Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/201—Filters in the form of arrays
• • 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
  • C08K5/0091—Complexes with metal-heteroatom-bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B47/00—Porphines; Azaporphines
  • C09B47/04—Phthalocyanines abbreviation: Pc
  • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
  • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
  • C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B47/00—Porphines; Azaporphines
  • C09B47/04—Phthalocyanines abbreviation: Pc
  • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
  • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
  • C09B47/0676—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having nitrogen atom(s) linked directly to the skeleton
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/30—Coordination compounds
  • H10K85/311—Phthalocyanine
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/30—Devices specially adapted for multicolour light emission
  • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

• the present invention relates to a colored curable composition and a color filter using the colored curable composition. Furthermore, it is related with the liquid crystal display device, organic electroluminescent element, and solid-state image sensor which used this color filter. Moreover, it is related with the manufacturing method of a color filter.
• color filters are colored curable compositions by containing a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components as necessary. It is manufactured by forming a colored pattern by using a photolithography method, an ink jet method or the like.
• color filters are used not only for monitors but also for televisions (TV) in liquid crystal display (LCD) applications, and there is a demand for lower power consumption as well as larger screens and higher image quality.
• color filters are required to have advanced color characteristics such as chromaticity, contrast, and high transmittance.
• color filters for image sensors solid-state imaging devices are required to further improve color characteristics, such as reduction of color unevenness, improvement of color resolution, and transmittance.
• dyes compounds having a wide variety of pigment bases such as phthalocyanine dyes, dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes are known (see, for example, Patent Documents 2 to 7).
• the colored curable composition used for a color filter or the like is required to have high color purity and no absorption (high transmittance) in an unnecessary part as a color filter. Moreover, high heat resistance and light resistance are also required.
• the present invention aims to reconcile such problems, and is a colored curable composition capable of producing a color filter having high heat resistance and light resistance without absorption in unnecessary portions as a color filter. The purpose is to provide goods. In particular, it is an object to provide a useful thing as a colored material for a green filter.
• a colored curable composition having high transmittance and excellent light resistance can be obtained by using a halogen-substituted phthalocyanine compound having a specific substituent.
• a halogen-substituted phthalocyanine compound having a specific substituent I found.
• the solubility is improved and aggregation between compounds can be suppressed, and the transmittance is improved while maintaining heat resistance and light resistance. I succeeded in making it happen.
• the present inventors have found that pattern formability can be improved and have completed the present invention. In particular, it has been found that when blended with a carboxylic acid binder, a remarkable effect is exhibited.
• a colored curable composition containing a phthalocyanine compound represented by the following general formula (1) A colored curable composition containing a phthalocyanine compound represented by the following general formula (1).
• General formula (1) (In the general formula (1), R 1 to R 4 are each a substituent represented by the following general formula (2) or a halogen atom, and p, q, r, and s are each 0 to In the general formula (1), the number of substituents represented by the general formula (2) is 1 to 12. R represents a hydrogen atom or a monovalent substituent, and M represents Cu.
• R 13 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• X 1 is —O—
• Ar 1 is an optionally substituted phenylene group
• Y 1 is —O—
• R 12 is an optionally substituted alkyl group.
• X 1 is —O—
• Ar 1 is a phenylene group which may have a substituent
• Y 1 is —C ( ⁇ O) —
• R 12 has a substituent.
• the colored curable composition according to ⁇ 1> or ⁇ 2> which is a good alkoxy group or an alkylamino group which may have a substituent.
• ⁇ 5> The colored curable composition according to any one of ⁇ 1> to ⁇ 4>, wherein the sum of p, q, r and s in the general formula (1) is 12 to 16.
• ⁇ 6> The colored curable composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a carboxylic acid binder.
• ⁇ 7> The colored curable composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a polymerizable compound and a photopolymerization initiator.
• ⁇ 8> The colored curable composition according to ⁇ 7>, wherein the photopolymerization initiator is an oxime compound or a biimidazole compound.
