Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3218—Carbocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
  • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
  • C08L63/04—Epoxynovolacs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings

Definitions

• the present invention relates to a curable composition, and specifically relates to a curable composition that can be suitably used for producing a color filter, and a color filter using the same.
• a liquid crystal display device is manufactured by separately manufacturing a color filter substrate and a TFT (Thin-Film-Transistor) substrate and attaching them with a liquid crystal sandwiched therebetween.
• the color filter substrate is coated with an alignment film such as polyimide for aligning the liquid crystal on the colored layer.
• the colored layer is required to have resistance to a highly polar solvent such as NMP (N-methyl-pyrrolidone) contained in the polyimide resin.
• NMP N-methyl-pyrrolidone
• a resin film (hereinafter sometimes referred to as “overcoat layer”) may be used as a planarizing film on the surface of the colored layer. NMP resistance is required for this resin film as well as the colored layer.
• Patent Document 1 proposes a photosensitive composition for a color filter colored layer containing hexaarylbiimidazole. Such a photosensitive composition is excellent in sensitivity and aims to improve solvent resistance. However, such a photosensitive composition also has a problem that NMP resistance is insufficient in a region where the pigment concentration is high. Patent Document 2 proposes a photosensitive composition for a color filter containing an epoxy resin, but it has never been excellent in NMP resistance, liquid storage stability, and coloring. Further, even in such a photosensitive composition, an area where the pigment concentration is high, and a colored pixel formed next to the black matrix in color filter production is exposed (repeated) many times until the color filter is completed. There was a problem that it became a rough state.
• a resist solution capable of forming a resin film and a color filter layer satisfying both NMP resistance, liquid storage stability, ITO deposition suitability and coloring has not been provided yet, and a resin having such performance. It has been desired to develop a colorant-containing curable resin composition capable of forming a film.
• the present invention provides a curable resin composition having high NMP resistance, ITO deposition suitability, liquid storage stability and high contrast, and a color filter using the same. Objective.
• ⁇ 1> Selected from (A) colorant, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) hexaarylbiimidazole polymerization initiator, (E) oxime initiator, and triazine initiator And (F) a polyfunctional epoxy compound having 4 or more functional groups, the content of the (F) polyfunctional epoxy compound with respect to the total solid content is in the range of 2 to 20% by mass, and (A) A curable composition having a colorant content in the range of 25 to 50% by mass.
• l is 5 to 100, and each R is independently a hydrogen atom or a methyl group.
• X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, and each A independently represents one having 1 to 12 carbon atoms.
• a substituted or unsubstituted alkoxy group, or —COO—R 9 (wherein R 9 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms), and n represents 1 to 3 An integer, and m is an integer of 1 to 3.
• X 1 , X 2 and X 3 each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms. However, two or more of X 1 , X 2 and X 3 are not simultaneously hydrogen atoms.
• the pigment (A) is a pigment represented by the following general formula (IV), C.I. I. Pigment Green 36, or C.I. I. Curing according to ⁇ 1>, which is Pigment Green 7, a pigment whose primary particle size is less than 10% by mass of particles having a primary particle size of less than 0.02 ⁇ m and less than 5% by mass of particles having a particle size exceeding 0.08 ⁇ m. Sex composition.
• ⁇ 6> The curable composition according to any one of ⁇ 1> to ⁇ 5>, wherein the colorant (A) is a pigment coated with a resin.
• the color pixel is a color filter formed of the curable composition according to any one of ⁇ 1> to ⁇ 6>.
• the primary particle diameter of the pigment For observation of the primary particle diameter of the pigment, a transmission electron microscope is suitable. For example, the total number of particles in the observation sample at a magnification of 3 to 100,000 times and the number of particles of the pigment of less than 0.02 ⁇ m and more than 0.08 ⁇ m.
• the particle size distribution can be grasped by measuring.
• the ratio of primary particles less than 0.02 ⁇ m and the ratio of primary particles exceeding 0.08 ⁇ m are obtained by observing the pigment powder with a transmission electron microscope, measuring the major axis of each primary particle, It can be obtained by calculating the proportion (number%) of pigment particles less than 0.02 ⁇ m and more than 0.08 ⁇ m.
