TWI332519B - Black composition and process for manufacturing the same - Google Patents

Description

1332519 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a black composition containing carbon black (car bon b 1 ack ). The present invention also relates to a method of producing a black composition containing carbon black. Further, the present invention relates to a color filter formed using the above black composition. [Prior Art] In the % color filter, a so-called black matrix (black _Ηχ) is generally formed between the filter segments of red (R), green (G), and blue (B) (the following article "Study" ) A grid-like black pattern. The function of the BM is to block the light from the backlight to improve the contrast and prevent the color mixture of adjacent pixels. It is a chemical conversion method. At present, it is developing to use gold such as chrome on a transparent substrate, #成化(4) jobs from steamed materials, and then by the micro-steps and money step H >

Method V is a method in which a fine pattern is formed by Fenbertian Mountain (a black component such as metal BM, & black is dispersed in a resin material, and is printed by a color method.

law). The method of forming a 微 次 ( ( ( ( ( ( ( ( ( ( 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂From the point of view of equipment cost, it is difficult to use the metal-like network in the (four) ❹ 歧 大型 大型 大型 大型 。 。 。 。 。 。 。 。 。 。 。 。 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Opinions and viewpoints of 'in recent years, 'Metal Metal BM' is the focus of (10) (10) and environmental issues. 318764 5 1332519 However, 'Resin BM virtual gold eyebrow RM phase μ-, Shi · "- W _) low The light-shielding property is low (the optical density is low = that is, the metal M is generally thicker than 臈.) to 1 is the desired light-shielding property 'relative to this' resin M if you want to get fish. It is necessary to make the film thickness thicker. In addition, the lower the shade of the tree (4), the thicker the film thickness must be. When the color light-emitting sheet is made, the light is not leaked, and the enamel is formed by overlapping the adjacent biliary layer. In the case of low fat ΒΜ, the difference between the overlap of μ and the layer becomes larger, resulting in a partial disturbance of the I I The problem of the liquid crystal alignment is to reduce the display quality. ^ I j In this background, resin enamel is seeking high light-shielding property. The early film thickness has a high 0D value. For example, a printing method, a lithography method, a method of forming a ruthenium by a printing method, a method of forming a pattern on a substrate by using a convex plate, or a pattern by a gravure, and a co-printing (Manket), a same-substrate A method of repeatedly transferring a plurality of patterns. However, the printing step is short, but the oil from the brush to the substrate (four) printing step, or the printing from the printing plate to the offset printing or from the substrate to the substrate. When the pull/ ktringness is generated, the linearity of the pattern is deteriorated, and the shape of the pattern is deteriorated. Therefore, in general, there is no such method of adoption. . In the first aspect of the invention, in order to improve the light-shielding property of the resin BM and to reduce the drop, the content of the light-shielding component such as carbon black in the composition is increased. However, in the method in which the content of the light-shielding component is increased, there is a problem that the stability of the composition is deteriorated, etc., which is 318,764. In order to make the BB's light-shielding property, it is recommended to use two kinds of shading materials and use the 0D value between h. That is, by means of the average grain protection of the magnetic force of the thousand rituals of the small carbon black w 仫 仫 仫 仫 奴 , , , , , , , , , , 提高 提高 : : : : : : : : : : : : : : : In the case of 'shading & α ^ , for example, Japanese Laid-Open Patent Publication No. Hei 9-133806, Japanese Laid-Open Patent Publication No. Hei 9-279-82 No. #"报,日本特平平1 1-80584 That is, a special black resin composition of No. 9-1338〇6 of Japan, which contains at least one kind of ψ ^ ^ ^ 2 kinds of different average particle diameters A carbon, a, and a photosensitive resin in which an average particle diameter of a 10 η type of stone anti-black is 40 to 130 nm. The average particle size of another carbon black is preferably 135 to 500 nm. Further, in the SI 2 publication, It is disclosed that the black paint composition comprises a light-shielding material and a polymer material, and the light-shielding material is a powder particle having a distribution of = (for example, carbon black), wherein the complex particle size distribution is preferably determined by a particle diameter of 5 Gnm or more. The large particle size distribution of the average particle size is composed of a (four) diameter distribution of the average particle size of the smaller diameter. Further, 曰本特开平u_8〇584 584 discloses that no black resist pattern is formed: ..., : is coated with a resin, and contains blacks having an average-minor particle diameter of at least 2 - more than one species. In Japanese Unexamined Patent Publication No. 584, the above-mentioned slave black is preferably one carbon black having an average primary particle diameter of 1 〇 to another carbon black having an average-secondary particle diameter of 45 to 300 nm. The average primary particle size difference is 3 〇 nm. The black and color composition contains carbon black 平均 with an average primary particle diameter of more than 4 犄, and there are defects such as opacity from the viewpoint of opacity. The difference between 318764 and 1332519 is 5 nm or more; and the black composition does not contain carbon black having an average primary particle diameter exceeding 40 nm. The black composition using individual carbon black has the tendency shown below. The black composition of (a) carbon black having an average primary particle diameter of 8 to 2 〇 nm alone is used in comparison with the black composition of carbon black having the same average weight and larger secondary particle diameter. The number of carbon black particles is large, which is advantageous from the viewpoint of light blocking property. However, due to high light blocking property, photocurability is deteriorated. Furthermore, the carbon black is difficult to be stably dispersed, and it is easy to introduce the problem of the black component after the development of the black component (or the "baseboard contamination"). On the other hand, (a2) a black composition of carbon black having an average primary particle diameter of 21 to 4 Å is used alone, as compared with a black composition of carbon black having an average primary particle diameter of the same weight alone. The number of carbon black particles per unit volume is advantageous in terms of photocurability, but the light blocking property is insufficient. Further, when the viscosity is high, it is difficult to modulate the black composition. Further, a black composition of carbon black having an average primary particle diameter of more than 40 nm is used, and a black composition of carbon black having an average primary particle diameter of 4 〇 (10) of the same weight is used: compared with the number of carbon black particles per unit volume. Less, although σ is advantageous in terms of light hardening It, however, the shape of light blocking and black matrix (especially linearity) is insufficient. (al) carbon black and 5, using an average primary particle diameter of 1 〇 to 18 (10) Carbon black is preferred, and it is more suitable to use carbon to the specific surface area. = When the surface area is less than 200~ carbon black, there is a tendency to cause the black matrix to be deteriorated and the adhesion is lowered, and the ratio is used. Large surface area 318764 10 1332519 2 : Vg carbon black 'has a tendency to stabilize the dispersion of carbon black. It is suitable for carbon black which has an average-minor particle size of less than 8 nm. It is suitable for (al) carbon black. 'U2) Carbon black is preferably used with an average primary particle size of $ & to black, and more preferably has a specific surface area of 4 to 6 Å. Reverse = carbon black having a specific surface area of less than 4 〇 mVg When there is a tendency to cause a decrease in color and a decrease in adhesion, the use ratio table When it is larger than carbon black, there is a tendency that the carbon black shirt is difficult to disperse. ' Further, if (al) carbon black and (a2) carbon black average - subgranules up to 5 nm, then (al) carbon black and (al) A2) When carbon black is used in combination, it is impossible to return the light-shielding property, and when the black composition is stored for a predetermined period of time, there is almost no change in the development speed or line width change. The method of the average primary particle size of black is obtained. The team... The 100% substance is diluted with the solvent contained in the black composition. (4) Wj dilution. The dilution was then air-dried on a simple table. The carbon black obtained was photographed with several fields of view using an electron microscope to obtain a photograph of the number:. The maximum particle size of about 2 to 3 carbon blacks is measured, and the average values of the measured values are averaged, and the average primary particle diameter is obtained. Regarding the inclusion of two kinds of color compositions, first, the particle size distribution based on the number of carbon j bodies contained in the black composition was determined. Then, in more than two kinds of carbon: each particle size distribution is taken as a normal distribution, from the shape of the particle size distribution and the peak branch, / 'according to the pre-specified Gauss function (Gauss function), the curve is fitted (curve_f i 11 i ng) 'And determine the distribution function. From the parameters of the distribution function of 318764 11 1332519, the average particle size of each carbon black is obtained. The average primary particle size usually represents the first decimal place as a rounded value (nm). The black composition of the present invention is characterized by comprising (al) carbon black having an average primary particle diameter of 8 to 20 nm and (a2) carbon black having an average primary particle diameter of 21 to 40 nm, the (al) and the (al) The difference in average primary particle diameter of a2) is 5 nm or more; and the black composition does not contain carbon black having an average primary particle diameter exceeding 40 nm. Such a black composition is preferably obtained by mixing (al) carbon black having an average primary particle diameter of 8 to 20 nm with (a2) carbon black having an average primary particle diameter of 21 to 40 nm, wherein 1) The difference from the average primary particle diameter of the (a2) is 5 nm or more. At this time, carbon black having an average primary particle diameter of more than 40 nm was not mixed. The average primary particle diameter of the carbon black before mixing can also be measured by the same method as described above using an electron microscope. (al) Carbon black having an average primary particle diameter of 8 to 20 nm and (a2) carbon black having an average primary particle diameter of 21 to 40 nro, and commercially available carbon black may also be used. (al) an average black particle size of 8 to 20 nm, which may be, for example, MONARCH of φ CABOT, or BLACK PERLS (1400, 1300, 1100, 1 000, 900, 880, 800, 700), VULCAN ( P, 9A32), manufactured by Mitsubishi Chemical # (2700B, 2650, 2600, 2450B, 2400B, 2350, 2300, 1 000, 990, 980, 970, 960, 950, 900, 850), MCF: 88, MA600, DEGUSSA Color Black (FW2000, FW2, FW2V, FWbFW18, S170, S160), Special Black (6, 5), Printex (95, 90, 85, 80, 75, 40, 60), SEAST (9H) SAF-HS, 9 SAF), Asahi Carbon Asahi #80, Columbian · Carbon ROYAL SPECTRA, NEO SPECTRA MARK (I and II), NEO SPECTRA AG, 12 318764 1332519

