TW201032002A - Photosensitive black-colored resin composition, black matrix substrate, and manufacturing method of color filter - Google Patents

Abstract

The present invention aims to provide a photosensitive black-colored resin composition, which is used to form black matrix of spacer, can prevent color mixture due to blending different color inks with adjacent color pixel layers without implementing special treatments such as plasma surface treatment, and can avoid pixel defects such as local trapping. The photosensitive black-colored resin composition contains, with respect to total fluoride content of all the solid components, 0.0008 to 0.005 mass% of fluoride surfactants having perfluoroalkyl at side chains.

Description

201032002 VI. Description of the Invention: [Technical Field] The present invention relates to a photosensitive black resin composition, a black matrix substrate, and a method of producing a color filter. More specifically, it relates to a photosensitive black resin composition for forming a partition wall pattern constituting a color filter, and particularly relates to a black matrix for forming a light-shielding partition wall for producing a color filter by inkjet printing. The photosensitive black resin composition is also related to a black matrix substrate prepared using the photosensitive black resin composition and a method of producing a color filter using the black matrix substrate. [Prior Art] A color filter is an optical element that is incorporated in a liquid crystal display device to color a display image, or an optical element that is incorporated in a solid-state image sensor to obtain a color image. These color filters are known to have a color filter having a colored pattern including a plurality of color φ color pixel layers formed adjacent to each other on the same plane on the substrate. Here, the colored pattern is composed of, for example, a color pixel layer of three primary colors of a red pixel layer, a green pixel layer, and a blue pixel layer, and a black matrix serving as a light shielding layer is formed between adjacent color pixel layers. The color pixel layers of the various colors are transparent layers colored in various colors, and the black matrix is black and substantially transparent to visible light. As a general method for producing a color filter, it is known that a colored photosensitive resin composition layer is formed on a substrate, and the colored photosensitive resin composition layer is composed of a solid component of a colored photosensitive resin composition containing various colorants. A method of manufacturing a photolithographic etching method in which a color pattern is formed on a substrate by irradiating light through a photomask and utilizing the properties of a coloring photosensitive resin composition layer which is soluble in a developing solution to be changed from -5 to 201032002 (for example, Japanese Patent Laid-Open No. 7_27 1 020). However, in the method of manufacturing a color filter of a photolithography method, after the coloring photosensitive resin composition is applied onto the surface of the substrate, it is necessary to repeat the step of exposing through the mask and developing and removing unnecessary portions, and the manufacturing steps are complicated. . Further, the cost of the expensive reticle, the depreciation cost of equipment such as coating equipment, exposure equipment, and developing equipment are necessary. Therefore, in order to simplify the manufacturing steps and to reduce the manufacturing cost, instead of the photolithography method, a method of forming a color pixel layer by an inkjet printing method has been proposed. In the inkjet printing method, a black matrix having a light-shielding property is generally used as a partition wall, and a color pixel layer is formed by printing ink for inkjet printing on an opening of the black matrix. However, when printing is performed, inkjet printing is performed. Since the solid content concentration of the ink is limited, in order to obtain a desired layer thickness and color density, it is necessary to print a plurality of times of inkjet printing with respect to the opening volume (opening area X partition wall height) of the black matrix. Use ink. As a result, the ink for printing inkjet printing overflows from the opening, and the ink which exceeds the black matrix of the partition wall is also infiltrated into the adjacent opening portion to cause "mixing". In view of the problem of the "color mixing", it has been proposed to fluorinate only the surface of the black matrix by plasma treatment in an atmosphere of a fluorine compound such as tetrafluoromethane, thereby increasing the liquid repellency with respect to the ink for inkjet printing. In addition, a method of adding an organic ruthenium compound or an organic fluorine compound to form a black matrix which imparts lyophobic property to ink of inkjet printing oil-6-201032002 has been proposed (for example, Japanese Patent No. 3328297). (Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2006-163233). In the case where the total detection intensity of all the negative ions on the surface of the black matrix which is the partition wall is 1 in total, the detection intensity of the fluoride ion is 0.3 to 0.6. The method. In the method disclosed in Japanese Patent No. 3328297, the surface of the black matrix is fluorinated by plasma treatment, so that the liquid repellency on the surface of the black matrix with respect to the ink for φ inkjet printing becomes a uniform sentence, but the plasma treatment step It is necessary to be a simplistic method. In the method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2006- 1 63 23 3, a black matrix is formed using a composition containing an organic ruthenium compound or an organic fluorine compound. The liquid-repellent black matrix of the ink for inkjet printing can prevent color mixture due to the incorporation of the color ink in the adjacent color pixel layers, but is insufficient in ensuring uniform liquid repellency of the entire black matrix surface. When the liquid repellency of the black matrix surface φ is not uniform, when the ink for inkjet printing is printed on the opening of the black matrix in the pixel region surrounded by the partition wall, the ink is poorly filled, that is, the "leakage" occurs. Pixel defect issues. Therefore, in the color filter produced in a state where the whitening occurs locally, there is a problem that light leakage occurs in the white portion. Further, when a black matrix is formed using a composition containing an organic cerium compound or an organic fluorine compound, first, the above composition is applied onto the entire surface of the substrate. Next, exposure is performed through a photomask having a desired pattern, and then development processing is performed to form a black matrix on the surface of the substrate. In the case of the substrate in which the black matrix of 201032002 is formed, in particular, when a black matrix having a large partition wall height is formed, an organic germanium compound or an organic fluorine compound remains on the surface of the substrate corresponding to the opening of the black matrix surrounded by the partition wall. Case. In the method disclosed in Japanese Laid-Open Patent Publication No. 2007-2563, the fluorine ion detection intensity of the surface of the black matrix which is the partition wall is specified, but the fluoride ion of the substrate surface corresponding to the opening of the black matrix is not defined. Detection intensity. Therefore, the method disclosed in Japanese Laid-Open Patent Publication No. 2007-256357 cannot be said to solve the problem that occurs when the organic fluorine compound remains on the surface of the substrate corresponding to the opening of the black matrix. When the organic ruthenium compound or the organic fluorine compound remains on the surface of the substrate corresponding to the opening of the black matrix, the liquid repellency of the ink for inkjet printing is also imparted to the surface of the substrate on which the color pixel layer is formed, and the opening portion is provided. The lyophobicity of the surface of the substrate causes whitening to occur. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a photosensitive black resin composition which can be formed into a black matrix which is a partition wall which is not subjected to a special surface treatment such as plasma treatment and can be prevented. The color mixture which occurs due to the mixing of the color inks between the adjacent color pixel layers can prevent the occurrence of local pixel defects such as whitening. Further, a black matrix substrate produced using the photosensitive black resin composition and a method of producing a color filter using the black matrix substrate are provided. The photosensitive black resin composition of the present invention is used for forming a photosensitive black of the black matrix in a color filter having a plurality of color pixel layers on a substrate and a black matrix -8 - 201032002 located between adjacent color pixel layers The resin composition is characterized in that it contains 0.0008 to 0.005 mass% of a fluorine-based surfactant having a fluoroalkyl group in a side chain, based on the fluorine content of all the solid components. According to the present invention, there is provided a photosensitive black resin composition for forming the black matrix in a color filter having a plurality of color pixel layers on a substrate and a black matrix between adjacent color pixel layers. Further, the photosensitive Φ black resin composition contains a fluorine-based surfactant having a fluoroalkyl group in a side chain of 0.0008 to 0.005 mass% based on the fluorine content of the total solid content. A photosensitive black resin composition containing a predetermined amount of a fluorine-based surfactant based on the fluorine content of all the solid components is a photosensitive black resin composition of a black matrix which is a partition wall, which is imparted with respect to the spray. The liquid repellency of the ink for ink printing can prevent color mixture caused by the mixing of the color inks between adjacent color pixel layers, and ensure uniform liquid repellency, thereby preventing occurrence of local pixel defects such as whitening. ❹ The content of the fluorine-based surfactant having a fluoroalkyl group in the side chain is less than 0.0008% by mass based on the fluorine content of the total solid content, and the liquid matrix formed by the black matrix is insufficient, not only The effect of preventing color mixture between adjacent color pixel layers is sufficiently exerted, and a structure such as a Bernal swirl cell is not preferable on the surface of the black matrix. In addition, when the content of the fluorine-based surfactant having a fluoroalkyl group in the side chain is more than 0.005 mass% based on the fluorine content of the total solid content, the substrate peripheral portion has no problem, but the outer peripheral portion (edge portion) of the substrate A pixel defect such as partial whitening occurs in the nearby color pixel layer. -9 ** 201032002 In the photosensitive black resin composition of the present invention, the fluorine-based surfactant preferably has a structural unit 1 represented by the following formula (1 a ) based on 100% by mass of all structural units. ～40% by mass, a compound having a ratio of 20 to 98% by mass of the structural unit represented by the following formula (1b), and a structural unit of 1 to 40% by mass represented by the following formula (1c). [1] R1 I —ch2 — c —I x′−l'-r2 (la) R3I —Chfe —C ————————————————————————————————————————————————————————————————————————————————————————————————————————— c --I x2 - L3 - Rf

(1c)