• the pigment powder is observed with a transmission electron microscope at a magnification of 3 to 100,000 times, a photograph is taken, the major axis of 1000 primary particles is measured, and less than 0.02 ⁇ m and more than 0.08 ⁇ m Calculate the percentage of primary particles. This operation was performed for a total of three locations by changing the location of the pigment powder, and the results were averaged.
• the inorganic pigment examples include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.
• the present invention particularly relates to C.I. I. Pigment Green 7, C.I. I.
• the effect is conspicuous when Pigment Green 36 and a pigment having a structure represented by the following formula (IV) are used. Furthermore, C.I. I. The effect is remarkable when Pigment Green 58 is used.
• the present invention relates to C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58 and a pigment selected from the pigment represented by the following formula (IV), the amount of particles having a primary particle size of less than 0.02 ⁇ m is less than 10% by mass in the total amount of the pigment, and the primary particle size is 0.08 ⁇ m. From the viewpoints of contrast and liquid storage stability, it is preferable that the amount of particles exceeds 5% by mass.
• R C each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, —N (CH 3 ) 2 , —N (C 2 H 5 ) 2 , —CF 3 , a chlorine atom Or represents a bromine atom. Particularly preferred are a hydrogen atom, a methyl group, and a chlorine atom.
• a fine and sized organic pigment can be used as necessary.
• the refinement of the pigment is a step of grinding it as a highly viscous liquid composition together with the pigment, the water-soluble organic solvent, and the water-soluble inorganic salts.
• Water-soluble organic solvents include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl An ether acetate etc. can be mentioned.
• examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
• the amount of the water-soluble inorganic salt used is 1 to 50 times the mass of the pigment, and a larger amount has a grinding effect, but a more preferred amount is 1 to 10 times the mass in terms of productivity, and further moisture is 1% or less. It is preferable that The amount of the water-soluble organic solvent used is in the range of 50% by mass to 300% by mass and preferably in the range of 100% by mass to 200% by mass with respect to the pigment.
• the operating conditions when the apparatus is a kneader are as follows: 200 rpm is preferable, and a relatively large biaxial rotation ratio is preferable because of a large grinding effect.
• one kind of halogenated phthalocyanine pigment can be used alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used.
• a disazo yellow pigment e.g., C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
• the mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200.
• one kind of zincated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used.
• a disazo yellow pigment e.g., C.I. I. Pigment Green 58 and C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
• the mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200.
• carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable.
• the mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. Dispersion stability becomes favorable by setting it as the said range.
• a photocurable composition that is uniformly dissolved is obtained.
• dye which can be used as a coloring agent The well-known dye conventionally used as a color filter use can be used.
• JP-A-8-62416 JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224
• the content of the colorant in the curable composition of the present invention is 25 to 50% by mass, more preferably 30 to 45% by mass, based on the total solid content (mass) of the composition.
• the color density is sufficient to ensure excellent color characteristics.
• an organic pigment as a colorant, and a pigment coated with a polymer compound in a pigment miniaturization step or a dispersion step. Even in pigments refined by coating the pigment with a polymer compound, the formation of secondary aggregates is suppressed, and the coated pigment with improved dispersibility that can be dispersed in the form of primary particles Further, it is possible to use a coated pigment excellent in dispersion stability in which primary particles are stably maintained.
• the pigment after the coating treatment of the present invention is washed with 1-methoxy-2-propanol, and the free amount is calculated.
• 10 g of the pigment was put into 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was allowed to settle for 8 hours at 80,000 rpm in a centrifuge, and the solid content of the supernatant was determined from the drying method.
• the mass of the polymer compound released from the pigment was determined, and the liberation rate (%) was calculated from the ratio to the mass of the polymer compound used in the initial treatment.
• the liberation rate of commercially available pigments can be measured by the following method. That is, after dissolving the entire pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. And calculated as “mass of the polymer compound used in the initial treatment”. Separately, the pigment is washed with 1-methoxy-2-propanol, and the obtained release amount is divided by this “mass of the polymer compound used in the initial treatment” to obtain the release rate (%). . The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. A preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.
• a solvent that dissolves the pigment for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid,
• the coating treatment is preferably carried out simultaneously in the pigment refinement step. Specifically, i) the pigment, ii) the water-soluble inorganic salt, and iii) a small amount of water-soluble that does not substantially dissolve ii).
