TWI361948B - Coloring photosensitive resin composition - Google Patents

Description

1361948 IX. Description of the Invention: [Technical Field and Field of the Invention] The present invention relates to a coloring photosensitive resin composition. [Prior Art] A color filter used in a color liquid crystal display device or a photographing device is formed by forming a color layer corresponding to three primary colors of red, green, and blue on a substrate on which a black matrix is formed in a pattern. Got it. In the past, in the subsequent steps such as the alignment film polishing treatment after the production of the color filter, the color layer of the colored layer (coloring pixel) having a pattern is insufficient, and when the liquid crystal panel is assembled, the The pressure of the partition plate interposed between the two substrates causes the colored layer to be easily deformed, so that the liquid crystal cell gap locally fluctuates, which causes problems such as display defects. The colored layer is formed of a colored resin composition. The colored resin composition is known to contain a coloring agent, a binder resin dispersant, a solvent, and a coloring photosensitive resin composition of the ceramics (refer to Japanese Patent Laid-Open No. Hei-1) No. 61/6 "Pre-supply the composition, and immersing the photosensitive resin layer in the non-exposed portion in the non-exposed portion to dissolve the water-repellent resin layer, because it contains the ceramic particles, and is:) I is reduced in the penetration rate of the dissolved portion (the average of S780 (10)), and there is a problem called insufficient developability. [Explanation] The purpose of the present invention is to provide a hardening of high hardness (four) (4) coffee 2 excellent, surface 315779 5 1361948 This volume has been thoroughly studied and found that a hardening can be formed, surface hardness is high In the coloring photosensitive resin composition of the resin layer, the present invention provides the following resin compositions of [1] to [11]. [1] A color-sensitive resin composition of a species, which is a coloring agent (A), a binder resin (B), a photopolymerizable compound (c), a photopolymerization initiator (D), and a pigment dispersant (E) And a solvent (one coloring photosensitive resin composition; the coloring photosensitive resin composition is applied onto a glass substrate to form a resin layer, and the resin layer is prebaked, and exposed by a mask, In the case of development and post-baking, the hardness of the cured resin layer obtained in the post-baking is expressed by the pencil hardness, and the photosensitive resin layer obtained by prebaking and exposing through a mask is performed at 3H or more and 9H or less. The penetration rate (average of 4〇〇 to 78〇nm) of the portion of the non-exposed portion where the photosensitive resin layer was dissolved after 12 seconds of immersion in a 25 t aqueous alkali solution stirred at 100 rpm was 98% or more. [2] The colored photosensitive resin composition of [1], wherein the binder resin (B) contains a resin composed of (f-based) acrylic acid. [3] The colored photosensitive resin composition of [1] or [2], wherein the composition is sticky In the total constituent unit of the resin (8), the content of the constituent unit derived from (fluorenyl)acrylic acid is 16 mol% or more and 4 mol% or less. [4] As in any of [1] to [3] The color-sensitive photosensitive resin composition, wherein the 'bonding resin (B) further contains a constituent unit derived from benzyl (meth) acrylate. [5] Any one of [1] to [4] A coloring photosensitive resin composition in which 'bonding (4) (8) further contains a resin of the formula (1) (4) (d). 315779 6 1361948

(In the formula (I), R1 and R2 each independently represent a hydrogen atom or a methyl group. [6] The colored photosensitive resin composition according to any one of [1] to [5], wherein t, the bonding is known The weight average molecular weight of the polystyrene (B) is 5, 〇〇〇 or more and 35,000 or less. [7] The colored photosensitive resin composition according to any one of [1] to [6], wherein t, the pigment dispersant (yttrium) is a polyester type, a polyamidene type, a polyurethane type, and an acrylic acid. Among the groups formed by the system, at least one of the surfactants is selected. [8] The colored photosensitive resin composition according to any one of [1] to [7] wherein the pigment dispersant (E) is an acrylic surfactant. [9] A method of forming a colored pattern, wherein a resin layer constituting the coloring photosensitive resin composition of any one of [1] to [8] is formed on a substrate, and the resin layer is shielded After the cover is exposed, it is developed, and then the post-baking is performed. [10] The method for forming a color pattern according to [9], wherein the temperature of the post-baking treatment is 180 Ϊ or more and 25 (TC or less. [11] A color filter containing a [9] or [10] The coloring pattern formed by the method. [Embodiment] 7 315779 1361948 The colored photosensitive resin composition of the present invention contains a coloring agent (A), a binding resin (B), a photopolymerizable compound ((:), light). (D), a pigment dispersing agent (E), and a coloring photosensitive resin composition of a solvent. The coloring photosensitive resin composition is applied onto a glass substrate to form a resin layer, and the resin layer is applied. Pre-baking, and performing the 'exposure, development, and post-baking through the mask, the hardness of the hardened resin layer obtained in the post-baking. According to the wrong pen hardness, it is '3H or more, 9H or less, and will be pre-baked. The photosensitive resin layer obtained after exposure through a mask was immersed in a 25 艽 aqueous alkali solution stirred at 100 rpm, and after 120 seconds, the surface of the non-exposed portion of the photosensitive resin layer was dissolved. Penetration rate (4〇〇 to 780nm level) The hardness of the cured resin layer (coating film) is 3JJ or more and 9H or less, preferably 4H or more and 9H or less, especially 5H or more, 9H. The hardened resin layer (coating layer) is a part of the pixel portion. If the pencil hardness is 3H or more and 9H or less, it is difficult to harden due to the step of forming the liquid aa alignment film which is performed after the pixel is formed. The resin layer (coating film) causes damage and is therefore excellent. The pencil hardness is measured by the square age method of JIS K54. The above prebaking preferably applies the colored photosensitive resin composition on a glass substrate 'and at 1003⁄4 It is applied for about 3 minutes. Pre-baked, and the photosensitive resin is obtained after exposure through a mask. The layer is immersed in 25 at a stirring of 100 rpm. (In an aqueous alkali solution, the aqueous alkali solution is usually based on mass. The fractional meter contains 0.05% of potassium hydroxide and 2% of aqueous solution of sodium butyl phthalocyanine. 315779 8 1361948 The non-warm of the photosensitive resin layer is also fading, and the part is immersed in Stir at 100rPm In the 25C water bath, the most 1V t town is dissolved within 120 seconds, especially within 1 second and 1 second. It is better than 1 second and 80 seconds, especially for 1 second or longer. Within 60 seconds, #伟> u, +, _ m is better. The time required for dissolution, if it is inside the above-mentioned dry circumference, is very good because it can suppress the color reduction and the production of the first thief. The non-exposed portion of the photosensitive resin layer was immersed in the 25 C aqueous solution under the gradual drop, and the transmittance of the photosensitive portion dissolved after 12 sec. (the penetration wavelength was (10) to (10) (10). The range of the flat 曰 曰 must be above m, lm or less, especially (10) or more is better than 99. 5% or more, 100% or less is more preferable. If it penetrates 98% or more and 1% or less, it is because of the bright shell of the color layer of the needle

