WO2009110434A1 - Curable composition and color filter - Google Patents
Curable composition and color filter Download PDFInfo
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- WO2009110434A1 WO2009110434A1 PCT/JP2009/053888 JP2009053888W WO2009110434A1 WO 2009110434 A1 WO2009110434 A1 WO 2009110434A1 JP 2009053888 W JP2009053888 W JP 2009053888W WO 2009110434 A1 WO2009110434 A1 WO 2009110434A1
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- carbon atoms
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- 0 *1c2c1cccc2 Chemical compound *1c2c1cccc2 0.000 description 2
Classifications
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- 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
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- 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
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- 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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Abstract
Description
また、着色層は独立して1色ずつ、ストライプ状またはモザイク状に画素が形成される。このため、着色層表面に凹凸ができるので、着色層の表面に平坦化膜として、樹脂被膜(以下、「オーバーコート層」という場合がある。)が用いられることがある。この樹脂被膜に対しても着色層と同様に耐NMP性が要求される。 In general, 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. At this time, the color filter substrate is coated with an alignment film such as polyimide for aligning the liquid crystal on the colored layer. For this reason, the colored layer is required to have resistance to a highly polar solvent such as NMP (N-methyl-pyrrolidone) contained in the polyimide resin.
In addition, the colored layer independently forms pixels in stripes or mosaics for each color. For this reason, unevenness is formed on the surface of the colored layer, and thus 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.
通常、カラーフィルタの評価に用いられる耐NMP性は50℃・10minで浸漬させた前後の色度変化で評価されるのに対し、上記した剥離液耐性は80℃・2min浸漬後の膨潤率で評価されるので、通常の着色層のままではCOA方式のカラーフィルタには使えない。 In a COA (Color-filter On Array) type liquid crystal display device, a colored layer that also serves as an interlayer insulating film is formed on the TFT. For this reason, in addition to the normal required characteristics as described above, the required characteristics for the colored layer are added as required characteristics such as the required characteristics for the interlayer insulating film, that is, the resistance to stripping solution. In order to satisfy these required characteristics, a resin film is also provided as a protective layer on the colored layer.
Usually, the NMP resistance used for the evaluation of the color filter is evaluated by the change in chromaticity before and after being immersed at 50 ° C. for 10 minutes, whereas the above-mentioned peeling solution resistance is the swelling ratio after immersion at 80 ° C. for 2 minutes. Since it is evaluated, it cannot be used for a COA type color filter with a normal colored layer.
また、特許文献2には、エポキシ樹脂を含むカラーフィルタ用の感光性組成物が提案されているが、決して耐NMP性と液保存安定性、着色に優れるものではなかった。
更に、係る感光性組成物においても顔料濃度が高い領域や、カラーフイルタ作成においてブラックマトリックスの次に作成される着色画素は、カラーフィルタの完成までに現像工程を多数回曝され(繰り返され)表面が荒れる状態となるといった問題点があった。 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.
即ち、本発明の課題は、下記の手段により達成されるものである。 As a result of intensive studies, (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a hexaarylbiimidazole-based polymerization initiator, (E) an oxime-based initiator, and a triazine-based initiator. The present inventors have found that the above problems can be solved by using a curable composition containing one or more selected from (F) and a polyfunctional epoxy compound having 4 or more functional groups.
That is, the object of the present invention is achieved by the following means.
本発明は、(A)着色剤、(B)アルカリ可溶性樹脂、(C)光重合性化合物、(D)ヘキサアリールビイミダゾール系重合開始剤、(E)オキシム系開始剤並びにトリアジン系開始剤から選択される1種以上、及び(F)4官能以上の多官能エポキシ化合物を含む硬化性組成物によって構成される。以下各構成素材、最適な構成要素について説明する。 Hereinafter, the best mode for carrying out the invention will be described in detail.
The present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a hexaarylbiimidazole polymerization initiator, (E) an oxime initiator, and a triazine initiator. It is comprised by the curable composition containing 1 or more types selected and the (F) polyfunctional epoxy compound more than tetrafunctional. Each constituent material and optimum constituent elements will be described below.
本発明の硬化性組成物に用いることができる着色剤としては、従来公知の種々の無機顔料又は有機顔料を用いることができる。また、必要によって染料も使用可能である。
顔料は、無機顔料または有機顔料を問わず、高透過率であることが好ましいことを考慮すると、できるだけ粒子径が小さく微少な粒子サイズの顔料を使用することが好ましく、ハンドリング性をも考慮すると、好ましくは平均一次粒子径0.01~0.3μm、より好ましくは0.01~0.15μmの顔料である。該粒径が前記範囲内であると、透過率が高く、色特性が良好であると共に、高いコントラストのカラーフィルタを形成するのに有効である。 (A) Colorant As the colorant that can be used in the curable composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Further, a dye can be used if necessary.
Regardless of whether the pigment is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible, considering the handling property, considering that it is preferable to have a high transmittance. Preferably, the pigment has an average primary particle diameter of 0.01 to 0.3 μm, more preferably 0.01 to 0.15 μm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast.
一次粒子サイズについての、0.02μm未満の一次粒子の割合、および0.08μmを超える一次粒子の割合は、顔料粉体を透過型電子顕微鏡で観察し、個々の一次粒子の長径を測定し、0.02μm未満及び0.08μmを超える顔料の粒子の割合(個数%)を算出することにより得ることができる。より具体的には、顔料粉体を透過型電子顕微鏡で3~10万倍で観察し、写真を撮り、1000個の一次粒子の長径を測定し、0.02μm未満、及び0.08μmを超える一次粒子の割合を算出する。この操作を顔料粉体の部位を変えて合計で3箇所について行い、結果を平均した。 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 μm and more than 0.08 μm. The particle size distribution can be grasped by measuring.
Regarding the primary particle size, the ratio of primary particles less than 0.02 μm and the ratio of primary particles exceeding 0.08 μm 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 μm and more than 0.08 μm. More specifically, 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 μm and more than 0.08 μm 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.
C.I.Pigment Yellow 11,24,108,109,110,138,139,150,151,154,167,180,185,
C.I.Pigment Orange 36,
C.I.Pigment Red 122,150,171,175,177,209,224,242,
C.I.Pigment Violet 19,23,32,
C.I.Pigment Blue 15:1,15:3,15:6,16,22,60,66,
C.I.Pigment Green 7,36,37;
C.I.Pigment Black 1、7 The following can be mentioned as a pigment which can be preferably used. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Black 1, 7
更にC.I.Pigment Green 58を用いたときに効果が顕著である。 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.
水溶性有機溶剤の使用量は、顔料に対して50質量%から300質量%の範囲であり、好ましくは100質量%から200質量%の範囲である。 本発明における湿式粉砕装置の運転条件については特に制限はないが粉砕メディアによる磨砕を効果的に進行させるため、装置がニーダーの場合の運転条件は、装置内のブレードの回転数は、10~200rpmが好ましく、また2軸の回転比が相対的に大きい方が摩砕効果が大きく好ましい。運転時間は乾式粉砕時間と併せて1時間~8時間が好ましく、装置の内温は50~150℃が好ましい。また粉砕メディアである水溶性無機塩は粉砕粒度が5~50μmで粒子径の分布がシャープで、且つ球形が好ましい。 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. Although there are no particular restrictions on the operating conditions of the wet pulverizing apparatus in the present invention, 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. The operation time is preferably 1 to 8 hours together with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt as a grinding medium preferably has a grinding particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.
例えば、赤の顔料として、アントラキノン系顔料、ペリレン系顔料、ジケトピロロピロール系顔料単独又はそれらの少なくとも1種と、ジスアゾ系黄色顔料、イソインドリン系黄色顔料、キノフタロン系黄色顔料又はペリレン系赤色顔料、アントラキノン系赤色顔料、ジケトピロロピロール系赤色顔料と、の混合などを用いることができる。例えば、アントラキノン系顔料としては、C.I.ピグメント・レッド177が挙げられ、ペリレン系顔料としては、C.I.ピグメント・レッド155、C.I.ピグメント・レッド224が挙げられ、ジケトピロロピロール系顔料としては、C.I.ピグメント・レッド254が挙げられ、色再現性の点でC.I.ピグメント・イエロー139またはC.I.ピグメント・レッド177と、C.I.ピグメント・レッド254との混合が好ましい。また、赤色顔料と他顔料との質量比は、100:5~100:80が好ましい。100:4以下では400nmから500nmの光透過率を抑えることが困難で色純度を上げることが出来ない場合がある。また100:81以上では発色力が下がる場合がある。特に、上記質量比としては、100:10~100:65の範囲が最適である。尚、赤色顔料同士の組み合わせの場合は、色度に併せて調整することができる。 These organic pigments can be used alone or in various combinations in order to increase color purity. Although the specific example of the said combination is shown below, it is not limited to this.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 139 or C.I. I. Pigment red 177 and C.I. I. Mixing with Pigment Red 254 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may decrease. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.
青色顔料と紫色顔料との質量比は、100:0~100:100が好ましく、より好ましくは100:70以下である。 As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.
