TW200533960A - Radiation sensitive composition for color filters, process for preparing the same, color filter and color liquid crystal display - Google Patents

Abstract

A radiation sensitive composition for color filters which can provide red pixels having a high light transmittance and a high contrast ratio without foreign matter or with a trace amount of foreign matter produced thereon at a high production yield. This composition comprises a pigment, an alkali-soluble resin, a polyfunctional monomer or a combination of a polyfunctional monomer and a monofunctional monomer, and a radiation sensitive radical generator. The pigment contains 20 wt% or more of C.I. Pigment Red 175 and has an average particle diameter r (unit: nm) of 50 to 300. The pixels having a film thickness of 1.60 μm and made of this composition provide a contrast ratio of 500 or more. The formed color filter is used in a liquid crystal display device.

Description

200533960 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a radiation-sensitive composition 'color filter and color liquid crystal display for color filters. More specifically, the present invention relates to a radiation-sensitive composition for a color filter. The composition includes a color filter for a transmissive and reflective color liquid crystal display and a color imaging device, and a color filter. Manufacture of a color filter with red pixels composed of the radiation-sensitive composition and a color filter for a color liquid crystal display containing the color filter. [Prior Art] Regarding the means for forming a color filter using a color radiation-sensitive composition, it is known to form a coating film of a color radiation-sensitive composition on a substrate or a substrate containing a light-shielding layer of a desired pattern. The mask of the desired pattern is exposed under radiation (hereinafter referred to as "exposure"), developed with an alkali developer to dissolve and remove unexposed parts, and obtained by baking in a clean oven or on a hot plate Method of color pixels (see JP-A 2- 1 445 02 and JP-A 3-53201) (here the term "JP-A" means "Unexamined Japanese Patent Application Gazette"). Because the liquid crystal display device that I am trying to include with the above color filters should have high brightness, the demand for color filters with high light transmittance is now growing. With the recent popularity of digital video recorders and high-view televisions, the demand for color LCDs that are high enough to display a deep blue winter sea or a bright red sunset -4- 200533960 (2) is not increasing. If the "darkness" of the black display part is not displayed clearly, an unsightly burr image will be obtained. Therefore, my attempt is to display high color density, pixels, or color layers with high color density and high contrast. As disclosed in JP-A 10-260309, it is known that C.I. Pigment Red 2 5 4 can effectively function as a pigment for red pixels that meet the above requirements. However, if a radiation-sensitive composition containing this pigment is used, foreign substances will generate B on the pixels, thereby reducing the yield. To deal with this problem, in recent years, there has been a great need for the development of a radiation-sensitive composition for a color filter that meets requirements such as high light transmittance and high contrast, and can provide red pixels with traces of foreign matter generated thereon. [Summary of the Invention] The object of the present invention is to provide a radiation-sensitive composition for a color filter. The composition can provide high yield with high light transmittance and high contrast, and φ has no foreign substance or a trace amount of foreign substance. The resulting red pixels. Another object of the present invention is to provide an advantageous method for preparing the radiation-sensitive composition of the present invention. Yet another object of the present invention is to provide a color filter composed of the radiation-sensitive composition of the present invention and a liquid crystal display device including the same. Other objects and advantages of the present invention will be apparent from the following description. First, the above-mentioned object and advantages of the present invention are achieved by using (A) pigment 200533960 (3), (B) alkali-soluble resin, (C) polyfunctional monomer or polyfunctional monomer and monofunctional monomer. And (D) a radiation-sensitive composition of a radiation-sensitive free radical generator, wherein the pigment (A) contains 20% by weight or more of CI Pigment Red 175 and has an average particle size r (unit: nm) of 50 to 300 ), And the composition is used for a color filter. Secondly, the above objects and advantages of the present invention are achieved by (A) pigment φ (B) alkali-soluble resin, (C) polyfunctional monomer or combination of polyfunctional monomer and monofunctional monomer, and (D ) A radiation-sensitive composition of a radiation-sensitive free radical generator is achieved, wherein the pigment (A) contains 20 weight. / 〇 or more c.I. Pigment Red 175, a pixel made of the radiation-sensitive composition with a thickness of ι 60 μm can provide a contrast of 500 or more, and the composition is used for a color filter. Radiation as used herein means visible light radiation, ultraviolet radiation, far-violet φ external radiation, electronic radiation, or X-radiation. Third, the above objects and advantages of the present invention are achieved by a method for preparing a radiation-sensitive composition, the method comprising (A) containing 20% by weight or more of CI Pigment Red 175 and having an average of more than 300 nm A pigment separation solution prepared by mixing and dispersing pigments in a particle size and dispersing in a solvent while grinding in a solvent, (B) a soluble resin, (C) a polyfunctional monomer or a polyfunctional monomer and a monofunctional The step of combining the base monomers and (D) the radiation-sensitive free radical generator. Fourth, the above purpose and advantages of the present invention are achieved by a color filter of a red pixel having the above radiation-sensitive composition (4). Fifth, the purpose and advantages of the present invention are achieved by a color liquid crystal display including the above color filter. [Embodiment] The present invention will be described in detail below. • (A) Pigment The pigment of the present invention includes C.I. Pigment Red 254 according to the color index (C.I .: issued by the Society of Dyeers and Colorists). The pigment of the present invention may further contain other pigments as necessary. The above other pigments are not particularly limited but are preferably organic pigments, because color filters require high purity, high light transmission, and heat resistance. Examples of other organic pigments include compounds classified into pigment groups according to color index (C.I.), specifically compounds having the following color index (C.I.) numbering φ:

CI Pigment Yell ow 12, CI Pigment Yellow 13, CI Pigment Yellow 1 4, CI Pigment Yello, w 1 7, CI Pigment Yellow 20 > CI Pigment Yellow 2 4, CI Pigment Yellow 3 1, CI Pigment Yellow 55 'CI Pigment Yellow 83 > CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138 ^ CI Pigment Yellow] 39, CI Pigment Yellow 150, CI Pigment Yellow 1 53, CI 200533960 (5)

Pigment Yellow 1 54, CI Pigment Yellow 155 > CI Pigment Yellow 166 'CI Pigment Ye 11 ow 1 6 8 and CI Pigment Yellow 21 1; CI Pigment 丨 Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 2 4, CI Pigment Orange 34, CI Pigment Orange 36, CI, Pigment Orange 38 > CI Pigment Orange 40, CI Pigment Orange 4 3, CI Pigment Orange 46, CI Pigment Orange 4 9, CI Pigment Orange 6 1, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 7 0, CI Pigment Orange 71, CI Pigment Orange '72, CI Pigment Orange 73 and CI Pigment Orange 74; and CI Pigment Red 11, CI Pigment Red 2, CI Pigment Red 5 、 C!. I. Pigment Red 17 、 CI Pigment Red 3 1 、 CI. Pigment Red 3 2 'CI Pigment Red 4] 、 CI · Pigment Red 122 、 CI Pigment Red 123 、 C. I. Pigment Red 144 、 CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI . Pigment Red 1 70, CI Pigment Red 171, CIPigment Red 176 'CI Pigment Red 177, C .: [.Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 1 85, CI Pigment Red 187 , CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI 200533960 (6)