• An organic solvent and iv) a step of adding a polymer compound and mechanically kneading with a kneader or the like (referred to as a salt milling step), a step of adding this mixture into water, stirring the mixture with a high speed mixer or the like, The slurry is filtered, washed with water, and dried if necessary.
• the polymer compound used for coating the pigment may be anything as long as it has an adsorptive group for the pigment.
• those coated with a polymer compound having a heterocyclic ring in the side chain are preferred.
• Such a polymer compound is preferably a monomer represented by the following general formula (1) or a polymer containing a polymer unit derived from a monomer comprising a maleimide or a maleimide derivative.
• a polymer containing a polymer unit derived from the monomer represented by the general formula (1) is particularly preferable.
• R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
• R 2 represents a single bond or a divalent linking group.
• Y represents —CO—, —C ( ⁇ O) O—, —CONH—, —OC ( ⁇ O) —, or a phenylene group.
• Z represents a group having a nitrogen-containing heterocyclic structure.
• the alkyl group for R 1 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
• alkyl group represented by R 1 has a substituent
• substituents include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms).
• alkoxy group preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.
• a methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.
• R 1 Specific examples of preferred alkyl groups represented by R 1 include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group may be mentioned.
• R 1 is most preferably a hydrogen atom or a methyl group.
• R 2 represents a single bond or a divalent linking group.
• the divalent linking group is preferably a substituted or unsubstituted alkylene group.
• the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
• the alkylene group represented by R 2 may be one in which two or more are connected via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
• the preferable alkylene group represented by R 2 include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
• examples of the substituent include a hydroxy group.
• Z represents a group having a heterocyclic structure.
• the group having a heterocyclic structure include phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, ansanthrone series, indanthrone series, and flavan.
• thioindigo dye structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, Heterocycles such as zothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine,
• These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, and the like. Can be mentioned.
• Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms.
• the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, and cyclic urea structure.
• a cyclic imide structure are preferable, and a structure represented by the following (2), (3) or (4) is particularly preferable.
• E represents a single bond, an alkylene group (eg, methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, etc.), —O—, —S—, —NR A —, and One selected from the group consisting of —C ( ⁇ O) —.
• R A represents a hydrogen atom or an alkyl group.
• the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group.
• E in the general formula (2) a single bond, a methylene group, —O—, or —C ( ⁇ O) — is preferable, and —C ( ⁇ O) — is particularly preferable.
• Y 1 and Y 2 each independently represent —N ⁇ , —NH—, —N (R B ) —, —S—, or —O—.
• R B represents an alkyl group
• the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
• Y 1 and Y 2 in the general formula (4) —N ⁇ , —NH—, and —N (R B ) — are particularly preferable.
• Examples of the combination of Y 1 and Y 2 include a combination in which one of Y 1 and Y 2 is —N ⁇ and the other is —NH—, and an imidazolyl group.
• ring B 1 , ring B 2 , ring C, and ring D each independently represent an aromatic ring.
• the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxa
• examples of the ring B 1 and the ring B 2 in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.
• examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.
• Examples of the ring D in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.
• a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.
• the physical property determination method of the specific dispersion resin is as follows.
• the physical property values of the resin and the like described in the present invention can be determined using the same method unless otherwise specified.
• Weight average molecular weight and number average molecular weight The measurement was performed in terms of polystyrene by GPC (gel permeation chromatography) measurement under the following conditions.
• TSKgel Multipore HXL-M Porous polydisperse type linear column manufactured by Tosoh Eluent: THF Flow rate: 1.0 ml / min Temperature: 40 ° C Detection condition: RI System: High-speed GPC equipment set (Tosoh HLC-8220) (Acid value) The 1-methoxy-2-propanol solution of the resin was determined by neutralization titration with a 1N aqueous potassium hydroxide solution.
• the pigment Even in the case of using the above-described coated pigment, it is more preferable to disperse the pigment using at least one dispersant and use it as a pigment dispersion composition. By containing this dispersant, the dispersibility of the pigment can be improved.
• the dispersant for example, a known pigment dispersant or surfactant can be appropriately selected and used.
• organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
• the content of the dispersant in the pigment dispersion composition is preferably 1 to 100% by mass and more preferably 3 to 70% by mass with respect to the mass of the pigment described above.
• a pigment derivative is added as necessary.