SUPERBA (ΝΕΟ MK III), SPECT SPECTRA MARK I ‘V, RAVEN » ‘ (5000, 7000, 5750, 5250, 3500, 3200, 2000, 1500), CONDUCTEX (40-220, SC), RAVEN C BEADS, etc. Among them, MONARCHC1100, 800) or BLACK PERLS (1100, .800) made by CABOT, PrinteX 95 made by DEGUSSA, #850 made by Mitsubishi Chemical is preferred, and PrinteX made by CABOT MONARCH 1100 or DEGUSSA is used. 95 is especially good. (al) Carbon black may be used alone or in combination of 2' or more.

(a2) carbon black having an average particle diameter of 21 to 40 nm, which may be, for example, VULCAN (XC72R, XC72), MOGUL L, BLACK PEARLS (L, 570, 520, 490, 480, 470, 460, CABOT) 450, 430, 420, 410), REGAL (660R, 660, 500R, 330R, 330, 300R, 250R, 250, 99R, 991), ELFTEX (5, 8, 12, PELLETS 115), manufactured by Mitsubishi Chemical Corporation ( 77, 7, 8, U, 100, 100R, 100S, 230, 200RB, 14), #(750B, 650B, 52, 50, 47, 45, 45L, 44, 40, 33, φ 32, 30, 95, 85, 260, 3230B, 3350B), CF9, DEGUSSA Special Black (4, 4A, 550, 350), PrinteX (150T, U, V, 140U, 140V, 55, 45, P, L6, L, 300, 30, ES23, 3, ES22, 35, XE2), NIPex35, East China Sea carbon SEAST [6ISAF, 600ISAF-LS, 5H-IISAF-HS, KH (N339), 3H HAF-HS, NH * (N351), 3 HAF, 3M, N LI-HAF, 300 HAF-LS, 116 MAF], Asahi's Asahi #75, Asahi #70 (-IH, -IN, -L), Asahi HS-500, Asahi F-200, RAVEN made by Colombian.Carbon (1 255, 1250, 1200, 1170, 1 040, 1035, 1030, BEADS, 1020, 1000, 890POWDWE, 13 318764 1332519 890POWDER, 850, 825BEADS), CONDUCTEX (97.5BEADS, • 900BEADS), etc. Among them, REGAL (300R, 250R, 250, 99R, 991) made by CABOT, ΜΑ (7, 1 Bu 100R), #(47, 45, 45L) made by Mitsubishi Chemical, PrinteX 55 and NIPex35 made by DEGUSSA It is better to use #47 from Mitsubishi Chemical, REGAL 250R from CABOT, printex 55 and NIPex35 from DEGUSSA. (a2) The carbon black may be used singly or in combination of two or more. Black, the weight ratio of (al) carbon black to (a2) carbon black contained in the composition, preferably (al) / (a2) = l / 3 to 1 / 30, and 1/3 to 1 /10 is better. When (al)/(a2) exceeds 1/3, that is, when (ai) is large, the stability of carbon black tends to become difficult. On the other hand, when (al)/(a2) is less than 1/30, that is, when (al) is less, when (ai) carbon black and (a2) carbon black are used together, it is impossible to expect to exhibit opacity and The tendency of the above-described black composition to have a stability effect. And the total amount of '(al) carbon black and (a2) carbon black is based on the total weight of the black component of the solid content (1% by weight), preferably 4% to weight%. 45 to 55 wt% is more preferred. Carbon black is usually present in aggregates where primary particles agglomerate each other. 'Aggregates can be conceptually used as a metaphor for grape bunches. The degree of development of the aggregate is referred to as a structure, and the height of the structure has an influence on dispersibility, coloring power, viscosity, and the like. In the present invention, by dry-pulverizing carbon black, a high-structure aggregate formed by agglomeration of primary particles of carbon black can be cut and fragmented, and the aggregates can be cleaved to obtain a low-structure aggregate. 14 318764 I332519 For the equipment used for dry pulverization of carbon black, use media such as grinders, ball mills, vibrating mills, etc., to use non-media such as pin mill, honing machine, MICROS Devices, etc. Further, the temperature at the time of dry pulverization is not particularly limited. However, from (10) to not, the pulverization time can be arbitrarily set. Although the stalk (al) m (a2) carbon black may be separately dried and pulverized and then mixed, it is preferable from the viewpoint of production efficiency that (a • carbon black is mixed and then dry pulverized. The (6) dye derivative contained in the black composition of the present invention is a compound in which a substituent is introduced into an organic dye. The organic dye includes a naphthalene which is generally not called a pigment, in addition to a compound generally called a dye. A pale yellow aromatic polycyclic compound, etc. The dye derivative is preferably one represented by the following formula (1). The dye derivative represented by the formula (1) is, for example, the following formula to (11) Derivative pigment derivative. _ General formula (1)