Wherein R1, R3 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, or -(8丨(0) :1!3)2〇)„1-8丨((:113)3, rule 4 represents an alkylene group having 2 to 8 carbon atoms, and R5 represents a hydrogen atom 'alkyl group having 1 to 12 carbon atoms'. a group or an aryl group having 6 to 20 carbon atoms; L1' L2 and L3 each independently represent a single bond, an alkyl group or a substituted alkyl group; and X1 represents a -co2-, -CONY1, or an aryl group. , X2 represents -〇-, -C02-, -CONY2-, an extended aryl group, or a divalent heterocyclic residue; Rf represents a fluoroalkyl group; η represents an integer of 2 to 20; further, m represents an integer of 〇~3 And Y1 and Y2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. According to the invention, the fluorine-based surfactant contained in the photosensitive black resin composition is a compound having a specific structure. The photosensitive black resin composition is a photosensitive black resin composition capable of forming a black matrix, which can more effectively prevent color mixture between adjacent color pixels, and can more effectively prevent pixel defects such as white leakage. -10 - 201032002 The present invention is also a black matrix substrate for manufacturing a black matrix substrate having a plurality of color pixel layers on a substrate and a color filter located adjacent to the black matrix between the color pixel layers. A black matrix substrate having a enamel matrix prepared using the photosensitive black resin composition is formed. According to the present invention, a black matrix substrate is used for manufacturing a color filter formed with a black matrix substrate, and the color filter is attached to a substrate. a black matrix serving as a partition wall between the plurality of color pixel layers and the adjacent color pixel layers, and the black matrix substrate is formed on the substrate to form a black matrix prepared using the photosensitive black resin composition. The matrix substrate has a black matrix which is a partition wall which is imparted with a liquid repellency with respect to the ink for inkjet printing in a uniform state. Therefore, inkjet printing which is printed on the opening of the black matrix by the inkjet printing method can be prevented. The ink penetrates the black matrix which becomes the partition wall, and the ink invades the adjacent opening part. The color mixing is also possible, and it is also possible to prevent the problem of local ink squeezing failure, φ, that is, preventing pixel defects such as whitening. Further, in the black matrix substrate of the present invention, the time-of-flight secondary ion mass spectrometer (TOF) -SIMS) In the detection result of the negative ions detected, the detection intensity ratio of the fluoride ions when the total detection intensity of all the negative ions is 1 is 0.15 or more and less than 0.3' on the surface of the black matrix, and corresponds to the opening of the black matrix. The surface of the substrate is preferably 〇·〇5 or less. According to the present invention, the detection intensity of all negative ions in the detection result of the negative ions detected by the time-of-flight secondary ion mass spectrometer (TOF-S IMS ) When the total amount is 1 and the nominal ratio of fluorine to -11 - 201032002 is 0.15 or more and less than 0.3 on the surface of the black matrix, the surface of the substrate corresponding to the opening of the black matrix is 0.05 or less. These black matrix substrates have a black matrix which is a partition wall which is imparted with a liquid repellency with respect to the ink for inkjet printing in a uniform state. Therefore, it is possible to prevent the ink for inkjet printing printed on the opening of the black matrix by the inkjet printing method from exceeding the black matrix serving as the partition wall, thereby causing the ink to enter the adjacent opening portion to be mixed, and it is also possible to prevent the ink from being locally generated. A problem of poor charging, that is, preventing pixel defects such as whitening. When the detection intensity ratio of the fluorine ion on the surface of the black matrix which becomes the partition wall is less than 〇·15, the liquid repellency of the black matrix with respect to the ink for inkjet printing is insufficient, and the color mixing prevention effect between adjacent color pixel layers cannot be sufficiently exhibited. . Further, when the fluorine ion detecting intensity ratio of the black matrix surface is 0.3 or more, a pixel defect such as partial whitening occurs in the color pixel layer in the vicinity of the outer peripheral portion (edge portion) of the substrate. Further, when the detection intensity ratio of the fluorine ion on the surface of the substrate corresponding to the opening of the black matrix exceeds 0.05, the liquid repellency with respect to the ink for inkjet printing is applied to the surface of the substrate on which the color pixel layer is formed, and the periphery of the substrate is made The color pixel layer in the vicinity of the portion (edge portion) is partially defective in pixel leakage such as whitening, and the color mixing prevention effect due to the liquid repellency of the black matrix surface is lowered. Further, in the black matrix substrate of the present invention, the film thickness of the black matrix is preferably 1.2 μm or more and 3.0 μm or less. According to the present invention, the black matrix of the black matrix substrate has a film thickness of 1.2 to 3.0 μm. When the film thickness is less than 1.2 μm, a sufficient amount of -12-201032002 ink in order to achieve a color density necessary for color reproduction cannot be filled in the opening portion of the black matrix, which is not preferable. When the film thickness exceeds 3·0 μm, it is difficult to form a black matrix substrate having a high-precision barrier pattern, and when the color filter substrate is used to manufacture a color filter, the color pixel layer and the isolation low difference become large, so that the liquid crystal cell is made. Design has become difficult and not good. In addition, the present invention is a method of manufacturing a color filter having a plurality of color pixel layers and a black matrix between adjacent color pixel layers on a substrate, the method comprising: φ using the aforementioned photosensitivity a black resin composition having a matrix on a substrate, and a black matrix substrate preparing step of preparing a black matrix substrate is printed by inkjet printing in a pixel region surrounded by a partition wall of an opening of a black matrix formed on a black matrix substrate The printing ink forms a pixel layer forming step of the color pixel layer. According to the present invention, a method of manufacturing a color filter is a method of manufacturing a plurality of color pixel layers of a substrate and a black color filter between adjacent color pixel layers, comprising a black matrix substrate preparing a pixel layer forming step. In the black matrix substrate preparation step, a black matrix substrate was prepared by forming a matrix of spacers formed in a uniform state by the liquid repellency of the ink for inkjet printing using a photosensitive black resin composition. Further, in the pixel layer forming step, the pixel region surrounded by the opening portion of the black matrix formed on the black matrix substrate is printed by inkjet printing to form a color pixel layer. In the pixel layer forming step, the pixel region surrounded by the partition wall in the black matrix substrate which is provided with the liquid-repellent wall of the inkjet printing ink in a uniform state is provided with the color-bonding of the black wall. The color is black, and the corresponding brush inkjet has a matrix step and the aforementioned sensation imparting a phase black moment, and the partition wall is printed with the isolated printing oil-13-201032002 ink, so that it can be prevented from exceeding the partition wall. The black matrix is infiltrated into the ink in the adjacent opening portion to prevent coloring, and it is possible to prevent local ink charging failure, and to prevent color defects such as whitening. [Embodiment] The object and features of the present invention And the advantages will be more apparent by the following detailed description and the accompanying drawings. The preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings. The photosensitive black resin composition of the present invention is used for forming a composition of a black matrix of a color filter having a plurality of color pixel layers on a substrate and being separated between adjacent color pixel layers The black matrix of the wall. The photosensitive black resin composition may be of a negative type or a positive type, but more preferably a negative photosensitive resin composition capable of setting a high optical density (negative photosensitive black resin composition) negative photosensitive black resin The composition contains an opacifier, a binder resin, an addition polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, a photopolymerization initiator, a fluorine-based surfactant described later, and a solvent. The opacifier can be a dye or an organic or inorganic pigment. Further, the dye and the pigment may be used in a mixed state. The inorganic pigment may, for example, be a metal compound such as a metal oxide or a metal salt, and specific examples thereof include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. -14- 201032002 Oxide or composite metal oxides, nitrides, nitrogen oxides. Further, examples of the organic pigment include compounds classified as pigments in a color index (issued by The Society of Dyers and Colourists). In particular, when a black matrix is formed, a black pigment is used as an opacifier. Examples of the black pigments include those described in the publications of JP-A-H05-311-1, pp. 6-11613, and JP-A-6-11613 Inorganic black enamel pigments, such as azomethanone, CI pigment black 1, and CI pigment black 7, described in JP-A No. 2-216102, and the like. The photosensitive black resin composition colored in black may further contain a red pigment, a green pigment, a blue pigment, a yellow pigment, a cyan pigment, a magenta pigment or the like as a pigment. The particle diameter of the opacifier is preferably from 0.005 to 0.2 μm, more preferably from 0.01 to Ο.ΐμπι, based on the average particle diameter. The light-shielding agent having such a particle diameter can be produced, for example, by a known method such as kneading. Further, it is preferable to contain the light-shielding agent in an amount of 5 to 30% by mass based on the total solid content of the photosensitive black resin composition. When the content of the light-shielding agent is less than 5% by mass, it is not possible to form a light-shielding partition wall having a sufficient optical density with a predetermined film thickness, and it is also inferior to the "pleat" or "side edge" of the cross-sectional shape of the partition wall, which is not preferable. . Further, when the content of the light-shielding agent exceeds 30% by mass, the fluidity of the photosensitive enamel composition is lowered, and it is difficult to form a partition having a uniform film thickness. The binder resin is a component of a negative photosensitive photosensitive resin composition, and a resin composition layer formed using the photosensitive black resin composition is imparted with a property of being dissolved in a developing solution in a region where the light is not irradiated from -15 to 201032002. Further, the binder resin also has a function as a dispersion medium for dispersing the light-shielding agent in the resin composition layer formed using the photosensitive black resin composition. The binder resin used in the negative photosensitive black resin composition may, for example, be an acrylic copolymer, a reaction product of an epoxy compound having two or more epoxy groups in a molecule and a carboxylic acid, and further a polycarboxylic acid. A polycarboxylic acid resin obtained by reacting an acid anhydride or the like. The acrylic copolymer may, for example, be a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith. The monomer having a carboxyl group may, for example, be an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated polycarboxylic acid such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid. Among them, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. The unsaturated dicarboxylic acid may, for example, be maleic acid, fumaric acid, itaconic acid, citraconic acid or mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride thereof, and specifically may be maleic anhydride, itaconic anhydride, citraconic anhydride or the like. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester thereof, specifically, for example, succinic acid mono(2-propenyloxyethyl) ester, succinic acid mono(2- Methyl propylene methoxyethyl) ester, mono(2-propenyl methoxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be a mono(meth)acrylate of a di-carboxyl polymer at both ends thereof, specifically ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate or the like. The above-mentioned carboxyl group-containing monomers may be used alone or in combination of two or more. -16-201032002 Other examples of copolymerizable with the above carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyl m-vinyltoluene, p-vinyltoluene, and the like. -chlorostyrene, polystyrene, m-methoxystyrene, p-methoxystyrene, mercaptobenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinyl ether , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glyceryl ether, p-vinylbenzyl glycidyl ether, an aryl φ alkenyl compound such as hydrazine; methyl acrylate, methyl methacrylate, Propylene, ethyl methacrylate, n-propyl acrylate, isopropyl methacrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl acrylate, isobutyl methacrylate Second butyl ester, second butyl methacrylate, third butyl butyl acrylate, 2-hydroxyethyl acrylate, methacryl ethyl ester, 2-hydroxypropyl acrylate, methacrylic acid 2- 3-hydroxypropyl hydroxyacrylate, 3-hydroxypropyl methacrylate, Cyclobutyric acid acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, methacryl butyl acrylate, allyl acrylate, methacrylic acid Allyl ester, propylene, benzyl methacrylate, cyclohexyl acrylate, phenyl methacrylate phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate 2-methoxyethyl acrylate, acrylic acid 2 -phenoxyethyl ester, 2-phenoxyethyl formate, methoxy diethylene glycol acrylate, methoxy glycol methacrylate, methoxy triethylene glycol acrylate, methyl glycol methyl Acrylate, methoxypropylene glycol acrylate, methyl, for example, toluene, ® - methoxyur-vinylbenzyl methyl condensate, ethyl acetate propyl ester, methyl, propylene ester, 2-hydroxyester formate, C 2-Hydroxy, methyl acid 4-benzyl hexyl acrylate, ester, methacryl diethylene trioxypropane-17- 201032002 diol methacrylate, methoxydipropylene glycol acrylate, A Oxydipropylene glycol methacrylate, isobornyl acrylate, methyl Isobornyl enoate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-benzene methacrylate Unsaturated carboxylic acid esters such as oxypropyl acrylate, glycerin monoacrylate, glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate 2- 2-dimethylamino acrylate Ethyl ester, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethyl methacrylate Alkyl propyl ester, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc. Aminoalkyl esters; glycidyl esters of unsaturated carboxylic acid such as glycidyl acrylate and glycidyl methacrylate; vinyl acetate such as vinyl acetate, vinyl propionate, vinyl butyrate or vinyl benzoate Esters; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; acrylonitrile, methyl propyl Acrylic acid, vinyl cyanide compound such as X-chloroacrylonitrile or vinyl cyanide; acrylamide, methacrylamide, α-chloropropenylamine, N-2-hydroxyethyl decylamine, hydrazine Unsaturated guanamines such as 2-hydroxyethyl methacrylamide; unsaturated quinones such as maleic imine, fluorene-phenyl maleimide, fluorene-cyclohexylmaleimide ; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, poly N-butyl methacrylate, a macromolecular monomer having a monopropenyl fluorenyl group or a monomethacryl fluorenyl group at the terminal of the polymer molecular chain of polyoxymethane. These monomers may be used singly or in combination of two or more kinds -18-201032002, respectively. The content "in terms of mass percentage" of the monomer unit having a carboxyl group in the above copolymer is usually about 1 to 50% by mass, preferably about 15 to 40% by mass. As the above acrylic polymer 'for example, (meth)acrylic acid/methyl (meth)acrylate copolymer, (meth)acrylic acid / benzyl (meth)acrylate copolymer (meth)acrylic acid / (Methyl)-propyl acrylate 2-hydroxyethyl/benzyl (meth) acrylate copolymer, (meth)acrylic acid / methyl (meth) acrylate / polystyrene macropolymer (A Acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromolecular copolymer, (meth) acrylate / (meth) acrylate / polystyrene macropolymer - Methyl)acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromolecular copolymer, (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate Ester/polystyrene macromer copolymer, (meth)acrylic acid / φ (hydroxy) 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromer copolymer , methacrylic acid / styrene / benzyl (meth) acrylate / N-phenyl maleimide copolymer, Methyl)acrylic acid/succinic acid mono(2-propenyloxyethyl)ester/styrene/(methyl) benzyl acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid / amber Acid mono(2-propenyloxyethyl)ester/styrene/allyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/benzyl (meth)acrylate Ester/N-phenylmaleimide/styrene/glycerol mono(meth)acrylate copolymer, and the like. Further, the term "(meth)acrylate" means -19 - 201032002 acrylate or methacrylate. Wherein 'preferably benzyl methacrylate/methacrylic acid copolymer, benzyl methacrylate/methacrylic acid/styrene copolymer, methyl methacrylate/methacrylic acid copolymer, methyl methacrylate/ A methacrylic acid/styrene copolymer or the like. The polystyrene-equivalent weight average molecular weight of the above acrylic polymer is preferably in the range of 3,000 to 400,000, more preferably in the range of 5,000 to 1,000,000. Further, the acid strontium is preferably in the range of 30 to 250, more preferably in the range of 60 to 180.