また、カーボンブラックとチタンブラックとの質量比は、100:0~100:60の範囲が好ましい。上記範囲とすることで分散安定性が良好となる。 Moreover, as a pigment suitable for the black matrix use, 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.
着色剤として使用可能な染料としては、特に制限はなく、従来カラーフィルタ用途として用いられている公知の染料を使用できる。例えば、特開昭64-90403号公報、特開昭64-91102号公報、特開平1-94301号公報、特開平6-11614号公報、特登2592207号、米国特許第4,808,501号明細書、米国特許第5,667,920号明細書、米国特許第5,059,500号明細書、特開平5-333207号公報、特開平6-35183号公報、特開平6-51115号公報、特開平6-194828号公報、特開平8-211599号公報、特開平4-249549号公報、特開平10-123316号公報、特開平11-302283号公報、特開平7-286107号公報、特開2001-4823号公報、特開平8-15522号公報、特開平8-29771号公報、特開平8-146215号公報、特開平11-343437号公報、特開平8-62416号公報、特開2002-14220号公報、特開2002-14221号公報、特開2002-14222号公報、特開2002-14223号公報、特開平8-302224号公報、特開平8-73758号公報、特開平8-179120号公報、特開平8-151531号公報等に記載の色素である。
化学構造としては、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アンスラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ペンゾピラン系、インジゴ系等の染料が使用できる。 In the present invention, when a dye is used as the colorant, a photocurable composition that is uniformly dissolved is obtained.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, JP-A 64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, US Pat. No. 4,808,501 Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, 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 dyes described in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.
遊離率は小さいほど顔料への被覆率が高く、分散性、分散安定性が良好である。遊離率の好ましい範囲は30%以下、より好ましくは20%以下、最も好ましくは15%以下である。理想的には0%である。 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%.
本発明においては、ソルトミリング時に上記iii)有機溶剤にiv)少なくとも一部可溶な樹脂を併用することにより、さらに微細で、表面がiv)少なくとも一部可溶な樹脂による被覆された、乾燥時の顔料の凝集が少ないものが得られる。
なお、iv)高分子化合物を加えるタイミングは、ソルトミリング工程の初期にすべてを添加してもよく、分割して添加してもよい。また分散工程で添加することも可能である。 The salt milling described above will be described more specifically. First, add a small amount of iii) a water-soluble organic solvent as a wetting agent to a mixture of i) an organic pigment and ii) a water-soluble inorganic salt, knead strongly with a kneader, etc., and then throw this mixture into water. Stir with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. When used in an oily varnish, it is possible to disperse the treated pigment before drying (referred to as filter cake) in the oily varnish while removing water by a method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.
In the present invention, at the time of salt milling, by using iv) at least a partly soluble resin in combination with the above iii) organic solvent, the surface is further refined, and the surface is coated with a resin that is iv) at least partly soluble. A pigment with little aggregation of the pigment is obtained.
Note that iv) the polymer compound may be added at the initial stage of the salt milling step, or may be added separately. It is also possible to add in the dispersion step.
R1のアルキル基としては、炭素数1~12のアルキル基が好ましく、炭素数1~8のアルキル基がより好ましく、炭素数1~4のアルキル基が特に好ましい。
R1で表されるアルキル基が置換基を有する場合、該置換基としては、例えば、ヒドロキシ基、アルコキシ基(好ましくは炭素数1~5、より好ましくは炭素数1~3がより好ましい。)メトキシ基、エトキシ基、シクロヘキシロキシ基等が挙げられる。 In the general formula (1), 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.
When the alkyl group represented by R 1 has a substituent, examples of the substituent include a hydroxy group and an 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.
R1としては、水素原子又はメチル基が最も好ましい。 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.
R2で表されるアルキレン基は、ヘテロ原子(例えば、酸素原子、窒素原子、又は硫黄原子)を介して2以上連結したものであってもよい。
R2で表される好ましいアルキレン基として具体的には、例えば、メチレン基、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基が挙げられる。
R2で表される好ましいアルキレン基が置換基を有する場合、該置換基としては、例えば、ヒドロキシ基、等が挙げられる。 In general formula (1), 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).
Specific examples of 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.
When the preferable alkylene group represented by R 2 has a substituent, examples of the substituent include a hydroxy group.
上記した中でも、一般式(2)におけるEとしては、単結合、メチレン基、-O-、又は-C(=O)-が好ましく、-C(=O)-が特に好ましい。 In the general formula (2), 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) —. Here, R A represents a hydrogen atom or an alkyl group. When R A 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, an ethyl group, or an 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.
Among the above, as E in the general formula (2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.
上記した中でも、一般式(4)における、Y1及びY2としては、-N=、-NH-、及び-N(RB)-が特に好ましい。Y1及びY2の組み合わせとしては、Y1及びY2のいずれか一方が-N=であり他方が-NH-である組み合わせ、イミダゾリル基が挙げられる。 In the general formula (4), Y 1 and Y 2 each independently represent —N═, —NH—, —N (R B ) —, —S—, or —O—. R B represents an alkyl group, and when 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.
Among the above, as 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.
(重量平均分子量および数平均分子量)
以下の条件のGPC(ゲルパーミエーションクロマトグラフィー)測定によりポリスチレン換算によって行った。
使用カラム:TSKgel MultiporeHXL-M (細孔多分散型リニアカラム)東ソー製
溶離液:THF
流量:1.0ml/min
温度:40℃
検出条件:RI
システム:高速 GPC 装置一式 (東ソ- HLC-8220)
(酸価)
樹脂の1―メトキシ―2-プロパノール溶液を,1規定水酸化カリウム水溶液によって中和滴定を行って求めた。 The physical property determination method of the specific dispersion resin is as follows. In addition, 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.
Column used: 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.
分散剤としては、例えば、公知の顔料分散剤や界面活性剤を適宜選択して用いることができる。 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.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.
このほか、2-ヒドロキシエチルメタクリレートを共重合したもの等も有用なものとして挙げられる。該ポリマーは任意の量で混合して用いることができる。 Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.
前記アルキル(メタ)アクリレート及びアリール(メタ)アクリレートの具体例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、トリル(メタ)アクリレート、ナフチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート等を挙げることができる。 Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.
(1)予めイソシアネート基とOH基を反応させ、未反応のイソシアネート基を1つ残し、かつ(メタ)アクリロイル基を少なくとも1つ含む化合物とカルボキシル基を含むアクリル樹脂との反応によって得られるウレタン変性した重合性二重結合含有アクリル樹脂、
(2)カルボキシル基を含むアクリル樹脂と分子内にエポキシ基及び重合性二重結合を共に有する化合物との反応によって得られる不飽和基含有アクリル樹脂、
(3)酸ペンダント型エポキシアクリレート樹脂、
(4)OH基を含むアクリル樹脂と重合性二重結合を有する2塩基酸無水物を反応させた重合性二重結合含有アクリル樹脂。 In order to improve the crosslinking efficiency of the curable composition in the present invention, a resin having a polymerizable group in an alkali-soluble resin may be used alone or in combination with an alkali-soluble resin not having a polymerizable group, an aryl group, ( A polymer containing a meth) acryl group, an aryloxyalkyl group or the like in the side chain is useful. The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and is further provided with photocurability and thermosetting. Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as each molecule contains an alkali-soluble group such as a COOH group and an OH group and a carbon-carbon unsaturated bond. .
(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin,
(2) an unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule;
(3) Acid pendant type epoxy acrylate resin,
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
具体例として、OH基を有する例えば2-ヒドロキシエチルアクリレートと、COOH基を含有する例えばメタクリル酸と、これらと共重合可能なアクリル系若しくはビニル系化合物等のモノマーとの共重合体に、OH基に対し反応性を有するエポキシ環と炭素間不飽和結合基を有する化合物(例えばグリシジルアクリレートなどの化合物)を反応させて得られる化合物、等を使用できる。OH基との反応ではエポキシ環のほかに酸無水物、イソシアネート基、アクリロイル基を有する化合物も使用できる。
また、特開平6-102669号公報、特開平6-1938号公報に記載のエポキシ環を有する化合物にアクリル酸のような不飽和カルボン酸を反応させて得られる化合物に、飽和もしくは不飽和多塩基酸無水物を反応させて得られる反応物も使用できる。 Of the above, the resins (1) and (2) are particularly preferable.
As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group in addition to the epoxy ring can be used.
Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.
更に、日本接着協会誌Vol.20、No.7、300~308頁に光硬化性モノマー
及びオリゴマーとして紹介されているものも使用できる。 Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers, can also be used.
また、特公昭48-41708号、特開昭51-37193号、特公平2-32293号、特公平2-16765号に記載されているようなウレタンアクリレート類や、特公昭58-49860号、特公昭56-17654号、特公昭62-39417号、特公昭62-39418号記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。更に、特開昭63-277653号、特開昭63-260909号、特開平1-105238号に記載される、分子内にアミノ構造やスルフィド構造を有する付加重合性化合物類を用いることによっては、非常に感光スピードに優れた光重合性組成物を得ることができる。市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ社製)、UA-7200」(新中村化学社製、DPHA-40H(日本化薬社製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共栄社製)などが挙げられる。
また、酸基を有するエチレン性不飽和化合物類も好適であり、市販品としては、例えば、東亞合成株式会社製のカルボキシル基含有3官能アクリレートであるTO-756、及びカルボキシル基含有5官能アクリレートであるTO-1382などが挙げられる。 Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.