So very good. J The color former (A)' used in the present invention may be an organic colorant or an inorganic colorant. The organic colorant may be an organic pigment or a material. Further, the organic colorant may be a synthetic color former or a natural colorant. The inorganic colorant may be an inorganic pigment such as a metal oxide, a metal salt, or an inorganic salt (physical pigment) of sulfuric acid. Among these colorants, it is preferred that the organic colorant be more preferably an organic pigment. The organic pigment and the inorganic pigment may, for example, be a compound classified as a pigment in Color Society (issued by The Society of Dyers and Colourists). Specifically, for example, CI Pigment Yellow 1, C. 丨. Pigment Yellow 3 CI Pigment Yellow 12, CI Pigment Yellow 13, C·I. Pigment Yellow 14% 315779 9 Feeder Steam 15, C·I. Pigment Yellow 16'cj pigment yellow π, ci pigment yellow 20, C t '" pigment yellow 24, C · I· pigment yellow 3i, c. I. pigment yellow 53, C. 1. pigment vapor 83, c. I. pigment yellow 86, c· I. Pigment Yellow 93, C·I·Pigment Yellow 94, C τ ••Pigment Yellow 109, C·I. Pigment Yellow No, CI Pigment Yellow 117, CI, material 125, CI Pigment Yellow 128, C. I·Pigment Yellow 137, C_I. Pigment Vapor 138, CI Pigment Yellow i39, c j. Pigment Yellow W7.C·] Pigment Yellow 148, C· Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI f 166, C·I. Pigment Yellow 173, c·I·Pigment Yellow i94, c.丨. Pigment 214 and other yellow pigments; CI Pigment Orange 13, C. I·Pigment Orange 31, CI Pigment Orange 36 , CI pigment dial 38, C. I·Pigment orange 4〇, c·丨. Pigment orange 42, C· I. Pigment orange 4 3, ρ τ • 1·Pigment orange 51, CI pigment orange 55, C·I. Pigment Orange 59, CI / Material _ 61, CI Pigment Orange 64, C·I·Pig Orange 65, CI Pigment Orange 7 1、c. I. Pigment orange 73 and other orange pigments; c. I. Pigment red 9, C· I·Pigment red 97, CI pigment red i〇5, c. I. , !::1 么么,, ' Work 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment l49, C. I·Pigment Red 166, c〗 Pigment Red 168, c I Pigment Red, Red I. Pigment Red 177, αι. Pigment Red 18〇, c.丨.Pigment red i92, c.工. Red 224 Γ τ / Yan Zhuang 215, αΐ. Pigment Red 216, CI·Pigment, 224, CI Pigment Red 242, c.丨. Yan CI ^1 4# έ r ^ , CI Pigment Red 2 6 4, ci Yanke Red, c. 〖·Pigment Red 265 and other red pigments; CI Pigment Blue 15, C. J•Pigment 趑' 4, CI Pigment Blue 15.6, c τ ^ 5· 3, αΐ. Pigment blue r τ .·Pigment blue 60 and other blue color oblique. c. L pigment purple 1, C · I. Pigment violet 19 wide, c · I. Pigment violet 23, CI 315779 10 1361948 Pigment violet 29U .Pigment Violet 38 and other purple pigments; 2 CL Pigment Violet 36, CI Pigment Violet CI Pigment Green 7, r C. L Pigment Magic, ^^ Branch Brown 25 and other color pigments; among these, the second C pigment. 1 hour 1. Pigment Yellow 150, "Pigment 2 = Pigment Red Heart C.!·Pigment Violet 23, Ci "2 Red_," at least one of the pigments is selected. .6, and "Organic_Materials_ Use 2 or more types. It can be used alone or in combination. For example, when forming a red image, it is best to use C. I. Pigment Yellow 139. There are c. 丨. Pigment Red 254 and when forming a green pixel, the most eight pigment yellow 138 constitutes a group of rents 丨3 has a C. L pigment yellow 150, C. I. Green 36. At least one pigment is selected in the group, and the group is C.L. When the blue pixel is formed, the most C.I. pigment violet 23 is formed. Broken 3 has CI Pigment Blue 15··6, and, in fact, the material: the organic pigment needs to be combined, such as: rosin treatment, using acidity introduced into the treatment, using f-based pigment derivatives, etc. The surface of the surface M ^ ^ Λ σ and the like are subjected to graft treatment on the surface of the pigment, and the micronization treatment of: ::: or the like, or the net treatment for removing impurities, and the ion exchange treatment using ionic impurities Wait for processing. Further, after the coloring photosensitive composition 315779 11 1361948 resin composition is prepared, a removal treatment such as ion exchange may be performed. When the solid content of the coloring photosensitive resin composition is 100 parts by mass, the content of the coloring agent (A) is usually 25 parts by mass or more and 60 parts by mass or less, preferably 27 parts by mass or more and 55 parts by mass. The amount is preferably 30 parts by mass or more and 50 parts by mass or less. When the content of the colorant (?) is 25 parts by mass or more and 6 parts by mass or less, since the color concentration is sufficient when used as a color filter, and the required amount of the binder resin is contained in the composition, sufficient formation can be achieved. The pattern of mechanical strength is therefore ideal. Here, the "solid content in the coloring photosensitive resin composition" means the remainder of the coloring photosensitive resin composition excluding the solvent (F). When the pigment used as the coloring agent (A) is used as the coloring photosensitive resin composition of the present invention, it is preferred that the particle size is the same. In order to form a uniform particle diameter of the pigment, for example, a method of performing a dispersion treatment by using a surfactant as a pigment dispersant (8) may be mentioned. The pigment dispersant (E) may, for example, be a polyoxyethylene alkyl ether system, a polyoxyethylene alkyl phenyl group, a polyester system, an acrylic system, a polyamine vinegar system or a polyamidene system. Such as a surfactant or the like, these may be used singly or in combination of two or more. The surfactant of the σ-polyoxyethylene-sintering system is, for example, a manufacturer (14102 Chemical Products, page 1286 (Chemical Industry News, January 29, 2002)). ”

R〇(CH2CH20)nH wherein R represents a carbon number 12 to 22, and n represents a 2 to 6 number of 315779 1361948 polyoxyethylene alkyl ether surfactants, for example, polyoxyethylene-ene Anthracene ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene hard, aliphatic ether, polyoxyethylene ether ether, polyoxyethylene 2-ethylhexyl ether, and the like. Commercial products of polyoxyethylene alkyl ether surfactants include, for example, BLAUNON-EL series, BLAUNON-CH series, BLAUNON-SR series, BLAUNON-EN series, BLAUNON-EH series, BLAUNON-DAL series, BLAUNON -DAI series, column, BLAUNON-DAH series, BLAUNON-OX series (all of which are made of Aoki Oil Co., Ltd.), etc., and other companies can also use the same level of _ polyoxyethylene alkyl ether surfactants, For example, there is a structure of the following formula (Chemical Products, No. 1287, page 14 (Chemical Industry News, January 29, 2002)).

In the formula, Μ represents an integer of 1 to 5, η represents a value of 2 to 60, and R represents an alkyl group having 12 to 22 carbon atoms or a phenyl group which may be substituted. Wherein, when m is 2 to 5, R may be the same or may be mutually different. A commercially available product of a polyoxyethylene alkyl phenyl ether surfactant can be exemplified by, for example, BLAUNON-NK, series, BLAUNON-N series, BLAUNON-DP series, BLAUNON-DNP system, column, BLAUNON-DSP series, BLAUNON -The TSP series, BLAUNON-PH series, BLAUNON-BA series, etc., can also be used in the same class of other companies. 13 315779 1361948 Polyester surfactants have a polyester construction. Examples of the polyester-based surfactant include, for example, Disperbyk-16 Butong 170 (manufactured by BYK Chemie Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like. The polyamidide surfactant has an ethyleneimine structure. The polyethylenimine-based surfactant can be exemplified by, for example, Sulpas 24(^(trade name, transliteration) (Rui Nejia) (company name, transliteration), and can also be used. Other grades of other companies. Acrylic surfactants have a propylene copolymerization structure. Examples of acrylic surfactants include Disperbyk 352, 354, 2 (10), 2001 CBYK Chemie, EFKA_polymer 4 〇1 (efka EM I CALS a system)' can also use the same grades of other companies. The polyurethane ester surfactant has a polyurethane structure. The polyurethane interface may be, for example, a polymer manufactured by Chemicals, Inc., and similar products of other companies may be used in the same manner. The surfactants other than the above can be exemplified by the following names: in--H Industrial (share), and Poly-Fu (transliteration) (Drum Brodak) Company name, transliteration) Gong Luo Laide (trade name two translation) = the ink chemical industry (shares) system, Fosley Aim (shares (eight trademarks) Cong Yi, the same as 1 (Sumitomo translation two = ( The r imine is made of a vinegar-based surfactant and a poly-acetic acid active agent, and the surfactant is used to select one surfactant, especially 315779 14 1361948. The amount of the pigment dispersant (E) is 1 part by mass of the average colorant (A), usually 1 part by mass or less, preferably 0.05 parts by mass or more, and 0.5 parts by mass. When the amount of the pigment dispersant (E) is 1 part by mass of the average colorant (A), when it is 1 part by mass or less, the pigment having a uniform particle size tends to be obtained, which is preferable because of the coloring of the present invention. The binder resin (B)' used in the resin composition preferably contains a structure sheet derived from (meth)acrylic acid The binder resin (B) is preferably one having a structural unit derived from (meth)acrylic acid and an acrylic copolymer composed of other monomers copolymerizable with it. Acrylic means acrylic acid and/or mercapto propylene. The above-mentioned structural unit derived from (meth)acrylic acid is preferably 16 mol or more in the total constituent unit constituting the binder resin (B). When the content of the (meth)acrylic acid unit is within the above range, the solubility in the non-pixel portion in the resin layer is excellent in the case of development and is in the non-pixel portion after development. It is preferable that the residue is not likely to remain. · Other copolymerizable monomers include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, and unsaturated carboxylic acid shrinkage. Glycerin g-types, vinyl carboxylates, unsaturated ethers, cyanoethylene compounds, unsaturated guanamines, unsaturated quinones, aliphatic conjugated dienes, poly- & knives Monopropylene sulfhydryl or monomethacryl hydrazine The above-mentioned acrylic copolymer may, for example, be a mercaptoacrylic acid/mercaptopropene 315779 15 1361948 acid oxime ester copolymer, methacrylic acid/benzyl methacrylate/stupyl ethylene copolymer, sulfhydryl group Acrylic acid/methacrylic acid series/f-based acrylic isobornic vinegar copolymer, methacrylic acid/styrene/mercapto acrylate/N-phenyl maleimide copolymer, and containing the following formula (I A copolymer or the like of the constituent components shown.