Pigment Red 214, C.I. pigment Red 220, C.I. Pigment

Red 221, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 254, C.I. Pigment Red 2 5 5, C.I. Pigment Red 262, C.I. Pigment Red 2 64, and C.I. Pigment Red 2 72. Among the above other organic pigments, at least one selected from C.I. Pigment Yellow 83, C.I. Pigment Yellow 139, C.I. Pigment Red 177, and C.I. Pigment Red 254 is preferably used. The above other organic pigments can be used alone or in combination of two or more. Among the pigments of the present invention, the content of CI Pigment Red 175 is 20% by weight or more, preferably 30% by weight or more, and particularly preferably 50% by weight. % Or more. By using this pigment, red pixels with high contrast and high light transmittance without foreign matter can be obtained. In the present invention, C.I. Pigment Red 175 and other pigments can be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof before use. The average particle diameter r (unit: nm) of the pigment used in the present invention is 50 to 300, preferably 50 to 200. By using pigments with an average particle size of 1 * above, red pixels with high contrast and high light transmittance without foreign matter can be obtained. The term "average particle diameter" as used herein means the average particle diameter of the second particles belonging to the basic particle (single crystallite) cluster of the pigment. Regarding the particle size distribution of the pigment secondary particles used in the present invention (hereinafter simply referred to as "particle size distribution"), the total amount of secondary particles is used as a reference