Q-ί~~X-Η [wherein Q represents an organic dye residue; X represents a direct bond, -CONH-Υ2-, -SO2NH-Y2- or _ch2NHCOCH2 NH-Y2- (where Y2 represents The alkyl group of the substituent may have a substituted aryl group of 318764 15 1332519 group; ., Υι represents ~NH- or; Z, when η is 1, represents a trans group, a methoxy group, and the following formula a substituent, -NH~X-Q (wherein Q and X are as defined above), and when η is 2 to 4, it represents a hydroxyl group, an alkoxy group, and a substituent represented by the following formula: _Υ3ϋ< R2 1 (wherein, Y3 represents -NH- or 〇_; m, R1 and Rz are as defined below." L and R2 each independently represent an alkyl group which may have a substituent, and L may be bonded to each other to form at least a heterocyclic ring containing a nitrogen atom; 2 Π1 represents an integer of 1 to 6; η represents an integer of 1 to 4], and a stretching group is, for example, a methylene group (such as a methyle column such as a strepto group or the like. The oxy group, the aryl group, and the aryl group are, for example, an f group, an ethoxy group, etc. an alkyl group, an ethyl group or the like, and the substituents of the groups are, for example,

318764 16 1332519 〇-(

Q-N

H

Q- JOgNH-

Q— -CH2NHCOCH2NH 1332519

-^ΝΗ〇-2 γ 'V (9) Τη V. (10) Q- — /Rl -3〇2ΝΗ^〇-Νγ^γ-Ν-(〇Η2^^ ^ R2

NH

HNK^S—Q

The organic dye constituting the dye derivative represented by the formula (1) is, for example, a phthalocyanine system, a quinacridone system, or a sputum ketone ketone (^11111 & 〇1^(1〇) 116〇111110116), 11 ketone (isoindolinone), quinone (quinophthalone), diketone mouth ratio of 17 and 0 to 0 each, perylene, perynone Department, indigo system, thioindigo system, dioxazine system, anthraquinone system, pyranthrone system, anthranthrone system, ketone Condensed polycyclic organic pigments such as (f lavanthrone), indanthrone, and metal complex, benzimidazolone, insoluble azo, fused azo, soluble azo, etc. Pigment or dye, light yellow aromatic polycyclic compound such as naphthalene. 18 318764 1332519 'Two or more (b) pigment derivatives may be used alone or in combination. (b) The amount of pigment derivative used' Based on the solid weight fraction of the black composition, U00 weight (four), 0.05 to 2 〇 % is preferably - more preferably 0.5 to 1% by weight, and when the content of the dye derivative is less than -% by weight of hydrazine, there is a tendency that the effect of dispersing carbon black is not sufficiently exhibited, and at 20% by weight There is a tendency that the dispersion of carbon black becomes unstable. When the (al) carbon black and (a2) carbon black are dry-pulverized, (b) the pigment derivative may be in U1) carbon black and (a2) carbon. Black dry crushed and added. Alternatively, the (b) pigment derivative may be mixed with (al) carbon black and (a2) carbon black, followed by dry pulverization, or when (al) carbon black and (a2) carbon black are dry pulverized ( b) Pigment derivatives. From the viewpoint of more favorable dispersion of carbon black, low viscosity and increased adhesion, it is preferred to add (b) a pigment derivative after dry pulverization of (al) carbon black and (a2) carbon black. Further, the (c) resin contained in the black composition of the present invention can be used, for example, with butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, vaporized polypropylene, polychlorinated chlorine. Ethylene, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin , thermoplastic resin such as carbonized resin, cellulose, polyethylene, polybutadiene, polyimide resin, epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, modified by rosin A thermosetting resin such as a fumaric acid resin, a melamine resin, a urea resin, or an alkali resin. In the (c) resin contained in the black composition, the resin represented by the following formula (12) is used from the viewpoint of improving the development property and reducing the film from 318764 19 1332519 4f -^ to facilitate the southing. The amount of the resin is preferably from 3% to 3% by weight, more preferably from 1 to 20% by weight based on the total amount of the resin. Formula (12) (HOOC kRl4c〇〇-R3—c〇〇4^ra. (wherein Ri represents a tetravalent aromatic tetracarboxylic acid compound residue; R2 represents a sterol residue; and R3 represents a lactone; Residue; m represents 2 or 3; n represents an integer of 1 to 5 〇, and t represents (4-π〇). An acid dianhydride compound providing an aromatic tetracarboxylic acid residue, for example, pyromellitic dianhydride , 3, 3', 4, 4,-biphenyltetraphthalic acid dianhydride, 9, 9, 贰 (3, 4 - dicarboxyphenyl) phthalic anhydride, 2, 3, 6, 7 - naphthalene tetradecanoic acid Di-anhydride, ethylene glycol trimellitic anhydride. Monohydric alcohol, for example, dodecanol, n-stearyl alcohol, isostearyl alcohol, glycerol di(methacrylate), pentaerythritol triacrylate, 2 B Further, the lactone is, for example, keto-lactone, cumene lactone, ε-caprolactone substituted with a ruthenium group. (c) The weight average molecular weight of the resin is from 丨^(10) to 1〇〇. , 〇〇〇 is better, and 2,000 to 50,000 is more preferable. If it is less than 1 〇〇〇, it will be sticky and not enough film strength, and if it exceeds 1 〇 〇 stomach, 〇〇〇 'There is viscosity increase, the coating is reduced In the present invention, the weight average molecular weight means a weight average molecular weight by gel permeation chromatography (ge, permeation chromatography: ^, ·) and polystyrene. (c) Resin can be used alone Depending on the solid content of the black composition (100% by weight), the ratio of the black composition (100% by weight) to 5 cc. When the amount is more than 50% by weight and the amount is less than 5% by weight, the coating film tends to be brittle, and when it is 60% by weight, the development property tends to be lowered in the case of lithography. In the black composition of 1-methoxy-2-propyl acetate, in order to fully disperse the carbon black, a color matrix is formed, and the solvent is contained in (4) solvent. The solvent may be cyclohexanone or ethylene. Alcohol ethyl hydrazine acetate (ethylc (1). (6) heart as D I fine 7 private one" 』 glycol methyl ether, diethylene glycol diethyl, ethyl benzene, ethylene glycol diethyl hydrazine, Propylene glycol monomethyl acetic acid vinegar, xylene, ethylene glycol wire (also known as ethyl cellulose), methyl • n-amyl ketone, propylene glycol monomethyl ether Toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropanol, butanol, isobutyl ketone, petroleum-based solvent, these may be used alone or in combination. One (4) the amount of solvent ' It is preferably 15 to 35 (10)% by weight, more preferably 250 to 2% by weight, based on the total weight of the solid content of the black composition (10), and the black composition of the present invention may further contain (e) _(ethyienic) unsaturated compound. The (4) material and the unsaturated compound contained in the black composition of the present invention are one having one or two or more ethylenically unsaturated double bonds in one molecule, and a monomer may be used. , oligomer, photosensitive resin. The monomer is, for example, (meth)propanoid 2-acetoxyacetate, 2-hydroxypropyl (meth)propionate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylic acid. Ester, trimethylolpropane tri(indenyl) acrylate, pentaerythritol tris(meth) propylene (tetra), dipentaerythritol hexa(methyl) propyl vinegar, and the like. Further, oligomer 318764 21 丄:>:>/;) 丄y -t can be (meth)acrylic acid acetal, amino carboxylic acid vinegar (mercapto) acrylonitrile, ester (曱Base) acrylate and the like. As the photosensitive resin, a photosensitive resin obtained by transferring an ethylenically unsaturated bond to a resin by a known method can be used. For example, a linear indicole having a reactive substituent such as a group, a slow group or an amine group present in the tree-salt can be used, and an isocyanate group can be used. a reaction of a (meth)acrylic acid compound or a cinnamic acid with a substituent such as a group or an epoxy group, and a photocrosslinkable group such as a (meth)acrylic group or a styrene group is introduced into the linear polymer. The moon of the tree. Further, a linear polymer containing an acid anhydride group such as a styrene-maleic anhydride copolymer or an α 埽L maleic anhydride copolymer, and a hydroxyl group such as a hydroxyalkyl (meth) acrylate may be used. A linear polymer obtained by semi-esterifying an acrylic compound. (e) The ethylenically unsaturated compound may be used singly or in combination of two or more. (e) The amount of the ethylenically unsaturated compound to be used is preferably from 5 to 3% by weight based on the total weight of the solid composition of the black composition (1% by weight), and is photohardenable and From the viewpoint of light imaging, it is particularly preferably from 7 to 28% by weight in an amount of from 10 to 25% by weight. When the content of the ethylenically unsaturated compound is more than 30% by weight, the linearity of the pattern shape of BM may occur, and the cross-sectional shape tends to be poor. When the content is less than 5% by weight, the sensitivity is lowered and the photocurability is insufficient. . The y. Preferably, it is preferably from 0.15 to 〇. 65, preferably from 至. 20 to 0.60. 22 318764 1332519 - Right Μ / P does not reach 〇. 1 〇, the sensitivity is reduced, if it exceeds 〇. The resulting black matrix has a linear shape of the pattern shape and the profile shape is not good, or sticky, etc. situation. ♦ The black composition of the present invention can further contain (f) a photopolymerization initiator. For the photopolymerization initiator, for example, acetoxiphenene-based photopolymerization initiator, benzoin can be used. a photopolymerization initiator, a benzophenone photopolymerization initiator, a thioxanthone (a fluorene photopolymerization initiator, a triterpene photopolymerization initiator) Carbazole (photograph), photopolymerization initiator, sodium photopolymerization initiator, photopolymerization initiator, borate photopolymerization initiator, phosphine photopolymerization initiator, hydrazine A photo-initiator, a titanocene photopolymerization initiator, etc., from the viewpoint of photocurability, starting from an oxime-based photopolymerization initiator, an imidazole-based photopolymerization At least one of a photopolymerization initiator and a borate photopolymerization initiator is preferred, and a ruthenium photopolymerization initiator is particularly preferred. The oxime photopolymerization initiator may be: 13) The ethyl ketone compound shown, that is, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazolyl]-bu (0-ethylindenyl): (13)