In the formula (I), R1 and R2 each independently represent a hydrogen atom or a fluorenyl group. Among them, it is preferred to use a methacrylic acid/benzyl methacrylate copolymer, a mercaptoacrylic acid/methacrylic acid stilbene styrene copolymer, a mercaptopropionic acid/mercaptoacrylic acid/mercaptoacrylic acid isobornyl sheet. a copolymer, a methyl acrylate, a component represented by the above formula (I) (R1 is a methyl group, R2 is a hydrogen atom V methacrylic acid ys copolymer, and a constituent component represented by the above formula (1) (RU methyl group, R2 is a hydrogen atom)/methacrylic acid τ ester copolymer. A binder resin having a composition represented by the formula (I) (for example, mercaptoacrylic acid / a constituent represented by the above formula (R1 is a fluorenyl group, and R2 is a hydrogen group) Atom)/mercaptopropionic acid copolymer), which is obtained by polymerizing methacrylic acid with methyl methacrylate vinegar to obtain a 2-component polymer, and then A method in which the component represented by the formula (11) is reacted, etc. can be obtained. 315779 1361948

In the formula (11), R2 represents a hydrogen atom. The acid of the point-junction resin (8) used in the present invention is preferably 6. To 135, especially 7. It is better to 135, if it is two at 50 to 150', because the solubility of the developer is improved, so that the unexposed part is easy to dissolve, and in addition, the high salty servant has not exposed the 4th and then shakes the right side. I ^ is also good when it comes to smashing the shirt because of the tendency of the residual exposure department to have a lot of money. Here, for the acrylic acid copolymer, the amount of potassium oxide required for t and the amount of potassium oxide;;) is usually determined by titration with an aqueous solution of potassium oxynitride, and the polyphenylene of the binder resin (8) is further obtained. Dilute conversion weight average molecular weight, usually 5, _ to 35, just, preferably 6, just up to 3q, delete, especially 7, 〇〇〇 to 28, deleted as good. When the molecular weight is 5, when it is added to % _, the hardness of the cured resin layer (coating film) is increased, and the residual film ratio is also high, and the solubility in the developer in the unexposed portion is preferably improved, and the resolution is improved. The tendency is therefore very good. The mass fraction of the solid content of the above-mentioned binder resin (8) with respect to the coloring photosensitive resin composition is usually 5% by mass or more and 5% by mass or less, preferably 10% by mass or more and 40% by mass or less, particularly 15% by mass. More than %, 35% or less is better. When the content of the above-mentioned binder resin is 5% by mass or more and 50% by mass or less, a pattern can be formed and it is preferable because of the tendency to improve the resolution and the residual film ratio. 315779 17 1361948 The photopolymerizable compound (C) used in the present invention is a compound obtained by polymerization of light and polymerization starting from an active radical generated by a photopolymerization initiator. The photopolymerizable compound (c) may, for example, be a compound having a polymerizable carbon-carbon unsaturated bond. The compound may be a monofunctional photopolymerizable compound, and may be a difunctional or trifunctional or higher polyfunctional photopolymerizable compound. The monofunctional photopolymerizable compound may, for example, be decyl phenyl carbitol acetate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like. The bifunctional photopolymerizable compound may, for example, be 16-hexanediol diacrylic acid vinegar, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethyl Acrylate, neopentyl glycol dipropylene dimethyl acrylate, triethylene glycol dipropylene axis, triethylene bis: acrylate, bisphenol A bis(acryloxyethyl) ether, 3_ Methyl pentanediol diacrylate, 3-methylpentanediol dimethacrylate, and the like. Examples of the photopolymerizable compound having a trivalent or higher functional group include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, alcohol triacrylate, pentaerythritol trimethacrylate, and pentaerythritol tetraacrylate vinegar. , pentaerythritol tetramethacrylate, dipentaerythritol pentaacetic acid vinegar, dipentaerythritol penta-f-acrylic acid vinegar, dipentaerythritol hexaacrylate vinegar, dipentaerythritol hexamethyl acrylate acid g, and the like. The above photopolymerizable compounds may be used alone or in combination of two or more. The content of the photopolymerizable compound (6) is based on the solid content of the colored photosensitive resin composition, and is usually 31% by mass based on the amount of ff. When the amount is less than or equal to 19% by mass, 2% of the mass% or more, 30% by mass or less, and the content of the substance (C) is preferably 16 minutes or less. When the photopolymerizable compound is sufficiently hardened and the residual film ratio is increased, the amount is 2% by weight or less = ==: the initiator (8), for example, phenethyl -2- or more of the di- ing, 2 ethane The compound may, for example, be diethoxyacetophenone, 2-methyl-I morpholino + (" phenylthio)propane, dipropyl propyl-!, T-dimethyl dimethyl alcohol, 2 _ _ _ Ben = 2 based ethoxy) phenyl] propyl ketone, 1-cyclohexyl hexyl = second bis, (i methyl ethyl) stupyl] propyl ketone + ketone oligo = special. For the t, it is preferred to use 2-methyl-2-morpholino + 2 thio)acetone. Further, a plurality of acetophenones and other photopolymerization initiators may be used in combination. Other photopolymerization initiators include, for example, an active radical generator which generates an active radical by irradiation of light, an acid generator, and the like. The triterpenoid compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-tert-methoxyphenyl)-1,3,5-three tillage, 2,4-bis (three gas) _6-(4-methoxynaphthyl)-1'3,5-three tillage, 2'4-bis(trimethyl)methyl-6-(4-methoxystyryl)-1,3, 5-trimium, 2,4-bis(trimethylmethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-trianthene, 2,4- Bis(trichloromethyl)_6_[2-(furan-2-yl)vinyl]-1,3,5-trim, 2,4-bis(trimethyl)_6_[2_ 315779 19 1361948 (4 -diethylamino-2-methylphenyl)vinyl]_l 3, 5-trinyl, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxy Phenyl)vinyl]-U 3, 5_three tillage, etc. • Bis-diimidazole compounds include, for example, 2, 2,-bis(o-chlorophenyl)-4, 4,, 5' 5'-tetraphenyldiimidazole, 2, 2'-bis (o-gas) Phenyl)-4,4',5,5, _tetrakis(p-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(o-phenyl)-4, 4,,. 5, 5 '-tetra(p-bromophenyl)biimidazole, 2, 2, bis(o-chlorophenyl)_4, 4,, 5,5-tetrakis(o-, p-dichlorophenyl) Mi Jun, 2,2'-bis(o-bromophenyl)-4, 4',5, 5'-tetraphenyldiimidazole, 2, 2'-bis(ortho-, p-dichlorobenzene_ _ base)-4' 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-chlorophenyl)-4,4,5,5-tetra(m-decyloxy) Phenyl) in combination with 2 p 2, 2, 2' _ bis (o-, o-dichlorophenyl)-4, 4', 5, 5' _ tetraphenyl diimidazole, 2, 2, - double (Neighboring _ Shi Xiao basic base) -4,4,5,5-tetraphenyl in combination with 0 0 m sitting, 2,2'-double (o-_indolyl)-4,4',5,5 '- Four stupid bases combined with 20-mazole. The lunar compound may, for example, be a thiol-based compound, and specific examples thereof include, for example, 1-(4-phenylthio-phenyl)-butane-12-dione, 2-post-oxime-formaldehyde Vinegar, Bu (4-stylthio-phenyl)_ Xin Shao_12_二纲2_ after + face benzoic acid g曰, 1~(4-phenylthio-styl)_octane_丨- Ketone post-acetate, 1-(4-phenylthio-phenyl)-butane-indole-ketone-oxime-acetate. The living radical generating agent may, for example, be a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound or a tri-grain-based compound. Examples of the ridiculous compound include benzoin, benzoin oxime ether, benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether and the like. The benzophenone-based compound may, for example, be benzophenone or o-phenylmercaptobenzene 315779 20 1361948 diethoxyanthracene. The thioxanthone-based compound can be exemplified, for example, as described above. The photopolymerization initiator may be used singly or in combination of plural kinds. In addition, a commercially available photopolymerization start-up aid may be used, for example, a trade name "EAB_F" (manufactured by Hodogaya Chemical Industry Co., Ltd.). In the colored photosensitive resin composition of the present invention, a combination of a photopolymerization initiator and a photopolymerization initiation aid may, for example, be a combination of diethoxyacetophenone/4,4bis(monoethylamino). Diphenyl fluorenone, 2-methyl-2-morpholino-1-(4-mercaptophenylthio)propane mono ketone, 4'-bis(diethylamino)benzophenone hydroxy group ^Methyl-1-phenylpropan-1-one/4,4,-bis(diethylamino)benzophenone, mercaptoacetone/4,4,_bis(diethylamino)diphenyl Methyl ketone, 2-hydroxy-2-methyl-1-[4-(hydroxyethoxy)phenyl]propan-1-one/4,4, mono-diamine) alum ketone, cyclohexyl benzophenone / 4,4' _ bis (diethylamine) benzoquinone, 2-rodentyl- 2 -methylmethylethylene) phenyl; propyl ketone oligomer / 4, 4, double (diethylamino) dimeromethyl H-benzyl-2-methylamino-W4_morpholino stupyl) Ding Xuan]_, a pair (diethylene armor: etc. among the 'best The use of 2_methyl-2-morpholinopurine, sulfonylthio)propanolone-1 ketone/4,4,-bis(diethylamino)diphenyl quinone was used. The photopolymerization starting agent such as Hai has an average of 1 mole, and the first is used in the first eight: above, below 5 mu. The following is preferably 0.01. The solvent (F) may, for example, be an aromatic ketone, _, vinegar or acid amine. 315779 23 monoether:: for example: tetrahydrofuran, tetrahydropyran, 1,4-dioxane, alcohol single scream, ethylene glycol monoethyl & 1, ethylene glycol monopropyl hydrazine, ethylene glycol single Dingyin, diethylene glycol monomethyl bond, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, di-glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, Ethyl alcohol monobutyl ether, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl (tetra) acid S, methyl cellulose acetate S, ethyl cellulose vinegar, butyl, butyl Alcohol acetate, propylene glycol methyl acetate, methoxybutyl acetate®, methoxypentyl acetic acid, anisole, phenylethyl ketone, methyl anisole, and the like. Examples of the aromatic hydrocarbons include benzene, hydrazine, diphenylbenzene, and trichost. Examples of the ketones include acetone, 2-butanone '2-pentanone, 3-pentanone, 4-pentanone, 4-mercapto-2-pentanone, cyclopentanone, and cyclohexanone. The alcohol may, for example, be decyl alcohol, ethanol, propanol, butanol, hexanol, cyclohexane, ethyl-if, or glycerin. Examples of the terpenoids include: ethyl acetate, n-butyl acetate, isobutyl acetonate, amyl acid ester, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid. Ethyl ester, butyl butyrate, alkyl esters, decyl lactate, acetamidine acetonide, methyl acetate acetal, ethyl acetate, butyl acetate, methyl methoxyacetate, methoxy Ethyl acetate, butyl oxyacetate, decyl ethoxyacetate, ethyl ethoxyacetate, decyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, decyl 3-methoxypropionate , 3-methoxypropionic acid ethyl ester, 3-ethyl lactyl propionate 曱 g, 3-ethoxypropionic acid ethyl s, '2-pyridyl propionate 曱g, 2 hydroxypropyl propionate, Propyl 2-hydroxypropionate, methyl 2-methoxypropionate, 2-315779 24 1361948 ethyl methoxypropionate, 2-methoxypropionic acid, propane ethoxypropionic acid, 2-, 2- Ethyl ethoxypropionate, 2 bis-methyl-methyl-propionic acid vinegar, 2-based 2-ethyl-2-propionate, 2-methoxy-2-f-propionic acid methyl vinegar, 2_ Ethoxyethyl 2-methyl propionate, decyl pyruvate, ethyl pyruvate, propyl pyruvate, acetamidine Methyl acetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-mercapto-3_methoxy Butyl acetate, 7-butyrolactone and the like. The brewing amines may, for example, be HN-dimethylacetamide, N,N-dimethylacetamide or the like. * Other solvents include, for example, methylpyrrolidone, n, n-dimethylamoxide, and the like. These solvents may be used alone or in combination of two or more. The content of the coloring-sensitive resin composition is usually 7% by mass or more and 95% by mass or less based on the mass fraction, and is preferably 75% by mass or more and 9% by mass. When the content is within the above range, since the flatness is good at the time of coating, and the display characteristics are good when the color filter is formed, t 3 has -, Wang Yugong: 3⁄4 mesh diol monomethyl ether acetate vinegar: and Γ Ethyl ethoxypropionate is in the group. When selected from the solvent of one type of cardinol, single T test acetic acid vinegar, and 3_ethoxypropionic acid B, combined with other solvents, the mixture is mixed (4) according to the mass = the relative use amount of the total solution sword, At least one solvent selected from the group consisting of propylene glycol monohydrate; =3⁄4 & 3_ethoxypropionic acid ethyl vinegar is preferably from 2 to 100% by mass, particularly preferably from 6 to 100% by mass. At least one 315779 25 k from propanol monomethyl _ acetic acid B q 7 in the group of glycoside ~ ^ propyl propionate U to form a group of 100 - Dan two, total solvent, according to the mass fraction 'such as at 50 to Berry. It is very good because it has a flatness that tends to be good. The oxidized human photosensitive resin composition may contain a conjugate, for example, after the coloring pattern is developed and then dried, and heat treatment, and the binder resin is allowed to cross. Further, it can also be obtained by heating to obtain a ring: _ Oxygen compound is because the binder resin is cross-linked, or by:

