y Representing a hydrogen atom, a halogen atom, -no2, a nh2 or a so3h 1287694 k represents an integer of 1 to 4, η represents an integer of 1 to 4, and Α represents a general formula

% indicates the 2-valent bond group, -S02NH — R3 —

Or a CH2NHCOCH3 — R3—, (original page 3) Z2 represents—NH—or a 〇—, I represents a non-radical, alkoxy, or the following formula /% or

The substituent "but" in the case where i is 1, Ζ3 may also be a ΝΗ-Z i - Q 〇 although the photosensitive black composition containing the dye derivative represented by the general formula (B) is heat-resistant The properties, the chemical resistance, and the like are excellent, but the dispersion stability, the sensitivity, the black matrix shape, the adhesion to the substrate, and the light blocking property fail to satisfy the required performance. -9- 1287694 (III) SUMMARY OF THE INVENTION: In summary of the invention, the present invention exhibits excellent characteristics in heat resistance, chemical resistance, and the like, and further relates to dispersion stability, sensitivity, black matrix shape, and substrate. A photosensitive black composition excellent in adhesion and light-shielding property is provided for the purpose of providing the black matrix substrate and the color filter. According to the first aspect of the present invention, there is provided a photosensitive black containing carbon black having a specific surface enthalpy of 50 to 200 m 2 /g, a dye derivative represented by the following general formula (A), and an ethylenically unsaturated compound. Composition. General formula (A):