• ⁇ 9> The colored curable composition according to any one of ⁇ 1> to ⁇ 8>, further comprising a yellow colorant.
• ⁇ 10> The colored curable composition according to ⁇ 9>, wherein the yellow colorant is an azo dye or a monomethine dye.
• R 1 to R 4 are each a substituent, a bromine atom, or a chlorine atom represented by the following general formula (2 ′), and p, q, r, and s are: Each represents 0 to 4, and the sum of p, q, r, and s is 12 to 16.
• the number of substituents represented by the general formula (2 ′) in the general formula (1 ′) is 4 to 12 R represents a hydrogen atom, and M represents Cu or Zn.
• General formula (2 ') (In the general formula (2 ′), X 1 represents —O—, Ar 1 represents a phenylene group, R 11 represents a hydrogen atom or a methyl group, n1 represents an integer of 1 to 3, and n1 represents 2 Or a plurality of R 11 may be the same or different in the case of 3.
• Y 1 represents —O—
• R 12 represents an alkyl group or an acyl group, and Y 1 represents —C ( ⁇ O) —.
• R 12 is an alkoxy group or an alkylamino group.
• ⁇ 14> Applying the colored curable composition according to any one of ⁇ 1> to ⁇ 13> on a substrate to form a colored layer, exposing the formed colored layer in a pattern, and developing And a step of forming a colored region.
• a liquid crystal display device, an organic electroluminescence element, or a solid-state imaging device having the color filter according to ⁇ 13> or the color filter produced by the method for producing a color filter according to ⁇ 14>.
• General formula (1 ') (In the general formula (1 ′), R 1 to R 4 are each a substituent, a bromine atom, or a chlorine atom represented by the following general formula (2 ′), and p, q, r, and s are: Each represents 0 to 4, and the sum of p, q, r, and s is 12 to 16.
• the number of substituents represented by the general formula (2 ′) in the general formula (1 ′) is 4 to 12 R represents a hydrogen atom, and M represents Cu or Zn.
• General formula (2 ') (In the general formula (2 ′), X 1 represents —O—, Ar 1 represents a phenylene group, R 11 represents a hydrogen atom or a methyl group, n1 represents an integer of 1 to 3, and n1 represents 2 Or a plurality of R 11 may be the same or different in the case of 3.
• Y 1 represents —O—
• R 12 represents an alkyl group or an acyl group, and Y 1 represents —C ( ⁇ O) —.
• R 12 is an alkoxy group or an alkylamino group.
• the present invention it is possible to provide a colored curable composition having high color purity, no absorption in a portion unnecessary as a color filter (high transmittance), and excellent light resistance. Therefore, it can be preferably used as a color filter, particularly as a green color filter. Furthermore, according to the present invention, it is possible to provide a liquid crystal display device and a solid-state imaging device in which the display image is vividly colored and exhibits high contrast.
• the colored curable composition of the present invention is characterized by containing a phthalocyanine compound represented by the general formula (1).
• a phthalocyanine compound represented by the general formula (1) Usually, two or more types of phthalocyanine compounds represented by the general formula (1) are included.
• General formula (1) (In the general formula (1), R 1 to R 4 are each a substituent represented by the following general formula (2) or a halogen atom, and p, q, r, and s are each 0 to In the general formula (1), the number of substituents represented by the general formula (2) is 1 to 12.
• R represents a hydrogen atom or a monovalent substituent
• M represents Cu.
• R 11 When n1 is 2 or 3, A plurality of R 11 may be the same or different, Y 1 represents —O—, —S—, —N—R 13 —, —SO 2 —, or —C ( ⁇ O) —, and R 12 represents one Represents a valent substituent.
• the ratio of the minimum value of the absorption intensity around 500 nm to the maximum value of the main absorption is 0 to 0.1. It is preferably in the range, and more preferably in the range of 0 to 0.02.