From ί = hardening', therefore, in the above-mentioned post-baking, it is preferable that the ruthenium is generated in the non-color pattern. Examples of the epoxy compound include a bisphenol fluorene type epoxy resin, a hydrogenated hydrazine type epoxy resin, a double fused F type epoxy resin, a hydrogenated two-shot type epoxy resin, a secret varnish type, and an aromatic system such as a phthalocyanine resin. Epoxy resin; alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl S resin, glycidylamine resin, epoxy resin, etc.; 演化 an evolutionary derivative of the above epoxy resin;

Epoxy compound of aliphatic compound, epoxy compound of alicyclic compound, epoxy compound of aromatic compound, epoxide of butadiene (co)polymer, epoxide of isobutylene (co)polymer And (meth)acrylic acid glycidyl Ss (co)polymer, triisoglycidyl triglycidyl ester, and the like. The content of the epoxy compound in the coloring photosensitive resin composition is usually 15% or less, preferably 0.5% or more and 12% or less, based on the mass fraction of the coloring photosensitive resin composition, particularly preferably More than 1% and less than 10% are more preferable. When the content of the above epoxy compound is 15% by mass or less, 315779 26 1361948, it is excellent because it is sufficiently hardened to increase the residual film ratio. The colored photosensitive resin composition of the present invention may further contain a polymer compound other than the surfactants, fillers, and binder resins, adhesion promoters, anti-cracking agents, ultraviolet absorbers, anti-agglomerants, and organic substances. Additives such as acids, organic amine compounds, and hardeners. The surfactant may be at least one surfactant selected from the group consisting of a lanthanoid surfactant, a fluorine-based surfactant, and a fluorine atom-containing lanthanide surfactant. The lanthanoid surfactant may, for example, be a surfactant having a decane bond. Specifically, for example, Dray (trade name, transliteration) DC3PA, with SH7PA, with DC11PA, with SH21PA, with SH28PA, with SH29PA, with SH30PA, polyether modified oyster sauce SH8400 (trade name: Dray禧矽(share) system); KP32, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460C矽(share) system) and so on. The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specifically, for example, Fronald (registered trademark, transliteration) FC430, with FC431C Sumitomo Seri Aim (share) system; Meijia Fake (registered trademark, transliteration) F142D, Tongyi 7 Bu with F172, Same as F173, same as F177, same as F183, same as R30 (made by Otsuka Ink Chemical Industry Co., Ltd.); Aifubu (registered trademark, transliteration) EF301, with EF303, with EF351, with EF352 (New Akita Chemicals Co., Ltd.) System); Sang Fulong (registered trademark 'transliteration) S381, with S382, with SC1 (H, with SC105C Asahi Glass Co., Ltd.); E5844 [(share) Daikin Fine 27 315779 U01948 = Institute of Magic, - Touch (all product names: ΒΜα_ company system), etc. The fluorine atom-containing ceramsite surfactant may, for example, be a surfactant having a fluorocarbon chain with a sulphur-oxygen bond. Specifically, for example, Mejiafake (commodity name, transliteration) leg, the same BL20, the same 75, the same ^77, the same running 3 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.), and the like. These surfactants may be used singly or in combination of two or more. The surfactant is in an amount of 6 parts by mass or less based on 100 parts by mass of the coloring photosensitive resin composition other than the surfactant, so that the amount is in the range of n parts by mass or more and 0.5 parts by mass or less. It is preferable that the content of the material (4) is less than 0.6 parts by mass, and it is preferable because it has a tendency to have good flatness. The filler may, for example, be fine particles such as glass or alumina. Examples of the polymer compound include polyethylene, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate vinegar. The adhesion promoter may, for example, be ethylene trimethoxy stone. , Ethyl J-milyl (tetra), vinyl tris(2-methoxyethoxy), sulphide, n-(2_^ylethyl)-3-aminopropylmethyldimethoxycarbazide , N-(2-aminoethylidene)-3-aminopropylpropyltrimethoxycarbazide, 3-aminopropyltriethoxylate = methoxypropoxypropyltrimethoxy-Xiyuan, 3_glycidoxy oxime II, *3 methyl-oxo oxime, Μ3,4-epoxycyclohexyl)ethyltrimethoxylate 夕 "milyl propyl decyl dimethyl Oxygen sulphur, gas propyl trimethoxy sulphate, 3-methyl propyl methoxy methoxy succinyl oxysulfide, 3 - benzyl propyl trimethoxy 315779 28 1361948 decane and the like. The antioxidant may, for example, be 4,4'-bis(6-t-butyl-3-methylphenol)sulfide or 2,6-di-t-butyl-4-methylphenol. The ultraviolet absorber may, for example, be a benzotriazole system such as 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-gasbenzotriazole; 2_hydroxy-4-xin-octane a benzophenone system such as oxy-benzidine or a benzoate such as 2, 4-di-t-butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate; - Three-tillage system such as (4,6-diphenyl-1'3'5-trin-2-yl)-5-hexyloxyphenol. The anti-agglomerating agent may, for example, be sodium polyacrylate or the like. The organic acid may, for example, be an aliphatic monocarboxylic acid such as citric acid, acetic acid, propionic acid, butyric acid, valeric acid, monomethyl acetic acid, caproic acid, diethyl acetic acid, heptanoic acid or octanoic acid; Acid, succinic acid, glutaric acid, adipic acid, pimelic acid, xin-g complex, azelaic acid, azelaic acid, malonic acid, methylmalonic acid, ethylmalonic acid: dimethyl Malonic acid, mercapto succinic acid, tetradecyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, tconic acid, etc. a family of diacids; j-tricarboxylic acid, aconitic acid, camphoric acid and other aliphatic tris (four); benzoic acid, toluic acid, cumic acid, 2,3-dimethylphenyl acid, benzoic acid and other aromatic Monocarboxylic acids; aromatic dibasic acids such as citric acid, isophthalic acid, and terephthalic acid; "trimellitic acid, trimesic acid, pyromellitic acid, pyromellitic acid, polycarboxylic acids, etc. The organic amine compound may, for example, be a normal diamine, isopropylamine, n-butylamine, 315779 29 1361948 isobutylamine, a second butylamine, a third butylamine, n-pentylamine, n-hexylamine, n-heptylamine. a monoalkylamine such as n-octylamine, n-decylamine, n-decylamine, n-undecylamine or n-dodecylamine; cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine a monocyclic alkylamine such as methylcyclohexylamine; methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, a dialkylamine such as a second butylamine, a di-tert-butylamine, a di-n-pentylamine or a di-n-hexylamine; a mono-cycloalkylamine such as a cyclohexylamine or an ethylcyclohexylamine; a cyclohexylamine; Cycloalkylamine; methyl ethylamine, methyl diethylene neck, -03 «· T-t-G amine, diethylamine, dimethyl-n-propylamine, diethyl n-propylamine, f-di-n-propylamine, -円 & & 丞 正 正 正 正 正 三 三 三 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正Trialkylamines such as pentylamine and tri-n-hexylamine; dialkyl-based monocyclic amines such as monomethylhexylamine and diethylcyclohexylamine; hexylamine ethyl dicyclohexylamine and tricyclic ring Monobutyryl diamines such as hexylamine; 2 butylamine a single class such as an alcohol, a 3-amino group + a propanol, a melamine- 2,1-propanol-amino group, a pentanol, a 6-amino group, a hexanol, a monocycloalkane such as a 4-amino group, an oxime Alcoholamines; Di-n-butanol amine alkanolamines; Diethanolamine, di-n-propanolamine, diisopropanolamine, butanolamine, n-pentanolamine, di-n-hexanolamine, etc. 315779 30 1361948 Dicycloalkanolamines such as bis(4-cyclohexanol)amine, · -; amine; tri-n-propanolamine, triisopropanolamine, n-diisobutanolamine, tri-n-pentanolamine, three Is one: n-butanolamine, tris(4-cyclohexanol)amine, etc.; tricyclic alcohols; di-alcoholamines; 3-amino-1,2-propylene glycol, 2-aminobutanediol , 4, yl], 3-butanediol, dimethyl::amino-alcohol, 3-diethylamino]'2-propylene glycol, 2-dimethylamine, 2-propanediethyl-2-diethylamine -1'2-propanediol and other amine chain burns: alcohols;, propanol, 4-amino-1,2, hexanediol, [amino hydrazine 3 ring, cycloalkanediol; Amino-based 4_amino ring phase methanol and other amine-containing ring 1-aminocyclopentanone methanol alkanone methanol; aminocyclohexanone methanol, 4-aminocyclohexane-methanol, 4_two Amino group-containing cyclopentane such as methylaminocyclopentane methanol, 4-diethylaminocyclopentane decyl alcohol, 4 dimethylaminocyclohexyl hydrazine H diethylaminocyclohexyl hexane Methanol; /5 _ alanine, 2-aminobutyric acid, > Aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-amino group An aminocarboxylic acid such as valeric acid, 5-aminopentanoic acid, 5-aminohexanoic acid, monoaminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid; aniline , o-mercaptoalkylamine, m-nonylaniline, p-nonylaniline, p-ethylaniline, p-n-propylaniline, p-isopropylaniline, p-n-butylamine, p- Aromatic amines such as tert-butylamine, N,N-didecylaniline, N,N-diethylaniline, p-methyl-N,N-didecylphenylamine; 31 315779 1361948 o-amine Aminobenzyl alcohols such as benzyl alcohol, m-amino T alcohol, p-amino T alcohol, p-dimethylamino decyl alcohol, p-diethylaminobenzyl alcohol; o-amino phenol, m- Aminophenol, p-aminophenol 'p-dimethylaminophenol, p-diethylaminophenol, etc. amine-based phenols; m-aminobenzoic acid, p-amine Benzoic acid, p - dimethylamino benzoic acid, p - diethylamino benzoic acid group and the like. The hardening agent may, for example, be a compound which reacts with a carboxyl group in a binder resin by heating, and may be a binder resin. Further, for example, a compound which is obtained by curing the colored pattern by a single polymerization can be obtained. The above compound may, for example, be an epoxy compound or an oxetane compound. Examples of the epoxy compound include a bisphenol fluorene epoxy resin, a hydrogenated bisphenol fluorene epoxy resin, a double F-based epoxy resin, a hydrogenated bisphenol F epoxy resin, a enamel paint epoxy resin, and the like. Aromatic (four) epoxy resin, aliphatic epoxy resin, heterocyclic epoxy resin, glycidol vinegar, quaternary glycidylamine resin, epoxy resin, etc., or moon t, =, epoxy Resin other than resin and its desertified street organisms = 曰 曰 知 方 方 方 方 方 方 方 壤 壤 壤 方 方 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Cool (4) polymer, triglycidyl isocyanate, etc. The glycidyl sulfonate can be exemplified by: bis (oxa s-butyl phthalate) _ ding phantom dimethyl vinegar, bis (oxetane) Burning) adipic acid vinegar (=% butyl 1 yuan) p-benzoate + methyl _, bis (oxyheterocyclohexane), etc. When the oxetane compound or the like is used, it may also contain an oxetane skeleton which can be used to produce a polyoxy-oxo-oxygen pentoxide-fired compound of the ring 315779 32 1361948. The compound may, for example, be a polyvalent (tetra), a multi-π citric acid needle, an acid generator or the like. Examples of the valence acid include _, 3, 4 - dihydoic acid, m-benzene; Aromatic polybutadiene M: T, such as formic acid, pyromellitic acid, trimellitic acid, U, 5,8-acid di-four-acid acid, 3,3,4'4'-diphenylmethyl-tetrazoic acid Aliphatic polycarboxylic acids such as glutaric acid, adipic acid, U, 3, butyl (tetra) acid, cis, mono-, fumaric acid, itaconic acid; hexahydrophthalic acid, Dicarboxylic acid-hydrogen sulfonyl tetra 11 phthalic acid, hexahydrobenzamide 1 bis to the present dicarboxylic acid, U 4 -cyclopentane tricarboxylic acid, carboxylic acid di-fired, cyclopentene 4... 1,2,4 Residual I, etc., such as 曰 兀 私 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = Aromatic multi-element = anhydride, sorrel needle, citraconic acid Xuan, 12-glycol succinyl (tetra) anhydride, and other aliphatic poly (4) (4); 2, 3, singer, tetra (tetra) dianhydride, trisodium sulphate, 3'4-two Methyltetrahydro-deanic anhydride, u,4-ring sputum ": liver M'2'4-cyclohexyl trisuccinic acid Xuan, Huanyuan, four acid-lower two needles, hydrogen stupid two 'cyclohexyl (tetra) acid dianhydride, humic acid field, methyl endomethylene tetraphthalic anhydride and other alicyclic polycarboxylic anhydrides; T soil B-alcohol Bis(trimellitic acid) liver, glycerol (trimellitic acid wall and other ester-containing 315779 33 mercapto carboxylic anhydrides, etc. Polycarboxylic anhydrides can also be used in the market