肟)], 〇-(ethinyl)-fluorene-(1_phenyl-2-oxo-2-(4,-methoxy 318764 23 1332519 naphthyl)ethylene)hydroxylamine, and the like. The imidazole-based photopolymerization initiator may, for example, be 2,2'-fluorene (o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole. Examples of the borate photopolymerization initiator include compounds represented by the following formulas (14) to (17):

(14) (15) (16) (17) N+~j-CH2CH2CH2CH3 j 4 Di-CH2CH2CH2CH3 For the acetophenone photopolymerization initiator, 4-phenoxydichloroacetamidine, 4- Tributyldichloroethane benzene, diethoxy acetophenone, 1-(4-isopropylphenyl)-2-pyridyl-2-mercaptopropan-1-, 1-cyclohexyl Phenyl 24 318764 丄: 532519 ketone, 2-benzyl-2-dimethylamino-i-(4-(n-morpholino)phenylbutin-dipyridyl, etc. Examples of the starting agent include benzoin, benzoin methyl ether, ge, ethyl benzoate, benzoin isopropyl, benzil dimethylketal, etc. The starting agent may, for example, be diphenyl ketone, stilbene benzoic acid, benzyl hydrazino benzoate, 4-phenyl diphenyl ketone 'residual diphenyl ketone, acrylated diphenyl ketone, 4 Benzyl fluorenyl _4, _ fluorenyl di > phenyl thioether, etc. In the case of a thioxanthone photopolymerization initiator, hepoxyketone, 2-oxazepinone , 2-methylthioxanthone, isopropyl thioxanthone, 2, 4-diisopropyl thioxanthone, etc. The photopolymerization initiator may, for example, be 2,4,6-trichloro_s_trin, 2-phenyl-4,6-indole (trichloroindenyl)_s-three tillage, 2_(opion to oxygen) Base benzene ^^'^-, (diqimethyl^"-three oxime" gas p-toluyl grouping ^-贰: trichloromethyl)-s-three tillage, 2 -piper〇nyl- 4,6_贰(trichloromethyl)-trimorphine, 2,4-quinone (trichloromethyl)_6_stupyl ss-trisyl, ('1 yl)-4,6-贰(trichloromethyl)-trimorphine, 2-mono(4-methoxy-j soil)_4'6贰(dichloromethyl)-s-three tillage, 2,4-trichloromethyl-(hu- Nl# 6-11 well, 2, 4~trichloromethyl-(4,-methoxystyryl)_6_ three tillage, etc. In the case of aerospace photopolymerization initiator, it can be cited as cold (2, 4 , 6-triterpene-based soil native phosphine oxide, 2,4,6-trimethyl succinyl diphenyl lining oxide 318764 25 1332519