• the pigment is introduced into the curable composition as fine particles by adsorbing a pigment derivative having a part having affinity for the dispersant or a polar group to the pigment surface and using it as an adsorption point of the dispersant.
• the re-aggregation can be prevented, and it is effective for constructing a color filter having high contrast and excellent transparency.
• the pigment derivative is a compound in which an organic pigment is used as a base skeleton and an acidic group, a basic group, or an aromatic group is introduced as a substituent in the side chain.
• organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned.
• light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included.
• Examples of the dye derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP-A-2005-234478, JP-A-2003-240938, JP-A-2001-356210, etc. can be used.
• the content of the pigment derivative according to the present invention in the pigment dispersion composition is preferably 1 to 30% by mass and more preferably 3 to 20% by mass with respect to the mass of the pigment.
• the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained.
• the filter When producing a filter, it can be configured to have high contrast with good color characteristics.
• the alkali-soluble resin is a linear organic polymer, and at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group that promotes (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.
• a known radical polymerization method can be applied.
• Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.
• X 1 , X 2 and X 3 each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms. However, two or more of X 1 , X 2 and X 3 do not take a hydrogen atom at the same time.
• Examples of the nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, the oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and the sulfur-containing heterocyclic group having 4 to 20 carbon atoms represented by R 4 include a thiolanyl group, Azepinyl group, dihydroazepinyl group, dioxolanyl group, triazinyl group, oxathianyl group, thiazolyl group, oxadiazinyl group, dioxaindanyl group, dihyanaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, oxazolyl group, isoxazolyl group , Thiazolyl group, isothiazolyl group, pyrazolyl group, furazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, pyrrolin
• q is preferably 1.
• p is preferably any one of 1, 2 and particularly preferably 1
• r is preferably any one of 0, 1, 2 and particularly preferably 1.
• Examples of the cycloalkyl group having 3 to 8 carbon atoms represented by R 11 include a cyclopentyl group and a cyclohexyl group. Among these, a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
• R 11 is preferably, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-hexyl group or the like.
• Examples of the cycloalkyl group having 3 to 8 carbon atoms represented by R 12 and R 3 include a cyclopentyl group and a cyclohexyl group. Among these, a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
• alkoxy group having 1 to 6 carbon atoms which is a substituent of the substituted phenyl group represented by R 12 and R 3 can be linear, branched or cyclic, and specific examples thereof are as follows. Can include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy and the like. Of these, alkoxy groups having 1 to 3 carbon atoms are preferable.
• halogen atom which is a substituent of the substituted phenyl group represented by R ⁇ 12> , R ⁇ 3 >, a fluorine atom, a chlorine atom, etc. can be mentioned, for example.
• the alkyl group having 1 to 12 carbon atoms represented by R 5 can be a linear, branched or cyclic alkyl group, and specific examples thereof include, for example, methyl group, ethyl group, n-propyl group. Group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl Group, n-undecyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group and the like. Among them, an alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is particularly preferable.
• the alkoxy group having 1 to 12 carbon atoms represented by R 5 can be a linear, branched or cyclic alkoxy group, and specific examples thereof include a methoxy group, an ethoxy group, n- Examples thereof include a propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, and an n-pentyloxy group. Among these, an alkoxy group having 1 to 2 carbon atoms is preferable. Of these, R 5 is particularly preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a methoxy group, or an ethoxy group.
• p is preferably any of 0, 1, 2 and particularly preferably 0 or 1.
• the triazine compound is an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6-tris ( Monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis ( Trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( ⁇ , ⁇ , ⁇ -trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl)
• Initiators other than the above hexaarylbiimidazole-based photopolymerization initiator, oxime-based initiator, and triazine-based initiator can also be used in combination.
• the following can be used as these initiators.
• halomethyl oxadiazole described in JP-A-57-6096, ketal, acetal, or benzoin alkyl described in each specification such as US Pat. No. 4,318,791 and European Patent Application No. 88050 Aromatic carbonyl compounds such as ethers, aromatic ketone compounds such as benzophenones described in US Pat. No. 4,199,420, (thio) xanthone-based or acridine-based compounds described in French Patent No. 2456741, Examples thereof include coumarin compounds described in Kaihei 10-62986 and sulfonium organic boron complexes disclosed in JP-A-8-015521.
• acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, active halogen compounds (halomethyloxadiazole series, coumarin series), acridine series and the like are preferable.