(A) wherein Q represents an organic functional residual functional group, X represents a direct bond, —CONH — Y 2 —, — S02NH — Y 2 — or —CH 2 NHCOCH 2 NH — Υ 2 —, Υ 2 represents an alkylene group or a aryl group which may also have a substituent. A group, Υ! represents an NH—or a Ο—, Ζ represents a hydroxy group, an alkoxy group, or a substituent of the formula (Ο: (as shown in the original formula (Ο) on page 4, but 'in η In the case of 1, Ζ may also be -ΝΗ -X - Q, Υ3 represents a ΝΗ- or a 0-, -10- 1287694 ^ and 1 independently represent a substituted or unsubstituted alkyl group and r2 may also be mutually Bonding to form a heterocyclic ring containing at least a nitrogen atom, m represents an integer of 1 to 6, and η represents an integer of 1 to 4. In the photosensitive black composition of the present invention, absorption of phthalic acid of carbon black Preferably, it is preferably 120 cc/100 g or less, and the secondary particle diameter of carbon black is preferably 20 to 50 nm. Further, according to the second aspect of the present invention, a black matrix substrate having a black matrix formed of the present luminescent black composition is provided. The average optical density of the color matrix is 1//m. The optical density of the dried film thickness is 3.0 or less. The third aspect of the invention provides a color filter for forming at least two color filter segments other than black on the matrix substrate of the present invention. DETAILED DESCRIPTION OF THE INVENTION First, the photosensitive black composition of the present invention will be described. The photosensitive black composition of the present invention a carbon black having a specific gravity of 50 to 200 m 2 /g, a dye represented by the above formula (Α), and an ethylenically unsaturated compound. The carbon black contained in the photosensitive black composition of the present invention is light-shielding. For black pigments and commercially available carbon blacks, examples are Mitsubishi Co., Ltd. #260, #25, #30, #32, #33, #44, #45, #45L, #47, #50, #52, MA7, MA8, MA100, MA100R, MA100S, MA230; Dijiasha Gonglintex L, Printex P, Plinx 30, Plint, or Ri dicarboxylic acid average 1 sense. Black is a good black philosophical derivative for the chemical stock 40, #, MAI 1 Division Pux 35 -11- 1287694, Plintex 40, Plintex 45, Printex 55, Plintex 60, Printex 300, Plettex 35 〇, Tehe 4, Tehei 350, Tehei 550, etc. Carbon black It may be used singly or in combination of two or more. In the case of carbon black, a specific surface area of 50 to 20 0 m 2 /g is used. When a carbon black having a specific surface area of less than 50 m 2 /g is used, a black matrix shape is caused. In the case of using carbon black which is larger than 200 m 2 /g, the dye derivative represented by the general formula (A) is excessively adsorbed in the carbon black, and in order to find each physical property, a large amount of the compound is obtained by the general formula (A). ) The necessity of the pigment derivative shown. In addition, in terms of sensitivity, it is preferable that the absorption amount of dibutyl phthalate (hereinafter referred to as "DBP") is 120 cc/100 g or less from the viewpoint of sensitivity, and the amount of DBP absorption must be reduced and Less is better. The DBP absorption amount can be measured by using an absorption meter (refer to Japanese Industrial Standard JIS K62 17-4). Further, the average primary particle diameter of carbon black is preferably 20 to 50 nm. It is difficult to obtain a high-concentration carbon black system having an average primary particle diameter of less than 20 nm, and it is difficult to obtain a photosensitive black composition having good long-term stability. When using a carbon black larger than 5 Οηπι, the black matrix shape is deteriorated. s reason. The content of the carbon black in the photosensitive black composition is preferably from 20 to 70% by weight, based on the solid content of the composition, and preferably from 30 to 60% by weight. When the content of the carbon black is less than 20% by weight, sufficient light-shielding property cannot be obtained, and when it is more than 7% by weight, it is difficult to obtain dispersion stability, and the sensitivity is lowered, and the formation of a black matrix becomes The possibility of difficulty. The dye derivative contained in the photosensitive black composition is subjected to the operation of dispersing carbon black in an ethylenically unsaturated compound as shown in the above formula (287). In the general formula (A), Q represents a residual functional group of the organic dye. Examples of the organic dye which provides the residual functional group q of the organic dye include an anthraquinone-based dye having an anthraquinone skeleton and a quinoxalinone-based dye having a quinolone skeleton. a ketone oxime dye, an isoindolinone dye having a heteroquinone @ 'full ketone I skeleton, a quinoline dye having a quinoline skeleton, and a diketopyrrolopyrrole dye having a diketopyrrolopyrrole skeleton An anthraquinone dye having a phenanthrene skeleton, an anthrone dye having an anthrone skeleton, an indigo dye having an indigo skeleton, a sulphur indigo dye having a sulphur indigo skeleton, a dioxazine dye having a dioxazine skeleton, and having a fluorene醌 之 之 醌 醌 醌 醌 、 、 、 、 、 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌a condensed polycyclic organic pigment such as a dansone dye or a metal complex, a benzimidazolone dye having a benzimidazolone skeleton, an insoluble azo dye, a condensed azo dye, or a soluble couple nitrogen It is a pigment or the like. Among these pigments, an anthraquinone-based dye, an anthraquinone-based dye, and a benzimidazolone-based dye are preferred. In the formula (A), X represents a direct bond, a CONH-Y2-, -S02NH-Y2-, or -CH2NHCOCH2NH-Y2-, wherein Y2 represents an alkyl group or an aryl group which may have a substituent. When a preferred example of ruthenium 2 is given, there are an alkyl group having 1 to 6 carbon atoms, a phenyl group or the like. In the formula (Α), Υι denotes a ΝΗ—or a 0—. In the formula (A), Z represents a hydroxyl group, an alkoxy group, or a formula (i) -13-1287694

Represents a substituent. However, in the case where η is 1, Z may also be -NH - X - Q. Where γ3 represents an NH or a 〇. The alkoxy group having 1 to 6 carbon atoms is preferred from the viewpoint of the hospitaloxy group represented by 2. In the formula (A) (also in the formula (i)), Ri and r2 each independently represent a substituted or unsubstituted alkyl group, or the core and r2 may be bonded to each other to form at least a nitrogen atom. Heterocyclic. The alkyl group represented by the formulas 1 and r2 is preferably an alkyl group of 1 to 6 carbon atoms. Further, in terms of the substituent of the alkyl group, alkoxy groups having a mercapto group and 1 to 6 carbon atoms are preferred. The heterocyclic ring in which R1 and R2 are bonded to each other to form a heterocyclic ring is preferably an imidazole group, an anthranylene group, a pyridyl group or a pyrrolidinyl group. In the formula (A) (also in the formula (i)), m represents an integer of 1 to 6. In the formula (A) (also in the formula (i)), n represents an integer of 1 to 4. In the case of the dye derivative represented by the formula (A), a dye derivative represented by the following general formulae (1) to (10) is exemplified. -14- 1287694