200533960 (7), it is estimated that the secondary particle size with (average particle diameter ± 100) n m or smaller is 70% by weight or more, preferably 80% by weight or more. Pigments with the above average particle size and particle size distribution can be mixed with commercially available C.I. Pigment Red (usually having a particle size greater than 300 nm) in the form of pigment mixture and as required Geostatic materials (usually having a particle size greater than 300 nm), and a dispersant and a solvent are prepared by dispersing in a solvent using a bead mill or a roll mill, for example. The dispersant used for the preparation of the pigment dispersion is suitably selected from the group consisting of cation type anionic and nonionic type dispersants. Among these, a urethane bond dispersant (hereinafter referred to as "urethane powder") is preferred. The above urethane bond is represented by the formula R-NH-COO-R (R R 'are each an aliphatic, cycloaliphatic, or aromatic monovalent or polyvalent organic group and the polyvalent organic group It is bonded to 3 or other groups containing another urethane bond) and may be present in the aliphatic and / or hydrophilic group contained in the urethane-based dispersant. The urethane-based dispersant may be present in the chain and / or side chain of the urethane-based dispersant and may have at least one urethane bond in the urethane-based dispersant. If two or more urethane bonds are present in the urethane-based dispersant, they may be the same or different. The urethane-based dispersant is a diisocyanate and / or a triisocyanate and a polyester having a hydroxyl group at one terminal and / or a polyester having a hydroxyl group at both terminals. Examples of the above diisocyanates include aromatic diisocyanates, such as benzenediisoesters including benzene-1,3-diisocyanate and benzene · 1,4-diisocyanate; including toluene · 2,4-diisocyanate, toluene · 2,5-diisocyanate " Ye 175 颜 颜 :::; Contains: Divided Bu: Group 丨 Examples of parent amine esters cyanate-10-200533960 (8), toluene-2, Toluene diisocyanates of 6-diisocyanate and methyl-3,5-diisocyanate; and including 丨, 2-xylene-3,5-diisocyanate, 1,2_monotoluene-3,6-di Isocyanate, 1,3-xylene · 2,4-diisocyanate,], 3_xylene-2,5_diisocyanate, 1,3-xylene-4,6-diisocyanate, 1,4- Xylene-2,5-diisocyanate and xylene diisocyanate of 丨, 4 · xylene-2,6_-isocyanate. Examples of the above triisocyanates include aromatic triisocyanates, such as benzene triisocyanates including benzene-1,2,4-triisocyanate, benzene · 1,2,5-triisocyanate, and benzene · 1,3,5 · triisocyanate. Class; including toluene-2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate and toluene-2,4,6-triisocyanate of toluene triisocyanate Class; and including 1,2-xylene-3,4,5-triisocyanate, 1,2-xylene-3,4,6-triisocyanate, 1,3-xylene-2,4, 5-triisocyanate, 1,3-xylene-2,4,6-triisocyanate, 1,3-xylene-4,5,6-triisocyanate, 1,4-xylene-2,3,5- Triisocyanates and 1,4-xylene-2,3,6-triisocyanate xylene triisocyanates. These diisocyanates and triisocyanates can be used alone or in combination of two or more. Furthermore, polyesters containing hydroxyl groups at one end and polyesters containing hydroxyl groups at both ends are selected from polylactones containing hydroxyl groups at one or both ends, for example, Polycaprolactone, polyvalerolactone containing hydroxyl groups at one or both ends, and polypropiolactone containing hydroxyl groups at one or both ends; and polycondensed polyesters containing radicals at one or both ends Class' e.g. poly-p-phenylene-11-200533960 (9) polyethylene terephthalate with one or both terminal hydroxyl groups and polybutylene terephthalate with one or both terminal hydroxyl groups. The polyesters having a hydroxyl group at one terminal or the polyesters having a hydroxyl group at both terminals may be used alone or in combination of two or more. The urethane-based dispersant of the present invention is preferably a reaction product of an aromatic diisocyanate and a polylactone having a hydroxyl group at one terminal and / or a polylactone having a terminal at both terminals. Reaction product of an isocyanate with a polycaprolactone having a hydroxyl group at one terminal and / or a polycaprolactone having a hydroxyl group at both terminals. Commercially available urethane-based dispersants include EFKA (EFKA Chemical Co., Ltd.), Disperbyk (BYK Chemie Co., Ltd.), and Disbaron (Kusumoto Kasei Co., Ltd.), which are known under the registered name series. The average weight in terms of polystyrene measured by gel permeation chromatography (GPC) of the urethane-based dispersant of the present invention is preferably 5,000 () to 50,000 ', more preferably 7,000 to 20,000 . The above urethane-based dispersants can be used alone or in combination of two or more. Based on 100 parts by weight of the pigment, the amount of fe: formic acid-based dispersant for the preparation of the pigment dispersion is preferably 〇〇〇part by weight or less, more preferably 0.5 to 100 parts by weight, and More preferably, it is 70 to 50 parts by weight, and particularly preferably 10 to 50 parts by weight. If the amount of the urethane-based dispersant is more than 100 parts by weight, the developability may be impaired. The solvent used for the preparation of the pigment dispersion liquid may be the same as that described later for use in the radiation-sensitive composition of the present invention -12-200533960 (10) color filter. The amount of the solvent used for the preparation of the pigment dispersion liquid is preferably 500 to 1,000 parts by weight, and more preferably 700 to 900 parts by weight based on 100 parts by weight of the pigment. To prepare a pigment dispersion using a ball mill, the pigment mixed solution is mixed and dispersed using glass beads or titanium oxide beads having a diameter of about 0.5 to j 0 mm while cooling with cold water or the like. • In this example, the bead charge rate is preferably 50 to 80 ° / 0 of the honing machine capacity and the amount of the pigment mixed solution injected is preferably 2 to 50% of the honing machine capacity. The processing time is preferably 2 to 50 hours, and more preferably 2 to 25 hours. To prepare a pigment dispersion using a roller mill, a three-roller honing machine or a double-roller honing machine may be used to process the pigment mixed solution while cooling with water or the like. The interval between the rollers is preferably 10 μm or less. And the shearing force φ is preferably 108 dyn / sec. The treatment time is preferably 2 to 50 hours, and more preferably 2 to 25 hours. The average particle diameter and particle size distribution of the pigment in the pigment dispersion liquid thus prepared can be measured by a dynamic light scattering method. (B) Alkali-soluble resin The alkali-soluble resin of the present invention is not particularly limited, as long as it can be used as a binder for the pigment (A) and in a developer, it is preferably used in the production of color dense film. It is sufficient to check the solubility of the developer. Test solubility a -13- 200533960 (11) Resin is' for example, a copolymerizable non-I package and monomer having, for example, a carboxyl group, a phenolic hydroxyl group, or a sulfonate group, and another copolymerizable unsaturated monomer (hereinafter referred to as Is a "copolymerizable unsaturated monomer"). Examples of radical copolymerizable unsaturated monomers (hereinafter referred to as "residual unsaturated monomers") include (meth) propionic acid, crotonic acid, α-chloropropionic acid, and Unsaturated monoacids such as cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic acid and methyl fumaric acid ) And other unsaturated dicarboxylic acids and their anhydrides; unsaturated polycarboxylic acids containing three or more carboxyl groups and their anhydrides; mono [2- (meth) acryloxyethyl] succinate and mono [2_ Mono ((meth) acryloxyalkyl] esters of polycarboxylic acids containing two or more residues, such as (meth) acryloxyethyl] phthalate; and ω-carboxy poly Mono (meth) acrylates of polymers containing carboxyl and hydroxyl groups at the end, such as caprolactone mono (meth) acrylate. Among these residue-containing unsaturated monomers, (meth) acrylic acid, mono [2- (meth) acryloxyethyl] succinate, and ω-residue polycaproate are preferred. Lactone mono (meth) acrylate. The above carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more. Examples of phenolic hydroxyl-containing copolymerizable unsaturated monomers include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy · α-methylstyrene, m-hydroxymethyl Styrene, p-hydroxy-α-methylstyrene, N-o-phenylcis butylene diimide, N-m-phenylcis butylene diimide, and N-p-phenylcis butylene Arylene diimide. 14-200533960 (12) These phenolic hydroxyl group-containing polymerizable unsaturated monomers can be used alone or in combination of two or more. Examples of sulfonate-containing polymerizable unsaturated monomers include isoprene sulfonic acid and p-styrene sulfonic acid. These sulfonate-containing polymerizable unsaturated monomers may be used alone or in combination of two or more. Examples of copolymerizable unsaturated monomers include polystyrene, poly (methyl) methacrylate, poly (n-butyl) methacrylate, and polysiloxane (hereinafter referred to as "megamonomers" ”) And other polymer molecular chains with one or two terminals containing (meth) acrylfluorenyl megamonomers; N-phenylcis-butenediimide, N-o-hydroxyphenylcisbutadiene Fluorenimine, N-m-hydroxyphenylcis-butenedifluoreneimine, N-p-hydroxyphenylcisbutenedifluoreneimine, N-o-methylphenylcisbutenedifluoreneimine, N-m-methylphenylcis-butenedifluoreneimine, N-p-methylphenylcisbutenedifluoreneimine, N-o-methoxyphenylcisbutadieneimine, N -M-methoxyphenylcis-butenedifluorene imines and N- (substituted) arylcis-butanediamines such as N-p-methoxyphenylcis butadieneimine, And substituted aryl-cis-butene-diimines such as N-cyclohexyl-cis-butene-diimide; styrene, α-methylstyrene, o-ethyl benzene toluene, m-vinyl toluene, p- Vinyl toluene, p-chlorostyrene, o-methoxystyrene, m-methyl Styrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-ethynyl benzyl methyl ether, o-vinyl Aromatic vinyl compounds such as benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; indene such as indene and] -methylindene; ( -15- 200533960 (13) methyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl methacrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, alkenyl (meth) acrylate Propyl ester, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate Ester, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (methyl ) Acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, 2-hydroxy-3-phenoxy (meth) acrylate Unsaturated carboxylic acid esters such as propyl propyl ester and glycerol (meth) acrylate; 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, (methyl 2-aminopropyl acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) propionic acid Unsaturated residual acid amine esters such as esters; unsaturated glycidyl esters such as glycidyl (meth) acrylate; carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate Acid vinyl esters; unsaturated methyl ethers such as vinyl methyl ether, vinyl ethyl ether and propyl glycidyl ether; (meth) propylene , Α-chloroacrylonitrile, ethylene dicyanide and other vinyl cyanide compounds; (meth) propane_amine, α-chloropropanamine, and N-2-ethyl (meth) acrylamide Isocracy -16- 200533960 (14) and amidines; and aliphatic conjugated diene such as 1,3-butadiene, isoprene and chloroprene. These copolymerizable unsaturated monomers may be used either individually or in combination of two or more. Among the above copolymerizable unsaturated monomers, mega monomers, N-substituted maleimides, 2-hydroxyethyl (meth) acrylate, and benzyl (meth) acrylate are preferred. And glycerol (meth) acrylate. Among the megamonomers, particularly preferred are polystyrene megamonomers and poly (meth) acrylate macromonomers, and among the substituted maleimides, N-phenyl maleimide is particularly preferred. Peryleneimine and N-cyclohexyl maleimide. The alkali-soluble resin of the present invention is preferably a copolymer of a carboxyl group-containing unsaturated monomer and a copolymerizable unsaturated monomer (hereinafter referred to as a "carboxyl group-containing copolymer"). The carboxyl-containing copolymer is preferably a copolymer of the following (hereinafter referred to as "carboxyl-containing copolymer (I)"): (a) a carboxyl-containing unsaturated monomer component and (b) at least one selected Self-polystyrene megamonomer, poly (meth) acrylate, N-phenyl-cis-butene-diimide, N-cyclohexyl-cis-butene-diimide, 2-hydroxyethyl (meth) acrylate Ester, benzyl (meth) acrylate and glycerol mono (meth) acrylate, and optionally (c) containing at least one selected from styrene, methyl (meth) acrylate, (meth) Allyl acrylate and phenyl (meth) acrylate. Particularly preferred are copolymers of the following (hereinafter referred to as "carboxyl-containing copolymers (I0)"): (a) containing (meth) acrylic acid as a basic component and, if necessary, [2- ( (Meth) acryloxyethyl] succinate-17-200533960 (15), (b) at least one selected from the group consisting of polystyrene megamonomer, poly (meth) acrylate, and N-phenylcis Butene difluorene imine, N-cyclohexyl maleimide diimide, 2-hydroxyethyl (meth) acrylate, benzoic acid (meth) acrylate, and glycerol mono (meth) acrylate And (c) at least one selected from the group consisting of styrene, methyl (meth) acrylate, allyl (meth) acrylate, and phenyl (meth) acrylate, as the case requires. Carboxyl-containing copolymer (Π) Illustrative examples include (meth) g acrylic acid, mono [2- (meth) acryloxyethyl] succinate, benzyl (meth) acrylate, and glycerol mono (methyl) Copolymers of acrylic esters, (meth) acrylic acid, mono [2- (meth) acryloxyethyl] succinate, N-phenylmaleimide diimide, styrene and A copolymer of allyl (meth) acrylate, (meth) acrylic acid, mono [2- (meth) acryloxyethyl] succinate, N-phenylmaleimide diimide, Copolymer of (methyl) benzyl acrylate and styrene, (meth) acrylic acid, mono [2- (meth) acryloxyethyl] succinate, N-cyclohexylcis-butene diφ Fluorene imine, copolymer of styrene and allyl (meth) acrylate, (meth) acrylic acid, mono [2- (meth) acryloxyethyl] succinate, N-cyclohexyl cis Butene diamidine, copolymer of benzyl (meth) acrylate and phenethyl ether, (meth) propionic acid, mono [2- (methyl) propanyloxyethyl] succinic acid Ester, N-phenyl maleic acid, imine, benzyl (meth) acrylate, copolymer of glycerol mono (meth) acrylic acid and styrene, (meth) acrylic acid, polycarboxylate Ester mono (meth) acrylate, N-phenyl maleic acid diimide, benzyl (meth) acrylate, copolymer of glycerol mono (meth) acrylate and styrene, (meth) ) Acrylic acid-18- 20053 3960 (16) Copolymer with 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, polystyrene macromonomer copolymer with phenyl (meth) acrylate, (meth) acrylic acid, Copolymer of benzyl (meth) acrylate and propylene glycol mono (meth) acrylate, co-existence of 2-hydroxyethyl (meth) acrylate (meth) acrylic acid and benzyl (meth) acrylate ^ (Meth) acrylic acid, copolymers of 2-hydroxyethyl (meth) acrylate and phenyl (meth) acrylate, (meth) acrylic acid, copolymers of hydroxyethyl (meth) acrylate and styrene, (Meth) acrylic acid, N-cyclohexyl cis-butylimide, imine, copolymer of benzyl (meth) acrylate and styrene, (meth) acrylic acid, polystyrene giant monomer, (meth) Propionic acid 2- Copolymer of ethyl acetate and benzyl (meth) acrylate, (meth) propionic acid, poly (meth) acrylic acid giant monomer, (meth) propionic acid chain B Copolymer of ester with benzyl (meth) acrylate, (meth) acrylic acid, N-phenyl maleic acid Amine, copolymer of benzyl (meth) acrylate and styrene and (meth) acrylic acid, N-phenylcis-butanedimine, benzyl (meth) acrylate, glycerol mono (methyl) Based) Copolymer of propionate and styrene. The content of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is preferably 5 to 50% by weight, and more preferably 10 to 40% by weight. If the above content is less than 5% by weight, the solubility of the prepared radiation-sensitive composition in an alkali developer may decrease. If the content is higher than 50% by weight, the solubility of the composition in the alkali developer becomes too high, so that if the composition is developed with the alkali developer, the pixels may fall off the substrate or the film surface of the pixels It may become rough. -19-d 200533960 (17) In the present invention, the weight-average molecular weight of an alkali-soluble resin component is measured by gel permeation chromatography (GP C, extraction solvent: tetrahydrofuran) from the viewpoint of polystyrene (hereinafter referred to as "Mw") is preferably 3,000 to 300,000, and more preferably 5,000 to 100,000. In terms of polystyrene, the number-average molecular weight of the alkali-soluble resin component measured by gel permeation chromatography (GPC 'elution solvent: tetrahydrofuran) (hereinafter referred to as "Mη") is preferably 3,000 to 60,000' more Good Place • 5,000 to 25,000. By using this alkali-soluble resin with the specified Mw or Mn, a radiation-sensitive composition with excellent developability can be obtained, whereby pixels with sharp pattern edges can be formed, and the light shielding of the substrate or unexposed parts during development Few residues, smudges and film residues are produced on the layer. The Mw / Mn of the alkali-soluble resin of the present invention is preferably from 1 to 5, and more preferably from 1 to 4. In the present invention, the alkali-soluble resin can be used alone or in combination of two or more kinds of φ. The amount of the alkali-soluble resin used in the present invention is based on 100 parts by weight of the pigment (A), preferably 10 to 1,000 parts by weight, and more preferably 20 to 500 parts by weight. If the amount of the alkali-soluble resin is less than 10 parts by weight, alkali developability may be reduced, or smudges and film residues may be generated on the substrate or the light-shielding layer of the unexposed portion. If the amount is more than 1,000 parts by weight, the concentration of the pigment is reduced, and it may be difficult to achieve the target color density of the film. (C) Combination of polyfunctional monomer or polyfunctional monomer and monofunctional monomer-20-200533960 (18) The polyfunctional monomer of the present invention is a monomer having two or more polymerizable unsaturated bonds body. Examples of polyfunctional monomers include di (meth) acrylates of butanediols such as ethylene glycol and propylene glycol; polyethylene glycols containing two or more ethylene oxide groups and two or more ethylene glycol groups Di (meth) acrylates of polyalkylene glycols such as propoxy polypropylene glycol; polyhydric alcohols containing 3 or more hydroxyl groups, such as glycerol, trimethylolpropane, pentaerythritol, and dipentaerythritol, and their Poly (meth) acrylates of carboxylic acid modified products; oligomeric (meth) acrylic acid such as polyester, epoxy resin, urethane resin, alkyd resin, siloxane resin, and spiro resin Esters; poly-1,3-butadiene with hydroxyl groups at both ends, polyisoprene with hydroxyl groups at both ends, and polycaprolactone with hydroxyl groups at both ends Dihydroxy (meth) acrylates of hydroxyl-containing polymers; and [2- (meth) acryloxyethyl] phosphate. Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols containing 3 or more hydroxyl groups and their modified products of dicarboxylic acids are preferred, such as trimethylolpropane tri ( Methacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Particularly preferred are trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, because the obtained pixels have high strength and smooth surfaces and the substrate or There is almost no stain or film residue on the light-shielding layer of the exposed portion. The above multifunctional monomers can be used alone or in combination of two or more. -21-200533960 (19) Based on 100 parts by weight of the alkali-soluble resin (B), the amount of the polyfunctional monomer in the present invention is preferably 5 to 500 parts by weight, more preferably 20 to 300. Parts by weight or less. If the amount of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the obtained pixel may be reduced. If the amount is more than 5000 parts by weight, alkali developability may be deteriorated, or smudges and film residues may be easily generated on the light shielding layer of the unexposed portion. In the present invention, a part of the polyfunctional monomer may be replaced by a monofunctional monomer having a polymerizable unsaturated bond. Examples of the above monofunctional monomers include the carboxyl-containing unsaturated monomers and copolymerizable unsaturated monomers already listed for the above alkali-soluble resin (B), N-vinyl succinimide, N -Vinyl-2-hexahydropyridone, N-vinylcaprolactam, N-vinylpyrrole, N-vinylpyridine, N-vinylimidazole, N-vinylimidazolidine, N-vinylindole Indole, N-vinylindololine, N-vinylbenzimidazole, N-vinylcarbazole, N-vinylhexachloropyridine, N-ethanylhexahydro < Bipyrazine, N-Ethylmorpholin and N-vinylphenoxazine · 'N- (Methyl) propanylmorpholine and commercially available (Toas (Osei Chemical Industry Co., Ltd.) M-5300 and M-5400. These monofunctional monomers may be used alone or in combination of two or more. Based on the total amount of the polyfunctional monomer and the monofunctional monomer, the amount of the monofunctional monomer is preferably 90% by weight or more. Less' is more preferably 50% by weight or less. If the amount of the monofunctional monomer is more than 90% by weight, the strength and surface smoothness of the obtained pixel may be deteriorated. -22- 200533960 (20) (D) Radiation sensitive free radical generator The radiation sensitive free radical generator (hereinafter simply referred to as "free radical generator") of the present invention is transparent to visible light radiation, ultraviolet radiation, Radicals such as extreme ultraviolet radiation, electron radiation, and X-radiation are exposed to form compounds that form radicals that can initiate the polymerization of the above component (C). Examples of the radical generator include acetophenone-based compounds, Biamid D-based compounds, triazine-based compounds, benzoin-based compounds, benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, xanthones and diazonium compounds. The above radical generators can be used alone or in combination of two or more. The radical generator of the present invention is preferably at least one selected from the group consisting of acetophenone-based compounds, biimidazole-based compounds and triazine-based compounds. Based on 100 parts by weight of the component (C), the radical φ generating dose of the present invention is preferably from 0.00 to 80 parts by weight, more preferably from 1 to 60 parts by weight. If the amount of the radical generating agent is Less than 0 · 0 1 parts by weight, it may be difficult to obtain a color filter having a predetermined pixel pattern due to incomplete curing by exposure. If the amount is more than 80 parts by weight, the formed pixels may be removed during development. The substrate is dropped. Examples of acetophenone-based compounds among the preferred free-radical generators of the present invention include 2-hydroxy-2-methyl-1-phenylpropanone, 2-methyl · 1_ [ 4- (methylthio) phenyl] -2 -morpholinylacetone-1, 2-benzyl-2 -dimethylamino-1-(4-morpholinylphenyl) butanone-1, 1-hydroxycyclohexylphenyl ketone, -23- 200533960 (21) 2,2-dimethoxy-u-diphenylethyl. I · ketone, I] octanedione and _ [4- (This thio group) phenyl: 1-2- (〇-benzidine oxime) Among these acetophenone compounds, 2-methyl-M4 · (methylthio) phenyl] -2 is particularly preferred -(Morpholinyl) acetone ", 2-benzyl-2-dimethylaminomorpholinylphenyl) butanone-; [, 1,2-octanedione and 1- [4- (. This thio group) phenyl L · 2 · (〇-Benzamoxime). The following acetophenone compounds can be used alone or in combination of two or more ^. The fluorenone-based compound as the radical generator of the present invention is based on 100 parts by weight of the component (C), and the amount of the acetone-based compound is preferably from 0.01 to 800 parts by weight, more preferably from 1 to 6 0 parts by weight, particularly preferably 1 to 30 parts by weight. If the amount of the acetophenone-based compound is less than 0.01 parts by weight, it may be difficult to obtain a color filter having a predetermined pixel pattern. If the amount is more than 80 parts by weight The formed pixels may fall off the substrate during development. Examples of the biimidazole-based compound include 2,2, -bis (2-chlorophenyl)-• 4,4 ', 5,5'-(4 -Ethoxycarbonylphenyl) -1,2, _biimidazole, 2,2, bis (2-bromophenyl) -4,4 ', 5,5'-(4-ethoxycarbonylphenyl)- 1,2, -biimidazole, 2,2, bis (2-chlorophenyl) · 4,4,5,5,5, -tetraphenyl-1,2, -biimidazole, • 2,2, bis ( 2,4-dichlorophenyl) -4,4,5,5,5-tetraphenyl-1,2, -biimidazole, • 2,2 '· bis (2,4,6-trichlorophenyl) ) -4,4,, 555, -tetraphenyl-1,2, -biimidazole, 2,2, bis (2-bromophenyl) -4,4,5,5, -tetraphenyl-1, 2, -biimidazole, 2,2'-bis (2,4 -Dibromophenyl) -4,4,5555, tetraphenyl-152, -biimidazole and 2,2, bis (2,4,6-tribromophenyl) -4,4,555, tetrabenzene 1-2,2, -biimidazole-24-200533960 (22) Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5, Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole And 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, and particularly preferably 2,2, -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2, -biimidazole. The above biimidazole-based compounds have excellent solubility in solvents, but do not produce insoluble products and foreign substances such as precipitates, etc., have high sensitivity, can use a small amount of energy exposure to completely promote the curing reaction without causing undesired The curing reaction of the exposed part. Therefore, after the exposure, the coating film can be clearly divided into a cured portion that is insoluble in the developer and an uncured portion that has high solubility in the developer, thereby forming a high-visibility color filter with a predetermined pixel pattern without underetching. Light film. The above biimidazole-based compounds can be used alone or in combination of two or more. If a biimidazole-based compound is used as the radical generator of the present invention, and based on 100 parts by weight of the component (C), the amount of the biimidazole-based compound is preferably from 0.0 1 to 40 parts by weight, more preferably from 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. If the amount of the biimidazole-based compound is less than 0.01 parts by weight, it may be difficult to obtain a color filter having a predetermined pixel pattern. If the amount is more than 40 parts by weight, the pixels formed during development may fall from the substrate or the film surface of the pixel surface may become rough. -Hydrogen Donor- If a biimidazole-based compound is used as the radical generator of the present invention, it is preferable to use it in combination with the following hydrogen donor to improve the sensitivity more than -25-200533960 (23). The term "hydrogen donor" as used herein refers to a compound that can provide a hydrogen atom to a radical formed by a biimidazole-based compound through exposure. The hydrogen donor of the present invention is preferably a thiol-based compound or an amine-based compound as defined below. The above thiol-based compound contains a benzene ring or heterocyclic ring serving as a mother core, and has one or more, preferably one to three, more preferably one or two, directly bonded to the parent of the molecule Nuclear thiol-based compounds (hereinafter referred to as "thiol-based hydrogen donors"). The above amine-based compound contains a benzene ring or heterocyclic ring serving as a mother core, and has one or more, preferably one to three, more preferably one or two, directly bonded to the mother core of the molecule Amine-based compounds (hereinafter referred to as "amine-based hydrogen donors"). The hydrogen donor may contain both a thiol group and an amine group. A detailed description of these hydrogen donors is provided next. # The thiol-based hydrogen donor may contain at least one benzene ring or heterocyclic ring, or both. If it contains two or more rings, fused rings may or may not be formed. If the thiol-based hydrogen donor contains two or more thiol groups, as long as at least one free thiol group is maintained, at least one other thiol group may be substituted with an alkyl group, an aralkyl group, or an aryl group. Furthermore, as long as at least one free thiol group is maintained, the thiol-based hydrogen donor may have a structural unit in which two sulfur atoms are bonded together by a divalent organic group such as an alkylene group, or the two sulfur atoms are two The structural unit of sulfide bond. -26- 200533960 (24) Furthermore, the position of the thiol-based hydrogen donor other than the thiol group can be replaced by a carboxyl group, a oxo group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxyline group Or substituted with a nitrile group. Examples of this thiol-based hydrogen donor include 2-thiol-benzothiazole, 2-thiol-benzazole, 2-thiol-benzimidazole, 2,5-dithiol * 1, 3,4-thiadiazole and thiol · 2,5-dimethylaminopyridine. Among suitable thiol-based hydrogen donors, 2,5-dithiol- •, 3,4-thiadiazole, and 2-thiol-2,5-dimethylaminopyridine are preferred. , And particularly preferably 2-thiol-2,5-dimethylaminopyridine. The molecule of the amine-based hydrogen donor may contain at least one benzene ring or heterocyclic ring, or both of them. If it contains two or more rings, it may or may not form a fused ring. At least one amine group of the amine-based hydrogen donor may be substituted with an alkyl group or a substituted alkyl group. The amine-based hydrogen donor may be substituted at a position other than the amine group by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, or a φnitrile group. Examples of the above amine-based hydrogen donor include 4,4, -bis (dimethylamino) methanone, 4,4, · bis (diethylamino) benzophenone, 4-diethyl Aminobenzophenone, 4-dimethylaminobenzophenone, ethyl-4-dimethylaminobenzoate '4-dimethylaminobenzoate and dimethylaminobenzoate Nitrile. Among these amine-based hydrogen donors, 4,4, -bis (dimethylamino) benzophenone and 4,4, -bis (diethylamino) benzophenone are preferred, and particularly preferred are 4,4'_bis (diethylamino) benzophenone. If a radical generator other than a biimidazole-based compound is used, an amine-based hydrogen-27- 200533960 (25) donor is used as a sensitizer. In the present invention, the above hydrogen donors can be used alone or in combination of two or more. Since the pixels formed during development hardly fall from the substrate and have high strength and sensitivity, it is preferable to use a combination of at least one thiol-based hydrogen donor and at least one amine-based hydrogen donor. Examples of the combination of a thiol-based hydrogen donor and an amine-based hydrogen donor include a combination of 2-thiolbenzobenzothiazole and 4,4, -bis (dimethylamino) benzophenone, 2-B sulfur Combination of alcoholic benzothiazole and 4,4, -bis (diethylamino) benzophenone, 2-thiolbenzoxazole and 4,4, _bis (dimethylamino) benzoic acid A combination of ketones' and a combination of 2-thiol benzoguazole and 4,4, -bis (diethylamino) benzophenone. A combination of 2-mercaptobenzoffazole and 4,4, -bis (dimethylamino) benzophenone and 2-mercaptobenzoffazole and 4,4, -bis (di A combination of ethylamino) benzophenone is particularly preferably a combination of 2-mercaptobenzoffazole and 4,4'-bis (dimethylamino) benzophenone. In the combination of a thiol-based hydrogen donor and an amine-based hydrogen donor, the weight of the thiol-based hydrogen donor # to the amine-based hydrogen donor is preferably 1: 1 to 1: 4, and more preferably 1: 1 to 1 : 3 ° If a hydrogen donor and a biimidazole-based compound are used in the present invention, the amount of the hydrogen donor is preferably 0.01 to 40 parts by weight, and more preferably 1 to 30 parts by weight based on the weight of the component (c). Parts, particularly preferably 1 to 20 parts by weight. If the amount of the hydrogen donor is less than 0.01 part by weight, the effect of improving the sensitivity may be reduced. If the amount is more than 40 parts by weight, the pixels formed during development may fall off the substrate. Examples of the above triazine-based compounds include 2,4,6-ginseng (trichloromethyl-28-200533960 (26))-symmetric-triazine, 2-methyl-4,6-bis (trichloromethyl) ) -Symmetric-pyrazine, 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) _symmetric-triazine, 2- [2_ (furan -2-yl) vinyl] -4,6-bis (trichloromethyl) -symmetric-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethanyl ] -4,6-bis (trichloromethyl) -symmetric-triazine, 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl ) -Symmetric-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -symmetric-triazine, 2- (4-ethoxystyryl) -4 , 6-bis (trichloromethyl) -symmetric-triazine and halogenated methyl groups such as 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) · symmetric-triazine compound of. Among the above triazine-based compounds, 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethylsymmetric-triazine) is preferred. The triazine compound can be used alone or in combination of two or more. If the triazine compound is used as the radical generator of the present invention, the amount of the triazine compound is preferably based on 100 parts by weight of the component (C). It is 0.0 1 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. If the amount of the triazine-based compound is less than 0 · 0 1 parts by weight, curing is incomplete due to exposure As a result, it may be difficult to produce a color filter having a predetermined pixel pattern. If the amount is more than 40 parts by weight, the pixels formed during development may fall off the substrate. Other additives