Also, urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
Further, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.
なおA、Xが複数存在する場合、互いに同一でも異なっていてもよいが、感度と熱安定性の観点から同一であることが好ましい。 In the formula (II), 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.
When there are a plurality of A and X, they may be the same or different from each other, but are preferably the same from the viewpoints of sensitivity and thermal stability.
R12及びR3は、各々独立に、水素原子、炭素数1~20のアルキル基、炭素数3~8のシクロアルキル基、置換もしくは無置換のフェニル基、又は炭素数7~20の脂環式炭化水素基(但し、炭素数7~8のシクロアルキル基を除く)を表し、前記フェニル基が置換されている場合の置換基は炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、フェニル基、又はハロゲン原子である。ここで、これらの置換基の数は、1~5個であることができる。
R4は、炭素数4~20の含酸素複素環基、炭素数4~20の含窒素複素環基、又は炭素数4~20の含硫黄複素環基を表す。
R5は、水素原子、炭素数1~12のアルキル基、又は炭素数1~12のアルコキシ基を表す。
また、qは1~5の整数を表し、pは0~5の整数を表し、rは0~6の整数を表し、p及びqは、p+q≦5を満たす。
なおR4およびR5が複数存在する場合は、それぞれ互いに同一でも異なっていてもよい。 In the general formulas (5) and (6), R 11 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group.
R 12 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic ring having 7 to 20 carbon atoms. Represents a hydrocarbon group (excluding a cycloalkyl group having 7 to 8 carbon atoms), and when the phenyl group is substituted, the substituent is an alkyl group having 1 to 6 carbon atoms, or a carbon group having 1 to 6 carbon atoms. An alkoxy group, a phenyl group, or a halogen atom. Here, the number of these substituents may be 1 to 5.
R 4 represents an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms.
R 5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
Q represents an integer of 1 to 5, p represents an integer of 0 to 5, r represents an integer of 0 to 6, and p and q satisfy p + q ≦ 5.
When a plurality of R 4 and R 5 are present, they may be the same as or different from each other.
これらのうち、炭素数4~20の含酸素複素環基が好ましく、特にテトラヒドロフラニル基、テトラヒドロピラニル基等が好ましい。 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, pyrrolinyl group, morpholinyl group, piperazinyl group, quinuclidinyl group, indolyl group, isoindoryl group, benzofuranyl group , Benzothiophenyl group, indolizini Group, chromenyl group, quinolinyl group, isoquinolinyl group, purinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, pteridinyl group, carbazolyl group, acridinyl group, phenanthridinyl group, thioxanthenyl group, phenazinyl group, phenothiazinyl group, phenoxy group Examples include a satinyl group, a phenoxazinyl group, a thiantenyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group.
Of these, an oxygen-containing heterocyclic group having 4 to 20 carbon atoms is preferable, and a tetrahydrofuranyl group, a tetrahydropyranyl group, and the like are particularly preferable.
エタノン,1-[9-エチル-6-(2-メチル-2-テトラヒドロピラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-2-テトラヒドロフラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-2-テトラヒドロピラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-3-テトラヒドロフラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-3-テトラヒドロピラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル] -,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-3-テトラヒドロフラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム); Specific examples of the compound represented by the general formula (5) or (6) include ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9.H.- Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
エタノン,1-[9-エチル-6-(2-メチル-4-テトラヒドロフラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-4-テトラヒドロピラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-4-テトラヒドロフラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-4-テトラヒドロピラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-5-テトラヒドロフラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-5-テトラヒドロピラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-5-テトラヒドロフラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-5-テトラヒドロピラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-2-テトラヒドロフラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-2-テトラヒドロピラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム); Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
エタノン,1-[9-エチル-6-(2-メチル-2-テトラヒドロピラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-3-テトラヒドロフラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-3-テトラヒドロピラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-3-テトラヒドロフラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-3-テトラヒドロピラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-4-テトラヒドロフラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-4-テトラヒドロピラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム); Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
エタノン,1-[9-エチル-6-(2-メチル-4-テトラヒドロピラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-5-テトラヒドロフラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-5-テトラヒドロピラニルオキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-5-テトラヒドロフラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-(2-メチル-5-テトラヒドロピラニルメトキシベンゾイル)-9.H.-カルバゾール-3-イル]-,1-(O-ベンゾイルアセチルオキシム);
エタノン,1-[9-エチル-6-[2-メチル-4-(2,2-ジメチル-1,3-ジオキソラニル)メトキシベンゾイル]-9.H.-カルバゾール-3-イル]-,1-(O-アセチルオキシム);
等を挙げることができる。 Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Etc.
R12及びR3は、各々独立に、水素原子、炭素数1~20のアルキル基、炭素数3~8のシクロアルキル基、置換もしくは無置換のフェニル基、又は炭素数7~20の脂環式炭化水素基(但し、炭素数7~8のシクロアルキル基を除く)を表し、前記フェニル基が置換されている場合の置換基は炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、フェニル基、又はハロゲン原子である。ここで、これらの置換基の数は、1~5個であることができる。
R5は、水素原子、炭素数1~12のアルキル基、又は炭素数1~12のアルコキシ基を表す。
また、pは0~5の整数を表す。
なお、R5が複数存在する場合は、互いに同一でも異なっていてもよい。 In the general formula (5 ′), R 11 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group.
R 12 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic ring having 7 to 20 carbon atoms. Represents a hydrocarbon group (excluding a cycloalkyl group having 7 to 8 carbon atoms), and when the phenyl group is substituted, the substituent is an alkyl group having 1 to 6 carbon atoms, or a carbon group having 1 to 6 carbon atoms. An alkoxy group, a phenyl group, or a halogen atom. Here, the number of these substituents may be 1 to 5.
R 5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
P represents an integer of 0 to 5.
In addition, when two or more R < 5 > exists, they may mutually be same or different.
上記のうち、R11としては、例えば、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ヘキシル基などが好ましい。 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.
Among the above, 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.
これらのうち、前記R5としては、特に、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、メトキシ基、エトキシ基が好ましい。 Further, 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.
また硬化性組成物の固形分に対して、(D)ヘキサアリールビイミダゾール系化合物は1.0~15質量%添加して用いるのが好ましく、より好ましくは3.0~10.0質量%である。この範囲であるとNMP溶剤による色度変化、膨潤耐性が良好で、かつITO蒸着適性が良好である。 In the present invention, the content of the (D) hexaarylbiimidazole compound is preferably in the range of 2 to 25% by mass with respect to the total solid content of the curable composition from the viewpoint of suppressing sensitivity variations. In the present invention, (D) a hexaarylbiimidazole-based photopolymerization initiator and (E) an oxime-based initiator or a triazine-based initiator are used in combination, and the ratio is from 1: 0.5 to 1: The range of 4 is more preferable, and the range of 1: 1 to 1: 3 is more preferable. When used within this range, chromaticity change by NMP solvent, swelling resistance is good, and ITO deposition suitability is good.
The (D) hexaarylbiimidazole compound is preferably added in an amount of 1.0 to 15% by mass, more preferably 3.0 to 10.0% by mass, based on the solid content of the curable composition. is there. Within this range, chromaticity change by NMP solvent and swelling resistance are good, and ITO deposition suitability is good.
例えば、特開平57-6096号公報に記載のハロメチルオキサジアゾール、米国特許第4318791号明細書、欧州特許出願公開第88050号明細書等の各明細書に記載のケタール、アセタール、又はベンゾインアルキルエーテル類等の芳香族カルボニル化合物、米国特許第4199420号明細書に記載のベンゾフェノン類等の芳香族ケトン化合物、仏国特許発明2456741号明細書に記載の(チオ)キサントン系又はアクリジン系化合物、特開平10-62986号公報に記載のクマリン系の化合物、特開平8-015521号公報等のスルホニウム有機硼素錯体等、等を挙げることができる。 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.
For example, 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.
特公平37-13034号公報に記載のスチリル系色素;特開昭62-143044号公報に記載の陽イオン染料;特公昭59-24147号公報記載のキノキサリニウム塩;特開昭64-33104号公報記載の新メチレンブルー化合物;特開昭64-56767号公報記載のアントラキノン類;特開平2-1714号公報記載のベンゾキサンテン染料;特開平2-226148号公報及び特開平2-226149号公報記載のアクリジン類;特公昭40-28499号公報記載のピリリウム塩類;特公昭46-42363号公報記載のシアニン類;特開平2-63053号記載のベンゾフラン色素;特開平2-85858号公報、特開平2-216154号公報の共役ケトン色素;特開昭57-10605号公報記載の色素;特公平2-30321号公報記載のアゾシンナミリデン誘導体;特開平1-287105号公報記載のシアニン系色素;特開昭62-31844号公報、特開昭62-31848号公報、特開昭62-143043号公報記載のキサンテン系色素;特公昭59-28325号公報記載のアミノスチリルケトン;特開平2-179643号公報記載の色素;特開平2-244050号公報記載のメロシアニン色素;特公昭59-28326号公報記載のメロシアニン色素;特開昭59-89303号公報記載のメロシアニン色素;特開平8-129257号公報記載のメロシアニン色素;特開平8-334897号公報記載のベンゾピラン系色素が挙げられる。 The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 New anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.