• ketal photopolymerization initiator examples include benzyldimethyl ketal and benzyl- ⁇ -methoxyethyl acetal.
• benzophenone photopolymerization initiator examples include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and the like. Can do.
• active halogen photopolymerization initiator examples include, for example, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl).
• Preferred examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.
• a sensitizing dye as necessary.
• the exposure of the wavelength that can be absorbed by the sensitizing dye promotes the radical generating reaction of the polymerization initiator component and the polymerization reaction of the polymerizable compound thereby.
• a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.
• sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
• polynuclear aromatics eg, pyrene, perylene, triphenylene
• xanthenes eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
• cyanines eg, thiacarbocyanine, oxacarbocyanine
• merocyanine Eg, merocyanine, carbomerocyanine
• thiazines eg, thionine, methylene blue, toluidine blue
• acridines eg, acridine orange, chloroflavin, acriflavine
• anthraquinones eg, anthraquinone
• squalium eg, Squalium
• the cresol novolac type includes Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above Toto Kasei), Denacol EM-125, etc. (above Nagase Kasei), and biphenyl type 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl and the like.
• l is an integer of 5 to 100, and each R is independently a hydrogen atom or a methyl group.
• the pigment dispersion composition and curable composition of the present invention can be suitably prepared using a solvent together with the above components.
• a chain transfer agent a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a colorant, a photopolymerization initiator, other fillers, Various additives such as a polymer compound other than the above alkali-soluble resin, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.
• chain transfer agents examples include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2- And mercapto compounds having a heterocyclic ring such as mercaptobenzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
• a chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
• the liquid properties (particularly fluidity) of the coating liquid can be improved, and the uniformity of coating thickness and the liquid-saving property can be improved. That is, the interfacial tension between the substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several ⁇ m is formed with a small amount of liquid. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed.
• the fluorine content of the fluorine-based organic compound is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
• the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.
• the fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Further, it is also effective in slit coating that is liable to cause liquid breakage.
• the addition amount of the fluorinated organic compound is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the photocurable composition.
• thermal polymerization initiator examples include various azo compounds and peroxide compounds.
• examples of the azo compounds include azobis compounds.
• Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.
• the curable composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability.
• various surfactants can be used. Among these, the above-mentioned fluorine-based surfactants and nonionic surfactants are preferable.
• nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particularly preferred.
• polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene triethyl ether
• Polyoxyethylene aryl ethers such as benzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene
• Nonionic surfactants such as thione condensates, which are commercially available from Kao Corporation, Nippon Oil & Fats Co., Ltd., Takemoto Oil & Fat Co., Ltd., ADEKA Co.
• additives can be added to the curable composition.
• additives include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and anti-aggregation agents such as sodium polyacrylate.
• Fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, and acid anhydrides added to hydroxyl group-containing polymers
• alcohol-soluble nylon, alkali-soluble resins such as phenoxy resin formed from bisphenol A and epichlorohydrin.
• aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid
• the curable composition of the present invention contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator (preferably together with a solvent) in the above-described colorant, and a surfactant or the like as necessary. It can be prepared by mixing and dispersing additives and mixing and dispersing using various mixers and dispersers.
• the mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.
• a mixture of a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is mixed into a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. Is used to grind the pigment while applying a strong shearing force, and then the mixture is put into water and made into a slurry with a stirrer or the like. Next, the slurry is filtered and washed with water to remove the water-soluble organic solvent and the water-soluble inorganic salt, and then dried to obtain a finer pigment. It is preferable to coat the pigment by adding a polymer compound before the miniaturization treatment.
• the curable composition of the present invention is applied to a substrate directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, etc., to form a photocurable coating film.
• a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, etc.
• the color filter of the present invention is formed on a substrate such as glass by using the curable composition of the present invention described above, and the curable composition of the present invention is formed directly on the substrate through another layer. For example, after forming a coating film on the top by slit coating, the coating film is dried, subjected to pattern exposure, and development processing using a developer can be sequentially performed. Thereby, the color filter used for a liquid crystal display device or a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.
• the photo-curing property of the present invention is also applied to a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is arranged.
• a color filter can be prepared by forming a patterned film made of the composition.
• the photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel.