• the phthalocyanine compound represented by the general formula (1) used in the present invention is a mixture of two or more types, p, q, r, s and a substituent represented by the general formula (2) in the general formula (1)
• the number of means the average value of the substituents in the mixture.
• R 1 to R 4 are each a substituent represented by the general formula (2) or a halogen atom.
• the halogen atom is preferably a bromine atom or a chlorine atom, and the halogen atom is preferably a bromine atom or a chlorine atom, and particularly preferably a chlorine atom.
• the substitution position of the halogen atom is the ⁇ -position of the phthalocyanine skeleton, the absorption wavelength becomes long wave, which can be suitably used for a green filter.
• the number of substitutions at the ⁇ -position is preferably 4 to 8 as the total number of ⁇ -positions in the phthalocyanine.
• R represents a hydrogen atom or a monovalent substituent, respectively.
• substituents include a substituent T described later, preferably an alkyl group or an alkoxy group, and more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
• R is particularly preferably a hydrogen atom, a methyl group or a methoxy group, and more preferably a hydrogen atom.
• M represents Cu, Zn, V ( ⁇ O), Mg, Ni, Ti ( ⁇ O), Mg, Sn or Si, preferably Cu, Zn or V ( ⁇ O), particularly preferably Cu or Zn is represented.
• X 1 represents —O—, —S—, —NR 13 — or —SO 2 —, preferably —O— or —SO 2 —, more preferably —O—.
• R 13 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
• Ar 1 represents an aromatic carbocyclic group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and is preferably an aromatic carbocyclic group.
• the aromatic carbocycle is preferably an aryl group having 6 to 24 carbon atoms and represents, for example, a phenylene group or a naphthylene group, and may further have a substituent.
• the aromatic heterocyclic ring is preferably a heterocyclic group having 1 to 18 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl. Group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group and the like, and may further have a substituent. Examples of the substituent include a substituent T described later.
• Ar 1 is more preferably a phenylene group which may have a substituent and a naphthylene group which may have a substituent, and particularly preferably a phenylene group which may have a substituent.
• Ar 1 preferably has no substituent.
• R 11 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
• n1 represents an integer of 1 to 3, more preferably 1 or 2. When n1 is 2 or 3, the plurality of R 11 may be the same or different.
• R 12 represents a monovalent substituent, and examples of the substituent include a substituent T described later, and these substituents may be further substituted with a substituent.
• R 12 is preferably an alkyl group which may have a substituent, an acyl group which may have a substituent, a sulfonyl group which may have a substituent, an alkoxy group which may have a substituent, Or an alkylamino group which may have a substituent, more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 12 carbon atoms which may have a substituent. And an alkylamino group having 1 to 12 carbon atoms which may have a substituent.
• the mass of the R 12 moiety per molecule of the phthalocyanine compound represented by the general formula (1) is preferably 200 to 2500, and more preferably 250 to 1500.
• An alkyl group preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having a carbon number of 2 to 18 alkenyl groups such as vinyl group, allyl group, 3-buten-1-yl group), aryl groups (preferably aryl groups having 6 to 24 carbon atoms such as phenyl group, naphthyl group), heterocyclic ring Group (preferably a heterocyclic
• Alkylthio group for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably arylthio group having 6 to 24 carbon atoms, for example, phenylthio group), heterocyclic thio group (preferably having carbon number) 1 to 18 heterocyclic thio groups such as 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably alkylsulfinyl group having 1 to 24 carbon atoms) For example, dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 2 carbon atoms) 4 arylsulfinyl groups such as phenylsulfinyl group, alkylsulfonyl groups (preferably alkylsulfonyl groups having
• phosphonyl group preferably phosphonyl group having 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, Phenylphosphonyl group
• a phosphinoylamino group preferably a phosphinoylamino group
• an alkaline aqueous solution solubilized part for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonimide group, a phenolic hydroxyl group, an acetoacetamide group, an acetoacetate group
• Substituents such as alkyl groups, alkyloxy groups, alkylthio groups, aryloxy groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups and the like in which these groups are substituted are preferably used.