増感色素の他の好ましい態様として、以下の化合物群に属しており、且つ、350~450nmに極大吸収波長を有する色素が挙げられる。
例えば、多核芳香族類(例えば、ピレン、ペリレン、トリフェニレン)、キサンテン類(例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンB、ローズベンガル)、シアニン類(例えばチアカルボシアニン、オキサカルボシアニン)、メロシアニン類(例えば、メロシアニン、カルボメロシアニン)、チアジン類(例えば、チオニン、メチレンブルー、トルイジンブルー)、アクリジン類(例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン)、アントラキノン類(例えば、アントラキノン)、スクアリウム類(例えば、スクアリウム)が挙げられる。 (Dye having a maximum absorption wavelength at 350 to 450 nm)
Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, 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).
本発明において、4官能以上の多官能エポキシ化合物とは、アルカリ可溶性樹脂のカルボキシル基と熱架橋する化合物をいい、熱架橋することによって架橋密度が高くなり、耐薬品性の向上が図られる。
本発明に使用できる多官能エポキシ化合物としては、ビスフェノールA型、クレゾールノボラック型、ビフェニル型、脂環式エポキシ化合物などで、エポキシ環を分子中に4個以上有する化合物である。 (F) A polyfunctional epoxy compound having 4 or more functional groups In the present invention, a polyfunctional epoxy compound having 4 or more functional groups means a compound that thermally crosslinks with a carboxyl group of an alkali-soluble resin. The chemical resistance is improved.
Examples of the polyfunctional epoxy compound that can be used in the present invention are bisphenol A type, cresol novolak type, biphenyl type, alicyclic epoxy compound, etc., and compounds having 4 or more epoxy rings in the molecule.
本発明に係る多官能エポキシ化合物の硬化性組成物中における含有量としては、顔料を除いた全固形分に対して、2~20質量%が好ましく、3~10質量%がより好ましい。該含有量が前記範囲内であると、膜の耐溶剤性に優れる。また、多すぎるとベーク後の黄着色により、カラーフイルタの品質が損われたり、少なすぎると耐NMP性に劣ってしまう問題が生じる。 In the composition of this invention, you may contain 2 or more types of polyfunctional epoxy compounds.
The content of the polyfunctional epoxy compound according to the present invention in the curable composition is preferably 2 to 20% by mass, more preferably 3 to 10% by mass, based on the total solid content excluding the pigment. When the content is within the above range, the solvent resistance of the film is excellent. On the other hand, when the amount is too large, the color of the color filter is deteriorated due to yellowing after baking, and when the amount is too small, the NMP resistance is inferior.
溶剤は、単独で用いる以外に2種以上を組み合わせて用いてもよい。 Solvents include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using independently.
連鎖移動剤は、1種単独で用いてもよく、2種以上を併用してもよい。 Examples of chain transfer agents that can be added to the curable composition of the present invention 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.
フッ素系有機化合物の添加量は、光硬化性組成物の全質量に対して、0.001~2.0質量%が好ましく、より好ましくは0.005~1.0質量%である。 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.
なお、混合分散工程は、混練分散とそれに続けて行なう微分散処理からなるのが好ましいが、混練分散を省略することも可能である。 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.
顔料と水溶性有機溶剤と水溶性無機塩類との混合物を、二本ロール、三本ロール、ボールミル、トロンミル、ディスパー、ニーダー、コニーダー、ホモジナイザー、ブレンダー、単軸もしくは2軸の押出機等の混練機を用いて、強い剪断力を与えながら顔料を摩砕した後、この混合物を水中に投入し、攪拌機等でスラリー状とする。次いで、このスラリーをろ過、水洗し、水溶性有機溶剤と水溶性無機塩を除去した後、乾燥し、微細化された顔料が得られる。微細化処理前に高分子化合物を添加して、顔料を被覆することが好ましい。 An example of the manufacturing method of the curable composition of this invention is shown below.
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.
なお、混練、分散についての詳細は、T.C.Patton著”Paint Flowand Pigment Dispersion”(1964年 John Wiley and Sons社刊)等に記載されている。
そして、上記のようにして得られた顔料分散組成物に、光重合性化合物、重合開始剤、およびアルカリ可溶性樹脂などを添加して、本発明の硬化性組成物を得る。 The beads are dispersed with a pigment and a dispersant and / or a pigment derivative and a solvent. Using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., fine dispersion with beads made of 0.01 to 1 mm particle size glass, zirconia, etc., pigment dispersion composition Get. It is also possible to omit the process of making the pigment finer.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.
And a photopolymerizable compound, a polymerization initiator, an alkali-soluble resin, etc. are added to the pigment dispersion composition obtained as mentioned above, and the curable composition of this invention is obtained.
プラスチック基板には、その表面にガスバリヤー層及び/又は耐溶剤性層を有していることが好ましい。このほかに、薄膜トランジスター(TFT)方式カラー液晶表示装置の薄膜トランジスター(TFT)が配置された駆動用基板(以下、「TFT方式液晶駆動用基板」という。)上にも本発明の光硬化性組成物からなるパターン状皮膜を形成し、カラーフィルタを作成することができる。その際に使用されるフォトマスクには、画素を形成するためのパターンのほか、スルーホールあるいはコの字型の窪みを形成するためのパターンも設けられている。TFT方式液晶駆動用基板における基板としては、例えば、ガラス、シリコン、ポリカーボネート、ポリエステル、芳香族ポリアミド、ポリアミドイミド、ポリイミド等を挙げることができる。これらの基板には、所望により、シランカップリング剤等による薬品処理、プラズマ処理、イオンプレーティング、スパッタリング、気相反応法、真空蒸着等の適宜の前処理を施しておくこともできる。例えば、TFT方式液晶駆動用基板の表面上、あるいは該駆動基板の表面に窒化ケイ素膜等のパッシベーション膜を形成した基板等を挙げることができる。 Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these substrates, solid-state imaging devices, and the like. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate, and a plastic substrate. On these substrates, a black matrix for isolating each pixel is usually formed, or a transparent resin layer is provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface. In addition, 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. Examples of 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. For example, 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.
プリベーク処理は、ホットプレート、オーブン等を用いて50~140℃の温度範囲で、好ましくは70~110℃程度であり、10~300秒の条件にて行なうことができる。高周波処理などを併用しても良い。高周波処理は単独でも使用可能である。 Usually, a pre-baking process is performed after application. If necessary, vacuum treatment can be performed before pre-baking. As the conditions for vacuum drying, 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.
現像液としては、未硬化部における光硬化性の硬化性組成物の塗膜を溶解する一方、硬化部を溶解しないものであれば、いずれのものも用いることができる。具体的には、種々の有機溶剤の組合せやアルカリ性の水溶液を用いることができる。 In the development process, 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.
前記アルカリ性の水溶液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、メタ硅酸ナトリウム、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、1,8-ジアザビシクロ-[5,4,0]-7-ウンデセン等のアルカリ性化合物を、濃度が0.001~10質量%、好ましくは0.01~1質量%となるように溶解したアルカリ性水溶液が挙げられる。アルカリ性水溶液には、例えばメタノール、エタノール等の水溶性有機溶剤や界面活性剤等を適量添加することもできる。
現像方式は、デイップ方式、シャワー方式、スプレー方式などいずれでもよく、これにスウィング方式、スピン方式、超音波方式などを組み合わせても良い。現像液に触れる前に、被現像面を予め水等で湿しておいて、現像むらを防ぐこともできる。また基板を傾斜させて現像することもできる。 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. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.
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.
リンス工程は通常は純水で行うが、省液のために、最終洗浄で純水を用い、洗浄はじめは使用済の純水を使用したり、基板を傾斜させて洗浄したり、超音波照射を併用したりできる。 After the development processing, after 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.
以上の操作を所望の色相数に合わせて各色毎に順次繰り返し行なうことにより、複数色の着色された硬化膜が形成されてなるカラーフィルタを作製することができる。 After rinsing, draining and drying are performed, and a heat treatment is usually performed at about 200 ° C. to 250 ° C. In this heat treatment (post-bake), 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.
By sequentially repeating the above operation for each color according to the desired number of hues, a color filter formed with a plurality of colored cured films can be produced.
前記ブラックマトリックスは、顔料としてカーボンブラック、チタンブラックなどの黒色顔料を用いた本発明の硬化性組成物を露光、現像し、その後必要に応じて更にポストベークして膜の硬化を促進させることで形成できる。 Although 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.