-15- 1287694

-16- 1287694 ester, diisopentyl hexa(meth)acrylate, and the like. Further, examples of the oligomer include epoxy (meth) acrylate, uric acid (meth) acrylate, and ester (meth) acrylate, and the photosensitive resin is exemplified by polyester or poly. A urethane, an epoxy resin, an acrylic resin, or the like is introduced into an ethylenically unsaturated double bond by an accepted method. The ethylenically unsaturated compound may be used singly or in combination of two or more. As the ethylenically unsaturated compound, trimethylolpropyl tris(meth)acrylate, isoamyl tris(meth)acrylate or diisopentyl hexa(meth)acrylate is preferred. The ethylenically unsaturated compound is preferably used in an amount of from 5% to 30% by weight based on the solid content of the composition. In the photosensitive black composition, when the composition is cured by ultraviolet irradiation to form a black matrix, a photopolymerization initiator is contained. As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyl-chlorobenzyl I, ethoxylated-chlorobenzidine I, 1 - (4-iso) are exemplified. Propyl phenyl)· 2 _ benzyl-2-methylpropan-1-one, 1-cyclohexyl phenyl ketone, 2-mercapto-2-dimethylamino-1-(4-morphin Acetophenone photopolymerization initiators such as butyl ketone; benzoin photopolymerization of benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl acetal Starting agent; diphenyl ketone, benzoin benzoic acid, methyl benzoyl benzoate, 4-phenyl diphenyl ketone, hydroxy diphenyl ketone, acrylated diphenyl ketone, 4-phenyl fluorenyl a diphenyl ketone photopolymerization initiator such as -4,-toluenediphenyl sulfide; thioxanthone, 2- chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, a thioxanthone photopolymerization initiator such as 4_diisopropylthioxanthone; 2,4,6-trichloro·s-trimethylene, 2-phenyl-4,6-bis(trichloromethyl)- Three-plowed, 2-(p-methoxyphenyl)-4,6--18- 1287694 bis(trichloromethyl)·all three tillage, 2-(p-tolyl)-4,6-double (three Methyl)--tris-trimium, 2-piperidin-4,6-bis(trichloromethyl)-all three-plowed, 2,4-bis(trichloromethyl)-6-styryl-three-plowed , 2-(naphthalen-1-indenyl)-4,6-bis(trichloromethyl)-all three tillage, 2-(4-methoxy-naphthalen-1-indenyl)-4,6-double (trichloromethyl)-all three tillage, 2,4-trichloromethyl-(piperidyl)-6-triazine, 2,4·trichloromethyl (4,-methoxystyryl)- 6-average three-tillage three-grain photopolymerization initiator; oxazole photopolymerization initiator, imidazole photopolymerization initiator, and the like. The photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably used in a proportion of 5% to 25% by weight of the solid content of the composition. Further, a sensitizer may be contained in the photosensitive black composition. Examples of the sensitizer include α-decyl decyl ester, decyl phosphine oxide, methyl phenyl acetate, benzyl ester, 9,10-phenanthrenequinone, anthracene, ethyl hydrazine, 4, 4' -Diethylisodiphenyl hydrazine, 3,3',4,4'-tetrakis(t-butylperoxycarboxy)diphenyl ketone, 4,4'-diethylaminodiphenyl ketone, and the like. These sensitizers can be used singly or in combination of two or more. The sensitizer is preferably used in a proportion of 3% to 60% by weight based on the weight of the photopolymerization initiator. Further, in the photosensitive black composition, since the composition is of an alkaline development type, an alkali-soluble resin may be contained. Further, the photosensitive black composition may contain a resin which does not have an alkali solubility together with an alkali-soluble resin for the purpose of imparting heat resistance or adhesion. Examples of the alkali-soluble resin include a (meth)acrylic copolymer or a styrene-maleic anhydride copolymer, a polyester resin having a carboxyl group, and the like. The alkali-soluble resin may be used in combination with two or more kinds of resins for various purposes such as heat resistance and solvent resistance of the coating film, and resistance to -19·1287694'. The black composition is preferably from 3 to 70% by weight, preferably from 5 to 60% by weight, based on the black component. When the content of the alkali-soluble resin is less than 3% by weight, the basic developability is lowered, and when it exceeds 70% by weight, the curability of the photosensitive black composition is lowered, or when the black matrix is used, the light-shielding property is lowered. . In the photosensitive black composition, a solvent may be contained in order to sufficiently disperse carbon black and form a black matrix having a desired film thickness. Examples of the solvent include cyclohexane, ethyl cyproterone, butyl cyproxil, acetic acid-^ 1-methoxy-2-propyl ester, diethylene glycol dimethyl ether, Ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl celecoxib, methyl-n-pentyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol , isopropanol, butanol, isobutyl ketone, petroleum solvent, and the like. Use these alone or in combination. The solvent is preferably used in a proportion of 60% to 95% of the total amount of the photosensitive black composition. In the photosensitive black composition, a chain transfer agent, a surfactant, a decane coupling agent, and other additives may be added for the purpose of improving coating properties, improving sensitivity, and improving adhesion. The photosensitive black composition can be obtained by mixing carbon black, a dye derivative represented by the formula (A), an ethylenically unsaturated compound, and, if necessary, a photopolymerization initiator, an alkali soluble resin, a solvent, and the like. The additive is produced by dispersion using various dispersing devices such as a three-roll honing machine, a two-roll honing machine, a sand mill, a kneader, and a honing machine. • 20- 1287694 Photosensitive black composition is a coarse particle of 5 // m or more, and a coarse particle of 1 // m or more by centrifugation, sintering filtration, membrane filtration, etc., with 0 · 5 // m The above is better for the removal of the coarser particles and the mixed ash. Next, a black matrix substrate will be described. The black matrix substrate is coated on a transparent substrate such as a glass plate, and a photosensitive black composition is applied by a coating method such as spin coating, slit coating, or roll coating, and then irradiated with an active energy ray from the coated surface side of the composition via a photomask, and impregnated. The development is carried out by spraying a developing solution in a solvent or an alkaline developing solution or by a sprayer or the like to remove the unirradiated portion, that is, the unhardened portion, and forming it by forming a black matrix of a desired shape. The film thickness of the photosensitive black composition is preferably in the range of 0.2 to 5 / zm (during drying), and is preferably in the range of 0.5 to 2 // m which is easy to obtain a balance between coatability and light shielding property. Further, the optical density of the dry film thickness of the average l//m black matrix is preferably 3.0 or more from the viewpoint of high light-shielding property. Although the optical density is preferably higher, it is desirable to be about 4.5 or less because it is difficult to obtain a hardened coating film when the active energy ray is ultraviolet light or visible light. As the alkaline developing solution, an aqueous solution such as sodium carbonate or sodium hydroxide can be used. An organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developing solution. Further, in order to enhance the exposure sensitivity by the active energy ray, after drying and drying the photosensitive black composition, a dry water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied to form - 21 - 1287694 After the film which is impaired by polymerization due to oxygen is prevented, the active energy ray is irradiated from the coated surface side of the composition. For active energy rays, electron beams, ultraviolet rays, and visible light of 400 to 50 Onm can be used. In terms of the radiation source of the electron beam irradiated from the coating surface side of the composition, a thermal electron ray gun, an electric radiation gun, or the like, and an ultraviolet ray and a visible light source (light source) of 4 Å to 00 nm may be used. 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 is used. Specifically, when it is a point light source, an ultrahigh pressure mercury lamp or a helium gas mercury lamp is often used because of the stable brightness. • Xin The active energy ray irradiated from the coated side of the composition can be set in a time range of 5 to 100 mJ*, but it is preferably 20 to 300 mJ which is easy to manage in engineering. Finally, the color filter will be explained. The color filter is attached to the black matrix substrate to form a color filter segment having a color other than black and having two colors. The color of the filter segment can be selected from blue, green, red, cyan, yellow, magenta, orange, purple, etc. 2~6 colors. It is also possible to form color filter segments having different concentrations from the colors of the same color system. · The method of forming the color filter segment on the black matrix substrate includes a gravure printing method, a negative letter printing method, a stencil printing method, and a light using a solvent developing type or an alkaline developing type coloring resist. A lithography method, an electrodeposition method