• X 1 is —O—
• Ar 1 is a phenylene group which may have a substituent
• Y 1 is —C ( ⁇ O) —
• R 12 is an alkoxy which may have a substituent.
• the phthalocyanine compound represented by the general formula (1) in the present invention is preferably a phthalocyanine compound represented by the following general formula (1 ′).
• General formula (1 ') (In the general formula (1 ′), R 1 to R 4 are each a substituent, a bromine atom, or a chlorine atom represented by the following general formula (2 ′), and p, q, r, and s are: Each represents 0 to 4, and the sum of p, q, r, and s is 12 to 16.
• the number of substituents represented by the general formula (2 ′) in the general formula (1 ′) is 4 to 12 R represents a hydrogen atom, and M represents Cu or Zn.
• General formula (2 ') (In the general formula (2 ′), X 1 represents —O—, Ar 1 represents a phenylene group, R 11 represents a hydrogen atom or a methyl group, n1 represents an integer of 1 to 3, and n1 represents 2 Or a plurality of R 11 may be the same or different in the case of 3.
• Y 1 represents —O—
• R 12 represents an alkyl group or an acyl group, and Y 1 represents —C ( ⁇ O) —.
• R 12 is an alkoxy group or an alkylamino group.
• the preferred range of each group of the general formula (1 ′) is the same as that of the general formula (1).
• the molecular weight of the phthalocyanine compound represented by the general formula (1) is preferably 900 to 4000, more preferably 1000 to 2500.
• the phthalocyanine compound can be synthesized according to the methods described in “Issued by Phthalocyanine, Inc. as a functional dye”, “Phthalocyanine—Chemistry and Function—Issued by IPC,” and the like.
• the compound of the present invention is a halogenated phthalocyanine, it can be synthesized by cyclizing a halide intermediate as described below to synthesize phthalocyanine or halogenating a phthalocyanine compound.
• the phthalocyanine of the present invention generally gives a complex mixture for the following reasons.
• the synthetic intermediate A of the phthalocyanine of the present invention is a mixture
• phthalocyanine is synthesized by using phthalonitrile, phthalic anhydride, or phthalimide as an intermediate and cyclizing them.
• the substituent may be introduced at either the ⁇ -position or ⁇ -position of the halogenated phthalonitrile, and when one is introduced, ⁇ 1 or ⁇ 1 is introduced.
• a mixture such as ⁇ 1- ⁇ 1, ⁇ 1- ⁇ 2, ⁇ 1- ⁇ 2, ⁇ 1- ⁇ 2 is given.
• the ratio of those introduced at the ⁇ -position is preferably high. Specifically, it is preferable that four or more of the eight ⁇ -positions have a substituent represented by the general formula (2).
• the phthalocyanine compound is a mixture having different substitution positions and substitution numbers, it is difficult to uniquely describe it as a structural formula. Further, the number of substitutions shown in the following table is a value obtained by approximating the average value of the number of substituents in the mixture, and may be a small number. Examples of the phthalocyanine compound used in the present invention will be given below, but the present invention is not limited thereto.
• the content of the phthalocyanine compound represented by the general formula (1) in the colored curable composition varies depending on the molecular weight and its extinction coefficient, but is 1 to 70 with respect to the total solid content of the colored curable composition. % By mass is preferable, and 10 to 50% by mass is more preferable. When the dye content is 10% by mass or more, a good color density (for example, a color density suitable for liquid crystal display) can be obtained, and when it is 50% by mass or less, pixel patterning becomes good. Is advantageous.
• the colored curable composition of the present invention may contain dye compounds and pigment compounds having other structures and dispersions thereof.
• the dye compound may have any structure as long as it does not affect the hue of the colored image.
• azo for example, Solvent Yellow 162
• anthraquinone for example, JP-A-2001-10881.
• Anthraquinone compounds phthalocyanine compounds
• xanthene compounds for example, CI Acid.