(重合体1の合成)
M-11(下記構造) 27.0g、メチルメタクリレート 126.0g、メタクリル酸 27.0g、および1-メトキシ-2-プロパノール 420.0gを、窒素置換した三つ口フラスコに導入し、攪拌機(新東科学(株):スリーワンモータ)にて攪拌し、窒素をフラスコ内に流しながら加熱して90℃まで昇温する。これに2,2-アゾビス(2,4-ジメチルバレロニトリル)(和光純薬(株)製V-65)を1.69g加え、90℃にて2時間加熱攪拌を行った。2時間後、さらにV-65を1.69g加え、3時加熱攪拌の後、重合体1の30質量%溶液を得た。得られた高分子化合物の重量平均分子量をポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー法(GPC)により測定した結果、2.0万であった。また、水酸化ナトリウムを用いた滴定から、固形分あたりの酸価は、98mgKOH/gであった。 <Synthesis example of polymer compound having heterocycle in chain>
(Synthesis of polymer 1)
M-11 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (new The mixture is stirred with Toshin Kagaku Co., Ltd .: Three-One Motor, and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. Two hours later, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 1 was obtained. As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000. From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g.
M-6(下記構造) 27.0g、メチルメタクリレート 126.0g、メタクリル酸 27.0g、および1-メトキシ-2-プロパノール 420.0gを、窒素置換した三口フラスコに導入し、撹拌機(新東科学(株):スリーワンモータ)にて撹拌し、窒素をフラスコ内に流しながら加熱して90℃まで昇温する。これに2,2-アゾビス(2,4-ジメチルバレロニトリル)(和光純薬(株)製V-65)を1.80g加え、90℃にて2時間加熱撹拌を行った。2時間後、さらにV-65を1.80g加え、3時加熱撹拌の後、重合体2の30質量%溶液を得た。ポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー法(GPC)により、得られた高分子化合物の重量平均分子量を測定した結果、2.1万であった。また、水酸化ナトリウムを用いた滴定から、固形分あたりの酸価は、99mgKOH/gであった。 (Synthesis of polymer 2)
M-6 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto) The temperature is increased to 90 ° C. by stirring while flowing nitrogen in the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. Two hours later, 1.80 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 2 was obtained. It was 21,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. From the titration with sodium hydroxide, the acid value per solid content was 99 mgKOH / g.
顔料(C.I.Pigment Red254 チバ・スペシャルティ・ケミカルズ製 CROMOPHTAL RED BP) 50g、塩化ナトリウム 500g、上記した重合体1の溶液 20g、およびジエチレングリコール100gをステンレス製1ガロンニーダー(井上製作所製)に仕込み、9時間混練した。次に、この混合物を約3リットルの水中に投入し、ハイスピードミキサーで約1時間撹拌した後に、ろ過、水洗して塩化ナトリウムおよび溶剤を除き、乾燥して被覆顔料1を調製した。 (Preparation of coated pigment 1)
Pigment (CI Pigment Red254 Ciba Specialty Chemicals CROMOPHTAL RED BP) 50 g, sodium chloride 500 g, 20 g of the above polymer 1 solution, and 100 g of diethylene glycol were 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.
被覆顔料1の調整で、Pigment Red254の代わりに、C.I.Pigment Green 36(日本ルーブリゾール社製 Monastral Green 6Y-CLを用いて、また重合体1の代わりに重合体2を用いて、他は被覆顔料1の調製と同様にして被覆顔料2を調製した。 (Preparation of coated pigment 2)
In the adjustment of the coating pigment 1, C.I. I. Pigment Green 36 (Monastral Green 6Y-CL manufactured by Nippon Lubrizol Co., Ltd.) was used in the same manner as in the preparation of the coated pigment 1 except that the polymer 2 was used instead of the polymer 1, and the coated pigment 2 was prepared.
被覆顔料2の調整で、Pigment Green 36の代わりに、C.I.Pigment Green 7(BASF社製 HELIOGEN Green L8730を用いて、他は被覆顔料2の調製と同様にして、被覆顔料3を調製した。 (Preparation of coated pigment 3)
Instead of Pigment Green 36, C.I. I. Pigment Green 7 (HELIOGEN Green L8730 manufactured by BASF Corporation) was used to prepare a coated pigment 3 in the same manner as the coated pigment 2.
被覆顔料2の調整で、Pigment Green 36の代わりに、C.I.Pigment Blue 15:6(BASF社製 HELIOGEN Blue L6700Fを用いて、他は被覆顔料2の調製と同様にして、被覆顔料4を調製した。 (Preparation of coated pigment 4)
Instead of Pigment Green 36, C.I. I. Pigment Blue 15: 6 (HELIOGEN Blue L6700F manufactured by BASF Corporation) was used to prepare a coated pigment 4 in the same manner as the coated pigment 2.
被覆顔料2の調整で、Pigment Green 36の代わりに、C.I.Pigment Violet 23(Clariant社製 HOSTAPERM VIOLET RL-NFを用いて、他は被覆顔料2の調製と同様にして、被覆顔料5を調製した。 (Preparation of coated pigment 5)
Instead of Pigment Green 36, C.I. I. Pigment Violet 23 (Clearant's HOSTAPERM VIOLET RL-NF) was used to prepare coated pigment 5 in the same manner as coated pigment 2 except that
被覆顔料1の調整で、混練時間を9時間のところを、それぞれ7時間、5時間にして、被覆顔料6、および被覆顔料7を調製した。 (Preparation of coated pigments 6 and 7)
By adjusting the coated pigment 1, the coated pigment 6 and the coated pigment 7 were prepared by changing the kneading time from 9 hours to 7 hours and 5 hours, respectively.
得られた顔料10gを1-メトキシ-2-プロパノール 100mL中に投入し、振とう機にて室温で3時間、振とうさせた。その後、遠心分離機にて、80,000rpm、8時間かけて顔料を沈降させた。上澄み液部分の固形分を乾燥法から求めた。顔料から遊離した高分子化合物の量を求め、処理に使用した高分子化合物との比から、遊離率(%)を算出した。遊離率は小さいほど顔料への被覆度が高い。
上記で得た被覆顔料1~7は、いずれも20質量%以下の遊離量を示し、被覆された顔料であることがわかった。 (Evaluation of pigment coverage)
10 g of the obtained 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 precipitated with a centrifugal separator at 80,000 rpm for 8 hours. The solid content of the supernatant was determined from the drying method. The amount of the polymer compound released from the pigment was determined, and the release rate (%) was calculated from the ratio with the polymer compound used in the treatment. The smaller the liberation rate, the higher the degree of coverage on the pigment.
The coated pigments 1 to 7 obtained above all showed a free amount of 20% by mass or less, and were found to be coated pigments.
被覆顔料1の顔料相当分35部に対し、分散剤としてディスパーエイド163(サンノプコ社製)7.0部、溶剤:プロピレングリコールメチルエーテルアセテート 200部の組成にて、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、混合溶液を調製し、さらに0.1mmφジルコニアビーズを用いたビーズ分散機ウルトラアペックスミル(寿工業社製)にて6時間分散処理を行なった。
同様に、被覆顔料種と分散剤の量とを、表1のように変更して、顔料分散液2~10を得た。ただし顔料分散液8における被覆顔料4と被覆顔料5の使用量の比は、95:5とし、合計の顔料相当分が35部となるように配合した。顔料とともに分散液に使用されることになる被覆高分子の量も表1に記した。 (Preparation of 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 mmφ 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.
また、顔料分散液15は、顔料分散液1の調製において、ビーズ分散機での6時間分散処理を、ホモジナイザー(回転数5000r.p.m.)による18時間の分散処理に変更した以外は、顔料分散液1の調製と同じで行った。 In Table 1, as the pigment dispersion 10, CROMOPHTAL RED BP manufactured by Ciba Specialty Chemicals was used as it was instead of using the coated pigment.
In addition, 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.
顔料分散液の1次粒子径の分布は、透過型電子顕微鏡で測定し、0.02μm未満、および0.08μmを超える粒子サイズの粒子の占める割合を、個数%で表1に示した。 (Measurement of primary particle size distribution of pigment dispersion)
The distribution of the primary particle size of the pigment dispersion was measured with a transmission electron microscope, and the proportion of particles having a particle size of less than 0.02 μm and greater than 0.08 μm was shown in Table 1 in number%.
得られた顔料分散液1にさらに以下の組成の成分を添加し、撹拌混合して本発明の硬化性組成物(カラーレジスト液)を調製した。
・(B)アルカリ可溶性樹脂:ベンジルメタクリレートとメタクリル酸(=70/30[モル比])との共重合体 重量平均分子量=30,000 20.8部
・(C)重合性化合物:日本化薬(株)製 DPHA 20部
・(D)重合開始剤:2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール 3部
・(E)重合開始剤:4-[o-ブロモ-p-N,N-ジ(エトキシカルボニル)アミノフェニル]-2,6-ジ(トリクロロメチル)-s-トリアジン 3部
・(F)多官能エポキシ化合物:DIC(株)製 エピクロン695 5部
・ジエチルアミノベンゾフェノン 0.5部
・N-フェニルメルカプトベンズイミダゾール 0.5部
・界面活性剤:(下記構造物1) 1.0部
・溶剤(プロピレングリコールメチルエーテルアセテート/エチルエトキシプロピオネート=8/2) 400部 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.