of forming a color material on a transparent conductive film by electrophoretic electrophoretic deposition of a colloidal particle, and a transfer method of transferring a color filter layer layer previously formed on a surface of a transfer substrate on a black matrix substrate Wait. Since the printing method can be patterned only by repeated printing and drying, the manufacturing method of the filtration-22-1287694 colorator is low in cost and excellent in mass productivity. Furthermore, the printing of high-precision and smooth micro-patterns has been made due to the development of printing technology. In the case where the color former is manufactured by the printing method, the ink fluidity on the printing machine is controlled, and the ink viscosity of the agent or the body pigment can be adjusted. The light lithography using a solvent developing type or an alkaline developing type coloring resist is applied to a black matrix substrate, and the coloring resist is applied by spin coating, slit coating, and roll coating, and then ultraviolet light is passed through the mask. After rinsing the unexposed portion with a solvent or an alkaline developing solution and forming the desired case, the same operation is repeated for the other colors to manufacture the color filter. The manufacturing method can produce a color filter that is more precise than the above printing method. The coloring resist is a resin which is prepared by replacing the carbon black of the photosensitive black composition of the present invention with a coloring agent of a desired color, and does not necessarily contain the dye derivative represented by the formula (A). In the coloring agent, a coloring agent excellent in various resistances can be used. However, from the viewpoint of light resistance and heat resistance and solvent resistance, it is preferred to use a pigment, and it is particularly preferable to use an organic pigment from the viewpoint of light absorption energy. A specific example of the color represented by the color indicator (CI). Yellow pigments are exemplified by pigment yellows 12, 13, 14, 20, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, 173 Wait. For the orange coloring agent, pigment oranges 13, 31, 36, 38, 42, 43, 51, 55, 59, 61, 64, 65, etc. are mentioned. For the red and magenta coloring agents, there are pigment red 9,97, and the fine dispersion method that can be advanced, and the method of exposure, such as coating, is also included, the sex or the number is large, 24 139 40, &gt; 122 - 23- 1287694, 123, 144, 149, 166, 168, 177, 190, 192, 215, 216, 224, 254, 255, etc., purple coloring agent, given pigment purple 19, 23, 29, 32, 33, 36, 37, 38, etc. For blue and cyan colorants, there are pigment blue 15 (15, 15: 1, 15:2, 15:3, 15:4, 15:6, etc.), 21, 22, 60, 64 green colorants. In terms of pigment greens 7, 10, 36, 47, etc. These colorants can be used in combination of two types of ♦ φ in order to obtain a desired color. - Hereinafter, the present invention will be specifically described based on examples. Also, in the examples, ''" and "%" are used to mean "parts by weight" and "% by weight". &lt;Preparation of Acrylic Resin Solution&gt; 800 parts of cyclohexane was placed in a reaction vessel, nitrogen gas was injected into the vessel and heated to 100 ° C, and 60.0 parts of methacrylic acid and 65.0 parts were added dropwise at the same temperature for 1 hour. a mixture of butyl methacrylate, 65.5% methyl methacrylate, and 10.0 parts of azobisisoacrylonitrile, further dissolved in 5 Torr after 5 hours of TC reaction. ο Part of azobisisoacrylonitrile 'into one 〇 (TC continued to react for 1 hour to synthesize the resin solution. After cooling to room temperature, sample about 2g of resin solution and heat dry at 180 °C for 20 minutes, determine non The volatile matter was prepared by adding cyclohexane to a resin solution previously synthesized to have a nonvolatile content of 20% to prepare an acrylic resin solution. Further, the weight average molecular weight of the acrylic resin was 40,000. &lt;Modulation of carbon black dispersion&gt; -24- 1287694 The carbon black and pigment derivative described in the following examples and comparative examples were uniformly mixed with 24 parts of the above acrylic resin solution and 40 parts of cyclohexane, using 1 mm diameter glass beads and a sanding machine for 5 hours. Disperse to modulate carbon Black dispersion. Table 1 shows the carbon black enthalpy used in the examples and comparative examples. Table 1 Carbon black average primary particle size DBP absorption (cc/lOOg) Specific surface basis (m2/g) #40 24nm 110 115 # 260 40nm 74 79 MA77 23nm 68 130 Black beads 800 17nm 68 210 MONARCH 120 75nm 71 25