The polycarboxylic acid resin which can be used as the binder resin, for example, a polycondensate of a compound represented by the following formula (2) and a polybasic acid or an anhydride thereof can be exemplified (refer to Japanese Laid-Open Patent Publication No. Hei-4-35 5450, No. A reaction product of an epoxy compound of a precursor of the formula (2) and a polyvalent carboxylic acid and/or a monocarboxylic acid, or a reaction product of a precursor of the formula (2), or a monocarboxylic acid, is disclosed in JP-A-H09-325494, JP-A-2000-281738 A polycondensate or the like with a polybasic acid or an anhydride thereof. [Chemical 2]

R,. I ch2=c-c-o-ch2-ch-ch2- 〇 OH

❹ R10

I C a C=CHj

It Ο [wherein R7 and R8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, R1G represents a hydrogen atom or a methyl group, and x represents a formula (2-1) to (2) -7) A divalent residue represented by any of the formulas R9 represents an alkylene group having 1 to ί of a carbon atom which may have a substituent. p An integer of 0 to 5 is shown as 'q means an integer of 1 to 10'. -20- 201032002 【化3】

(2-7)

(2-3)

(2 - 6)

As the polybasic acid, for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl endomethylenetetrahydrophthalic acid can be exemplified. , hexachloronorbornene dicarboxylic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, 4,4'-diphenyl phthalate represented by biphenyl Tetracarboxylic acid, diphenyl ether tetracarboxylic acid, and the like. The acid anhydride of the polybasic acid may, for example, be an acid anhydride of the above polybasic acid. The polybasic acid or its acid anhydride may be used alone or in combination of two or more kinds thereof, and the amount of the compound to be reacted with the compound represented by the formula (2) and the polybasic acid or its polybasic acid anhydride may be used. The amount of the ear is usually from 5 to 95%, preferably from about 1 to about 90%, in terms of the molar ratio. Further, among the above binder resins, a resin containing a polycarboxylic acid is preferred. The acid 値' of the binder resin used in the negative photosensitive black resin composition is usually 70 to 170, preferably 80 to MO. Further, the polystyrene-equivalent weight average molecular weight of the binder resin is usually from 1,000 to 50,000, preferably from 1,500 to 20,000. The binder resin used in the negative photosensitive resin composition is usually 5 to 90% by mass, preferably 10 to 60% by mass based on the total solid content of the photosensitive black resin composition of the period from 21 to 201032002. The range of mass % is contained. The compound which can be subjected to addition polymerization having an ethylenically unsaturated bond contained in the negative photosensitive black resin composition is, for example, a compound selected from at least one ethylenically unsaturated bond at the terminal, preferably having 2 The compound of the above ethylenically unsaturated bond may be a monomer, a prepolymer such as a dimer, a trimer or an oligomer, a mixture thereof or the like, or a copolymer thereof or the like. As the above monomer, for example, an ester of an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid or maleic acid with an aliphatic polyol compound, an unsaturated carboxylic acid and a fat can be exemplified. A group of polyamine compounds such as decylamine. The ester of the unsaturated carboxylic acid and the aliphatic polyol compound may, for example, be ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, tetramethylene di Alcohol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether, trimethylolethane three Acrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate Ester, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene methoxyethyl) isocyanurate Acrylates such as polyester acrylate oligomers; tetramethylene glycol dimethacrylate-22- 201032002, triethylene glycol dimethacrylate 'neopentyl glycol dimethacrylate, three Methyl propane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, hydrazine, 3-butanediol dimethacrylate, hexanediol dimethyl Acrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbus Sugar alcohol tetramethacrylate, φ bis [p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloxy) Ethoxylated methacrylates such as ethoxy)phenyl]dimethyl ketone; ethylene glycol diitaric acid ester, propylene glycol conjugated acid ester, hydrazine, 3 · butanediol II itaconate, I, 4 - butanediol diitaconate, tetramethylene glycol isaconate, pentaerythritol diitaconate, sorbitol tetraconate, etc.; ethylene glycol dicrotonate , crotonic acid such as tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradodetoic acid ester Ethylene glycol diisocrotonate, pentaerythritol diisobarium phthalate, sorbitol tetraisocrotonate, etc.; ethylene glycol dimaleate, triethylene glycol dimaleate Maleate such as ester, pentaerythritol dimaleate or sorbitol tetramaleate. As the decylamine of the unsaturated carboxylic acid and the aliphatic polyamine compound, for example, methylene bis-acrylamide, methylene bis-methyl decylamine, 1,6-hexamethylene bis- can be exemplified. Acrylamide, 1,6-hexamethylenebis-methylpropenylamine, di-ethyltriamine tripropenylamine, benzodimethylbisacrylamide, benzodimethylbismethyl decylamine Wait. As another example of the monomer, for example, an ethylene obtained by adding a polyisocyanate compound having 2 to 23 - 3,003,200 or more isocyanate groups in the molecule and a vinyl monomer represented by the following formula (3) can be exemplified. A carbamic acid ester compound or the like. R21 R22 (3) ch2=c-c-o-ch2-ch-oh Ο [wherein R21 and R22 each independently represent a hydrogen atom or a methyl group].

The above-mentioned vinyl urethane compound is exemplified by a compound containing two or more polymerizable vinyl groups in one molecule described in Japanese Patent Publication No. Sho 48-41, No. 708, and JP-A-53-37 1 93 The urethane acrylates described in Japanese Laid-Open Patent Publication No. SHO-48-64 No. Hei. A polyfunctional acrylate or methacrylate. Further, as a photocurable monomer and an oligomer, it can also be used as a photocurable monomer and an oligomer in 协会本接志志, Vol.20, No. 7, 300-308 (1984).

The amount of the above-mentioned compound having an ethylenically unsaturated bond and which is addition-polymerizable is usually 0.5 to 50% by mass, preferably 1 to 1% by mass based on the total solid content of the photosensitive black resin composition. 40% by mass The photopolymerization initiator contained in the negative-type photosensitive black resin composition is not particularly limited as long as it is a compound capable of initiating polymerization of a compound having an ethylenically unsaturated bond and addition polymerization, and benzene is exemplified. Ethyl ketone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator, triazine photopolymerization initiator, -24-201032002 An azole photopolymerization initiator or the like. As the present ethyl ketone photopolymerization initiator, for example, acetophenone, 2-hydroxy-2-methyl-1-phenylpropane-b aldehyde, 2-hydroxy-2-methyl-oxime-H- ( 2 -hydroxyethoxy: 1, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholinyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(butyl An alkane-p-ketone, an oligomer of 2-hydroxy-2-methyl-i-[4-(1-methylφ-alkan-1-one, etc. as a benzoin photopolymerization initiator, for example, benzene Occasion methyl ether, benzoin ethyl ether, benzoin-isobutyl ether, etc. As a benzophenone-based photopolymerization initiator, for example, methyl ketone, methyl o-benzylbenzoate, 4 _Phenyldimercapto-4'-methyldiphenyl sulfide, 3,3,,4,4'-tetra(di)-benzophenone, 2,4,6-trimethylbenzophenone, etc. φ is a thioxanthone photopolymerization initiator, for example, thioxanthone, 4-isopropylthioxanthone, 2,4-diethylchlorothioxanthone, 1-chloro-4-propoxythiophene Toxane ketone, etc. As a triazine-based photopolymerization initiator, for example, dichloromethyl)-6-p-methoxystyryl-s-trisylmethyl-6-(1-p-dimethyl) Aminophenyl 丨, 3_ butyl; 2 - Chloromethyl-4-amino _6_p-methoxy styryl-1-yl)-4,6-bis-trichloromethyl-s-triazine, 2-(4-)-4, 6-bis-dichloromethyl-3_triazine, 2-(4-ethoxyl group may be exemplified by diethoxy ketone, benzyl dimethyl condensate > phenyl] propan-1-one-1- (4 -Methylthiobenzene 4-morpholinylphenyl)vinyl)phenyl]propene may, for example, be benzoin isopropyl ether or benzoin, and examples thereof include dibenzophenone and 4-benzyltributyl. The peroxycarbonyl group can be exemplified by 2-isopropylthioxanthone and 2,4-di, and 2,4-bis(,2,4-bis(trichlorosuccinyl)-s-triazine's-triazine is exemplified. ,2-(naphthalene-methoxy-naphthalen-1-ylxan-1-yl)_4,6- -25- 201032002 bis-trichloromethyl-S-triazine, 2-(4-butoxy- Naphthalen-1-yl)-4,6-bis-trichloromethyl-s-triazine, 2-[4-(2-methoxyethyl)-naphthalen-1-yl]-4,6-double -trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl)-naphthalen-1-yl]-4,6-bis-trichloromethyl-s-triazine, 2 -[4-(2-butoxyethyl)-naphthalen-1-yl]-4,6-bis-trichloromethyl-3-triazine, 2-(2-methoxy-naphthalene-1- -4,6-bis-trichloromethyl-s-triazine, 2-(6-methoxy-5-methyl-naphthalen-2-yl)-4,6-bis-trichloromethyl -s-triazine, 2-( 6-methoxy-naphthalen-2-yl)-4,6-bis-trichloromethyl-s-triazine, 2-(5-methoxy-naphthalen-1-yl)-4,6-double -Trichloromethyl-s-triazine, 2-(4,7-dimethoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-s-three, 2- (6 -ethoxy-naphthalen-2-yl)-4,6-bis-trichloromethyl-s-triazine, 2-(4,5-dimethoxynaphthalen-1-yl)-4,6 - bis-trichloromethyl-s-triazine, 4-[p-oxime, fluorenyl-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s Triazine, 4-[o-methyl-p-indole, indole-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazine, 4-[p-indole, indole-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazine, 4-[o-methyl-p-anthracene, Ν-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazine, 4-(p-indole-chloroethylaminophenyl)-2,6 - bis(trichloromethyl)-s-triazine, 4-(p-indole-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazine, 4-[p-indole, indole-bis(phenyl)aminophenyl]-2,6-di(trichloromethyl)-8-triazine, 4-(p-1,3-chloroethylcarbonylaminobenzene) Base-2,6-di(trichloromethyl) -s-triazine, 4-[p-indole-(p-methoxyphenyl)carbonylaminophenyl]_2,6-di(trichloromethyl)-s-triazine, 4-[inter- Ν,Ν-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazine, 4-[m-bromo-p-anthracene, fluorene-di (Ethoxycarbonylmethyl-26-201032002) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-chloro-p-N,N-di ( Ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-fluoro-p-N,N-di(ethoxycarbonyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-bromo-p-indole, indole-bis(ethoxycarbonylmethyl)aminobenzene -2,6-bis(trichloromethyl)-s-three exposure, 4-[o-chloro-p-indole, indole-bis(ethoxycarbonylmethyl)aminophenyl-2,6 - bis(trichloromethyl)-s-triazine, 4-[o-fluoro-p-indole, indole-bis(ethoxycarbonylmethylmethyl)aminophenyl]-2,6-di ( Trichloromethyl)-8-triazine, 4-[o-bromo-p-indole, indole-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s- Triazine, 4-[o-chloro-p-indole, indole-bis(chloroethyl)aminophenyl]-2,6-di(trichloro) Methyl)-s-triazine, 4-[o-fluoro-p-indole, indole-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazine , 4-[m-bromo-p-indole, indole-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazine, 4-[m-chloro- Ν-Ν, Ν-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazine, 4-[m-fluoro-p-anthracene, fluorene-di ( Chloroethyl)aminophenyl]-2,6-φ bis(trichloromethyl)-s-triazine, 4-(m-bromo-p-anthracene-ethoxycarbonylmethylaminophenyl) -2,6-bis(trichloromethyl)-s-triazine, 4-(m-chloro-p-indole-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethane) -s-triazine, 4-(m-fluoro-p-indole-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazine, 4- (o-bromo-p-oxime-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-8-triazine, 4-(o-chloro-p--> -ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(o-fluoro-p-indole-ethoxycarbonylmethylaminobenzene -2,6-bis(trichloromethyl)-s-triazine, 4-(m-bromo-p-indole-chloroethylaminophenyl)-2,6--27 - 201032002 bis(dichloromethyl)-s-triazine, 4·(m-chloro-p-_N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-three Xiao, 4_ (m-p-chloroethylaminophenyl)-2,6-di(trichloromethyl)_s_triazine, 4_(o-bromo-p-N-chloroethylaminobenzene Base)-2,6-bis(trichloromethyl)-triazine, 4_(o-chloro-p-N-chloroethylaminophenyl)_2,6-bis(trichloromethyl)-s — Triazine, 4-(o-fluoro-p-_N-chloroethylaminophenyl)_2,6-bis(trichloromethyl)-s-triazine, and the like.