The epoxy resin is hard (four), and for example, a hardener of a tree wax is used. The above 700" (Asahi Chemical Industry Co., Ltd.), Shangya: Good. Dana EH transliteration) (New Japanese physicochemical (share) system),: mouth of Jiade shoulder (trade name, chemical system). (Fantasy), the product name "Win" (the new Japanese acid generator) is as described above. The hardener may be used singly or in combination of two or more. It is known that the coloring photosensitive resin of the present invention is used. The coloring photosensitive resin composition of the present invention is applied to a substrate or a coloring photosensitive resin composition layer which is applied to a substrate to form a solid in advance (hereinafter referred to as "substrate, etc." Then, the applied resin layer is pre-baked to remove volatile components such as a solvent, and then exposed to the resin layer by a mask, and then exposed to a resin layer such as an aqueous solution. Developing, and performing post-baking to form a hardened resin layer. This step is regarded as a one-step 'and a method of using a colored photosensitive resin composition containing other colors and repeatedly operating, and finally forming a color chopper having three colors of RGB Examples of the substrate include a glass substrate, a tantalum substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyimide substrate, a polyimide substrate, and an A1 substrate. A substrate having a flat surface such as a GaAs substrate, and the substrate may be subjected to a pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, an ion plating treatment, a sputtering treatment, a gas phase reaction treatment, or a vacuum evaporation treatment. A charge coupling element 315779 34 1361948 (CCD. Charge Caupled Devices) or a thin film transistor (TFT: Thin) may be formed on the surface of the above-mentioned ruthenium substrate or the like.

Film Transistor). When the colored photosensitive resin composition is applied onto the above substrate, for example, only the colored photosensitive resin composition of the present invention is subjected to a spin coating method (spin coating method), a casting method, a roll coating method, a slit type, and the like. A general coating method such as a spin coating method or a slit coating method is applied to a substrate, and then a volatile component such as a solvent is volatilized by heating (prebaking). According to this, a resin composed of a solid component of a color-sensitive resin composition can be formed on a substrate or the like.

Floor. It is a person who exposes a hard layer which is composed of a solid component of a colored photosensitive resin composition. Exposure is only required to illuminate the light through a reticle (4). Light can usually be called 2 lines (wavelength 436nm), 丨 line (wavelength