As the oxime photopolymerization initiator, ethyl hydrazine or the like is used. There may be mentioned 9,1 〇-phenanthrenequinone, camphor, or two or more kinds of the above (f) photopolymerization initiators may be used singly. (5) The preferred embodiment of the photopolymerization initiator is used, and 丨vw A ^ Θ is used in the form of a solid composition of the black component, and the liquefied juice is preferably 0.5 to 50% by weight, preferably 2 It is better to reset the % to 20. Further, (1) the ratio of the weight (1) of the photopolymerization initiator to the weight (8) of the (4) ethylenically unsaturated compound (Ι/Μ). .1〇 to 1〇〇 is preferred. · ΐ5 to U0 is better', especially from 0.20 to 〇6〇. If Ι/Μ does not reach the condition of low sensitivity, if Ι/Μ exceeds 1〇〇, there is a linearity defect in the shape of the case of (10), which is poor in cross-sectional shape or relative to the width of the mask. The width of the pattern like the latter becomes thicker. The black composition of the present invention may contain (g) a polyfunctional thiol as a chain transfer agent. (g) The polyfunctional thiol may be, for example, a compound having two or more mercapto groups, and examples thereof include hexanedithiol, decanedithiol, and 1,4-butanediol thioglycol g gg 1 '4 - Butanol thioglycolic acid|Glycol, thioethanol, self-property, ethylene glycol thiopropionate, trimethylolpropane thioglycolate, trimethylol Propane thiopropionate, trimethylolpropane ginseng (3_mercaptobutyrate), pentaerythritol thioglycolate, pentaerythritol thiopropionate vinegar, triterpenic propionate ginseng (2_ hydroxyethyl) Isocyanurate, anthracene, 4_dimercapto-based, 2,4,6-triweisyl-3-triazino, 2-(1^,1^-dibutylamino) -4,6-dimercapto-s-three tillage, trishydroxypropyl propane (3_mercaptoisobutyric acid 26 318764 1332519 vinegar) and the like. These (4) polyfunctional thiols may be used singly or in combination of two or more. Among these (g) polyfunctional thiols, use trimethylolpropane thiopropionate, trihydrocarbyl propane ginseng (3-mercaptobutyrate), trimethylolpropane ginseng (3-mercapto) Isobutyrate or the like is preferred. /, and, (g) a multi-t capable thiol, if combined with the above (1) photopolymerization initiator ', which is a combination of the s-photopolymerization initiator, increases sensitivity and enhances photocurability, thus Preferably. (g) a polyfunctional thiol, based on the total weight of the solid component of the black composition (100 weight% is preferably used in an amount of from 0.1 to 30% by weight, more preferably from 1 to 20% by weight) When the amount is less than 1% by weight, the effect of adding a functional thiol may be insufficient, and if it exceeds 3% by weight, the resolution is too high, or the stability of the black composition is lowered: The black composition of the invention may contain a sensitizer. Regarding the sensitizer, (for example, α-decyloxy ester, decylphosphine oxide, methyl phenyl glyoxylate, benzil, 9 , 10_phenanthrenequinone, camphorquinone, ethylhydrazine, 4,4曰,-diethylisoindophenolone, 3,3,,4,4,-fluorene (t-butylperoxycarbonyl benzophenone) 4,4 monoethylaminodiphenyl ketone, etc. The sensitizer may be used alone or in combination of two or more. The amount of the sensitizer used is the total solid weight of the tired composition. The basis (1% by weight) is preferably from 1 to 5% by weight, more preferably from 0.5 to 3% by weight. In order to improve coating properties, improve sensitivity and increase adhesion For other purposes, other additives such as surfactants, Shixia couplers, etc. may be added to the black composition of the invention. 318764 27 1332519 The black composition can be obtained by using carbon black, a pigment derivative, a resin, a solvent, and Mixing olefinic unsaturated compounds, photopolymerization initiators and other additives as needed, using three roller mills, two roller mills, sand grinders, kneaders, attritors (attrit〇r), MICROS type The ultra-wet powder is produced by dispersing various dispersing devices such as a crusher. • The black composition removes coarse particles of 5# m or more by means of centrifugation, sintering filters, membrane filters, etc. The above coarse particles are preferred, and the coarse particles of 〇.5/am or more are more preferable) and the mixed powdery dust is preferred. Next, the color filter of the present invention will be described. A black composition containing an ethylenically unsaturated compound and a photopolymerization initiator in addition to carbon black, a pigment derivative, a resin, and a solvent, and a method of producing a color light-passing sheet by a lithography method is taken as an example. The present invention is not limited thereto. The color filter of the present invention has a BM formed by the black composition of the present invention on a transparent substrate such as a glass plate, and a color of at least two colors other than black. The segment is preferred. The color of the color segment is selected from blue, ,, ochre, work color, moon green, yellow, magenta, color, purple, etc., about 2 to 6 colors. A color section having a different concentration is formed by the color of the same color system. The BM can be coated on the transparent substrate by a spin coating method, a slit coating method (4) coating method, a roller coating method, and a coating method. After the black composition of the present invention is irradiated with an active energy ray by a mask, the coated surface of the ruthenium composition, and then impregnated with a solvent or an image-forming liquid' or by a spray method (Indo (4) 318764 28 丄, etc. The spray imaging solution is formed by imaging. The range of the core component (i.e., the uncured portion) is removed, and the coating of the black component is preferably dried. The balance between the applicability and the light-shielding property is preferably 5 to 2 _.卞衡至2^^ The optical density of each dry film thickness 2 (four) (when dry)