The oxazole-based photopolymerization initiator may, for example, be 2-trichloromethyl-5-styryldiazole or 2-trichloromethyl-5(p-cyanostyryl)-1. 3,4-oxadiazole, 2_trichloromethyl_5_(p-methoxystyryl)-1,3,4-oxadiazole, 2_trichloromethyl_5_ (p-butoxy Styryl)_1,3,4·oxadiazole, 2·trichloromethyl_5_(p-hydroxystyryl)-1,3,4-oxadiazole, 2_trichloromethyl_5 • (p-chlorostyryl)·1,3,4-oxazole, 2-trichloromethyl·5_(p-methoxyphenyl)-^, “oxazole, 2-dichloromethyl” _5•(p-butoxyphenyl)oxadiazole, 2·dichloromethyl·5·(2 •naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl _ 5-( 曰(2 benzofuryl)vinyl)anthracene, 3,4 chelate, I trichloromethyl-5-(d-(6-methoxy-2-benzofuranyl)vinyl , oxazole, 2, dichloromethyl- 5 (2-benzofuranyl)-i, 3,4-oxadiazole, etc. Further, 'as a photopolymerization initiator', for example, 2, 4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4,5,5-tetraphenyl-1,2 -biimidazole, 1〇_butyl-2-chloroacridone, 2_ethyl awake, benzoyl, 9,1 〇 phenanthrene quinone, phenylglyoxylate methyl ester, one mega In the photopolymerization initiator, a triazine-based photopolymerization initiator having a dichloromethyl group introduced into -28 - 201032002 and a chelate-diazole-based photopolymerization initiator having a trichloromethyl group introduced therein are preferably used. The triazine-based triazine-based photopolymerization initiator may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine. , 2,4-bis(trichloromethyl)_6_(4-methoxynaphthyl)-^, bicene, 2,4-bis(trichloromethyl)_6·piperidin-丨, 3,5 _Triazine ' 2,4• bis(dichloromethyl)-6-(4-methoxystyryl)-13,5-triazine, 2,4-double φ (trichloromethyl)_6- [2-(5-methylfuran-2-yl)ethylidene]-1,3,5-triazine, 2,4-bis(trichloromethyl)_6_[2_(furan-2-yl) Ethyl]·1,3,5-triazine, 2,4-bis(trichloromethyl)_6_[2-(4-diethylamino-2-methylphenyl)ethenyl]-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl) secondary The oxadiazole-based photopolymerization initiator to which trichloromethyl group is introduced, for example, is exemplified by 2-trichloromethyl-5-styryl-1,3,4-oxine Diazole, 2-trichloromethyl-5-(p-cyanostyryl)-indole, 3,4-oxadiazole, 2-trichloromethyl-9 5-(p-methoxystyrene Base)-丨,^^oxadiazole, 2_trichloromethyl-5_(p-butoxystyryl)·1,3,4-oxadiazole, 2_trichloromethyl_5_(cold -(2-benzofuranyl)vinyl)-I 3,4-oxadiazole and the like. These photopolymerization initiators may be used alone or in combination of two or more. The negative photosensitive black resin composition may contain a photopolymerization initiation aid. As the photopolymerization initiation aid, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-diaminoaminobenzoate, and 4- Isoamyl dimethylaminobenzoate, 4-dimethylaminobenzene-29- 201032002 2-ethylhexyl formate '2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine , 4,4,-bis(dimethylamino)benzophenone (commonly known as Michler), 4,4'-bis(diethylamino)benzophenone, 9,10·dimethoxyanthracene , 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. These photopolymerization initiation aids may be used alone or in combination of two or more. When the aforementioned photopolymerization initiator is used, it is used in an amount of 1 mol based on the photopolymerization initiator, usually 〇1 to 10 mol. The total amount of the photopolymerization initiator and the photopolymerization initiation aid is usually from 1 to 50% by mass, preferably from 3 to 30% by mass, based on the total solid content of the photosensitive black resin composition. The solvent contained in the photosensitive black resin composition may, for example, be an ester, an ether, a ketone or an aromatic hydrocarbon. As the ester, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid can be exemplified. Ethyl esters such as ethyl ester, butyl butyrate, methyl lactate, ethyl lactate; methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, Alkoxyacetic acid alkyl esters such as butyl oxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate Esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate , ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-B Methyl oxypropionate, -30- 201032002 2-Ethoxyethyl propionate, 2-hydroxy-2-methylpropanoate, 2·hydroxy-2-methylpropanoate, 2-A Methyl oxymethylpropionate, ethyl 2-acetoxymethylpropionate, pyruvic acid Ester, pyruvic acid ethyl ester, propionic acid, malonic Si vinegar, wine methyl acetate, ethyl acetate, acetyl, 2_ oxobutanoate, 2_-oxobutyrate and the like. As the ether, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethyl alcohol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve ethane acrylate, ethyl cellosolve can be exemplified. Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, monoethyl alcohol monobutyl ether, propylene glycol methyl ether acetate, propanol ethyl acid acetate, propylene glycol Ethyl ether acetate and the like. The ketones 'for example, methyl ethyl ketone, cyclohexanone, 2 - heptanone, 3-heptanone and the like can be exemplified. As the scented hydrocarbons, for example, toluene, xylene, toluene or the like can be exemplified. Among the above solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxylated propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, Butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate 'butyl carbitol acetate, and propylene glycol methyl ether acetate. The solvent may be used singly or in combination of two or more kinds, and the amount thereof is usually selected from the range of 2 to 50% by mass based on the mass percentage of the total solid content of the photosensitive black resin composition. (Positive-type photosensitive black resin composition) -31 - 201032002 The positive-type photosensitive black resin composition contains a light-shielding agent, a photosensitizer, a fluorine-based surfactant, and a solvent, which will be described later. The mask contained in the positive photosensitive black resin composition may be the same as the above-mentioned negative photosensitive black resin-constituting photo-agent and solvent. In the positive photosensitive black resin group, the layer formed by using the photosensitive black resin composition is provided with a layer in which the light is not irradiated, and the adhesive resin is also used in the photosensitive black resin. In the resin composition layer, the branching agent for dispersing the light-shielding agent is used as a positive-type photosensitive black resin composition. For example, a polymer compound having a phenol resin or a polyhydroxystyrene-based hydroxyl group, a methacrylic acid copolymer can be exemplified. A polymer compound containing a carboxyl group such as a substance or the like contains a phenolic hydroxyl-soluble resin. In addition, the alkali-soluble resin is preferably an alkali-soluble resin having curability, and examples thereof include a curable alkali-soluble resin, an epoxy group, an oxetane group, and a tetrahydrofuranyl group. As the positive photosensitive black resin composition, for example, a compound having a diazonium group or the like can be exemplified. The compound may, for example, be 1,2-diazonium sulfonate sulfonate, 1,2-diazonium sulfonate decylamine, 1,2-heavy amine or the like. It is preferably 1,2-diazonaphthoquinone sulfonate. The binder resin and the coating contained in the solvent are components of the resin composition. Further, a binder resin such as a resin which has a function as a bulk medium, and a base containing a phenol, an acrylic acid copolymer or a carboxyl group, such as a resin, is curable. For example, a sensitizer having a vinyl butyrolactone skeleton or the like may be used as the diazonium difluoride, 1,2-diazonaphtazinylsulfonium sulfonate 201032002, and the negative and positive photosensitive black resin compositions as described above may also be used. It contains additives such as a thermal polymerization inhibitor, a chelating agent, a polymer compound other than the binder resin, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor. The thermal polymerization inhibitor is contained in order to prevent the thermal polymerization of the compound having an ethylenically unsaturated bond and addition polymerization when it is retained in the photosensitive black resin composition. As the thermal polymerization inhibitor, for example, hydroquinone, Φ-p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-Asia Nitrophenylhydroxylamine sulfonium salt and the like. When the thermal polymerization inhibitor is contained, the content thereof is usually about 0.01 to 5% by mass based on the total mass of the photosensitive black resin composition. Further, examples of the chelating agent include glass, alumina, and the like. Examples of the polymer compound other than the binder resin include PTFE, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. As the adhesion promoter, for example, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl) can be exemplified. )-3-Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxyphthalate , 3-glycidoxypropyltrimethoxy sand, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Baseline, 3-chloropropylmethyldimethoxydecane, 3-chloropropane-33-201032002 alkane, P-based _ is violet i -2-, as a carboxylic acid, acid, etc. Acid propyl succinyl benzene tricarboxylate succinic acid carboxylic acid trimethoxy decane, 3-methyl propylene methoxy propyl trimethoxy sulfonium 3-mercaptopropyl trimethoxy decane, and the like. As the antioxidant, for example, 2,2-thiobis(4-E 6-tert-butylphenol), 2,6-di-t-butylphenol or the like can be exemplified. Further, as the external absorbent, for example, 2-(3-tert-butyl-5-methyl; hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone can be exemplified. Further, as the aggregation preventing agent, for example, sodium polyacrylate or the like can be exemplified. Further, the photosensitive black resin composition of the present invention may contain an acid, an organic amine compound or the like. As the organic carboxylic acid, for example, formic acid, acetic acid, propyl butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, octyl aliphatic monocarboxylic acid; oxalic acid 'malonic acid, Succinic acid, glutaric acid, acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid malonic acid, ethylmalonic acid, dimethylmalonic acid, methyl An aliphatic dicarboxylic acid such as succinic acid methyl succinic acid or citraconic acid; an aliphatic tricarboxylic acid such as glycerin tricarboxylic acid, uranium or camphor tricarboxylic acid; benzoic acid, toluic acid, isobenzoic acid, 2,3-dimethyl Aromatic carboxylic acids such as benzoic acid and 3,5-dimethylbenzoic acid; phthalic acid, isophthalic acid, terephthalic acid, partial acid, trimesic acid, benzoic acid, and benzene Aromatic such as acid: phenylacetic acid, hydrogenated atropine, hydrogenated cinnamic acid, mandelic acid, benionic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamic acid, coumaric acid An organic acid having a molecular weight of 1,000 or less, such as an umbrella acid. As the organic amine compound, an organic 201032002 amine compound having a molecular weight of 1,000 or less is preferably used, and examples thereof include n-propylamine, isopropylamine, n-butylamine, isobutylamine, and tert-butylamine. - amylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, Cyclohexylamine, o-methylcyclohexylamine, m-methylcyclohexylamine, p-methylcyclohexylamine, o-ethylcyclohexylamine, m-ethylcyclohexylamine, p-ethylcyclohexyl Mono(cyclo)alkylamines such as amines; methyl ethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propyl-propylamine, di-n-propylamine, diisopropyl Amine, di-n-butylamine, diisobutylamine, di-tert-butylamine, di-n-pentylamine, di-n-hexylamine, methyl•cyclohexylamine, ethyl•ring Di(cyclo)alkylamines such as hexylamine, dicyclohexylamine; dimethyl-ethylamine, methyl•diethylamine, triethylamine, dimethyl-n-propylamine, diethyl • n-propylamine, methyl • di-n-propylamine, ethyl • Di-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-t-butylamine, tri-n-pentylamine, Tri- (n-hexylamine), dimethyl-cyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine, etc. Alkylamines; 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol a mono(cyclo)alkanolamine such as 6-amino-1-hexanol or 4-amino-1-cyclohexanol; diethanolamine, di-n-propanolamine, diisopropanolamine, di- a di(cyclo)alkanolamine such as n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine or bis(4-cyclohexanol)amine; triethanolamine, Tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tris(4-cyclohexyl) Tri(cyclo)alkanolamines such as amines; amines; 3-amino-1,2-35-201032002 Propylene glycol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol , 4-amino-1,3-butanediol, 4-amino-1,2-cyclohexane Alcohol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino group- Amino (cyclo)alkanediols such as 1,3-propanediol, 2-diethylamino-1,3-propanediol; 1-aminocyclopentane methanol, 4-aminocyclopentane methanol, 1-amine Cyclohexane methanol, 4-aminocyclohexane methanol, 4-dimethylaminocyclopentane methanol, 4-diethylaminocyclopentane methanol, 4-dimethylaminocyclohexane methanol, 4- An amino group-containing cycloalkane methanol such as diethylaminocyclohexane methanol; alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4- An aminocarboxylic acid such as an aminocyclohexanecarboxylic acid or the like. Further, for example, a compound in which an amine group is directly bonded to a phenyl group may, for example, be a compound in which an amine group is bonded to a phenyl group through a carbon chain. As the compound in which the aforementioned amine group is directly bonded to the phenyl group, for example, aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, p-n-propylaniline can be exemplified. , p-isopropylaniline, p-n-butylaniline, p-t-butylaniline, 1-naphthylamine, 2-naphthylamine, N,N-dimethylaniline, anthracene, fluorene-diethyl Aromatic amines such as aniline, p-methyl-hydrazine, hydrazine-dimethylaniline; o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethyl Aminobenzyl alcohols such as aminobenzyl alcohol and p-diethylaminobenzyl alcohol; o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, -aminophenols such as diethylaminophenol; m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, etc. 201032002 Formic acid (derivatives), etc. The above-mentioned organic carboxylic acid and organic amine-based compound may be used alone or in combination of two or more. When the organic carboxylic acid or the organic amine-based compound is used, the content of the photosensitive black resin composition is generally 0.001 to 15% by mass, preferably 0.001 to 15% by mass, based on the total mass of the photosensitive black resin composition. 〇. 〇1~1 〇% by mass. The photosensitive black resin composition of the present invention has a fluorine-based surfactant having a fluoroalkyl group in its side chain. The fluorine-based surfactant having a fluoroalkyl group in the side chain may be any of a nonionic surfactant, a cationic surfactant, and an anionic surfactant. Here, the fluoroalkyl group is a generic term for a fluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with a fluorine atom, and a fluoroalkyl group in which a part of hydrogen atoms in the alkyl group is substituted with a fluorine atom. Any group of linear or branched. Those having an oxygen atom in the fluoroalkyl group (for example, cf3-(ocf2cf2)2-, etc.) are also included in the definition of the fluoroalkyl group of the present invention. The chain length of the alkyl group φ is preferably from 3 to 12 carbon atoms, and more preferably a linear perfluoroalkyl group. The surfactant-based surfactant is preferably a structural unit represented by the following formula (ia): 1 to 4% by mass based on the total mass % of all structural units, and is represented by the following formula (lb). A compound having a structural unit ratio of from 20 to 98% by mass and a structural unit of from 1 to 4% by mass represented by the following formula (1c). -37- 201032002 R1 I —CH2 ~* C — I X’-L’~R2 (la) R3 R*

I I CH2 —C— — CHi —C —

I I 0,\〇-L*~fR4-〇3^R5 x -L -Rf (1b) (1c)

Φ ' Rl ' R3 and R6 each independently represent a hydrogen atom or a fluorenyl group having 1 to 5 carbon atoms. R 2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, or -(31((^3)) 2〇)〇1_31((;^3)3,114 represents an alkylene group having 2 to 8 carbon atoms. R represents a nitrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorenyl group or a carbon number of 6 to 20 The aryl group; L1, L2 and L3 each independently represent a single bond, a pendant or substituted alkyl group; X1 represents -C02-, -CONY1-, or an aryl group X represents 〇-'-C02- , -CONY2-, an aryl group, or a divalent heterocyclic residue; Rf represents a fluoroalkyl group; η represents an integer of 2 to 20, and m represents an integer of 0 to 3 'Y1 and γ2 each independently represent hydrogen Atom or a number of carbon atoms of 1 to 5]. R1' R2, R3 and R6 are at least one alkyl group having 1 to 5 carbon atoms.