Further, the pigment derivative 0 pigment derivative 1 used in the following examples and comparative examples is shown below.

-25- 1287694 Pigment Derivative 2

CuPfc (CuPc pigment derivative 3 一

Μ_聊频· Resveratrol Residual Functional Group) Η Η

[Example 1] I • Carbon black ("40" manufactured by Mitsubishi Chemical Corporation) 1〇·〇份•Pigment derivative 1 〇. 5 parts [Example 2] • Carbon black ("360" by Mitsubishi Chemical Corporation) 8.0 Parts • Pigment Derivatives 2 〇. 3 parts [Example 3] • Carbon black ("Mt 77" manufactured by Mitsubishi Chemical Corporation) 12.0 parts • Pigment derivatives 3 1 . 〇 [Comparative Example 1] • Carbon black (manufactured by CABOT Co., Ltd.) Black beads 800") 8.0 parts • Pigment derivatives 1 〇 · 2 parts [Comparative Example 2] • Carbon black ("MONARCH 120" manufactured by CABOT Co., Ltd.) 1 〇·〇份•Pigment derivatives 2 0.8 parts -26- 1287694 &lt;; Long-term stability evaluation of carbon black dispersion&gt; The long-term stability was evaluated by comparing the viscosity of the carbon black dispersion after dispersion to the viscosity after storage at 40 ° C for 7 days. The results are shown in Table 2. &lt;Preparation of photosensitive black composition&gt; 60 parts of carbon black dispersion and 4.3 parts of trimethoxypropyl triacrylate ("Nippon Chemical Co., Ltd.") were uniformly stirred and mixed, and 1.4 parts of photopolymerization was carried out. After the starter ("Erga Qiuya 907" made by Ciba Geji Co., Ltd.), 2 parts of sensitizer ("Eb-F" from Baotu Valley Chemical Co., Ltd.), and 21.6 parts of cyclohexane, The photosensitive black composition was prepared by filtering with a filter of 1 // m. With respect to the obtained photosensitive black composition, sensitivity, black matrix shape, glass adhesion, and optical density were evaluated by the following methods. The results are shown in Table 2. 感 [Sensitivity] After coating the photosensitive black composition on a glass substrate of 10 cm x 10 cm by spin coating, a dry film thickness of 1 // m was prepared by drying at 70 ° C for 15 minutes. Coating film. Then, an ultra-high pressure mercury lamp was used to expose 1 〇〇mJ/cm2 of ultraviolet light through a reticle. Next, after the unexposed portion was sprayed with an aqueous solution of sodium carbonate, the unexposed portion was washed with ion-exchanged water, and the film thickness after development of the exposed portion was measured. The results are shown in Table 2. [Black matrix shape] A black matrix substrate was produced in the above manner. The evaluation was made by observing the linearity of the shape of the black matrix formed in the exposed portion by an optical microscope. The results are shown in Table 2. [Glass Adhesion] -27- 1287694 A photosensitive black composition was applied onto a glass substrate by the above method, and an ultraviolet ray of 300 m J / c m 2 was exposed through a photomask using an ultrahigh pressure mercury lamp. Next, after the unexposed portion was developed using an aqueous sodium carbonate solution, it was washed with ion-exchanged water and the unexposed portion was removed, and heated at 23 ° C for 1 hour. Next, the glass adhesion of the coating film was evaluated by following the TIS K5400 checkerboard adhesion test method, and the number of peelings in the board of 1 〇 棋 was counted. The results are shown in Table 2. [Optical Concentration] After the photosensitive black composition was applied to the glass substrate by the above method, it was heated at 230 ° C for 1 hour. The optical density (0D) of the thus obtained photosensitive black composition-coated substrate was measured by a Markbes concentration meter (GRETAG D200-II) to determine the optical density in the film thickness. The results are shown in Table 2. Table 2: Long-term stability of carbon black dispersion carbon black dispersion. Black matrix shape glass adhesion optical density Example 1 〇 △ 〇〇 3.6 / β m Example 2 Ο 〇 Δ 〇 3.6 / β m Example 3 〇〇 Ο 〇 3.8 / β m Comparative Example 1 XXXX 2.9/ β m Comparative Example 2 △ XXX 3.5/ ^ m In Table 2, long-term stability: 〇; viscosity after storage at 7 ° C for 7 7 7 viscosity after production ; 1 · 3 △ ; 1.3$ at 70 ° C after 7 days of viscosity / -28 - 1287694 viscosity afterwards &lt; 1. 8 X; after 7 保存 storage at 40 ° C viscosity / viscosity after fabrication ^ 1.8 sensitivity: 〇; film thickness g〇.95//m △; 0.90/zmS film thickness &lt; 0.95ym x ; film thickness &lt;0.90 &quot;m black matrix shape: 〇; good linearity △: partial straight line Good sex X; poor linearity of glass: 〇; number of strips of checkerboard &lt; 3 △; number of strips of 3 S board nets &lt; 10 X; number of strips of checkerboard net ^ 10 As shown in Table 2, in the case where carbon black having a specific surface area of 50 to 200 m 2 /g was not used, long-term stability and feeling of the carbon black dispersion could not be obtained. , Leading to poor shape of the black matrix, peeling becomes adhesion can not be obtained. On the other hand, when carbon black having a specific surface area of 50 to 200 m 2 /g is used, the carbon black dispersion has good long-term stability and excellent sensitivity, and the black matrix has a good shape and good adhesion. As described above, with the present invention, carbon black can be stabilized and divided at a high concentration. Moreover, the photosensitive black composition of the present invention achieves high sensitivity by long-term stability and stupidity, and the photosensitive black composition of the present invention has good black matrix shape, glass adhesion, and optical density. A black matrix substrate that constitutes the performance required for a black matrix. (S) Schematic description: None. -29-