• the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
• These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
• a substrate in which a passivation film such as a silicon nitride film is formed on the surface of a TFT liquid crystal driving substrate or a surface of the driving substrate can be used.
• a method for applying the curable composition of the present invention to a substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter referred to as a slit nozzle coating method).
• a slit nozzle coating method a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter referred to as a slit nozzle coating method).
• the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, when a fifth generation glass substrate (1100 mm ⁇ 1250 mm) is coated by the spinless coating method.
• the discharge amount of the curable composition from the slit nozzle is usually 500 to 2000 microliter / second, preferably 800 to 1500 microliter / second, and the coating speed is usually 50 to 300 mm / second, Preferably, it is 100 to 200 mm / second.
• the solid content of the curable composition is usually 10 to 20%, preferably 13 to 18%.
• the thickness of the coating film (after pre-baking treatment) is generally 0.3 to 5.0 ⁇ m, preferably 0.5 to 4. It is 0 ⁇ m, most preferably 0.8 to 3.0 ⁇ m.
• a pre-baking process is performed after application.
• vacuum treatment can be performed before pre-baking.
• the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
• the pre-baking treatment is performed in a temperature range of 50 to 140 ° C., preferably about 70 to 110 ° C., using a hot plate, an oven or the like, and can be performed under conditions of 10 to 300 seconds.
• a high frequency treatment or the like may be used in combination. The high frequency treatment can be used alone.
• the color filter for a liquid crystal display device is preferably an exposure using a proximity exposure machine or a mirror projection exposure machine mainly using h-line or i-line, and the exposure amount is 5 to 300 mJ / cm 2 , more preferably 10 to 150 mJ /. cm 2 , more preferably 10 to 100 mJ / cm 2 .
• the uncured portion after exposure is eluted in the developer, and only the cured portion remains.
• the development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds. Any developer can be used as long as it dissolves the coating film of the photocurable curable composition in the uncured portion while not dissolving the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
• Examples of the organic solvent include the above-described solvents that can be used when preparing the pigment dispersion composition or the curable composition of the present invention.
• Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, An alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is used at a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned.
• the development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development. In addition, development can be performed with the substrate inclined.
• a rinsing step for washing and removing excess developer drying is performed, and then heat treatment (post-baking) is performed to complete the curing.
• the rinsing process is usually performed with pure water. However, to save liquid, pure water is used in the final cleaning. At the beginning of cleaning, used pure water is used, the substrate is tilted and cleaned, and ultrasonic irradiation is performed. Can be used together.
• a heat treatment is usually performed at about 200 ° C. to 250 ° C.
• the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.
• the application of the curable composition of the present invention has been described mainly focusing on the application to a color filter, it can also be applied to the formation of a black matrix that isolates each colored pixel constituting the color filter.
• the black matrix is formed by exposing and developing the curable composition of the present invention using a black pigment such as carbon black or titanium black as a pigment, and then further post-baking as necessary to promote film curing. Can be formed.
• Pigment CI Pigment Red254 Ciba Specialty Chemicals CROMOPHTAL RED BP
• sodium chloride 500 g 20 g of the above polymer 1 solution
• 100 g of diethylene glycol 100 g was charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). Kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare coated pigment 1.
• pigment dispersion 1 With a composition of Disperse Aid 163 (manufactured by San Nopco Co., Ltd.) 7.0 parts, Solvent: Propylene glycol methyl ether acetate 200 parts with respect to 35 parts of the pigment equivalent of the coated pigment 1, the number of revolutions was 3, using a homogenizer. 3,000 rpm, mixed for 3 hours to prepare a mixed solution, and further dispersed for 6 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mm ⁇ zirconia beads. It was. Similarly, pigment dispersions 2 to 10 were obtained by changing the coating pigment type and the amount of the dispersant as shown in Table 1. However, the ratio of the amount of the coated pigment 4 and the coated pigment 5 used in the pigment dispersion 8 was 95: 5, and the total pigment equivalent was 35 parts. The amount of coating polymer to be used in the dispersion along with the pigment is also listed in Table 1.
• the pigment dispersion 15 was prepared by changing the 6-hour dispersion process in the bead disperser to the 18-hour dispersion process with a homogenizer (rotation speed: 5000 rpm) in the preparation of the pigment dispersion 1. The same procedure as in the preparation of pigment dispersion 1 was performed.