(B) Alkali-soluble resin: copolymer of benzyl methacrylate and methacrylic acid (= 70/30 [molar ratio]) Weight average molecular weight = 30,000 20.8 parts (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, diethylaminobenzophenone 0.5 part, N-phenylmercaptobenzimidazole 0.5 part, surfactant: (Structure 1 below) 1.0 part, solvent (propylene glycol) Ether acetate / ethyl ethoxypropionate = 8/2) 400 parts of
実施例1の硬化性組成物の組成において、顔料の種類と量、アルカリ可溶性樹脂の量、重合性化合物の量、重合開始剤の種類と量、および多官能エポキシ化合物の量を表2のように変更して、実施例2~16、および比較例1~6の硬化性組成物を調整した。 (Examples 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.
*2:2,2’-ビス(o-クロロフェニル)-4,4’,5,5’-テトラ-(3,4-ジメトキシフェニル)ビイミダゾール
*3:チバ・スペシャルティ・ケミカルズ製 オキシム系開始剤 OXE-01(下記に示すオキシム1)
*4:オキシム3(前記例示化合物の5’-2の化合物)
*5:オキシム4(前記例示化合物の5’-3の化合物)
*6:2官能のエポキシ化合物 DIC(株)製 エピクロン850-LC In Table 2, * 1 used the same compound as in Example 1. * 2 to * 6 are shown below.
* 2: 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) biimidazole * 3: Oxime initiator manufactured by Ciba Specialty Chemicals OXE-01 (Oxime 1 shown below)
* 4: Oxime 3 (compound 5′-2 of the above exemplified compound)
* 5: Oxime 4 (compound 5′-3 of the above exemplified compounds)
* 6: Bifunctional epoxy compound DIC Corporation Epicron 850-LC
特許第3264364号公報記載の方法でTFT基板を作成した。即ち、アクティブマトリクス基板に、ゲート信号線並びに付加容量電極を形成し、この上にゲート絶縁膜を形成し、半導体層、及びチャネル保護層を形成し、TFTのソース、及びドレインとなるn+Si層を形成した。 (Creation of TFT substrate)
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.
実施例1において、顔料分散液1を顔料分散液15とした以外は、実施例1と同様にして硬化性組成物を調整し、実施例1と同様の評価を行った。結果は表3に示す。 (Comparative 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.
実施例1において、顔料分散液1を顔料分散液10とした以外は、実施例1と同様にして硬化性組成物を調整し、実施例1と同様の評価を行った。結果は表3に示す。 (Comparative Example 8)
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 10 in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.
実施例1において、(F)多官能エポキシ化合物 エピクロン695をEHPE-3150(ダイセル化学工業社製、多官能エポキシ樹脂)に変更して硬化性組成物を調整し、実施例1と同様の評価を行った。結果は表3に示す。 (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.
[色度変化]
各着色基板の分光特性を大塚電子(株)製分光測光器MCPD-2000によって測定した後、各試験片を50℃NMP(N-メチルピロリドン)溶液に10分間浸漬する。次いで、純水でリンスし、85℃60分乾燥した後、再度分光特性を測定し、NMP浸漬によってどれだけ色度が変化したかをΔE*abで表した。ここでΔE*abとは、L*a*b*表色系における色差を意味する。色差の変化ΔE*abの値で評価した。
(評価基準)
A: ΔE*abが2未満
B: ΔE*abが2以上3未満
C: ΔE*abが3以上5未満
D: ΔE*abが5以上 [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 ΔE * ab. Here, ΔE * ab means a color difference in the L * a * b * color system. The change in color difference ΔE * ab was evaluated.
(Evaluation criteria)
A: ΔE * ab is less than 2 B: ΔE * ab is 2 or more and less than 3 C: ΔE * ab is 3 or more and less than 5 D: ΔE * ab is 5 or more
各着色基板をN-メチルピロリドン(溶剤)中に60℃で30分間浸漬し、経過後取り出して着色基板表面の表面粗さを光学顕微鏡で観察し、下記の評価基準にしたがって評価した。
(評価基準)
A:全く変化しなかった。
B:浸漬前からの変化はなかった。溶液が微妙に着色した。
C:表面に若干の変化がみられた。溶液が着色した。
D:表面がざらざら状に変化してしまった。溶液が着色した。 [Swelling resistance]
Each colored substrate was immersed in N-methylpyrrolidone (solvent) at 60 ° C. for 30 minutes, taken out after the lapse of time, and the surface roughness of the colored substrate surface was observed with an optical microscope, and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: No change at all.
B: There was no change from before immersion. The solution was slightly colored.
C: Some change was observed on the surface. The solution became colored.
D: The surface has changed into a rough shape. The solution became colored.
インジウムチンオキシド(ITO)を常法に従い、蒸着(膜厚1400Å、蒸着温度200℃)した後、光学顕微鏡で詳細に観察した。 [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.
表面粗さを、原子間力顕微鏡(AFM)、セイコーインスツルメンツ株式会社製のSPA-400AFMにてRa値を測定した。評価基準は以下の通り。
A: 3nm未満
B: 3nm以上8nm未満
C: 8nm以上10nm未満
D: 10nm以上 [Surface]
For the surface roughness, 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
光学顕微鏡にて500倍にて観察を行った。評価基準は以下の通り。
A: 表面が非常に平滑である。
B: 平滑である。
C: 微妙な凹凸が見られる。
D: 凹凸が見られる。 [Wrinkle]
Observation was performed at 500 times with an optical microscope. The evaluation criteria are as follows.
A: The surface is very smooth.
B: Smooth.
C: Subtle unevenness is observed.
D: Unevenness is seen.
得られた硬化性組成物を50℃で14日間間保存し、現像時間の変化を評価した。
(評価基準)
現像時間の評価は、ガラス基板上に塗布された感材を現像し、ガラス基板が残渣なくクリアになる時間を評価した。
A: 現像時間に変化なし。
B: 現像時間の遅れが5秒未満であった。
C: 現像時間が5以上10秒未満遅くなった。
D: 現像時間が10秒以上遅くなった。 (Liquid storage stability)
The obtained curable composition was stored at 50 ° C. for 14 days, and the change in development time was evaluated.
(Evaluation criteria)
Evaluation of development time evaluated the time which develops the photosensitive material apply | coated on the glass substrate, and a glass substrate becomes clear without a residue.
A: No change in development time.
B: Development time delay was less than 5 seconds.
C: The development time was delayed by 5 or more and less than 10 seconds.
D: The development time was delayed by 10 seconds or more.
着色基板の着色樹脂被膜の上に偏光板を置いて着色樹脂被膜を挟み込み、偏光板が平行時の輝度と直交時の輝度とをトプコン(株)社製のBM-5を用いて測定し、平行時の輝度を直交時の輝度で除して得られる値(=平行時の輝度/直交時の輝度)を、コントラストを評価するための指標とした。
(評価基準)
A: 8000以上。
B: 6000以上8000未満。
C: 4000以上6000未満。
D: 4000未満。 〔contrast〕
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. A value obtained by dividing the parallel brightness by the orthogonal brightness (= the brightness when parallel / the brightness when orthogonal) was used as an index for evaluating the contrast.
(Evaluation criteria)
A: 8000 or more.
B: 6000 or more and less than 8000.
C: 4000 or more and less than 6000.
D: Less than 4000.
基板上に感光性組成物を塗布し、評価用感光層を作製した。尚、硬化性組成物は調液後すぐに使用した。次いで、実施例で用いた露光装置で、15段ステップウエッジパターン(ΔlogE=0.15)を用いて露光(60mJ/cm2)し、現像した。現像条件は実施例1と同じとした。そして、現像後のベタ段(現像により厚さが変化していない段数)の段数を以下の評価基準に従い評価した。
A: 11段以上であった場合
B: 8~10段であった場合
C: 6~7段であった場合
D: 5段以下であった場合 〔sensitivity〕
The photosensitive composition was apply | coated on the board | substrate and the photosensitive layer for evaluation was produced. The curable composition was used immediately after preparation. Next, the exposure apparatus used in the examples was exposed (60 mJ / cm 2 ) using a 15-step step wedge pattern (Δlog E = 0.15) and developed. The development conditions were the same as in Example 1. Then, the number of solid stages after development (the number of stages whose thickness did not change due to development) was evaluated according to the following evaluation criteria.
A: When it is 11 steps or more B: When it is 8 to 10 steps C: When it is 6 to 7 steps D: When it is 5 steps or less
以上の評価をもとに、C、Dが1項目もない水準をAと判定した。Dが1項目でもあればD、Dが全くなくCがある水準はCとして総合評価した。 〔Comprehensive evaluation〕
Based on the above evaluation, a level having no C and D items was determined as A. If D is one item, D and D were not present at all, and C was evaluated as C.
比較例5は、比較的良好な結果であるが、これは顔料濃度が小さく、淡色であるので、実用的ではない。 From Table 3, the sclerosis | hardenability which contains any one of a hexaarylbiimidazole type | system | group polymerization initiator, an oxime type initiator, or a triazine type initiator, and contains the polyfunctional epoxy compound more than tetrafunctional with respect to all solid content. It can be seen that the composition exhibits the effects of the present invention, is excellent in NMP resistance, ITO vapor deposition, and liquid storage stability, has good contrast, and has high sensitivity.