Claims (1)

1287694 The Year of the Pasture Factory is repaired in the month (3⁄4 is replacing the page I No. 93 1 1 7 5 95 "Photosensitive black composition, using its black matrix substrate and color filter" patent case (amended on May 19, 2006) X. Patent application scope: 1 · A photosensitive black composition containing: (a) carbon black having a specific surface area of 50 to 2 〇〇m 2 /g, and the average primary particle diameter of the carbon black is 20 to 50 nm (b) a pigment derivative represented by the formula (A), (wherein Q represents an organic pigment residue, X represents a direct bond, -CONH-Y2-, -S02NH-Y2-, or a CH2NHCOCH2NH-Y2-, and Y2 represents an alkylene or aryl group which may have a substituent, Υ! Representing a hydrazine, or a hydrazine, Ζ represents a hydroxy group, an alkoxy group, or a substituent represented by the formula (i), However, in the case where η is 1, Z may also be an NH - X - Q, Υ3 represents a ΝΗ- or -〇-, and 1287694 l and r2 each independently represent a substituted or unsubstituted oxime, or Ri and R2 may also be bonded to each other to form a heterocyclic ring containing at least a nitrogen atom, m represents an integer of 1 to 6, and η represents an integer of 1 to 4; and (c) an ethylenically unsaturated compound in which a composition is used The carbon black is contained in a ratio of 20 to 70% by weight based on the total weight of the solid component. 2. The photosensitive black composition of claim 1, wherein the carbon black dibutyl phthalate has an absorption of 120 cc/100 g or less. 3. The photosensitive black composition according to the first aspect of the invention, wherein the pigment derivative represented by the formula (A) is contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the carbon black. 4. The photosensitive black composition of claim 3, which is an ethylenically unsaturated compound containing a proportion of 5% to 30% by weight of the solid content of the composition. A black matrix substrate comprising a black matrix formed of the photosensitive black composition according to any one of claims 1 to 4. 6. The black matrix substrate of claim 5, wherein the optical density of the dry film thickness of the average 1 // m black matrix is 3.0 or more. A color filter in which a color filter segment of at least two colors other than black is formed as in the black matrix substrate of claim 5 of the patent application. • 2 -