1 is / shading point of view and m. G or more is better, U

妒^佳 is especially good at 3·8 or above. The light concentration is preferably as high as possible. When the energy ray is ultraviolet light or visible light, it is difficult to obtain a hard coating film. As the alkali developing solution, an aqueous solution such as copper carbonate or hydroxide steel can be used, or an organic test such as =-methyl benzylamine or triethanolamine can be used. Further, an antifoaming agent or a surfactant may be added to the developing solution. Furthermore, in order to improve the exposure sensitivity generated by the active energy ray, after the black composition is applied, the (four) water-soluble neo-soluble resin (for example, polyvinyl alcohol or water-soluble propylene foscar wax) may be dried. After forming a film which can prevent polymerization inhibition by oxygen, the active energy ray is irradiated from the coated surface side of the composition. As the active energy ray, an electron beam, an ultraviolet ray, or a visible light of 4 Å to 50 nm can be used. In terms of the line source of the electron beam irradiated from the coated surface side of the composition, a thermal electron emission gun, an electric field emission, or the like can be used. Further, in the case of ultraviolet rays and a line source (light source) of visible light of 400 to 500 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal hydride lamp, a gallium lamp, a xenon lamp, a carbon arc lamp or the like can be used. Specifically, for the point source, due to the brightness stability, 318764 29 1332519 uses ultra-high pressure mercury lamps and mercury lamps. Irradiation from the coated surface side of the composition = The active energy ray can be appropriately set within the range of 5 to ΙΟΟΟ π κ ;; however, from the viewpoint of engineering management, it is preferably in the range of 20 to 300 ffl. • The color filter section can be formed by gravure 〇f fset printing, waterless offset printing, screen u • sCreen printing, using solvent imaging or alkali imaging. Photolithography of a resist, an electrophoresis method in which a coloring material is electrically formed on a transparent conductive film by electrophoresis of colloidal particles, and a layer of a filter section previously formed on a surface of the transfer substrate is transferred The printing method printed on the β-ruthenium substrate can be patterned by repeating printing and drying. Therefore, when it is used as a color filter manufacturing method, the cost is low and the mass productivity is excellent. Further, due to the development of printing technology, it is possible to perform printing with a fine pattern having high dimensional accuracy and smoothness. When a color filter is produced by a printing method, the control of the fluidity of the ink on the printing press is very important. The viscosity of the ink can be adjusted by a dispersing agent or a body pigment pigment. • Photolithography using a solvent-developing or alkali-developing coloring resist on a transparent substrate forming M by spin coating, slit c〇ating, and roller A coating method such as a coating method, a method of applying a coloring resist, followed by ultraviolet exposure through a photomask, and rinsing an unexposed portion of a reducing agent or an alkali developing solution to form a desired pattern, and repeating the same operation for other colors. A method of making a color filter. This manufacturing method can produce a color filter which is more precise than the above printing method. The coloring anti-money agent is a resist obtained by replacing the carbon black contained in the black 318764 30 1332519 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 d). As the coloring agent, various coloring agents excellent in resistance can be used. However, from the viewpoints of light resistance, heat resistance, and solvent resistance, it is preferable to use a pigment, and to use an organic pigment from the viewpoint of the light absorbing ability. .. is especially good. A specific example of a representative pigment can be expressed by a color index (c〇1〇r index) (CI). The coloring agent can be a yellow pigment (yellow pigmend2, 13, 14, 20, 24, 83, 86, 93, 94, 109, 110, 117, 125, Lu 137, 138, 139, 147, 148, 153, 154, 166, 173, etc. Orange colorants can be orange pigments 13, 3, 36, 38, 40, 42, 43, 5, 55, 59, 6 and 64, 65, etc. Red and magenta The coloring agent may be red pigment 9, 97, 122, 123, 144, 149, 166, 168, 177, 190, 192, 215, 216, 224, 254, 255, etc. It can be a purple pigment (vl〇let pigment) i9, ginseng 23, 29, 32, 33, 36, 37, 38, etc. & color and dynasty coloring agent can be blue pigment (blUe pi gment) 15 ( 15, 15: 1, 15: 2' 15: 3, 15: 4, 15: 6, etc.), 21, 22, 60, 64, etc.,, 'The coloring agent of the twilight can be green pigment (green pi, 1 〇, 36, 47, etc. These colorants may be combined in a desired color or in combination of two or more. The above is a color filter of Bm by lithography. a manufacturing method, however, it is also possible to use a black composition containing the carbon black, the pigment derivative, the 31 318764 1332519 resin and the solvent of the present invention, and the electroforming method and the dry method combined with the previously known printing method and lithography method. The film transfer method or the like forms βΜ. The present invention will be described below based on the examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" and "%" respectively indicate "Parts by weight" and "% by weight" [Preparation of Resin Solution (1)] In a gas introduction tube, a thermometer, a condenser, and a container, propylene glycol monomethyl hydrazine acetate is added as a second gas injection; The mixture is heated to 80 ° C. Then, a mixture of the following monomers and a thermal polymerization initiator is added dropwise to the reaction vessel at the same temperature for polymerization. 20. 0 parts 10. 0 parts 35.0 parts 15. 0 parts 4. 0 parts 20.0 parts of methacrylic acid decyl methacrylate methacrylate n-butyl laurate methyl methacrylate 2 - ethyl acetoacetate 2, 2 ' - azobisisobutyronitrile Acrylic vinegar modified with isopropylphenol oxirane (East Asian synthesis) "Aronix M-110" manufactured by the company) After the completion of the dropwise addition, the mixture was reacted at 8 Torr for 3 hours, and then azobisisobutyronitrile was added to the reaction vessel to dissolve the hexahydrate in 5 parts of cyclohexanone. 'The mixture was further reacted at 80 t for 1 hour to obtain a propylene fo with tree: solution. After the solution of the acrylic resin having a weight average molecular weight of about 4% acid resin is cooled to room temperature, the solution is taken out as a sample 318764 32 丄•= at 18 (TC heating and drying for 20 minutes, measuring non-volatile The synthetic acrylic resin solution Yin, ,,, silly, added propylene glycol soap methyl ether acetic acid, and the nonvolatile content was 30% by weight to prepare a resin solution (1). [Resolution of Resin Solution (2)] U ;^(4) Gas-conducting tube, thermometer, condenser, (4) Reaction: = 'Additional 1_12 decyl alcohol 62·6 parts' Buji (4) 287.4 parts and = Catalyst ^ Butyl tin (ίν) oxidation 1 part of the mixture, the mixture was obtained, and: I was charged into the vessel. The mixture was heated in the 12th generation for 4 hours, and then mixed. After the determination of the solid content, it was confirmed that the (10) weighting reaction of the raw material was carried out in the reaction (four). 36 parts of liver of pyromellitic acid, and the mixture was reacted at 12 ° C for 2 hours. It was confirmed by acid value measurement that 98% by weight or more of the acid was obtained, and the resin was obtained after the reaction was terminated. The resin is a white solid under the usual dish. The weight average molecular weight is about 3 The price of acid is (10) KJ)H/g. The resin solution (2) was prepared by adding cyclohexanone to the resin and making the nonvolatile content 3 wt%. [Preparation of Carbon Black Dispersions A to K] The carbon black prepared dispersions shown in Table 1 were used. The blending composition shown in Table 2 and the proportion of carbon black 丨 00 parts, 4 parts of the pigment derivative represented by the following formula (18), 70 parts of the resin solution (1) were mixed, and diluted with cyclohexanone to obtain a final solid content of 20 A mixture of % by weight. By using the obtained mixture, a glass bead having a diameter of 0.8 was used and dispersed by a paint shaker for 2 hours to prepare a carbon black dispersion A to κ. In addition to the dispersion F, a viscosity of 40 mPa was obtained. · Dispersion below s. Dispersion F, due to its extremely high viscosity, the viscosity after dispersion reaches 20〇mPa·s or more, and the room temperature is gel 318764 33 1332519', so it cannot be prepared into a black composition. The body i was subjected to dry pulverization (device: MICROS, pulverization time: 1 minute, pulverization temperature: 7 〇t:) by using the compounding composition and the mixing ratio shown in Table 2, and the carbon was obtained. The body B is prepared by the same operation. The carbon black dispersion], - except for using the compounding composition and the mixing ratio shown in Table 2, the carbon black component and the pigment derivative represented by the following formula (18) are 4 parts. The mixture was subjected to dry pulverization (device. MICROS, pulverization time: 1 〇 minute 'pulverization temperature: 7 〇. 〇), and was prepared in the same manner as in the dispersion B. The carbon black dispersion κ was used in addition to the resin solution. (1) 5 6 parts and 14 parts of resin solution (2), Instead of the resin solution (1), 70 parts were prepared in the same manner as in the dispersion G. (Formula 18) 3 N HN-^~/

Table 1: Carbon black manufacturer name used Average primary particle size specific surface area referred to as CABOT MONARCH 1100 14nm 240mz/g M-1100 DEGUSSA PrinteX 95 15nm 250m2/g P-95 Mitsubishi Chemical #47 23nm 132m2/g #47 CABOT REGAL 250R 35nm 50ra2/g R250R DEGUSSA NIP ex 35 31nm 65m2/g N-35 CABOT MONARCH 120 75nm 25m2/g M-120 318764 34 1332519 I 2 : carbon black dispersion -__ '--_ carbon black (al) carbon black (a2) Other carbon black dispersion A M-1100 20 parts #47 80 parts dispersion B, I, J M-1100 20 parts R250R 80 parts one __^: body C M-1100 10 parts R250R 90 parts D R250R 100 parts one E M-1100 20 parts R250R 40 parts M-120 40 parts F M-1100 100 parts dispersion G, K ' ' --------- P-95 20 parts R250R 80 parts L__^ Dispersion Η ---- P-95 20 parts N-35 80 parts [Examples 1 to 13 and Comparative Examples 1 to 4] (Modulation of black composition) The composition and ratio of the formulation shown in Table 3 were used to mix the mixture. After mixing and mixing to the homogenous sentence, the mixture was filtered through a 2 a ra filter to obtain a black composition. With respect to the obtained black composition, sensitivity, stability, light blocking property (0D value per unit film thickness), and pattern shape of BM were evaluated in accordance with the following methods. The results obtained are shown in Table 4. 318764 35 1332519