Comparative Example 5 is a relatively good result, but this is not practical because the pigment concentration is small and the color is light.
被覆顔料2の調製でPigment Green 36の代わりにランクセス社製黄色顔料 E4GN GTを用いて、他は被覆顔料2の調製と同様にして被覆顔料8を調製した。
被覆顔料8の被覆度の評価は被覆顔料1の評価と同様の方法で行った。被覆顔料8は、20質量%以下の遊離量を示し、被覆された顔料であることがわかった。 (Preparation of coated pigment 8)
A coated pigment 8 was prepared in the same manner as the coated pigment 2 except that a yellow pigment E4GN GT manufactured by LANXESS was used instead of Pigment Green 36 in the preparation of the coated pigment 2.
Evaluation of the coating degree of the coated pigment 8 was performed in the same manner as the evaluation of the coated pigment 1. The coated pigment 8 showed a free amount of 20% by mass or less, and was found to be a coated pigment.
被覆顔料8の顔料相当分35部に対し、分散剤としてディスパービックbyk161(ビックケミー社製)7.0部、溶剤:プロピレングリコールメチルエーテルアセテート 200部の組成にて、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、混合溶液を調製し、さらに0.1mmφジルコニアビーズを用いたビーズ分散機ウルトラアペックスミル(寿工業社製)にて6時間分散処理を行なった。
同様に、被覆顔料種と分散剤の量とを、表4のように変更して、顔料分散液11、12を得た。ただし顔料分散液11における被覆顔料2と被覆顔料8の使用量の比は、83:17とし、顔料分散液12における被覆顔料2と被覆顔料8の使用量の比は63:37とし、合計の顔料相当分が45部となるように配合した。
顔料とともに分散液に使用されることになる被覆高分子の量も表4に記した。 (Preparation of pigment dispersion)
With a composition of Dispersic byk161 (manufactured by BYK Chemie) 7.0 parts as a dispersant and 200 parts of solvent: propylene glycol methyl ether acetate with respect to 35 parts of the pigment equivalent of the coated pigment 8, 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 mmφ zirconia beads. It was.
Similarly, the pigment dispersions 11 and 12 were obtained by changing the coating pigment type and the amount of the dispersant as shown in Table 4. However, the ratio of the usage amount of the coating pigment 2 and the coating pigment 8 in the pigment dispersion 11 is 83:17, and the ratio of the usage amount of the coating pigment 2 and the coating pigment 8 in the pigment dispersion 12 is 63:37. The amount corresponding to the pigment was 45 parts.
The amount of coating polymer to be used in the dispersion along with the pigment is also listed in Table 4.
得られた顔料分散液11又は12にさらに以下の組成の成分を添加し、撹拌混合して本発明の硬化性組成物(カラーレジスト液)を調製した。
・(B)アルカリ可溶性樹脂:ベンジルメタクリレートとメタクリル酸(=70/30[モル比])との共重合体 重量平均分子量=8,000(45質量%濃度のプロピレングリコール物メチルエーテル溶液) 19.09部
・(C)重合性化合物:日本化薬(株)製 カヤラッドDPHA 35.75部
・(D)重合開始剤:(上記オキシム1、3、4および下記オキシム2:表5中、オキシムの「種」の欄に1~4と記載) 10.88部
・(E)重合開始剤:2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール 7.25部
・(F)多官能エポキシ化合物:DIC(株)製エピクロン695 3.75部
・ジエチルアミノベンゾフェノン 2.00部
・N-フェニルメルカプトベンズイミダゾール 1.88部
・界面活性剤:DIC(株)製 メガファックF-781F 0.21部
・溶剤(プロピレングリコールメチルエーテルアセテート/エチルエトキシプロピオネート=8/2) 400.0部 (Example 17)
Components of the following composition were further added to the obtained pigment dispersion 11 or 12, and the mixture was stirred and mixed to prepare the curable composition (color resist solution) of the present invention.
(B) Alkali-soluble resin: copolymer of benzyl methacrylate and methacrylic acid (= 70/30 [molar ratio]) Weight average molecular weight = 8,000 (45% by mass propylene glycol methyl ether solution) 09 parts. (C) Polymerizable compound: Nippon Kayaku Co., Ltd. Kayarad DPHA 35.75 parts. (D) Polymerization initiator: (Oxime 1, 3, 4 and oxime 2 below: In Table 5, 10.88 parts ・ (E) Polymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 7.25 parts · (F) polyfunctional epoxy compound: DIC Corporation Epicron 695 3.75 parts · diethylaminobenzophenone 2.00 parts · N-phenylmercaptobenzimidazole 8 parts Surfactant: DIC (Ltd.) Megafac F-781F 0.21 parts Solvent (propylene glycol methyl ether acetate / ethyl ethoxypropionate = 8/2) 400.0 parts
特許第3264364号公報記載の方法でTFT基板を作成した。即ち、アクティブマトリクス基板に、ゲート信号線並びに付加容量電極を形成し、この上にゲート絶縁膜を形成し、半導体層、及びチャネル保護層を形成し、TFTのソース、及びドレインとなるn+Si層を形成した。 (Creation of TFT substrate)
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.
被覆顔料2の調製でPigment Green 36の代わりに、Pigment Green 58(DIC社製)を用いて、他は被覆顔料2の調製と同様にして被覆顔料9を調製した。
被覆顔料9の被覆度の評価は、被覆顔料1の評価と同様の方法で行った。被覆顔料9は、20質量%以下の遊離量を示し、被覆された顔料であることがわかった。 (Preparation of coated pigment 9)
A coated pigment 9 was prepared in the same manner as the coated pigment 2 except that Pigment Green 58 (manufactured by DIC) was used instead of Pigment Green 36 in the preparation of the coated pigment 2.
Evaluation of the coating degree of the coated pigment 9 was performed in the same manner as the evaluation of the coated pigment 1. The coated pigment 9 showed a free amount of 20% by mass or less, and was found to be a coated pigment.
被覆顔料9の顔料相当分35部に対し、分散剤としてディスパービックbyk161(ビックケミー社製)7.0部、溶剤:プロピレングリコールメチルエーテルアセテート 200部の組成にて、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、混合溶液を調製し、さらに0.1mmφジルコニアビーズを用いたビーズ分散機ウルトラアペックスミル(寿工業社製)にて6時間分散処理を行なった。
同様に、被覆顔料種と分散剤の量とを、表7のように変更して、顔料分散液13、14を得た。ただし顔料分散液13における被覆顔料9と被覆顔料8の使用量の比は83:17とし、顔料分散液14における被覆顔料9と被覆顔料8の使用量の比は63:37とし、合計の顔料相当分が45部となるように配合した。
顔料とともに分散液に使用されることになる被覆高分子の量も表7に記した。 (Preparation of pigment dispersion)
With a composition of Dispersic byk161 (manufactured by Big Chemie) 7.0 parts as a dispersant and 200 parts of solvent: propylene glycol methyl ether acetate with respect to 35 parts of the pigment equivalent of the coated pigment 9, 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 mmφ zirconia beads. It was.
Similarly, the pigment dispersions 13 and 14 were obtained by changing the coating pigment type and the amount of the dispersant as shown in Table 7. However, the ratio of the usage amount of the coating pigment 9 and the coating pigment 8 in the pigment dispersion 13 is 83:17, and the ratio of the usage amount of the coating pigment 9 and the coating pigment 8 in the pigment dispersion 14 is 63:37. The corresponding amount was 45 parts.
The amount of coating polymer to be used in the dispersion along with the pigment is also listed in Table 7.
得られた顔料分散液13、14にさらに以下の組成の成分を添加し、撹拌混合して本発明の硬化性組成物(カラーレジスト液)を調製した。
・(B)アルカリ可溶性樹脂:ベンジルメタクリレートとメタクリル酸(=70/30[モル比])との共重合体 重量平均分子量=8,000(45質量%濃度のプロピレングリコール物メチルエーテル溶液) 19.09部
・(C)重合性化合物:日本化薬(株)製 カヤラッドDPHA 35.75部
・(D)重合開始剤:上記オキシム1~4 10.88部
(表8中、オキシムの「種」の欄に1~4と記載)
・(E)重合開始剤:2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール 7.25部
・(F)多官能エポキシ化合物:DIC(株)製エピクロン695 3.75部
・ジエチルアミノベンゾフェノン 2.00部
・N-フェニルメルカプトベンズイミダゾール 1.88部
・界面活性剤:DIC(株)製 メガファックF-781F 0.21部
・溶剤(プロピレングリコールメチルエーテルアセテート/エチルエトキシプロピオネート=8/2) 400.0部 (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.