The alkyl group may be linear or branched, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl 'second butyl. . The alkylene group having 2 to 8 carbon atoms represented by R4 may be linear or branched, and examples thereof include an exoethyl group, a propyl group (methyl exoethyl group), and a trimethylene group. , tetramethylene, hexamethylene. When R5 is an alkyl group having 1 to 12 carbon atoms, the alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl 'n-propyl group, an isopropyl group, and a positive one. Butyl, isobutyl, t-butyl, 2-ethylhexyl, n-dodecyl. When R5 is a fluorenyl group, examples thereof include an ethyl group, a propyl group, and a benzhydryl group. The carbon number of the carbon-38-201032002 is usually about 2 to 10. When R5 is an aryl group having 6 to 20 carbon atoms, examples thereof include a phenyl group, a tolyl group, and a naphthyl group. When at least one of L1, L2 and L3 is an alkylene group, the alkylene group may be linear or branched, and examples thereof include an ethyl group, a propyl group, and a trimethylene group. Tetramethylene and hexamethylene have a carbon number of usually about 2 to 8. When at least one of L1, L2 and L3 is a substituted alkylene group, as an example thereof, a φ straight chain such as an exoethyl group, a propyl group, a trimethylene group, a tetramethylene group or a hexamethylene group may be exemplified. The hydrogen atom of the branched alkyl group is substituted by an aryl group or a hydroxyl group of a phenyl group, and the number of carbon atoms is usually 2 to 20. When at least one of X1 and X2 is an aryl group, examples thereof include a phenyl group and a naphthyl group, and the number of carbon atoms is usually 6 to 20. When X2 is a divalent heterocyclic residue, examples thereof include a residue obtained by removing two hydrogen atoms from a heterocyclic ring such as a pyridine ring, a pyrimidine ring, a azoazine ring or a thiazole ring, and the number of carbon atoms is usually 3 to 10. When at least one of Y1 and Y2 is an alkyl group having 1 to 5 carbon atoms, the alkyl group may be linear or branched, and examples thereof include methyl group, ethyl group, and n-propane φ. Base, isopropyl, n-butyl, isobutyl, second butyl. Further, the fluorine-based surfactant further preferably wherein R2 in the formula (la) represents a compound of -(Si(CH3)2〇)m-Si(CH3)3, that is, at least a fluoroalkyl group and an olefinic group are used. A fluorine-based copolymer obtained by polymerizing a monomer of a bond with a monomer containing an organic oxime chain and an ethylenic double bond. Further, the photosensitive black resin composition of the first embodiment of the present invention contains 0.0008 to 0.005 mass% (8 to 50 ppm) of a fluorine-based surfactant based on the fluorine content of all the solid components. Such a photosensitive black resin composition can be preferably used in a composition for forming a black matrix, which has a plurality of color pixel layers on a substrate and is located between adjacent color pixel layers. A black matrix in the color filter of the black matrix of the isolation wall. That is, a photosensitive black resin composition containing 0.0008 to 0.005 mass% (8 to 50 ppm) of a fluorine-based surfactant having a fluoroalkyl group in a side chain, based on the fluorine content relative to the entire solid content, is used. It can form a composition of a black matrix which is a partition wall, and imparts liquid repellency to the partition wall with respect to the ink for inkjet printing, thereby preventing color mixture caused by the incorporation of the color ink between adjacent color pixel layers, and ensuring uniformity. The lyophobic nature of the sentence prevents the occurrence of pixel defects such as local leakage. Further, in the photosensitive black resin composition of the first embodiment, the content of the fluorine-based surfactant itself having a fluoroalkyl group in the side chain can be appropriately adjusted depending on the mass ratio of fluorine in the molecular weight, but usually It is about 0.01 to 0.03 mass% (100 to 300 ppm) with respect to all solid components. When the content of the fluorine-based surfactant having a fluoroalkyl group in the side chain is less than 8 ppm based on the fluorine content of all the solid components, the liquid repellency of the black matrix which is formed as a partition wall is insufficient, and The color mixing prevention effect between adjacent color pixel layers cannot be sufficiently exerted, and the black matrix surface produces a Benar swirling-like structure, which is less preferable. In addition, when the content of the fluorine-based surfactant having a fluoroalkyl group in the side chain is more than 50 ppm based on the fluorine content of all the solid components, there is no problem in the central portion of the substrate. However, the outer peripheral portion (edge portion) of the substrate A pixel defect such as partial whitening occurs in the nearby color pixel layer. Here, it has -40- on the side chain in terms of fluorine relative to the total solid content.

201032002 The fluorine-based surfactant content of the fluoroalkyl group can be obtained by multiplying the molecular weight ratio of the fluorine-based surfactant having a fluoroalkyl group in the chain by the mass ratio of the fluorine-containing active agent in the side chain in all the solid components. Find out. Further, when the fluorine-containing component is only a fluoroalkyl group in the side chain, the fluorine content in the solid component can be determined by oxygen combustion-ion. Further, in the case where the fluoroalkyl group having a fluorine-based interfacial living chain of a fluoroalkyl group has fluorine in the side chain, the fluorine content in the entire solid content is in the above range, that is, the component has a side chain. When the fluorine-based interface fluorine-containing component of the fluoroalkyl group contains fluorine of the fluorine-containing component, the fluorine content of the phase is desirably within the above range. Further, the molecular weight of the fluorine-based surfactant is preferably 15,000 in terms of molecular weight in terms of polystyrene from the prevention of color mixture defects and the solvent of the surfactant itself, and the photosensitive black resin composition of the present invention is isolated. In addition to the black matrix of the wall, a photo spacer for the purpose of the gap can also be used. With the photosensitive spacer of the present invention, high-precision pitch and shape can be prevented, and interference with effective pixels can be prevented. (Black matrix substrate) Next, the surfactant-based chromatographic analytical agent is used in the fluorine-based interface solid component in which the photosensitive black resin in the side is used, in addition to the side fluorine. As long as the phase is available. Further, in addition to the solid active agent, 25,000 Å of all solids were prevented from being formed and the solubility of the pixels was measured, except that the pillars were formed to control the composition of the liquid crystal cell resin (black-41 - 201032002 color matrix substrate formed by the column product) The black matrix substrate is used for manufacturing a color filter. The color filter has a plurality of color pixel layers on a substrate and a black matrix which is a partition wall between adjacent color pixel layers. The black resin composition is applied onto a substrate to form a photosensitive black resin composition layer 'optical light is irradiated onto the photosensitive black resin composition layer through a photomask' by developing the irradiated photosensitive black resin composition layer. Fig. 1A to Fig. 1C are diagrams showing a procedure for manufacturing a black matrix substrate 7. The fabrication of the black matrix substrate 7 is started as a substrate 2 for forming a substrate of a black matrix. As the substrate 2, for example, Examples of the glass substrate, the ruthenium substrate, and the like include a polycarbonate substrate, a polyester substrate, and an aromatic polyamide substrate. a resin substrate such as a polyamide amide substrate or a polyimide substrate, and the substrate 2 may be subjected to a reagent treatment, a plasma treatment, an ion plating treatment, a sputtering treatment, or the like by a reagent such as a decane coupling agent. The pretreatment such as a gas phase reaction treatment or a vacuum vapor deposition treatment is applied. Next, the photosensitive black resin composition of the present invention described above is applied to one surface in the thickness direction of the substrate 2. As the coating method, for example, a spin coating method can be used. A known coating method such as (spin coating method), a cast coating method, a roll coating method, a slit coating method, a slit and a spin method, or a non-spin coating method, and coating a photosensitive black resin composition After drying on the surface of the substrate 2, the solvent is evaporated and the solvent is volatilized. As shown in Fig. 1A, a photosensitive black resin composition layer 1 having a predetermined film thickness is formed on the substrate 2. Next, as shown in Fig. 1B, the light is transmitted. The cover 3 irradiates the photosensitive layer 1 with the photosensitive black resin group -42-201032002. The photosensitive layer 1 is formed of a photosensitive black resin composition layer 1 using a negative photosensitive black resin composition. The mask 3 is attached, for example. The light shielding layer 32 is provided on the surface of the glass plate 31, etc. The light 4 is shielded by the light shielding layer 32. The portion of the glass plate 31 where the light shielding layer 32 is not provided is the light transmitting portion 33, and the light 4 is transmitted through the light transmitting portion 33. The photosensitive black resin composition layer 1 is irradiated onto the photosensitive black resin composition layer 1, and the pattern of the photosensitive black resin composition layer 1 is φ printed and exposed. Further, in order to improve the exposure sensitivity, PV A may be coated on the surface of the glass plate 31. As the light ray 4, ultraviolet rays such as g-line (wavelength 436 nm) and i-line (wavelength 3 65 nm) are usually used. Preferably, the light 4 is irradiated with parallel light to the photosensitive black resin composition layer 1, usually through the light. The cover array (not shown) or the like is irradiated. The exposure of the photosensitive black resin composition layer 1 can be performed by using a known projection exposure apparatus or a line type exposure apparatus through the mask 3, or can be used. A maskless photographic device with a laser as a light source is used. The amount of irradiation of the light 4 may be based on the content of the light-shielding agent in the photosensitive black composition, the kind or content of the binder resin, the type or content of the compound having an ethylenically unsaturated bond and addition-polymerizable, and the photopolymerization initiator. The type or content, and the wavelength of the light source, the reading wavelength, and the power used in the exposure apparatus are appropriately selected. After the exposure of the photosensitive black resin composition layer 1 is completed, development is carried out. In the development, the photosensitive black resin composition layer 1 after exposure may be brought into contact with the developer. As the developer, for example, an alkaline aqueous solution can be used. As the alkaline water-43-201032002 solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, hydrogen can be used. Water-soluble basic compound such as tetramethylammonium oxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecene The aqueous solution has a concentration of usually 0.001 to 1% by mass, preferably 0.01 to 1% by mass, based on the mass of the aqueous alkaline solution. The alkaline aqueous solution described above may contain a water-soluble organic solvent such as methanol or ethanol, or an interfacial surfactant. An organic solvent can be used as the developer, and for example, a solvent contained in the photosensitive black resin composition can be appropriately combined and used. The developing method is not particularly limited. For example, it can be developed by a immersion developing method (immersion developing method), a rinse developing method "spray developing method", or a stick developing method (repelling developing method). The developing temperature is usually in the range of 10 to 40 ° C, and the developing time is usually 10 to 300 seconds. By the development, the light-irradiated area in which the light 4 in the photosensitive black resin composition layer 1 is not irradiated is dissolved in the developer and removed. On the other hand, the light-irradiating region of the photosensitive black resin composition layer 1 irradiated with the light 4 remains on the substrate 2, and as shown in Fig. 1C, a black matrix (partition wall pattern) 5B can be formed on the surface of the substrate 2. Black matrix substrate 7. The portion where the photosensitive black resin composition layer 1 is dissolved and removed by the development treatment becomes the opening portion 7a of the black matrix 5?. In the present embodiment, in the black matrix substrate 7, the height of the partition wall (the thickness of the black matrix 5BM) A of the black matrix 5BM is preferably 1.2 to 3.0 μm. When the height A of the partition wall A of the black matrix 5BM is less than 1.2 μm, the ink jet printing ink of a sufficient amount of the color density of 201032002 required for color reproduction cannot be filled in the opening portion 7a of the black matrix 5ΒΜ. When the height A of the partition wall exceeds 3.μιη, it is difficult to prepare not only the black matrix substrate 7 on which the high-precision partition wall pattern is formed, but also the height difference between the color pixel layer and the partition wall when the color filter is manufactured using the black matrix substrate 7. Large, the design of the liquid crystal cell becomes difficult and not good. Further, in the present embodiment, the width Β of the partition wall in the black matrix 5 of the black matrix substrate 7 is usually set to about 50 μm or less, preferably about 10 to 20 μm. Further, the opening portion 7a of the black matrix 5A in the region surrounded by the partition wall is generally rectangular, and the corner portion may have an arc shape having a radius of about several μη from the viewpoint of the ink filling property. When the opening 7a of the black matrix 5 Β 为 is square, the side length C of the opening 7a is usually set to about 20 to 150 μm. Moreover, when the opening 7a of the black matrix 5BM is a rectangle,