• Example 1 Components of the following composition were further added to the obtained pigment dispersion 1, and the mixture was stirred and mixed to prepare the curable composition (color resist solution) of the present invention.
• C Polymerizable compound: Nippon Kayaku DPHA 20 parts
• D Polymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 3 parts
• E polymerization initiator : 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 3 parts
• F polyfunctional epoxy compound: DIC Corporation Epiclon 695 5 parts, diethylaminobenzophen
• Example 2 to 16 and Comparative Examples 1 to 6 In the composition of the curable composition of Example 1, the type and amount of pigment, the amount of alkali-soluble resin, the amount of polymerizable compound, the type and amount of polymerization initiator, and the amount of polyfunctional epoxy compound are as shown in Table 2. The curable compositions of Examples 2 to 16 and Comparative Examples 1 to 6 were prepared.
• a TFT substrate was prepared by the method described in Japanese Patent No. 3264364. That is, a gate signal line and an additional capacitor electrode are formed on an active matrix substrate, a gate insulating film is formed thereon, a semiconductor layer and a channel protective layer are formed, and n + Si serving as a TFT source and drain. A layer was formed.
• Each obtained curable composition was spin-coated on the TFT substrate so that the film thickness after pre-baking was 2.4 ⁇ m, and dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 60 mJ / cm 2 (illuminance 20 mW / cm 2 ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer.
• the coating film that has been subjected to the photo-curing treatment and the development treatment as described above is heat-treated in a 220 ° C. oven for 1 hour (post-baking), and a colored resin coating for forming a color filter is formed on the glass substrate, A colored substrate was produced.
• Example 7 A curable composition was prepared in the same manner as in Example 1 except that the pigment dispersion 1 was changed to the pigment dispersion 15 in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.
• Example 33 In Example 1, (F) polyfunctional epoxy compound Epicron 695 was changed to EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., polyfunctional epoxy resin) to prepare a curable composition, and the same evaluation as in Example 1 was performed. went. The results are shown in Table 3.
• NMP resistance [Chromaticity change] After measuring the spectral characteristics of each colored substrate using a spectrophotometer MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., each test piece is immersed in a 50 ° C. NMP (N-methylpyrrolidone) solution for 10 minutes. Next, after rinsing with pure water and drying at 85 ° C. for 60 minutes, the spectral characteristics were measured again, and the amount of chromaticity changed by NMP immersion was expressed as ⁇ E * ab.
• ⁇ E * ab means a color difference in the L * a * b * color system. The change in color difference ⁇ E * ab was evaluated. (Evaluation criteria) A: ⁇ E * ab is less than 2 B: ⁇ E * ab is 2 or more and less than 3 C: ⁇ E * ab is 3 or more and less than 5 D: ⁇ E * ab is 5 or more
• ITO deposition Indium tin oxide (ITO) was vapor-deposited (film thickness 1400 mm, vapor deposition temperature 200 ° C.) according to a conventional method, and then observed in detail with an optical microscope.
• the Ra value was measured with an atomic force microscope (AFM) and SPA-400AFM manufactured by Seiko Instruments Inc.
• the evaluation criteria are as follows. A: Less than 3 nm B: 3 nm or more and less than 8 nm C: 8 nm or more and less than 10 nm D: 10 nm or more
• a polarizing plate is placed on the colored resin film of the colored substrate, the colored resin film is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal are measured using BM-5 manufactured by Topcon Corporation.
• B 6000 or more and less than 8000.
• C 4000 or more and less than 6000.
• D Less than 4000.
• Each obtained curable composition was spin-coated on the TFT substrate so that the film thickness after pre-baking was 2.4 ⁇ m, and dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 60 mJ / cm 2 (illuminance 20 mW / cm 2 ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer.
• Example 25 Components of the following composition were further added to the obtained pigment dispersions 13 and 14, and the mixture was stirred and mixed to prepare the curable composition (color resist solution) of the present invention.
• C Polymerizable compound: Nippon Kayaku Co., Ltd. Kayrad DPHA 35.75 parts.
• Example 26 In the composition of the curable composition of Example 25, the type and amount of pigment, the amount of alkali-soluble resin, the amount of polymerizable compound, and the type and amount of polymerization initiator were changed as shown in Table 8, and Example 26 to 32 curable compositions were prepared. In Table 8, * 1 used the same compound as in Example 1.

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