The radiation-sensitive composition for use in the color filter of the present invention includes (A -29-200533960 (27)) to (D) and other additives as necessary. The above additives include materials such as glass or alumina; polymer blends such as polyvinyl alcohol or poly (fluoroalkyl acrylate); non-ionic, cationic or anionic surfactants; vinyltrimethoxysilane , Vinyltriethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl · methyl · dimethoxysilane, N -(2-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxy Propylpropyl.methyl • dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl · methyl · dimethoxysilane, 3- Adhesion accelerators such as chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or 3-thiolpropyltrimethoxysilane; 2,2-thiobis (4-methyl -6-tertiary butyl phenol) or 2, 6-tertiary butyl phenol and other antioxidants; 2- (3-tertiary butyl-5-methyl-2-hydroxyphenyl) -5-chloro UV absorbers such as benzotriazine or alkoxybenzophenone; polypropylene And sodium aggregation inhibitor. Solvent The radiation-sensitive composition for the color filter of the present invention contains the above components (A) to (D) and other additives as necessary, and is preferably prepared into a liquid composition by adding a solvent. An appropriate solvent can be selected as long as it disperses or dissolves the components (A) to (D) constituting the radiation-sensitive composition and other additives, does not react with these, and has appropriate volatility. Examples of the solvent include propylene glycol monomethyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl-30-30200533960 (28) -based ethers; for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether (Poly) alkylene glycol monoesters such as acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Alkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; such as methyl ethyl ketone, 2-heptanone, and Ketones such as 3-heptanone; for example, diacetone alcohol (also known as 4-hydroxy-4-methylpent-2--2-ketone) and keto alcohols such as 4-hydroxy-4-methyl-hexan-2-one ; For example, alkyl lactates such as methyl lactate and ethyl lactate; for example, ethyl 2-hydroxy-2-methylpropionate, ethyl glycolate, 2-hydroxy-3-methylbutyrate, 3-methyl Methyloxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-acetate 3-methoxybutyl ester, 3-methyl-3-methoxybutyl acid, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, propionic acid Other esters such as n-butyl, ethyl butyrate, n-propyl butyrate, iso-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, and ethyl 2-oxobutyrate; such as toluene and dioxoate Aromatic hydrocarbons such as toluene; and amines such as N-methylpyridine, N, N-dimethylformamide, and N, N-dimethylacetamide. Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, glycerol monomethyl ether acetate, and propylene glycol monoethyl ether are preferred in terms of solubility, pigment dispersibility, and coatability. Acid acetate, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 3-methoxypropionate, j-ethoxypropionate, j -Ethyl ethoxy propionate, propionate 3-methyl-31-200533960 (29) propyl-3-methoxybutyl, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate , N-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate and ethyl pyruvate. Furthermore, for example, benzylethyl ether, di-n-hexyl ether, acetone acetone, isophorone, ethyl hexanoate, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, High-boiling solvents such as ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate are used in combination with this solvent. These high boiling point solvents can be used alone or in combination of two or more. The amount of the solvent is not particularly limited, but from the viewpoint of fluidity and stability of the composition, my intention is to ensure that the total amount of all ingredients except the solvent in the composition is preferably 5 to 50 weight. / 〇, particularly preferably 10 to 40% by weight of rhenium. Method for forming color filter Next, a method for forming the color filter of the present invention by using the radiation-sensitive composition for a color filter of the present invention is provided. The method for forming a color filter includes the following steps (1) to (4) in order: (1) forming a coating film of the radiation-sensitive composition of the present invention on a substrate, and (2) making at least a portion of the coating film Exposure under radiation; (3) developing the coating film after exposure; and (4) heating the coating film after development (hereinafter referred to as "post-baking"