The size of the opening portion 7a is usually set to 20 to 150 pm x 70 to 50 (the black matrix substrate 7 prepared after the development process), and when the alkaline water-soluble φ liquid is used as the developing solution, it is washed and heated after the development treatment. In order to make the black matrix 5BM exhibit sufficient stability with respect to the ink for inkjet printing without causing deformation such as dissolution or swelling, the heat treatment is usually carried out at 150 to 250 ° C for 5 to 30 minutes. In the black matrix substrate 7, the black matrix 5BM is prepared by using the photosensitive black resin composition of the present invention. Therefore, it is composed of a partition wall which is imparted with a liquid repellency with respect to the ink for inkjet printing in a uniform state. Ink printing ink "printed in the opening 7a of the black matrix 5BM by the ink printing method can prevent the ink from exceeding the black-45-201032002 matrix 5BM which is the partition wall and invade the adjacent opening portion 7a to cause color mixing, thereby preventing local ink sputum from occurring. Poor charging problem, which can prevent pixel defects such as whitening, and by time-of-flight secondary ion mass spectrometer (Time of Flight) Secondary Ion Mass Spectroscopy, abbreviated as: T OF -SIMS) In the detection result of the negative ions detected, the total negative ion detection intensity of the black matrix substrate 7 is 1 and the fluoride ion detection intensity ratio at the time of the nominalization is better as the partition wall. The surface of the black matrix 5BM is 0.15 or more and less than 0.3, and the surface of the substrate 2 corresponding to the opening 7a of the black matrix 5BM is 0.05 or less. The surface of the black matrix 5BM corresponds to the opening 7a of the black matrix 5BM. The fluorine ion detection intensity ratio in the surface of the substrate 2 can be controlled to a specific range by adjusting the content of the fluorine-based surfactant in the photosensitive black resin composition used in forming the black matrix 5BM. It is used in relation to the entire solid content. In the fluorine content, the photosensitive black resin composition containing 0.0008 to 0.005 mass% (8 to 5 (?? 111) of a fluorine-based surfactant can be formed into a black matrix by forming a black matrix 5BM on the substrate 2. The fluoride ion detection intensity ratio of the surface of the 5BM is 0.15 or more, and the surface of the substrate 2 corresponding to the opening portion 7 a of the black matrix 5 B 氟 is fluoride ion. Measuring the intensity of the square of the black-matrix substrate 〇5 7 ratio.

The surface of the black matrix 5 与 and the surface of the substrate 2 corresponding to the opening portion 7 a of the black matrix 5 氟 have a fluorine ion detection intensity ratio of the black matrix substrate 7 controlled to the above-described specific range, and are provided in a uniform state with respect to inkjet printing. A black matrix 5BM of the lyophobic barrier wall using ink. In the case of the inkjet printing method, the inkjet printing ink printed on the opening 7a of the black matrix 5BM by the inkjet printing method can prevent the ink from entering the adjacent opening portion 7a by the black matrix 5BM which is the partition wall, and can be prevented from being mixed. Preventing the occurrence of local ink squeezing problems, that is, preventing the occurrence of pixel defects such as whitening, and the black matrix 5BM surface of the partition wall has a fluorine ion detection intensity ratio of less than 0.15, and the black matrix 5BM which becomes the partition wall is printed with respect to inkjet. The liquid repellency of the φ ink is insufficient, and the effect of preventing color mixture between adjacent color pixel layers cannot be sufficiently exhibited. Further, when the fluorine ion detecting intensity ratio of the surface of the black matrix 5BM is 0.3 or more, pixel defects such as partial whitening occur in the color pixel layer in the vicinity of the outer peripheral portion (edge portion) of the substrate 2. Further, when the ratio of the fluorine ion detection intensity of the surface of the substrate 2 corresponding to the opening 7a of the black matrix 5BM exceeds 0.05, the liquid repellency with respect to the ink for inkjet printing is also imparted to the surface of the substrate 2 on which the color pixel layer is formed. A pixel defect such as partial whitening occurs in the color pixel layer in the vicinity of the outer peripheral portion (edge portion) of the substrate 2, and the color mixing prevention effect due to the liquid repellency of the surface of the φ black matrix 5BM is lowered. (Manufacture of Color Filter) Next, a method of manufacturing the color filter of the present invention will be described. 2A and 2B are sequence diagrams showing a method of manufacturing a color filter. 3A and 3B are schematic views showing the constitution of a color filter. The manufacturing method of the color filter includes a black matrix substrate preparing step and a pixel layer forming step. <Black matrix substrate preparation step> -47 - 201032002 Black matrix substrate preparation step is a step of preparing a black matrix substrate, and as described above, a black matrix substrate 7 on which a black matrix 5BM is formed on the substrate 2 is prepared. <Pixel layer forming step> In the pixel layer forming step, inkjet printing is performed by inkjet printing on the opening portion 7a of the black matrix 5BM of the pixel region surrounded by the partition wall formed on the black matrix substrate 7. A color pixel layer is formed using ink. The color pixel layer is composed of a red color pixel layer, a green color pixel layer, and three primary color pixel layers of a blue color pixel layer. In the pixel layer forming step, as shown in FIG. 2A, inkjet printing heads 1 OR, 10G, and 10B are used to print various colors on the specific opening portion 7a of the black matrix 5BM, corresponding to the respective colors of the formed color pixel layer. Inkjet printing inks 1 1 R, 1 1 G, 1 1 B. The head for inkjet printing is not particularly limited, and a known nozzle such as a piezoelectric method, a bubble jet (registered trademark) method, or an electrostatic method can be used, and a piezoelectric method is particularly preferable. Further, as the ink for inkjet printing, a monomer or oligomer containing a known color former prepared by a known method, a dispersant, a crosslinkable molecule polymerized by heat or light, a binder resin, and polymerization can be used. A known ink for inkjet printing such as an initiator and a solvent. When inks 1 1 R, 1 1 G, and 1 1 B of inkjet printing of various colors are printed on the specific opening 7a of the black matrix 5BM, the color pixel layer is formed because the solid concentration of the ink of each color is restricted. In order to obtain a desired layer thickness and coloring density, it is necessary to print a plurality of times of inkjet printing ink 1 1 R with respect to the volume (opening area x partition wall height) of the opening portion 7a of the black matrix 5BM 201032002. , 1 1 G, 1 1 B. In the pixel layer forming step of the present embodiment, 'color inks are printed on the opening portion 7a of the black matrix 5BM which is provided with the liquid repellency to the inkjet printing inks 1 1 R, 1 1 G, and 1 1 B in a uniform state. Since 11R, 11G, and 11B prevent the ink from exceeding the black matrix 5BM which is the partition wall and invade the adjacent opening portion 7a to cause color mixing, it is possible to prevent the occurrence of local ink squeezing problems, that is, to prevent occurrence of pixel defects such as whitening. The inkjet printing inks 1 1 R, 1 1 G, and 1 1 B of various colors are printed on the specific openings 7a of the black matrix 5, and if exposed to heat or light, as shown in FIG. The opening portion 7a of the black matrix 5 BM of the color ink forms a red color pixel layer 5R, a green color pixel layer 5G, and a blue color pixel layer 5B. Thus, as shown in FIG. 3A, the color pattern 5 composed of the color pixel layers 5R, 5G, and 5B of the three primary colors and the color of the black matrix 5BM φ serving as the partition wall between the adjacent color pixel layers can be manufactured. Filter 6. Further, the color filter 6 shown in FIG. 3A corresponds to the opening portion 7a of the black matrix 5B that is formed in a square shape, and the color pixel layers 5R, 5G, and 5B of various colors are formed by correspondingly forming Color pixel layers 5R, 5G, and 5B of various colors are formed in the opening portion 7a of the rectangular black matrix 5BM, and the color filter 60 shown in Fig. 3B can be manufactured. (Examples) Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the examples. -49- 201032002 (Impact of fluorine-based surfactant content in photosensitive black resin composition) <Synthesis of fluorine-based surfactant> [Synthesis of fluorine-based surfactant 1]

In a glass flask equipped with a stirring device, a condenser, and a thermometer, 29 parts by weight of a fluoroalkyl group-containing acrylate monomer represented by the following formula (4) and an organic oxime represented by the following formula (5) are added. 26 parts by weight of an ethylenically unsaturated monomer, 45 parts by weight of a monoacrylate compound having a polyoxyethylene (molecular weight of 400) in a side chain (single terminal is a methoxy ether), and 200 parts by weight of propylene glycol monomethyl ether acetate One part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise under a nitrogen gas stream under reflux, and the mixture was refluxed at 80 ° C for 12 hours to carry out a polymerization reaction to obtain a fluorine-based surfactant 1. [6] 0 f3c(cf2)5, a 1 / , (4) (H3C) 3.SiOSi(CH3)2

• . . . (5)

The fluorine-based surfactant 1 is a compound having the following structural units and ratios: in the formula (la), R1 is a methyl group, X1 is -C〇2-, L1 is an exoethyl group, and R2 is - (SUCHshOh-SUCHsh The structural unit is 26% by mass: in the formula (lb), R3 is a hydrogen atom, l2 is a single bond, R4 is an exoethyl group, η is 9, and R5 is a methyl group having a structural unit of 45 mass%; and formula (lc) In the structure, the ruler 6 is a methyl group, the X2 is -C〇2-, the L3 is an exoethyl group, and the Rf is a perfluorohexyl group. The structure is -50 to 201032002, which is 29% by mass. [Synthesis of a fluorine-based surfactant 2] The fluoroalkyl group-containing acrylate monomer represented by the formula (4) was changed to 21 parts by weight, and the organic ruthenium-containing unsaturated monomer represented by the formula (5) was changed to 18 parts by weight, and had a side chain. The polyacrylate (molecular weight 4 Å) monoacrylate compound (single terminal methoxy ether) was changed to 58 parts by weight, and further, 3 parts by weight of 2-hydroxyethyl methacrylate was added, and a fluorine-based interface was added. The active agent 1 is subjected to a polymerization reaction in the same manner to obtain a fluorine-based surfactant 2. The fluorine-based surfactant 2 has the following structural units and ratios of compounds. In the formula (la), R1 is a methyl group, X1 is -C02-, L1 is an exoethyl group, and R2 is - (the structural unit of SKCHhhOh-SKCHsh is 18% by mass; in the formula (la), R1 is a methyl group, X1 is -C02-, L1 is an exoethyl group, and R2 is a hydroxyl group. The structural unit is 3% by mass: in the formula (lb), R3 is a hydrogen atom, L2 is a single bond φ, R4 is an exoethyl group, and η is 9. R5 is a structural unit of a methyl group of 58% by mass; and in the formula (lc), R6 is a methyl group, X2 is -C02-, L3 is an exoethyl group, and Rf is a perfluorohexyl group. The structural unit is 21% by mass. Example 1) A mixture of 40 parts by mass of a black pigment (CI Pigment Black 7) and 12 parts by mass of a polyurethane dispersant] 52 parts by mass of a binder resin [Example (6) Reaction product of 30 parts by mass of the compound and 50 parts by mass of biphenyltetracarboxylic dianhydride and 5 parts by mass of tetrahydrophthalic anhydride. -51 - 201032002 ] 33 parts by mass, having an ethylenically unsaturated bond And 11 parts by mass of the compound dipentaerythritol hexaacrylate which can be added and polymerized, and 5.0 parts by mass of 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine of the photopolymerization initiator, Double of photopolymerization initiator 3.0 parts by mass of ketone, 0.68 parts by mass (relative to total solid content: 65 ppm, fluorine content relative to all solid components: ll ppm) fluorine-based surfactant 1, and solvent propylene glycol monomethyl ether acetate 3 58 mass The mixture was mixed to obtain a photosensitive black resin composition of Example 1.