^to®I: CQ^ Comparative Example 4| Η 58.00 i 14.41 CO d 24.41 100.00 a* CO d r> Comparative Example 3| D 58.00 14.41 3 <9 2 S ο 24.41 100.00 σ> ο o Comparative Example 2| D 58.00 I 13.801 s «0 σ>c> S? 24.411 1 100.00 β» CO ο Comparative Example 1 D 58.00 L 14Λ1Ι C>JS Ο S [24,411 1 100.00] Ο» CO ο c? _Example 13| ! 5K. Oo 1 14.411 CM 5 CD Γ·; 1 24.411 I 100.001 sd CO 1 J 1 U.41| CM S <〇r·; 1 24.411 1 100-00 〇>«τ>c> c*» 1 58.00 1 14.411 cy oi CD 〇1-24.411 I 100.00: ο» «τ» dso Example 10 58.00 1 13.671 csi s 1 24.411 1 100.001 ο s eM CO o' ! Example 9 58.00 1 12.331 S to r^; 1 24.411 1 100.001 sf=> r- 5 Example 8 B 56.00 15.131 s G> 1 24.411 Γ100.00 «σ o u>: Example 7 B 58.00 ί 14.411 cw CO os· ο 1 24.411 1 100.001 0> o CO o Implementation Example 6 I 58.00 13.80 s C%J <〇〇> Ο ? c> 24.411 1 100.00 〇> oo Example 5 H 58.00 [14.411 3 s 24.4! I 100.001 〇> odo 贲Example 4 〇i 14.411 3 1 24.41] 1 100.001 〇> d e->: Example 3 ic 丨58.00 i 14-411 CM s ο 1 24TTI 丨100 toilet 9»CO o r> CO I Example 2 B 58.00 ! 14.411 This esi s 1 100.00! 〇> CO o | Example 1 A 58.00 一刚 esi VO o Ljm I 100.00Ι 〇><*>c> 1 ΓηαβϊΊ CO CM s eo Broken black dispersion i Delivery mm 荽τ >Kr ★ < 4.铋CQ m Φ 〇Φ {&Q effect ί Q. \ 2 s \ llofi (遛 chain hf 颧-e )_domain¢ffr-澍τ ("69ε 3Jn3BboJI"^lm々sls a 15^5330.00Βΐ3)® Λ-卜-(硇埏(磡举嚓-5-3-1-4绪砩&--^-2--?»--2#<1<>^ν·ι7^ςο#φ ^^τ fi—骛-.Ζ II I Wi4s - - S' inch* S · 7 (碏蚪«4鸯)¥ - .Ζ*Ζ ("Saxo 3J3SJI"袈e<-5sl2 13 A+JIB a 39Q .S eqo. (¢ ¥ over 91〇-5-1--|-[^-7¥4.'16-(Pei 婳私硪&--2丫9-硇0-61-1£-- <#φχ)*τ-®»0)#♦安w'lcyou(coI)¥fFT 2£5遛Helmet loaded €^截0^#·^ : Money: once shouted? Buried J, 吟: ® ® 欤 欤 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : Hexapropyl phthalate (DPHA) photopolymerization initiator A: an oxime photopolymerization initiator represented by the formula (13) (an ethyl ketone compound 'i.e., 1-[9-ethyl-6-(2-fluorenyl) Benzyl hydrazinyl)-9H-carbazol-3-yl]-1-(0-ethyl fluorenyl) - "Iggaric OXE02" manufactured by Ciba Specialty Chemicals, Inc.) Photochemical initiator B. 2,2 -3⁄4 (o-p-phenyl)_4, 5, 4', 5'-tetraphenyl-1, 2'-linked scented polymerization initiator C: borate photopolymerization initiator photopolymerization initiator D represented by formula (14): 2 -Benzyl-2-dimethylaminomorpholino) Benzo)butan-1-one ("Irgacure 369", manufactured by Ciba Specialty Chemicals Co., Ltd.) Polyfunctional thiol: trihydroxymercaptopropane ginseng (3-mercaptobutyric acid) Ester) Solvent: cyclohexanone [sensitivity] The black composition was applied to a glass substrate of 1 〇cm x 1 〇cm by spin coating, and then dried by 7G ° C '15 minutes to make a film having a dry film thickness. 'And measure the film thickness. Then 'Using an ultra-high pressure mercury lamp, through the mask, the coating film is exposed by ultraviolet light of various exposure amounts (mj/cm2). After the coating film is dissolved in carbon water, the water is exchanged by the material. The unexposed portion was removed by washing, and the film thickness of the exposed portion after the development and washing was measured, and the minimum exposure amount (mj/cm2) obtained by the film thickness of 95% or more of the film thickness before the development was used as the sensitivity. The sensitivity 1G i 5G mI/em2 was evaluated as ^Q (good), and the first mask pattern was exceeded to form a strip-shaped black matrix pattern. 318764 37 1332519 [Stability] For the black composition that was just prepared, and the 7-day color composition was stored in 4 〇, the development speed and line width were compared, and the stability was evaluated. ... (developing speed) The film composition was measured by spin coating of the black composition and the film thickness was measured. The time when the coating film disappeared was measured by using a carbon steel steel water-image for the coating film. The measurement time was divided by the measurement > 疋, 子, and the time per unit film thickness (second//zm) was taken as the development speed. The development speed after the storage is evaluated as 〇 (good) with respect to the change in the development speed before storage, and is evaluated as χ (bad) when it exceeds 15% of the soil, and the speed becomes low. ). - Ai is between (line width) using the black composition before and after storage: rr method 'In the exposure amount is formed into a strip shape: ... ΐ Use the microscope to determine the line width. However, due to the entanglement of Example 10, and the degree of object sensitivity was low, it was exposed at 300 mJ/cm2. When the line width of the strip-shaped (10) pattern formed by the object before use is changed within +7, the evaluation is 0 (good), and the case of super-deformation or thickening of the line is evaluated as x (bad).疋 line 1, field: When the image speed is evaluated as x, it is judged that the stability is poor, and it is no longer [shading (optical density (OD))]. The two-color composition is coated by the same method as the "sensitivity" evaluation. On the second board, do not perform the exposure step and work on the job! After hours, measure the film; The optical density (〇D) of the black composition obtained on the substrate was measured by a Macbeth densitometer (GRETAG D2(Mi)), and the measured optical density (0D) was divided by the measurement film. Thickness, and obtain the optical density per unit film thickness (〇D/# m). [Shape] . The same method as the "sensitivity" evaluation, the exposure amount is 70mJ/cm2, and the shape of the strip is BM pattern. The shape of the strip-shaped βΜ pattern was prepared, and the linearity and the cross-sectional shape were observed using an optical microscope or an electron scanning microscope. The black composition of Example 10 was not sensitive, and the light was exposed at 3 μm/cm 2 . (Linearity) A case where there is no defect or jaggedness in the straight line portion is evaluated as linear 〇 (good), and a case where the straight portion is uneven or defective is evaluated as linear Δ (slightly bad), The case where the straight line portion is uneven or the majority of defects are evaluated as linearity x (bad). (Sectional shape) The cross-sectional shape is a positive trapezoid (the bottom edge in contact with the glass is wider than the upper base) and is perpendicular to the cross-sectional shape. Evaluation is 〇 (Good), the cross-sectional shape Φ is the overhang (the upper base is wider than the bottom edge of the glass contact), and the cross-sectional shape is evaluated as x (bad). [Viscosity] Using the TVE-20L type viscometer (East machine) The viscosity of the black composition was measured at 25 rpm and 20 rpm. [Adhesiveness] The black composition was applied to a glass substrate by the same method as the "sensitivity" evaluation, and the exposure step was performed without 〇ΐWhen heating for 丨 hours. For the obtained black composition coating film, according to the JIS K54 棋 board grid adhesion 318764 39 1332519 test method, Jia glass adhesion. Peeling by rapid curing of high performance epoxy resin The following agent (the room temperature i-hour hardening type) was attached to the head of the test, and (by its own gravity) was then applied to the checkerboard-shaped coating film. After heating for 5 minutes in the 9th generation, the bolt was manually removed from the coating film. Since the snail is smaller than the l_xl_xl00 checkerboard, the non-peeling area of the coating film = the ratio of the contact area with the bolt indicates the adhesion. Further, the adhesion is calculated according to the following formula (19). Sex (%), will count The result is evaluated from the level of © to ><4. In addition, when the value obtained by the calculation formula (19) is less than the decimal point, the result is rounded off as the value of the adhesion. ) Adhesive «Number of checkerboards on the contact surface of the bolts - Number of the bolts attached to the 臈 ) /) / (Number of the checkerboards of the bolt contact faces) xl00, ◎ : 80% $ Adhesiveness S 100% 〇: 60 %$ Adhesion<80% △ : 30%$ Adhesion< 60% x : 20%<Adhesion< 3〇% 318764 40 1332519