(B) Alkali-soluble resin: copolymer of benzyl methacrylate and methacrylic acid (= 70/30 [molar ratio]) Weight average molecular weight = 8,000 (45% by mass propylene glycol methyl ether solution) 09 parts. (C) Polymerizable compound: Nippon Kayaku Co., Ltd. Kayrad DPHA 35.75 parts. (D) Polymerization initiator: 10.88 parts of the above oxime (in Table 8, “Species” of oxime) 1 to 4 in the column)
(E) Polymerization initiator: 7.25 parts of 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (F) Polyfunctional epoxy compound: DIC Corporation ) Epiklon 695 3.75 parts ・ Diethylaminobenzophenone 2.00 parts ・ N-phenylmercaptobenzimidazole 1.88 parts ・ Surfactant: DIC Corporation Megafac F-781F 0.21 part ・ Solvent (propylene glycol) Methyl ether acetate / ethyl ethoxypropionate = 8/2) 400.0 parts
顔料分散液1~10および15の調製において、それぞれ分散剤をディスパービックbyk161(ビックケミー社製)に変更した以外は、顔料分散液1~10および15の調製と同様にして、顔料分散液16~26を調製した。 (Preparation of pigment dispersions 16 to 26)
In the preparation of pigment dispersions 1 to 10 and 15, pigment dispersions 16 to 15 were prepared in the same manner as in pigment dispersions 1 to 10 and 15, except that the dispersant was changed to Dispersic byk161 (manufactured by Big Chemie). 26 was prepared.
得られた顔料分散液16~26を、顔料分散液1と同様にして、0.02μm未満、および0.08μmを超える粒子サイズの粒子の占める割合を、評価し、個数%で表10に示した。顔料分散液16~26の顔料使用量、被覆高分子の量、および分散剤の量も表10に示す。 (Evaluation of pigment dispersions 16 to 26)
The obtained pigment dispersions 16 to 26 were evaluated in the same manner as in the pigment dispersion 1, and the proportion of particles having a particle size of less than 0.02 μm and more than 0.08 μm was evaluated. It was. Table 10 also shows the amount of pigment used in the pigment dispersions 16 to 26, the amount of coating polymer, and the amount of dispersant.
実施例1の硬化性組成物の組成において、顔料の種類と量、アルカリ可溶性樹脂の量、重合性化合物の量、重合開始剤の種類と量、および多官能エポキシ化合物の量を表11のように変更して、実施例34~49、比較例9~14の硬化性組成物を調整した。 (Adjustment of the curable compositions of Examples 34 to 49 and Comparative Examples 9 to 14)
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 11. The curable compositions of Examples 34 to 49 and Comparative Examples 9 to 14 were prepared.
実施例16において、顔料分散液16を顔料分散液26とした以外は、実施例1と同様にして硬化性組成物を調整した。 (Adjustment of the curable composition of Comparative Example 15)
In Example 16, a curable composition was prepared in the same manner as in Example 1 except that the pigment dispersion 16 was changed to the pigment dispersion 26.
実施例16において、顔料分散液16を顔料分散液25とした以外は、実施例1と同様にして硬化性組成物を調整した。 (Comparative Example 16)
A curable composition was prepared in the same manner as in Example 1 except that the pigment dispersion 16 was changed to the pigment dispersion 25 in Example 16.
実施例16において、(F)多官能エポキシ化合物 エピクロン695をEHPE-3150(ダイセル化学工業社製、多官能エポキシ樹脂)に変更して硬化性組成物を調整した。 (Adjustment of the curable composition of Example 50)
In Example 16, (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.
得られた実施例34~50、比較例9~16の硬化性組成物を用いて実施例1と同様にして以下の評価を行い、結果を表12にまとめた。 (Evaluation of Examples 34 to 50 and Comparative Examples 9 to 16)
Using the obtained curable compositions of Examples 34 to 50 and Comparative Examples 9 to 16, the following evaluation was performed in the same manner as in Example 1, and the results are summarized in Table 12.
Claims (7)
- (A)着色剤、(B)アルカリ可溶性樹脂、(C)光重合性化合物、(D)ヘキサアリールビイミダゾール系重合開始剤、(E)オキシム系開始剤並びにトリアジン系開始剤から選択される1種以上、及び(F)4官能以上の多官能エポキシ化合物を含み、
全固形分に対する該(F)多官能エポキシ化合物の含有量が2~20質量%の範囲であり、且つ、該(A)着色剤の含有量が25~50質量%の範囲である硬化性組成物。 1 selected from (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a hexaarylbiimidazole polymerization initiator, (E) an oxime initiator, and a triazine initiator. A polyfunctional epoxy compound having at least a species and (F) tetrafunctional or higher,
A curable composition in which the content of the (F) polyfunctional epoxy compound is in the range of 2 to 20% by mass and the content of the (A) colorant is in the range of 25 to 50% by mass with respect to the total solid content object. - 前記(F)多官能エポキシ化合物が、下記一般式(I)で表される化合物である請求項1に記載の硬化性組成物。
- 前記(D)ヘキサアリールビイミダゾール系重合開始剤が,下記一般式(II)、または一般式(III)で表される重合開始剤である請求項1に記載の硬化性組成物。
- 前記(A)着色剤が、下記一般式(IV)で示される顔料、C.I.Pigment Green 36、及び、C.I.Pigment Green 7から選択される顔料であって、該顔料の全量中、一次粒子サイズ0.02μm未満の粒子が10質量%未満であり、且つ、一次粒子サイズ0.08μmを超える粒子が5質量%未満である顔料である請求項1記載の硬化性組成物。
- 更に前記(A)着色剤が、C.I.Pigment Green 58を含む顔料であって、該顔料の全量中、一次粒子サイズ0.02μm未満の粒子が、10質量%未満であり、且つ、一次粒子サイズ0.08μmを超える粒子が、5質量%未満である顔料である請求項1記載の硬化性組成物。 Further, the colorant (A) is C.I. I. Pigment Green 58, and in the total amount of the pigment, particles having a primary particle size of less than 0.02 μm are less than 10% by mass, and particles having a primary particle size of more than 0.08 μm are 5% by mass. The curable composition according to claim 1, wherein the curable composition is a pigment that is less than a pigment.
- 前記(A)着色剤が、樹脂で被覆された顔料である請求項1に記載の硬化性組成物。 The curable composition according to claim 1, wherein the colorant (A) is a pigment coated with a resin.
- TFT基板上に直接又は他の層を介して形成された各着色画素上に直接もしくは他の層(液晶層を除く)を介して画素電極が形成されているカラーフィルタにおいて、前記各着色画素は、請求項1に記載の硬化性組成物により形成されているカラーフィルタ。 In the color filter in which the pixel electrode is formed directly or via another layer (excluding the liquid crystal layer) on each colored pixel formed directly on the TFT substrate or via another layer, each colored pixel is A color filter formed of the curable composition according to claim 1.
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CN1529833A (en) * | 2001-05-15 | 2004-09-15 | 昭和电工株式会社 | Photosensitive coloring composition, colour filter using said composition and production method thereof |
JP2004045697A (en) * | 2002-07-11 | 2004-02-12 | Sumitomo Chem Co Ltd | Colored photosensitive resin composition |
JP2004109423A (en) * | 2002-09-18 | 2004-04-08 | Sumitomo Chem Co Ltd | Color photosensitive resin composition |
JP4338479B2 (en) * | 2003-09-04 | 2009-10-07 | 富士フイルム株式会社 | Color filter and manufacturing method thereof |
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2009
- 2009-03-02 JP JP2009047752A patent/JP2010024434A/en not_active Abandoned
- 2009-03-02 KR KR1020107018620A patent/KR20100131437A/en not_active Application Discontinuation
- 2009-03-02 WO PCT/JP2009/053888 patent/WO2009110434A1/en active Application Filing
- 2009-03-02 CN CN200980107350.5A patent/CN101959923B/en not_active Expired - Fee Related
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JPH10186124A (en) * | 1996-12-24 | 1998-07-14 | Mitsubishi Chem Corp | Resist composition for color filter and color filter |
JP2000249826A (en) * | 1999-03-03 | 2000-09-14 | Jsr Corp | Radioactivity sensitive composition for color filter |
JP2004246105A (en) * | 2003-02-14 | 2004-09-02 | Fuji Photo Film Co Ltd | Dye-containing hardening composition, color filter and its manufacturing method |
JP2006028455A (en) * | 2004-07-21 | 2006-02-02 | Fujifilm Electronic Materials Co Ltd | Curable resin composition, resin film for color filter by using the same and color filter |
JP2007047756A (en) * | 2005-07-12 | 2007-02-22 | Fujifilm Electronic Materials Co Ltd | Photocurable composition, color filter, and method for producing same |
JP2007041082A (en) * | 2005-07-29 | 2007-02-15 | Fujifilm Holdings Corp | Photosensitive resin composition for liquid crystal display element, color filter using same and method for producing same, and lcd display device |
JP2007128060A (en) * | 2005-10-04 | 2007-05-24 | Fujifilm Electronic Materials Co Ltd | Photocurable composition and color filter obtained by using the same |
JP2007249117A (en) * | 2006-03-20 | 2007-09-27 | Nippon Steel Chem Co Ltd | Resin composition for color filter and color filter |
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CN102033427A (en) * | 2009-09-30 | 2011-04-27 | 富士胶片株式会社 | Colored photosensitive resin composition for ultraviolet laser, pattern forming method, color filter, method for manufacturing color filter, and display device |
Also Published As
Publication number | Publication date |
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KR20100131437A (en) | 2010-12-15 |
CN101959923A (en) | 2011-01-26 |
JP2010024434A (en) | 2010-02-04 |
CN101959923B (en) | 2013-01-23 |
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