【化8】

Η

I o-ch2-ch-ch2-o-cc=ch2 OH Ο (6) (Example 2) The amount of addition of the fluorine-based surfactant 1 was changed to 130 pPm with respect to the total solid content ( A photosensitive black resin composition of Example 2 was obtained in the same manner as in Example 1 except that the fluorine content of all the solid components was 22 ppm. (Example 3) The same procedure as in Example 1 was carried out except that the amount of addition of the fluorine-based surfactant 1 was changed so that the content of the total solid content was 21 Oppm (the fluorine content of all the solid components: 3 5 ppm). The photosensitive black resin composition of Example 3. 52-201032002 (Example 4) The same as Example i except that the amount of addition of the fluorine-based surfactant was changed to 160 Ppm (the fluorine content of all solid components: 27 ppm) with respect to the total solid content. The photosensitive black resin composition of Example 4 was obtained. (Example 5) The fluorine-based surfactant 2 was changed to the fluorine-based surfactant 2, and the content of the fluorine-based surfactant 2 relative to the total solid content was 260 Ppm (the fluorine content relative to the total solid content: 4) A photosensitive black resin composition of Example 5 was obtained in the same manner as in Example 1 except for 5 ppm. (Comparative Example 1) A photosensitive black resin composition of Comparative Example 1 was obtained in the same manner as in Example 1 except that the fluorine-based surfactant 1 was not added. (Comparative Example 2) The content of the surfactant based on the entire solid component was changed to 100 ppm, except that the fluorine-based surfactant 1 was changed to the organic lanthanoid surfactant represented by the following formula (7). 1 - The photosensitive black resin composition of Comparative Example 2 was obtained in the same manner. 【化9】

AcO-POA-(-SKCH3)2〇-l-POA-Ac ---(7) -53- 201032002 [wherein, POA represents a polyoxyalkylene structure, and '^ represents an ethylidene group]. (Comparative Example 3) The same procedure as in Comparative Example 2 was carried out except that the amount of the organic lanthanoid surfactant added by the formula (7) was changed so that the content of the surfactant relative to the entire solid content was 8 〇 PPm. The photosensitive black resin composition of Comparative Example 3. (Comparative Example 4) The same procedure as in Comparative Example 2 was carried out except that the amount of the organic lanthanoid surfactant added by the formula (7) was changed so that the content of the surfactant relative to the entire solid content was 16 〇 Ppm. The photosensitive black resin composition of Comparative Example 4. (Comparative Example 5) A comparative example was obtained in the same manner as in Example 1 except that the amount of the fluorine-based surfactant 1 was changed so that the content of all the solid components was 32 ppm (the fluorine content of all the solid components was 6 ppm). A photosensitive black resin composition of 5. (Comparative Example 6) A comparison was made in the same manner as in Example 1 except that the amount of the fluorine-based surfactant 1 was changed so that the content of all the solid components was 320 ppm (the fluorine content of all the solid components: 5 4 ppm). Photosensitive black of Example 6 201032002 Color resin composition. <Production of Black Matrix Substrate> The photosensitive black resin compositions of Examples 1 to 5 and Comparative Examples 1 to 6 were applied to an alkali-free glass substrate by a spin coating method (Model: #1 737, Corning Co., Ltd.) The product was heated in a vacuum oven and heated at 10 ° C for 90 seconds to form a photosensitive black resin composition layer composed of a solid φ component of each photosensitive black resin composition on the alkali-free glass substrate. The thickness of the photosensitive black resin composition layer formed by heat treatment at 230 ° C for 20 minutes is reflected by the coating conditions of the spin coater, whereby the thickness of the photosensitive black resin composition layer is adjusted to a predetermined thickness. The film thickness of the photosensitive black resin composition layer is the height of the partition wall in the black matrix to be described later. The film thickness was measured using a film thickness meter (trade name: Dektak, manufactured by ULVAC Co., Ltd.). Next, on the alkali-free glass substrate on which the photosensitive black resin composition layer was formed, the mask was passed through a mask having a specific partition wall pattern, and the ultraviolet ray was irradiated close to the gap φ 15 〇 μη (the amount of irradiation was 100 mJ/cm 2 : converted by I line) ) for exposure. A reticle having a repeating pattern having a CD 19 pm and a rectangular opening portion 66X 226 μm was used as the partition wall pattern. Then, the exposed photosensitive black resin composition layer was subjected to a 26 t x 80 second rinse development by a developing solution (CD liquid: Fujifilm Electronic Materials Co., Ltd., diluted 50 times), followed by washing with pure water. In a clean oven, it was fired at 230 °C for X20 minutes to obtain a black matrix (5 cases of blackening of the black color of the partition wall and the application of 4). The example of the board is the base of the moon. ' Ν 案 -55- 201032002 The black matrix in the black matrix substrate manufactured by the composition, the contact angle was measured using various standard solvents, and the surface energy was measured by the Zismanri method, and the measurement results were 22.9 nN/m and 23.0 nN/m, respectively. Manufacture of color filter> [Preparation of ink for inkjet printing] Preparation of 15 parts by mass of CI Pigment Blue 15 as a coloring agent: 2, 2 parts by mass of CI Pigment Violet 23, 7 parts by mass of a polyester-based dispersant, The balance was a blue colorant dispersion of dipropylene glycol monomethyl ether acetate (DPMA) as a solvent, and a green colorant dispersion and a red colorant dispersion were prepared in the same manner as shown in Table 1. 1] Red colorant dispersion (parts by mass) Green colorant dispersion (parts by mass) Blue colorant dispersion (parts by mass) Colorant PR242 10 - - PR177 10 - PG36 • 12 - PY150 5 - PB15:6 - 15 PV23 • - 2 Dispersant Dispersant 1 1 7 - - Dispersant 2 • 7 - Dispersant 3 Unloading - 7 Solvent EDGAC 74 - - DPMA - 75 77

In Table 1, PR242 indicates CI·Pigment Red 242' PR177 No C.1·Yan-56-201032002 Red 177, PG36 indicates CI Pigment Green 36, PY150 indicates CI Pigment Yellow 150, and PB15: 6 indicates CI Pigment Blue 15 : 6, PV2 3 represents CI Pigment Violet 23. Further, EDGAC represents diethylene glycol monoethyl ether acetate, and DPMA represents dipropylene glycol monomethyl ether acetate. To 61 parts by mass of the prepared blue pigment dispersion liquid, 4 parts by mass of an acrylic resin and 35 parts by mass of diethylene glycol monobutyl ether (BDG) as a solvent were added to prepare an ink for blue inkjet printing. Similarly, the ink for green inkjet printing and the ink for red inkjet printing were prepared in accordance with the composition shown in Table 2. [Table 2] Ink for inkjet printing (parts by mass) Green (parts by mass) Blue (parts by mass) Colorant dispersion 90 86 61 Acrylic resin 3 2 4 EDGAC 7 _ - Solvent DPMA _ 12 BDG - - 35 In 2, EDGAC represents diethylene glycol monoethyl ether acetate, DPMA represents dipropylene glycol monomethyl ether acetate, and BDG represents diethylene glycol monobutyl ether. [Preparation of color filter] In the opening of the black matrix in each of the black matrix substrates produced using the photosensitive black resin compositions of Examples 1 to 5 and Comparative Examples 1 to 6, an inkjet printing head was used. At the same time, red ink 120pL, green oil-57-201032002 ink 120pL, blue ink 130pL, and pre-dried at 40 ° C x 2 minutes, baked at 230 ° C x 20 minutes to prepare a color filter. [Evaluation] For each of the color filters prepared as above, visual observation and microscopic observation were carried out, and the state of ink filling in the opening portion of the black matrix and the presence or absence of color mixing between adjacent pixel layers were evaluated. As for the ink filling state, it is particularly noted that the ink squeezing failure (leakage) occurring on the peripheral portion (edge adjacent pixel) of the color filter screen is evaluated in the same manner as the state of the center of the screen. There is no such thing as a "〇", and there is a situation where a white leak occurs as ‘‘χ,,. As for the color mixture between adjacent pixel layers, the case where color mixing does not occur is referred to as "χ" when "混" is mixed. Moreover, as for the comprehensive evaluation, the case of "leak white" and "mixed color" did not occur as "〇", and the case of any kind of occurrence was referred to as "χ". The evaluation results are shown in Table 3. 201032002 [Table 3]

Photosensitive black resin composition partition wall height (μιη) Evaluation result No. Surfactant leakage white color mixed comprehensive evaluation type addition amount (ppm) Fluorine conversion addition amount (PPm) Center portion edge portion Example 1 Fluorine-based surfactant 1 65 11 2.2 〇〇〇〇 Example 2 Fluoride-based surfactant 1 130 22 1.6 〇〇〇〇 Example 3 Fluoride-based surfactant ΐ 210 35 1.5 〇〇〇〇 Example 4 Fluoride-based surfactant 1 160 27 2.1 〇〇〇〇 Example 5 Fluoride-based surfactant 2 260 45 2.3 〇〇〇〇Comparative Example 1 Not added 0 0 1.6 〇〇XX Comparative Example 2 Lanthanide surfactant 100 0 2.3 〇X 〇X Comparative Example 3 矽Surfactant 80 0 2.3 〇XXX Comparative Example 4 Lanthanide surfactant 160 0 1.6 XX 〇X Comparative Example 5 Fluorinated surfactant 1 32 6 2.1 〇〇XX Comparative Example 6 Fluorinated surfactant 1 320 54 2.2 XX 〇X As apparent from Table 3, the preparation of the photosensitive black resin composition of Examples 1 to 5 containing 8 to 50 ppm of a fluorine-based surfactant based on the fluorine content of the entire solid content was used. A color filter, color mixing does not occur φ, pixel defect trapping nor the like occur. Further, Fig. 4 shows a surface enlarged photograph of a color filter prepared by using the photosensitive black resin composition of the embodiment, and Fig. 5 shows the surface of a color filter prepared using the photosensitive black resin composition of the comparative example. Zoom in on the photo. The surface of the color filter of FIGS. 4 and 5 is enlarged, and it is also known that the color filter prepared by using the photosensitive black resin composition of the comparative example is subjected to pixel defects such as color mixing and whitening. On the contrary, the embodiment is used. The color filter prepared by the photosensitive black resin composition did not cause pixel defects such as color mixing and whitening. -59- 201032002 (Impact of Fluoride Ion Intensity Ratio in Black Matrix Substrate) <Preparation of Photosensitive Black Resin Composition> [Modulation of Photosensitive Black Resin Composition 1] Anti-Suning Agent [Black Pigment (CI Pigment Black 7) 40 parts by mass and a mixture of 12 parts by mass of a polyurethane dispersant] 5 2 parts by mass, a binder resin [300 parts by mass of the compound represented by the above formula (6) and biphenyltetracarboxylic acid Reaction product of 50 parts by mass of anhydride and 50 parts by mass of tetrahydrophthalic anhydride] 33 parts by mass of 11 parts by mass of compound dipentaerythritol hexaacrylate having ethylenically unsaturated bond and addition polymerizable, photopolymerization initiator 5.0 parts by mass of 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 3.0 parts by mass of dimethanone of photopolymerization initiation aid, and 2.8 parts by mass (relative to all Content of solid content: 260 ppm, fluorine content with respect to all solid components: 4 7 ppm) Mixing of fluorine-based surfactant 1 and solvent propylene glycol monomethyl ether acetate 3 58 parts by mass to obtain a photosensitive black resin composition 1. [Preparation of photosensitive black resin composition 2] The content of the fluorine-based surfactant 1 was changed so that the content of all the solid components was 21 Oppm (the fluorine content of all solid components: 40 ppm), and In the same manner as the photosensitive black resin composition 1, a photosensitive black resin composition 2 was obtained. [Preparation of photosensitive black resin composition 3] The content of the fluorine-based surfactant 1 was changed so as to be 105 ppm based on the total solid content of the solid-60-201032002 (the fluorine content relative to the total solid content: 2 Op) In the same manner as the photosensitive black resin composition 1, a photosensitive black resin composition 3 was obtained. [Preparation of photosensitive black resin composition 4] A photosensitive black resin composition 4 was obtained in the same manner as in the photosensitive black resin composition 1 except that the fluorine-based surfactant 1 was not added. [Preparation of photosensitive black resin composition 5] The content of the fluorine-based surfactant 1 was changed, and the content of all the solid components was 35 ppm (fluorine content with respect to all solid components: 6 ppm), and photosensitivity In the same manner as the black resin composition 1, a photosensitive black resin composition 5 was obtained. [Preparation of the photosensitive black resin composition 6] φ In addition to changing the amount of the fluorine-based surfactant 1 to be added, the content of the total solid content is 315 ppm (the fluorine content relative to the total solid content: 5 7 ppm), and In the same manner as the photosensitive black resin composition 1, a photosensitive black resin composition 6 was obtained. <Production of Black Matrix Substrate> (Example 6) The photosensitive black resin composition 1 was applied onto an alkali-free glass substrate (Model: #1737, manufactured by Corning Incorporated) by a spin coating method, vacuum-61 - 201032002 After drying, the film was heated at 100 ° C for 90 seconds to form a photosensitive black resin composition layer composed of a solid component of the photosensitive black resin composition 1 on an alkali-free glass substrate. The film thickness after the heat treatment of the photosensitive black resin composition layer formed at 230 ° C for 20 minutes is reflected as the coating condition of the spin coater, whereby the thickness of the photosensitive black resin composition layer is adjusted to a predetermined thickness. The film thickness of the photosensitive black resin composition layer is the height of the partition wall in the black matrix to be described later. The film thickness was measured using a film thickness meter (trade name: Dektak, manufactured by ULVAC Co., Ltd.), and the result was 1.6 μm. Next, on the alkali-free glass substrate on which the photosensitive black resin composition layer is formed, a mask having a specific partition wall pattern is passed through to irradiate ultraviolet rays close to the gap of 15 μm (the irradiation amount is 100 mJ/cm 2 : by the I line). Conversion) for exposure. A reticle having a repeating pattern of a CD 19 pm and a rectangular opening portion of 66 x 226 μm was used as the partition wall pattern. Next, the exposed photosensitive black resin composition layer was subjected to a rinsing development at 26 ° C for 80 seconds by a developing solution (CD liquid: Fujifilm Electronic Materials Co., Ltd., diluted 50 times), followed by washing with pure water. The film was fired at 23 ° C for 20 minutes in a clean oven to obtain a black matrix substrate of Example 6 in which a black matrix (wall pattern) was formed. With respect to the obtained black matrix substrate of Example 6, the surface of the black matrix was measured using TRIFT2 (measurement beam diameter: 5 to 1 Ο μιη) manufactured by Physical Electronics Co., Ltd. using a time-of-flight secondary ion mass spectrometer (TOF-SIMS). Fluoride ions in the surface of the substrate corresponding to the opening of the black matrix. The measurement of the fluoride ion is performed on the upper surface of the black matrix corresponding to the vicinity of the edge where the ink collapse is likely to occur, and the surface of the black matrix is opened -62-201032002, and the signal intensity of all negative ions with respect to each surface is used. The intensity ratio of the integral enthalpy is compared. The measurement results of the fluorine ions in the black matrix substrate of Example 6 were such that the ratio of the fluoride ion detection intensity of the upper surface of the black matrix was 0·28' to the surface of the substrate corresponding to the black matrix opening. 03 φ (Example 7) A black matrix substrate of Example 7 having a partition wall height of 1.5 μm was obtained in the same manner as in Example 6 except that the photosensitive black resin composition 1 was changed to the photosensitive black resin composition 2. In the black matrix substrate of the seventh embodiment, the fluorine ion detection intensity ratio of the upper surface of the black matrix is 〇_22', and the ratio of the fluoride ion detection intensity of the substrate surface corresponding to the black matrix opening portion is 〇. 〇 2. φ (Example 8) A black matrix substrate of Example 8 having a barrier entanglement of 2.3 μm was obtained in the same manner as in Example 6 except that the photosensitive black resin composition 1 was changed to the photosensitive black resin composition 3. In the black matrix substrate of Example 8, the fluorine ion detection intensity ratio was 0.29 on the upper surface of the black matrix, and the fluoride ion detection intensity ratio on the substrate surface corresponding to the black matrix opening portion was 〇.〇4 . (Comparative Example 7) -63-201032002 A black matrix substrate of Comparative Example 7 having a partition wall height of 1.6 μm was obtained in the same manner as in Example 6 except that the photosensitive black resin composition 1 was changed to the photosensitive black resin composition 4. . In the black matrix substrate of Comparative Example 7, the fluorine ion detection intensity ratio was 0.001 or less on the upper surface of the black matrix, and the fluoride ion detection intensity ratio on the surface of the substrate corresponding to the black matrix opening was 0.001 or less. (Comparative Example 8) A black matrix substrate of Comparative Example 8 having a partition wall height of 1.6 μm was obtained in the same manner as in Example 6 except that the photosensitive black resin composition 1 was changed to the photosensitive black resin composition 5. The fluorine ion measurement result of the black matrix substrate of the comparative example 8 is that the fluoride ion detection intensity ratio on the upper surface of the black matrix is 〇1.2, and the fluoride ion detection intensity ratio on the substrate surface corresponding to the black matrix opening portion is 0.02. .