Comparative Example 4 ω η CSI IA < 〇〇〇 <〇d < ο 1 ) Comparative Example 3 Q none Ο 〇X 1 (D to < ο. Γ3 t£><3 Comparative Example 2 Q none m 0 X 1 CD η <3 0 (D ui 〇Comparative example 1 Q 1 rare tA CQ < 0 〇X ω tri < ο (D tr>< 贫例13 ΙΛ ΙΑ TO < 〇〇〇 α> Ρ3 Ο 0 IA o If Example 12 r U> m < 〇〇〇ο Ο 0 ΙΩ iei o Example 11 will \A m < 〇〇〇ρ V Ο ο n ui Poor Example 10 < m CM ο X 〇〇α> C0 < ο 5 <3 Example 9 m stroke < 0 0 〇ρ XX 5 o Example 8 m u> CO < 0 〇〇Q Ο ο s < 7 m tA n ο 0 〇〇q Ο 0 o <D o Example 6 m V \f> n CD 0 〇〇ο 0 ο 5 @ 贲Example 5 X ΙΟ < 〇〇〇α d ο ο » Vi o Example 4 ο ΙΑ in m < 0 〇〇σ>. CO 0 0 CO Ό o Example 3 ο ▼ in CQ < 0 0 0 «! CO 0 0 oo Example 2 CD Ui CO < 〇 0 〇ο 0 ο <*> IA o Example 1 < n CM < 0 0 〇» σί ο ο 5 ® image speed line width linearity i section shape carbon black dispersion black <a1) average primary particle size /nm f E i^4 31 ^ l ? ε W, race 4 light Aggregation Initiality Sensitivity Stability 0D/Mm Shape Viscosity/mPa-S Adhesion 41 318764 1332519 It can be understood from Table 4 that Examples 1 to 13 of the present invention are excellent from the viewpoint of high light-shielding property and stability. Further, in Comparative Examples 1 to 4, Examples 11 and 12 in which carbon black was subjected to dry treatment were more excellent from the viewpoint of low viscosity and adhesion.

42 318764

Claims (1)

1332519 _.________ Patent Application No. 95144119—/一"W (June 8, 1999) X. Patent Application: Substitute for the Year of the Year (曰) £ Replacement Page 1. A black composition, The invention comprises (al) carbon black having an average primary particle diameter of 8 to 2 〇 nm, (a2) carbon black having an average primary particle diameter of 21 to 4 〇 nm, (b) a pigment derivative, (c) a resin and ( d) a black composition of a solvent characterized in that the weight ratio of the above (al) carbon black to the above (a2) carbon black is (al) / (a2) = 1/3 to 1/30, the above (ai) carbon The total amount of black and the above (a2) carbon black is based on the total weight of the solid content of the black composition (1 〇〇% by weight), and is 40 to 60% by weight of the above (al) carbon black and the above (a2) The difference in average primary particle diameter of carbon black is 5 mn or more, and the black composition does not contain carbon black having an average primary particle size exceeding 4 〇 nm. 2. A black composition which is (al) carbon black having an average primary particle diameter of 8 to (a2) carbon black having an average primary particle diameter of 21 to 4 〇 nm, (b) a pigment derivative, (c) a resin and (1) a black composition obtained by mixing a solvent, characterized by a weight ratio of the above (al) carbon black to the above (a2) carbon black ^ (al) / (a2) = l / 3 to 1 /30 ' The total amount of the above (al) carbon black and the above (a2) carbon black is based on the total weight of the black component solids (100 weights of mash juice is 40 to 60% by weight, the above (al) carbon (10) The difference between the average and the secondary particle diameter of carbon black is 5 μ or more, and is mixed with carbon black having an average primary particle diameter of more than 4 〇 nm. 3· For example, the black composition of the second item of the patent scope is Among them, the dry pulverized (al) carbon black and (a2) carbon black are used. 4.= The black composition of the patent scope Scope! or 2, wherein the granules are complex (4) olefinic unsaturation Compounds and (1) Photopolymerization from 318764 Rev. 43 Patent Application No. 95144119 (June 8, 1999) 5. If the scope of application for patents is ΐϋ 曰 曰 人 仏 a a a a a a a a a a a a a a a a a Wherein, the (f) light, and the "«* polymerization initiation η start-up initiator. 夕种九汆6. The black composition of the first or second item of the range, wherein the black, and The complex contains (g) a polyfunctional thiol. 7_ 2 The black composition of the scope of the patent or the item 2, wherein the (8) pigmented matter contains the color formula (1) of the blanking formula (1) Wherein Q represents an organic dye residue; X represents a direct bond, -CONH-Y2-, _S〇2NH_y2- or -Μ_-γ2- (wherein Υζ represents a stretching group which may have a substituent or may have a substitution之 表 表 ΝΗ 或 或 或 表 表 表 表 η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η χ is defined as described above, ζ when η is 2 to 4, represents a hydroxyl group, an alkoxy group, and a substituent represented by the following formula: 44 318764, Rev. 1332519, No. 95144, No. 19 Patent Applicant' (99 June 8th) (wherein γ3 represents -ΝΗ- or; m, R1 and R2 are as defined below); 匕 and R2 each independently represent an alkyl group which may have a substituent, and R] and R2 may be bonded to each other to form at least a nitrogen atom. Heterocycle; m represents an integer from 1 to 6; η represents an integer from 1 to 4. For example, the black composition of claim 4 (4), wherein the black (C) resin (ρ) and the black composition (e) the weight of the ethylenically unsaturated compound (M) The ratio (M/p) is 〇i〇 to 0.70. A method for producing a black composition, characterized in that (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) pigment derivative The mixture is mixed to obtain a mixture, and the obtained mixture is subjected to dry pulverization, and the dry pulverized mixture is mixed with (c) a resin and (d) a solvent, wherein the (a) carbon black and the above (a2) carbon black are mixed. The weight ratio is (al) / (a2) = 1/3 to 1/3 〇, and the total amount of the above (al) carbon black and the above (a2) carbon black is based on the total solid weight of the black composition U ( 100% by weight) is from 4 to 6% by weight. Ίίο. A method for producing a black composition, characterized in that (ai) carbon black having an average primary particle diameter of 8 to 20 nm and (a2) carbon black having an average primary particle diameter of 21 to 40 nm are mixed to obtain a mixture , the mixture will be obtained 318764 revision 45 1332519 Yannian April f曰 repair (吏) is replacing page -_____ Patent application No. 95144119 for dry pulverization, and will be dried # ("^6^ 8 θ) And the dry unbranched mixture is mixed with (b) a pigment derivative, (8) a resin, and (4) a solvent, wherein a weight ratio of the (ai) carbon black to the (a2) carbon black is (al)/(a2) = 1/ 3s, the total amount of the above (al) carbon black and the above (a2) carbon black is 4 〇 to 6 〇 by weight based on the total weight of the solid content of the black composition (100% by weight). 11. A color filter The sheet is characterized by comprising: a transparent substrate; and a black matrix formed on the transparent substrate by using the black composition according to any one of claims 1 to 8. 46 318764 revision