3 "65_ material. Light is irradiated through a reticle. Here, the "mask" is a light-shielding layer that shields light on the surface of a glass plate. The portion in which the light-shielding layer is not provided in the glass plate is (10) a light-transmissive portion that penetrates, and the colored photosensitive resin composition layer is subjected to a predetermined exposure by a pattern in accordance with the pattern of the light-transmitting portion to generate an unirradiated portion that is not irradiated with light. Area, spotlight irradiation area: the amount of light in the irradiation area is the same as the bonding resin: heavy: average molecular 1, monomer ratio, content, photopolymerizable compound type or content:: photopolymerization initiator type or content It is appropriately selected from the types of photopolymerization start-up aids or factors including $. After exposure, development is carried out. In terms of development, it is only necessary to contact the exposed resin layer with the developer. Specifically, the substrate having the resin layer state formed on the surface is immersed in the development: 315779 35 1361948 The developer may, for example, be: An aqueous solution of a basic compound such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium oxyhydroxide or tetradecyl ammonium hydroxide. The unilluminated area which is not irradiated with light in the colored photosensitive resin composition layer is removed by development. In addition, the light-irradiated area remains as it is and forms a pattern. After development, the sample pattern is usually obtained by washing and drying. Further, after the development and drying, the post-baking may be carried out in a baking furnace or the like to form a cured resin layer. The mechanical strength of the pattern is enhanced by post-baking. When the colored photosensitive resin composition further contains a hardening-curing agent, the colored pattern can be hardened more, and the mechanical strength can be further improved. The post-baking temperature is usually 18 (rc or more, 25 or less, preferably 2 〇〇 'C or more, 2301 or less. When the post-baking temperature is within the above range, it is excellent because it causes sufficient hardening. The post-baking time is usually 5 ^ 40 minutes, preferably 10 to 36 minutes, especially 15 to 3 minutes. The right rear baking material is in the above range (4), which is very good due to sufficient hardening. Therefore, when the coloring pattern of the coloring agent is replaced by the coloring photosensitive tree, and the resin layer is exposed to the substrate again after exposure to the substrate, After development, the coloring pattern can be further formed by replacing the color of the coloring agent contained in the coloring resin composition, and repeating the above operation, the coloring pattern can be re-opened to form a color pattern, and the color can be manufactured. The filter is used to perform the evaporation of the ITO film on the obtained color filter, and the color chopper obtained therein contains the above colored pattern by using the color filter of 315779 36 , you can make a better LCD The coloring photosensitive resin composition of the present invention is excellent in developability because of a good residue, and can form a cured resin layer having a high surface hardness, and the cured resin layer is also excellent in solvent resistance because a cross-sectional shape can be formed. A resin hardened layer which is tapered to a rectangular shape and has no roughness on the surface is therefore suitable for a coloring pattern used for a color-blocking liquid crystal display device or a photographic element, and is suitable for use in the formation of the color filter. [Embodiment] The present invention will be described in more detail based on examples and the like, although the invention is not limited by the examples. Example 1 [Modulation of coloring photosensitive resin composition 1] The following 1 (Α) to (F) Mixing to obtain a coloring photosensitive resin composition (A) C·I. Pigment Blue 15 : 6 (1.967 parts by mass) (A) CI Pigment Violet 23 (0· 〇 3 〇 parts by mass) (E) Polyester-based dispersant (〇. 599 parts by mass) % (B) Copolymer of methacrylic acid and benzyl methacrylate [The composition ratio of methacrylic acid unit to benzyl methacrylate unit by mass ratio (mol ratio) is 3: 7. Weight average molecular weight MW) is 25, 〇〇〇] (1.764 parts by mass) - (C) dipentaerythritol hexaacrylate ("KAYARADDPHA", manufactured by Nippon Kayaku Co., Ltd. (1. 176 parts by mass) (D) 2 卞 base ~ 2 - dimethylamino _i - (4-morpholinophenyl) butanone y ketone (〇·353 parts by mass) 315779 37 1361948 (D2) 4, 4'-bis(diethylamino) dimethyl ketone (rEAB_F) (made by Hodogaya Chemical Industry Co., Ltd.) (0. 118 parts by mass) Epoxy compound [o-phenol phenolic epoxy resin, "Smect epoxy ESCN-195XL-80" (trade name, transliteration) (Sumitomo Chemical Industry Co., Ltd.) (〇. 294 parts by mass), and - (F) propylene glycol monoterpene ether acetate (23. 700 parts by mass) [Formation of colored layer] On glass substrate (Connik ( On the surface of the company, the "#173?" surface was coated with the colored photosensitive resin group obtained in the above, and the volatile component was allowed to stand at 100 ° C for 3 minutes. Volatilized to form a colored photosensitive resin composition layer 1A. After cooling, the colored photosensitive resin composition layer was irradiated with i-line [wavelength 365 nm] over the entire surface without a photomask interposed therebetween. The i-line source is an ultra-high pressure mercury lamp, and the amount of illumination is set to 150 mJ/cm2. Second, at 25. (: developer (according to mass fraction, containing 0.5% potassium hydroxide, sodium butyl naphthalene sulfonate 〇. 2% aqueous solution), dipping for 120 seconds to develop 'purified after pure water A blue colored layer was formed on the entire surface of the glass substrate, and the coated substrate was baked at 220 ° for 20 minutes to form a colored photosensitive resin composition of 1 Å. Further, after cooling the layer 1 ' The colored photosensitive resin composition layer was irradiated with an i-ray [wavelength: 365 nm] through a mask to expose the light. The i-line light source was an ultrahigh pressure mercury lamp, and was irradiated with parallel light, and the amount of the irradiation light was set to 150 mJ/cm 2 . For forming line widths 3/im, 4/zm, 5ym, 6ym, 7/zm, 8/zm, 9/zm, 10/im, 20//m, 30/zm, 40/im, 50/zro, And a mask for the linear color pixel of 100. Then, the exposed glass 38 315779 1361948 substrate [the coloring photosensitive resin composition layer is formed on the surface], in the 2 5 developing solution [by mass fraction, Each contains an aqueous solution of 5% potassium hydroxide 、, butyl naphthalene sulfonate, sodium 0.2%, dipped for 120 seconds to develop, and washed with pure water. After the net, use 22 (TC heating for 20 minutes, the formation of blue pixel 1 (> [evaluation] 1A layer of 25 艽 developer under stirring [depending on the mass fraction, respectively, containing potassium hydroxide 0. 05 %' of sodium butyl naphthalene sulfonate 〇. 2% aqueous solution], after being immersed for 120 seconds and developed, and then washed with pure water, no solidification phenomenon was observed in the developer, and the coating layer was dissolved. For the particle size distribution of the developer solution in which the above coating film has been dissolved, a MicrotracUPA particle size distribution analyzer [upa 150, 9230 UPA, (LEED & NORTHRUP COMPANY)] is used, and the measurement is performed by the light dispersion method. 1. 