(Comparative Example 9) The black matrix substrate of Comparative Example 9 having a partition wall height of 1.6 μm was obtained in the same manner as in Example 6 except that the photosensitive black resin composition 1 was changed to the photosensitive black resin composition 6. In the black matrix substrate of Comparative Example 9, the fluorine ion detection intensity ratio on the upper surface of the black matrix was 0.33, and the fluoride ion detection intensity ratio on the substrate surface corresponding to the black matrix opening portion was 〇. 8. <Production of Color Filter> -64 - 201032002 [Preparation of ink for inkjet printing] Preparation of CI Pigment Blue 15: 6 by mass of 15 parts by mass of colorant, Pigment Violet 23 of 2 parts by mass, dispersion of polyester A blue colorant dispersion composed of 7 parts by mass of a solvent and 77 parts by mass of a solvent of dipropylene glycol monomethyl ether acetate. Similarly, a green colorant dispersion and a red colorant dispersion were prepared in accordance with the compositions shown in Table 1 above. To 61 parts by mass of the prepared blue pigment dispersion liquid, 4 parts by mass of acrylic acid φ lipid and 35 parts by mass of dipropylene glycol butyl ether of a solvent were added to prepare an ink for blue ink jet printing. Similarly, the ink for green inkjet printing and the ink for red inkjet printing were prepared in accordance with the composition shown in Table 2 above. [Preparation of Color Filters] In the black matrix openings of the black matrix substrates of Examples 6 to 8 and Comparative Examples 7 to 9, the inkjet printing head was used, and the red ink 120pL and the green ink 120pL' blue were simultaneously filled. The color ink 130 pL was predried at 40 ° C for 2 minutes, and then baked at 230 ° C for 20 minutes to prepare a color filter. [Evaluation] For each of the color filters prepared as described above, visual observation and microscopic observation were carried out to evaluate the ink filling condition in the black matrix opening portion and the presence or absence of color mixing between adjacent pixel layers. As for the ink filling condition, it is particularly noted that the ink squeezing failure (leakage) occurring on the peripheral portion (edge adjacent pixel) of the color filter screen is evaluated together with the squeezing state at the center of the screen. The case where no whitening occurs is referred to as "〇". The case where whitening occurs is referred to as "X,'. To -65-201032002, when the color mixture between adjacent pixel layers does not mix, "作为", when color mixing occurs, “X ”. As for the comprehensive evaluation of “leak white” and “mixed color”, the evaluation result is “〇”, and “anything” is “X” and “X”. The evaluation results are shown in Table 4. [Table 4]

Black unilateral lotus plate photosensitive black resin composition m ϊ result number partition wall height (μιη) Fluoride ion detection intensity than gas phase surfactant at the edge portion of the white mixed color evaluation of the partition wall surface opening substrate surface addition amount ( Ppm) Fluorine-added amount (ppm) Example 6 1.6 0.28 0.03 260 47 〇〇〇 Example 7 1.5 0.22 0.02 210 40 〇〇〇 Example 8 2.3 0.29 0.04 105 20 〇〇〇 Comparative Example 7 1.6 < 0.001 <0.001;0.001 0 0 〇XX Comparative Example 8 1.6 0.12 0.02 35 6 〇XX Comparative Example 9 1.6 0.33 0.18 315 57 X 〇X As shown in Table 4, the fluoride ion detection intensity ratio used on the surface of the black matrix is 0.1 5 or more. 0.3, and the color filter prepared on the black matrix substrate of Examples 6 to 8 in which the fluorine ion detection intensity ratio of the substrate surface corresponding to the black matrix opening portion is 〇.5 or less does not cause color mixing, and does not occur. Pixel defects such as whiteout. The present invention can be embodied in other various forms without departing from the spirit or essential characteristics thereof. Therefore, the foregoing embodiments are merely illustrative in all respects, and the scope of the invention is in the Further, variations or modifications belonging to the scope of the patent application are also within the scope of the invention. -66- 201032002 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A to FIG. 1C are sequence diagrams showing a method of manufacturing a black matrix substrate. FIG. 2A and FIG. 2B are sequence diagrams showing a method of manufacturing a color filter. Fig. 3A and Fig. 3B show a schematic view of the color filter structure. Fig. 4 is a magnified photograph of the surface of a color filter prepared by using the photosensitive black resin composition of the example. Fig. 5 is a magnified photograph of the surface of a color filter prepared by using the photosensitive black resin composition of the comparative example. [Explanation of main component symbols] 1 : Photosensitive black resin composition layer 2 : Substrate 3 : Photomask 3 1 : Glass plate 32 : Light shielding layer 3 3 : Light transmitting portion 4; Light 5 : Coloring pattern 5 B : Blue pixel Layer 5BM: Black matrix 5 G : Green pixel layer 5R : Red pixel layer - 67 - 201032002 6, 60 : Color filter 7 : Black matrix substrate 7 a : Opening portion 10B : Inkjet printing head 1 0 G : Spray Ink printing head 1 OR : Inkjet printing head 1 1 B : Inkjet printing ink 1 1 G : Inkjet printing ink 1 1 R : Inkjet printing ink

-68-

Claims (1)

201032002 VII. Patent application scope: 1. A photosensitive black resin composition for forming a photosensitive black resin composition of a black matrix, the black matrix having a plurality of color pixel layers on the substrate and adjacent colors a black matrix in a color filter of a black matrix between pixel layers, characterized in that it contains 0.0008 to 0.005 mass% of a fluorine-based surfactant having a fluoroalkyl group in a side chain with respect to a fluorine content of all solid components. . (2) The photosensitive black resin composition according to the first aspect of the invention, wherein the fluorine-based surfactant has a structural unit represented by the following formula (la) based on a total of 100% by mass of all structural units. a compound having a ratio of 1 to 40% by mass, a structural unit represented by the following formula (1b): 20 to 98% by mass, and a structural unit represented by the following formula (lc): 1 to 40% by mass; R* I R3 R6 | 1 —CHi —C — | 1 —CHe —C — I 1 —CH2 — c — 1 X1 - L1 - R2 I \〇-L2 Thousand R4-〇^*R5 X2 - L3 - Rf (la) (lb) (lc) [wherein, R1, R3 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R2 represents a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. 'Hydroxyl, or -(8丨((:113)20) „1-3丨(<:113)3,114 represents an alkylene group having 2 to 8 carbon atoms, and R5 represents a hydrogen atom and a carbon atom number of 1. An alkyl group of -12, a fluorenyl group, or an aryl group having 6 to 20 carbon atoms, and L1, L2, and L3 each independently represent a single bond, an alkylene group or a substituted alkyl group, and X1 represents -C〇2_, -CONY1-, or -69 - 201032002 Extending an aryl group, X2 represents -Ο-, -C02-, -CONY2-, aryl- or divalent heterocyclic residue, Rf represents a fluoroalkyl group, and η represents an integer of 2 to 20' and 'm' An integer of ～3, Y1 and Y2 each independently represent a hydrogen atom or a propylene group having 1 to 5 carbon atoms. 3. A black matrix substrate formed by using the photosensitive property of claim 1 or 2 a black matrix black matrix substrate prepared by a black resin composition for producing a color filter having a plurality of color pixel layers and a black matrix between adjacent color pixel layers on a substrate, which is formed with an opening a black matrix substrate of a black matrix. 4. A black matrix substrate according to claim 3, wherein all negative ions are detected by a negative ion detected by a time-of-flight secondary ion mass spectrometer (TOF-S IMS ) The detection intensity ratio of the fluoride ion when the total detection intensity is 1 is 0.15 or more on the surface of the black matrix, which is less than 0.3, and is 0.05 or less on the surface of the substrate corresponding to the opening of the black matrix. Such as applying for a patent The black matrix substrate of item 3 or 4, wherein the black matrix has a film thickness of 1·2 μm or more and 3.0 μm or less. 6. A method of manufacturing a color filter having a plurality of color pixel layers on a substrate And a method for manufacturing a color filter of a black matrix between adjacent color pixel layers, comprising: forming a black matrix on the substrate using the photosensitive black resin composition of claim 1 or 2, preparing black a step of preparing a black matrix substrate of a matrix substrate, and printing inkjet printing by inkjet printing in a pixel region surrounded by a partition wall of -70 - 201032002 corresponding to an opening of a black matrix formed on a black matrix substrate The ink layer forms a pixel layer forming step of the color pixel layer. -71 -