J -32-200533960 (30) Next, provide detailed instructions for each step. -Step (1)-If necessary, a light shielding layer for defining a portion for forming a pixel is formed on the surface of the substrate, and the liquid radiation-sensitive composition of the present invention is applied to the substrate and pre-baked to evaporate Solvent to form a coating film. The substrate used in this step is made of glass, silicon, polycarbonate, polyester, aromatic polyamine, polyamido-imino, polyimide, polyether, glass olefin, or hydrogenated The product is a ring-opening polymer. The substrate may be appropriately pretreated by, for example, chemical treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, gas vapor reaction, or vacuum deposition. To apply the liquid composition to a substrate, a suitable coating technique such as spin coating, die coating, or roll coating can be used. Regarding the pre-baking conditions, the resin composition is preferably pre-baked at 70 to 110 ° C. for 2 to 4 minutes. After removing the solvent, the thickness of the coating film of the resin composition is preferably 0.1 to 10 μηι, more preferably 0.2 to 8.0 μηι, and particularly preferably 0.2 to 6.0 μηι. -Step (2)-After that, the formed coating film is exposed to radiation through a mask having an appropriate pattern. The radiation used in this step may be visible radiation, ultraviolet radiation, far ultraviolet radiation, electronic radiation, and X-radiation. The transmission preferably has a wavelength of 190 -33-a 200533960 (31) to 450 nm. The amount of radiation is preferably about 10 to 10,000 J / m2. -Step (3)-Then, the coating film is preferably developed using an alkali developer to remove the unexposed portion of the coating film. The above developer is preferably sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazobicyclo- [5.4.0] -7-undecene or 1 , 5 · diazobicyclo- [4 · 3 · 〇] -5-nonene. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant may be added to the above alkaline developer. The coating film is usually washed after alkali development. Shower (shower) development, spray development, dip (immersion) development, puddle development, etc. can be used. Regarding the development conditions, it is preferable to perform the development at room temperature for 5 to 300 seconds-step (4)-by post-baking the developed coating film, a radiation-sensitive composition having a radiation-sensitive composition for a color filter can be prepared. A substrate of a predetermined red pixel pattern formed by the cured product. Regarding the conditions of the post-baking, it is preferable to heat-coat at 180 to 230 ° C for 20 to 40 minutes. The thickness of the formed pixel film is preferably 0.5 to 5.0 μηι, more preferably -34- 200533960 (32) 1.5 to 3.0 μm 〇 Furthermore, 'the liquid composition containing green and blue pigments dispersed therein is dispersed. Repeat the above steps (1) to (4) to form a blue pixel pattern and a green pixel pattern on the same substrate, thereby forming a colored layer with predetermined red, edge, and blue pixel patterns on the substrate. . In the present invention, the order of forming the color pixel patterns is not limited to the above order. Color filter The color filter of the present invention contains a red pixel composed of the radiation-sensitive composition of the present invention. With a film thickness of 1.60 μm, the red pixel of the color filter of the present invention has a high light transmittance and a high contrast of 500 or more, more preferably 1,000 or more. In addition, the red pixels of the color filter of the present invention have no or little foreign matter on them. The color filter containing red pixels has a high contrast of 5,000 or more and there is no foreign matter thereon. The radiation-sensitive composition of the color filter of the prior art cannot be obtained. The color filter of the present invention is very useful for transmissive and reflective color liquid crystal displays, color imaging devices, color sensors, and the like. Color liquid crystal display The color liquid crystal display of the present invention includes the color filter and light sheet of the present invention. °-35- 200533960 (33) The color liquid crystal display of the present invention may have a suitable structure. For example, a color filter is formed on a substrate separated from a driving substrate with a thin film transistor (TFT), and the driving substrate and the substrate containing the color filter are opposed to each other with a liquid crystal layer sandwiched therebetween. The way in which they are joined together. Alternatively, a color filter is formed on a driving substrate on which a thin film transistor (TFT) is formed, and the driving substrate including an ITO (aluminum-doped indium oxide) electrode is opposed to each other with a liquid crystal layer sandwiched therebetween. The latter structure can significantly improve the numerical aperture, thereby obtaining a bright, high-definition liquid crystal display device. The radiation-sensitive composition of the present invention can provide a high-yield red pixel with high light transmittance and high contrast, and no foreign matter is generated thereon or there is a trace amount of foreign matter. Examples The following examples are provided to further illustrate the purpose of the present invention, but should not be construed as limiting. Synthesis Example 1 1 part by weight of 2,2M azabis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol monomethyl ether acetate were poured into a flask equipped with a cooling tube and a stirrer. Then 15 parts by weight of methacrylic acid, 25 parts by weight of N-phenyl maleic acid diimide, 35 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol monomethacrylate, 15 parts by weight Parts of styrene and 2.5 parts by weight of α-methylstyrene dimer serving as a chain transfer agent were poured into a flask, and the inside of the flask was replaced with nitrogen, and the resulting solution was gently stirred, and -36- 200533960 (34 ) The temperature was raised to 80 ° C, and the solution was polymerized by maintaining the temperature for 3 hours. After that, the temperature was increased to 100 ° C, 0.5 part by weight of 2.2'-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was further performed for 1 hour to obtain a copolymer solution (solid content: 33.1). % By weight). The resulting copolymer had a Mw of 35,000 and a Mη of 10,000. This copolymer solution was labeled as resin (B-1 ρ Synthesis Example 2) 2.7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol monoformate. Ether ether acetate was poured into a flask equipped with a cooling tube and a stirrer, and then 15 parts by weight of methacrylic acid, 10 parts by weight of ω-carboxy polycaprolactone mono (meth) acrylate, and 18.75 parts by weight of N-phenyl Maleimide, 35 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol mono (meth) acrylate, 1125 parts by weight of styrene, and 25 parts by weight of methyl serving as a chain transfer agent Styrene dimer was poured into the flask, and the inside of the flask φ was replaced with nitrogen to gently stir the resulting solution, and the temperature of the reaction solution was raised to 80 ° C, and the solution was polymerized by maintaining the temperature for 3 hours. 'The temperature was raised to 100. (: 0.3 parts by weight of 2.2 M azobis (2,4-dimethylvaleronitrile) was added, and polymerization was further performed for 1 hour to obtain a copolymer solution (solid content 3 3 · 0% by weight). The prepared copolymer has a Mw of 15,000 and a Mn of 7,000. This copolymer solution is labeled Tree Moon Purpose (B-2). Example 1 -37- 200533960 (35) Using Diamond Fine Mill (registered name, manufactured by Mitsubishi Materials Co., Ltd.). Ball mill with a bead diameter of 0 mm will be 40 weight Part of a mixture of C. I. Pigment Red 175 and CI · Pigment Yellow 254 serving as a pigment (A) in a weight ratio of 50/50, 10 parts by weight of EFKA-47 serving as a dispersant, and 100 parts by weight serving as a solvent A mixed solution consisting of ethyl 3-ethoxypropionate is mixed together and dispersed! A pigment dispersion is prepared in 2 hours. Φ If the average particle diameter of the pigment contained in the obtained pigment dispersion is measured by a dynamic light scattering method, The average particle diameter is 140 nm. 100 parts by weight of the pigment dispersion liquid, 70 parts by weight of the resin (B-1) serving as the alkali-soluble resin (B), and 80 parts by weight serving as the polyfunctional monomer. (C) of diquaternary tetraol hexaacrylate, 50 parts by weight of 2-benzyl-2-dimethylamino (4-morpholinylphenyl) butanone-1 serving as a photoinitiator (D) And 1,000 parts by weight of propylene glycol monomethyl ether acetate serving as a solvent are mixed together to prepare a liquid resin group成 物 （R 1）. # This liquid resin composition (R 1) is applied to the surface of a soda-lime glass substrate with a surface forming a Si 〇2 film for preventing sodium ion elution by using a spin coater. It was pre-baked in a clean oven heated at 90t for 10 minutes to form a 2.0 μηι-thick coating film. After that, the substrate was cooled to room temperature and the coating film was exposed to 5,000 J / cm2 through a photomask using a high-pressure mercury lamp. With radiation of wavelengths 3 6 5 nm, 405 nm and 4 3 6 iim. This substrate was then immersed in a 0.04% by weight aqueous solution of potassium hydroxide at 23 ° C as a developer for 1 minute to develop, rinsed with ultrapure water, dried with air, and post-baked at 250 t 30 minutes -38- 200533960 (36) minutes to form a red stripe pixel pattern on the substrate. This pixel pattern has a thickness of 1.6 μm. Evaluation of foreign matter and chromaticity If the formed pixel pattern is observed through an optical microscope, no foreign matter is seen on the pixel. When using TC-1800 (Tokyo Denshoku Co., Ltd.) color analyzer to evaluate the chromaticity of a pixel, (X, y, Y) = (0.65 0, 0.30, 20.0). The maximum 値 and minimum 透射 of the transmitted light intensity were measured while being irradiated from the back with a fluorescent lamp (wavelength 380 to 780 nm) while sandwiching between the two deflecting plates and turning the deflecting plate on the front side. The contrast obtained by dividing the maximum 値 by the minimum 为 is 1,800. Example 2 A liquid composition (R 2) was prepared in the same manner as in Example 1, except that 40 parts by weight of C.I. Pigment Red 175 serving as a pigment (A) and 10 parts by weight of BYK-200 1 serving as a dispersant were used. When the average particle diameter of the pigment contained in the obtained pigment dispersion was measured by a dynamic light scattering method, the average particle diameter was 140 nm. A red stripe pixel pattern having a film thickness of 1.60 μm was formed on the substrate and evaluated in the same manner as in Example], but using a liquid composition (R2 -39- 200533960 (37) results' not on the pixel Foreign matter was seen. The chromaticity of the pixel was (χ y5 Y) = (0.650, 345, 19.0) and the contrast was 2,500. Example 3 A liquid composition (R3) was prepared in the same manner as in Example 1, but using 40 parts by weight of a mixture of CI · Pigment • Red 175 and CI Pigment Yell 0w 254 serving as 40/60 of the pigment (a), and 70 parts by weight of a resin (B-2) serving as an alkali-soluble resin (B), and The pigment dispersion was prepared by dispersing for 4 hours. If the average particle diameter of the pigment contained in the prepared pigment dispersion was measured by dynamic light scattering method, the average particle diameter was 250 nm. It was formed on the substrate to have a size of .60 μπι The film thickness of the red stripe pixel pattern was evaluated in the same way as in Example 1, but using the liquid composition (R3) ° results that no foreign matter was seen on the pixel. The chromaticity of the pixel was (X, # y, Y ) = (0 · 650, 0 · 338, 18.0) and the contrast is 500. Example 4 A liquid composition (R4) was prepared in the same manner as in Example 1, but using 40 parts by weight of C.I. Pigment serving as 80/20 of the pigment (a)