0 β m or less. In addition, the average penetration ratio of the glass portion after the coating layer is dissolved is 780 nm or more. Next, 'based on the test method described in J IS K 5400, the pencil hardness tester is a pencil. "Mitsubishi Hi-uni", the highest hardness that did not damage the coating film when the applied load was 9 8n was taken as the measured value. Needle_ For the 1B layer pencil strength of the previously formed coating film, using the above method The measured result, the pencil strength is 4H. In addition, the blue image formed In 1C, the cross-sectional shape was a positively pushed-out surface without roughness, and the performance of the colored photosensitive resin composition 1 was good. Example 2 [Preparation of Colored Photosensitive Resin Composition 2] 315779 39 1361948 In addition to Substituting Example 1 The polyacetal-based dispersant was used instead of the poly-ethylenimine-based dispersant, and the others were mixed as in Example 1 to obtain a colored photosensitive resin composition 2. [Evaluation] The same operation as in Example 1 was carried out except that instead of the colored photosensitive resin composition i obtained in Example 1, and the coloring photosensitive resin composition 2 obtained above was used, the 2A layer was stirred. In the next 25 t developing solution, after dipping for 120 seconds and developing, "after washing with pure water, no solidification phenomenon was observed in the developing solution, and the coating layer was dissolved. The particle size distribution of the coating layer component which had been dissolved in the developing solution was measured, and as a result, the maximum particle diameter was 1.0 / / m or less. Further, the glass portion transmittance (average of 400 nm to 780 nm) after the coating layer was dissolved was 98% or more. Next, as with the measurement of the pen strength of the 2B layer of the embodiment, the pencil strength was 4H. Further, in the formed blue pixel %, the cross-sectional shape was a forward tapered shape, and the surface was free from coarse sugar, and the performance of the colored photosensitive resin composition 2 was good. Alignment 3 [Preparation of the color photosensitive resin composition 3] In addition to the use of the polyester-based dispersing agent used in the embodiment 1, the ester-based dispersing agent was used instead, and the others were mixed as in the example, and it was known. 'Coloring photosensitive resin composition 3. [Evaluation] The same operation as in Example 1 was carried out except that the coloring photosensitive resin composition obtained in Example 1 was replaced with the coloring photosensitive resin composition 3 obtained as described above, and the same operation was carried out as in Example 1, and the layer 3A was used. In the liquid solution, after dipping 12_(4), _pure==4 no solidification was observed in the developer, and the coating layer was dissolved. The particle size distribution of the coating layer component which has been dissolved in the developer is measured, and the maximum particle diameter is 1. 0 # m or less. Further, the glass portion transmittance (average of 400 nm to 780 nm) after the coating layer was dissolved was 98% or more. Next, as in the measurement of the pencil strength of the layer 3B of Example 1, the pencil strength was 4H. Further, in the formed blue pixel 3C, the cross-sectional shape was pushed up and the surface was free from roughness, and the performance of the colored photosensitive resin composition 3 was good.盅 盅 Μ [Preparation of coloring photosensitive resin composition 4] In place of the binder resin (Β) used in Example 1, it is changed to a copolymer of acrylic acid and benzyl methacrylate [mercaptoacrylic acid unit, and The composition ratio of the benzyl acrylate unit was mixed as in Example 1 except that the mass ratio (mol ratio) was 3:7, and the weight average molecular weight (Mw) was 36,000] (1.764 parts by mass). The colored photosensitive resin composition 4 was obtained. [Evaluation] The same operation as in Example 1 was carried out except that instead of the colored photosensitive resin composition i obtained in Example 1, and the coloring photosensitive resin composition 4 obtained above was used, the 4A layer was stirred. In the next 25 〇c developing solution, after being immersed for 120 seconds and developed, it was washed with pure water, and no solidification phenomenon was observed in the developing solution, and the coating layer was dissolved. The particle size distribution of the coating layer component of the dissolved 315779 41 1361948 in the developing solution was measured, and as a result, the maximum particle diameter was 1.0//ni or less. Further, the glass portion transmittance (average of 400 nm to 780 nm) after dissolution of the coating layer was 95% or less of 95%. Next, as in the measurement of the pencil strength of the layer 4B of Example 1, the pencil strength was 5H. Further, in the blue pixel 4C to be formed, the cross-sectional shape was positively pushed, but the zigzag shape was found, and the performance of the colored photosensitive resin composition 4 was inferior. Comparative Example 2 [Preparation of Colored Photosensitive Resin Composition 5] _ In addition to the binder resin (B) used in Substituting Example 1, a copolymer of mercaptoacrylic acid and mercapto acrylate was used instead [methacrylic acid unit] And the composition ratio of the benzyl methacrylate unit, according to the mass ratio (mol ratio) of 3:. 7, the weight average molecular weight (Mw) is 4, 8 〇〇], the rest are the same as in the first embodiment The coloring photosensitive resin composition 5 was obtained by mixing. [Evaluation] In place of the coloring photosensitive resin composition 1 obtained in Example 1, and the coloring photosensitive resin composition 5 obtained as described above, the same operation as in Example 1 was carried out, and the layer 5A was used. After being immersed in a 25 t developing solution under stirring for 120 seconds and developed, and then washed with pure water, no solidification phenomenon was observed in the developing solution, and the coating layer was dissolved. The particle size distribution of the coating layer which has been dissolved in the developer is measured, and the maximum particle size is below 1. 〇 " m. Further, the average penetration of the glass portion after the coating layer was dissolved to 780 nm was 98% or more. Secondly, as in the measurement of the pencil strength of the layer 5B of Example 1, the strength of the pen is 315779 42 1361948. Further, in the blue pixel 5C formed by the newspapers and the society, the cross-sectional shape is positive, but the surface is coarse green. The ancestors are rough and the residual film ratio is also low, and the performance of the colored photosensitive resin composition 5 is poor. Example 4 [Preparation of Color Test Photosensitive Resin Composition 6] In place of the polyacetate component (IV) used in Substituting Example 1, a C-based dispersant was used instead, and the binder resin (8) was changed to methacrylic acid and A. The ratio of the ratio of the methacrylic acid unit to the methacrylic acid vinegar unit, the mass ratio (molar ratio) is 35: 65, and the weight average molecular weight (Mw) is 10千]', and the same as in Example 1, except that no epoxy compound was added, a colored photosensitive resin composition 6 was obtained. [Evaluation] The same operation as in Example 1 was carried out except that the coloring photosensitive resin composition obtained in Example 1 was replaced with the coloring photosensitive resin composition 6 obtained above, and the layer 6A was stirred. In the developing solution of 251, after being immersed for 120 seconds and developed, it was washed with pure water, and no solidification phenomenon was observed in the developer, and the coating layer was dissolved. The particle size distribution of the coating layer component which has been dissolved in the liquid solution is measured, and the maximum particle size is 1. 0//II1 or less. Further, the glass portion transmittance (average of 4 〇〇 nm to 780 nm) after dissolution of the coating layer was 98% or more. Next, as in the measurement of the pencil strength of the layer 6B of Example 1, the pencil strength was 9H. Further, in the formed blue pixel 叱, the cross-sectional shape was positively pushed and the surface was free from coarse image, and the performance of the colored photosensitive resin composition 6 was good. 315779 43 1361948 Example 5 [Preparation of coloring photosensitive resin composition 7] In place of the binder resin (B) used in the substitution example 4, it was changed to mercaptoacrylic acid, thiol acrylate T ester, and formula (1) [formula] In the formula (1), R1 represents a methyl group, and R2 represents a copolymer of a component represented by a hydrogen atom] [a mercaptoacrylic acid unit, a T-ester of methacrylic acid, and a composition ratio of a component represented by the above formula (1), depending on the composition The ratio of 堇 (mole ratio) is 25: 60: 15, and the weight average molecular weight (Mw) in terms of polystyrene is 9000] ', and no epoxy compound is added, and the others are mixed as in Example 1 to obtain Coloring photosensitive resin composition 7 ^