Red 175 and CI Pigment Red] 77 mixture, 70 parts by weight of resin (B-2) serving as the soluble resin (B), and 10 parts by weight of BYK-200 serving as a dispersant, and mixed and dispersed ] 6 hours to prepare a pigment dispersion.

-40- (38) 200533960 If the average particle diameter of the pigment contained in the pigment dispersion obtained by the dynamic light scattering method is measured, the average particle diameter is 80 nm. A red stripe pixel pattern with a film thickness of 1.60 μm was formed on the substrate and evaluated in the same manner as in Example 1, but using the liquid composition (R4) °, as a result, no foreign matter was seen on the pixels. The chromaticity of a pixel is (χ, y, Υ) = (0.650, 0.342, 18.0) and the contrast is 2,200. Example 5 A liquid composition (R 5) was prepared in the same manner as in Example 1, except that 40 parts by weight of a mixture of CI Pigment Red 175 and CI · Pigment Red 177 serving as 35/65 of the pigment (A) and 10 parts by weight were used. BYK-1 65 'as a dispersant was mixed and dispersed for 8 hours to prepare a pigment dispersion. When the average particle diameter of the pigment contained in the obtained pigment dispersion was measured by a dynamic light scattering method, the average particle diameter was 20 () nm. Φ A red stripe pixel pattern with a film thickness of 1.6 μm was formed on the substrate and evaluated in the same manner as in Example 1, but using the liquid composition (R5). As a result, no foreign matter was seen on the pixel . The chromaticity of a pixel is (X, y, Y) = (0.650, 0.323, 16.0) and the contrast is 1,000. Comparative Example 1 A liquid composition (r 1) was prepared in the same manner as in Example 1, but using 40 parts by weight] 5/8 5 of c. 1. Pigment R ed 1 7 5 and C. I.- 41-200533960 (39) Pigment R ed 2 5 4 The mixture acts as a pigment (A) and uses i 0 parts by weight of B YK-200 1 as a dispersant. When the average particle diameter of the pigment contained in the obtained pigment dispersion was measured by a dynamic light scattering method, the average particle diameter was 140 nm. A red stripe pixel pattern with a film thickness of 1.60 μm was formed on the substrate and evaluated in the same manner as in Example 1, but using a liquid composition (r 1) ° • The chromaticity of the pixel was (X, y , Y) = (0.650, 0.336, 19.0) and the contrast is 940. However, the number of foreign substances on the pixels is 20 in an area of 100 μm × 100 μm on average, which means that the produced product cannot be used as a color filter. Comparative Example 2 A liquid composition (r2) was prepared in the same manner as in Example 1, except that 40 parts by weight of CI Pigment Red 254 Φ serving as the pigment (a) and 10 parts by weight of BΥK-2000 serving as a dispersant were used, and Mixing and dispersing were performed for 16 hours to obtain a pigment dispersion. When the average particle diameter of the pigment contained in the obtained pigment dispersion was measured by a dynamic light scattering method, the average particle diameter was 100. A red strip-like pixel pattern having a film thickness of 1.6 μm was formed on the substrate and evaluated in the same manner as in Example 1, but using the liquid composition (r2) °, the chromaticity of the pixel was (X, y, Y) = (〇.65〇, 0335, 18.0) and the contrast is 1,500. However, the number of foreign substances on the pixels is on average -42-(40) 200533960 There are 80 in the area of 100 μη X 100 μιη, That means that the obtained product cannot be used as a color filter. Comparative Example 3 A liquid composition (r3) was prepared in the same manner as in Example 1, but 40 parts by weight of C.I. Pigment Red 208 serving as the pigment (a) and 10 parts by weight of SOLSPERSE 24000 serving as a dispersant were used. When the average particle diameter of the pigment contained in the obtained pigment dispersion was measured by a dynamic light scattering method, the average particle diameter was 140 nm. A red stripe-like pixel pattern having a film thickness of 1.60 μm was formed on the substrate and evaluated in the same manner as in Example 1, but using the liquid composition (r3) ° result 'no foreign matter was seen on the pixel. The chromaticity of a pixel is (χ, y5 Υ) = (0.65 0, 0.3 06, 1 2.5) and the contrast is 2 50. Comparative Example 4 A liquid composition (r4) was prepared in the same manner as in Example 2, but mixed and dispersed for 30 minutes to obtain a pigment dispersion. When the average particle diameter of the pigment contained in the obtained pigment dispersion was measured by a dynamic light scattering method, the average particle diameter was 400 nm. A red stripe pixel pattern having a film thickness of 1.60 μm was formed on the substrate and evaluated in the same manner as in Example, but using the liquid composition (r4) °, no foreign matter was seen on the pixels. Pixel chromaticity is (X, -43- 200533960 (41) y, Y) = (0.650, 0.343, 15.0) and contrast is 350

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Claims (1)

(1) (1) 200533960 10. Scope of patent application1. A radiation-sensitive composition comprising (A) a pigment, (B) a soluble resin, (C) a polyfunctional monomer or a polyfunctional monomer and a monomer Combination of functional monomers and (D) a radiation-sensitive free radical generator, wherein the pigment (A) contains 20% by weight or more of CI · Pigment Red 175 and has an average particle diameter r (unit: nm) of 50 to 300 ), And the composition is used for a color filter. 2. A radiation-sensitive composition comprising (A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer or a combination of a polyfunctional monomer and a monofunctional monomer, and (D) radiation Sensitive free radical generator, wherein the pigment (A) contains 20% by weight or more of CI · Pigment R ed 1 7 5 and pixels composed of the radiation-sensitive composition and having a film thickness of 1.60 μm can be provided Contrast of 5000 or more, and the composition is used for a color filter. 3. The radiation-sensitive composition according to item 1 or 2 of the patent application scope, wherein the pigment (A) further comprises at least one selected from CI Pigment Yellow 83, CI Pigment Yellow 139, CI Pigment Red 177, and CI Pigment Red 254. . 4. A method for preparing a radiation-sensitive composition according to item i or 2 of the scope of patent application, comprising (A) containing 20 weight. Pigment dispersion liquid prepared by mixing pigments having an average particle size of greater than 300 nm and mixing and dispersing them in a solvent while pulverizing in a solvent, (B) Alkali-soluble resin, (C) a polyfunctional monomer or a combination of a polyfunctional monomer and a monofunctional monomer, and (D) a radiation-sensitive radical generator-45-200533960 (2) step of combining together. 5. A color filter comprising a red pixel composed of a radiation-sensitive composition according to any one of claims 1 to 3. 6. A color liquid crystal display including a color filter in the scope of patent application No. 5. -46-200533960 VII. Designated representative map: (1) The designated representative circle of this case is: (No) Figure (2) The component representative symbol of this representative 元件 Brief description: 8. If there is a chemical formula in this case, please disclose the most Chemical formula that can show the characteristics of the invention ... -3-