Except that the coloring photosensitive resin composition i obtained in Example 1 was replaced, and the coloring photosensitive resin composition 7 obtained above was changed to the same operation as in Example 1, the 7A layer was stirred under 25 < In the t developing solution, after being immersed for 120 seconds and developed, and then washed with pure water, no solidification phenomenon was observed in the developing solution, and the coating layer was dissolved and the coating layer component dissolved in the shirting liquid was dissolved. The particle size distribution was measured, and as a result, the maximum particle diameter was 1.0//m or less. Further, the glass penetration rate (average of 400 nm to 780 nm) after dissolution of the coating layer was 98% or more. Next, as in the measurement of the pen strength of the layer 1 and 7B, the pencil strength of the 315779 44 1361948 is 9H. Further, in the formed blue pixel 7C, the cross-sectional shape is positively pushed and the surface is not rough, and the performance of the colored photosensitive resin composition 7 is good. (1) Modification of the coloring photosensitive resin composition 8 In place of the bonding resin (B) used in the embodiment 4, the bonding resin (B) used in the embodiment 5 was used, and no epoxy compound was added. The others were mixed as in Example 1 to obtain a colored photosensitive resin composition 8. [Evaluation] _ In place of the coloring photosensitive resin composition i obtained in Example 1, and the coloring photosensitive resin composition 8 obtained as described above, the same operation as in Example 1 was carried out, and the layer 8A was After stirring for 25 seconds in a developing solution of 25 ° lt, the developer was washed with pure water, and no solidification phenomenon was observed in the developer, and the coating layer was dissolved. The particle size distribution of the coating layer component which has been dissolved in the developer is measured, and the maximum particle diameter is 1.0 or less. Further, the glass portion transmittance (average of 400 nm to 780 nm) after dissolution of the coating layer was 98% or more. · Secondly, as in the measurement of the pencil strength of the layer 8B of Example 1, the pencil strength was 9H. Further, in the formed blue pixel 8C, the cross-sectional shape was positively pushed and pulled, and the surface was not rough, and the coloring photosensitive resin was composed, and the performance of the object 8 was good. Example 7 [Preparation of Colored Photosensitive Resin Composition 9] In place of the binder resin (B) used in Substituting Example 1, it was changed to methyl propylene 315779 45 1361948 olefinic acid, benzyl methacrylate, and styrene copolymerization. The composition ratio of the methacrylic acid unit, the methacrylic acid vinegar unit, and the styrene unit is 30:60:10 according to the material to enthalpy ratio (Mole ratio), and the weight average molecular weight (Mw) is 16 in terms of polystyrene. Other than 10,000, the others were mixed as in the example to obtain a colored photosensitive resin composition 9. [Evaluation] Except that the coloring photosensitive resin composition i obtained in Example 1 was replaced with the coloring photosensitive resin composition 9 obtained as described above, the same operation as in Example 1 was carried out, and the layer 9A was stirred. In the next 25 乞 developing solution, after being immersed for 120 seconds and developed, and then washed with pure water, no solidification phenomenon was observed in the developing solution, and the coating layer was dissolved. The particle size distribution of the coating layer component which has been dissolved in the developer is measured, and the maximum particle diameter is 1.0 or less. Further, the glass portion transmittance (average of 400 nm to 780 nm) after dissolution of the coating layer was 98% or more. Next, as in the measurement of the pencil strength of the layers of Example 1, 9B, the pencil strength was 6H. Further, in the formed blue pixel 9C, the cross-sectional shape is positively pushed and the surface is not rough, and the performance of the colored photosensitive resin composition 9 is good. Example 8 [Preparation of Colored Photosensitive Resin Composition 1 〇] Copolymerization of p-based acrylic acid, benzyl methacrylate, and isobornyl methacrylate was carried out in place of the binder resin (B) used in Example 1. The composition ratio of the methacrylic acid unit, the benzyl methacrylate unit, and the isobornyl methacrylate unit is 〇:6〇:1(), 315779 46^61948 The polystyrene-equivalent weight average molecular weight (Mw) was 6,000 Å, and the remaining hydrazine was mixed as in Example 1 to obtain a colored photosensitive resin composition ♦ 1 〇. [Evaluation] v The same operation as in Example 1 was carried out except that instead of the colored photosensitive resin composition 1 obtained in Example 1, and the coloring photosensitive resin composition 丨0 obtained as described above was changed, The layer was immersed in a 25 lt.t developing solution for a period of 120 seconds, and after development, and then washed with pure water, no solidification phenomenon was observed in the developing solution, and the coating layer was dissolved. The particle size distribution of the coating layer component which had been dissolved in the developer was measured, and the maximum particle size was 1.0 or less. Further, the glass portion transmittance after dissolution of the coating layer (average of 40 〇 nm to 780 nm) was 98 ° /. the above. Next, as measured by the pencil strength of Example 1 '10B layer, the pencil strength was 7H. Further, in the formed blue pixel 1 〇 (:, the cross-sectional shape was positively pushed and the surface was not rough, and the performance of the colored photosensitive resin composition 10 was good. 315779 47

Claims (1)

Commission (-Ί, + Please patent scope: Patent application is replacing page i coloring photosensitive resin composition' contains: colorant (A), binder resin (B), photopolymerizable compound (c;), light a coloring photosensitive resin composition of a polymerization initiator (D), a pigment dispersant (E), and a solvent (F); the binder resin (B) is a resin containing a constituent unit derived from (meth)acrylic acid ( However, the binder resin (B) does not simultaneously contain: a constituent unit derived from the N_substituted maleimide, and a source derived from an epoxycyclohexylmethyl group (6?(^7〇7〇1〇1^乂7111^) a constituent unit of (meth) acrylate of 1:1^1) and/or a constituent unit derived from a (meth) acrylic acid ester having a propylene group (〇χ i rany 1); The constituent unit of the resin (^) does not have an imidazole ring. I. The pigment dispersant (E) is composed of a polyester group, a polyamidene type, a polyurethane type, and an acrylic type, and at least one of them is selected. Surfactant (only, the pigment dispersant (E) does not have a 4-stage ammonium salt group); in the coloring photosensitive resin composition When the solid content is 100 parts by mass, the content of the colorant (A) is 25 parts by mass or more and 6 parts by mass or less; and the amount of the pigment dispersant (E) is 1 part by mass based on 1 part by mass of the coloring agent (A). The content of the photopolymerizable compound (c) is 5% by mass or more and 50% by mass or less based on the mass fraction of the solid content of the coloring photosensitive resin composition. The mass of the photopolymerization initiator (D) is 0.1% by mass. The mass of the photopolymerization compound (C) is 0.1% by mass. More than 30 parts by weight; the content of the solvent (F) in the coloring photosensitive resin composition, by mass fraction (amendment) 315779 48 1361948 Patent No. 093112369, patent application, April 29, pp. '70% by mass or more and 95% by mass or less; the colored photosensitive resin composition is applied onto a glass substrate to form a resin layer, and the resin layer is prebaked, and exposed and developed through a mask. After baking, in post-baking The hardness of the obtained hardened resin layer is expressed by the pencil hardness, and above, below 9jj, and the photosensitive resin layer obtained by prebaking and exposure through a mask is 255⁄4 under stirring at 100 rpm. In the alkali aqueous solution, the transmittance (average of 400 to 780 nm) at a portion of the non-exposed portion where the photosensitive resin layer is dissolved after 120 seconds is 98% or more and 1% or less. In the coloring photosensitive resin composition of the first aspect, the constituent unit content derived from (mercapto)acrylic acid in the total constituent unit constituting the binder resin (B) is 16 mol% or more, 4〇莫Less than the ear. 3. The coloring photosensitive resin composition according to claim 1 or 2, wherein the binder resin (B) further comprises a constituent unit derived from (mercapto)acrylic acid vinegar. 4. The coloring photosensitive resin composition of the patent application section (...), wherein the bonding resin (8) further contains a tree of the constituent unit represented by the formula (1) (Revised) 315779 49 1361948 Patent Application No. 093112369, | April 29, pp. Amendment Replacement Page (in the formula (I), f and R2 respectively represent independent hydrogen atoms or methyl groups). 5. The colored photosensitive resin composition according to claim 1 or 2, wherein the polystyrene-reduced weight average molecular weight of the binder resin (B) is 5,000 or more and 35 or less. 6. The colored photosensitive resin composition of claim M or 2, wherein the 'pigment dispersant (E) is an acrylic surfactant. A method of forming a colored pattern, wherein a resin layer composed of the colored photosensitive resin composition according to any one of claims 1 to 6 is formed on a substrate, and the resin layer is interposed The mask is exposed and then 'developed' followed by post-baking. 8. The method for forming a colored pattern according to item 7 of the patent application scope, wherein the temperature of the post-fire and the treatment is 180 Ϊ or more and 25 (TC or less). The color illuminator is included in the application patent range 7 or The colored pattern formed by the method of item 8. 50 (amendment) 315779