• pigment compounds include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, Indigo, thioindigo, isoindoline, isoindolinone, pyranthrone, isoviolanthrone and the like.
• perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, perinone compound pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, and Pigment Violet. 42, quinacridone such as Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 207, or Pigment Red 209, quinacridone compound pigment, Pigment Red 206, Pigment Orange 48, or Pigment Orange 49 Quinone compound pigment, anthraquinone compound pigment such as pigment yellow 147, anthanthrone compound pigment such as pigment red 168, pigment Benzimidazolone compound pigments such as Pigment Brown 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185; Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144
• the colorant is preferably a yellow colorant, more preferably pigment yellow 150 or pigment yellow 139, and a preferred dye is C.I. I. Solvent Yellow 4, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 93.
• the yellow colorant is preferably a monomethine dye, and the yellow colorant is more preferably a monomethine dye represented by the following general formula (5).
• R 11 represents an alkyl group or a vinyl group, and R 12 represents an aromatic ring group having a substituent.
• R 11 is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
• R 12 is preferably a phenyl group or a naphthyl group, and the substituent is preferably an alkylsulfonylamino group, a vinylsulfonylamino group, an arylsulfonylamino group, an alkylcarbonylamino group, a vinylcarbonylamino group, or an arylcarbonylamino group.
• An alkylsulfonylamino group is preferred.
• the alkyl group having 1 to 12 carbon atoms may have an unsaturated bond, and examples of such a substituent include an allylsulfonylamino group.
• the dye or pigment When the dye or pigment is blended as a dispersion, it can be adjusted according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.
• the content of the dye or pigment can be used within a range that does not impair the effects of the present invention, and is 0.5% by mass to 70% by mass with respect to the total solid content of the colored curable composition of the present invention. preferable. Further, it is preferably added to the colored curable composition so that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05.
• the colored curable composition of the present invention preferably contains at least one polymerizable compound.
• the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.
• a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention.
• These may be in any chemical form such as, for example, monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.
• Examples of monomers and their (co) polymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (co) polymers It is a polymer.
• unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
• esters amides
• these (Co) polymers preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (co) polymers It is a polymer
• a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
• an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
• an ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetra Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tria Relate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate,
• methacrylic acid esters examples include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol.
• itaconic acid esters for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol Diitaconate, sorbitol tetritaconate, etc., and crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, etc.
• ethylene glycol diisocrotonate pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc.
• ethylene glycol dimaleate triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetra malate, and the like.
• esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are preferably used.
• the ester monomers described above can also be used as a mixture.
• amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
• examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.
• urethane-based addition-polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl group.
• Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
• Vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Compounds and the like.
• CH 2 C (R) COOCH 2 CH (R ′) OH (A) [In General Formula (A), R and R ′ each independently represent H or CH 3 . ]
• the structure, details of usage such as single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the colored curable composition.
• a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable.
• those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) are used in combination.
• a method of adjusting both sensitivity and intensity is also effective.
• the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the colored curable composition.
• the method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination.
• a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.
• the content of the polymerizable compound in the total solid content of the colored curable composition is not particularly limited, and is 10 from the viewpoint of more effectively obtaining the effects of the present invention.
• % By mass to 80% by mass is preferable, 15% by mass to 75% by mass is more preferable, and 20% by mass to 60% by mass is particularly preferable.
• the colored curable composition of the present invention preferably contains at least one photopolymerization initiator.
• the photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
• the photopolymerization initiator examples include at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like.
• Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116. Among these, an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.
• the oxime compound (hereinafter also referred to as “oxime-based photopolymerization initiator”) is not particularly limited, and is described in, for example, JP-A No. 2000-80068, WO 02 / 100903A1, and JP-A No. 2001-233842. These oxime compounds are mentioned.
• the compound represented by the following general formula (1) is more preferable as the oxime compound from the viewpoints of sensitivity, time stability, and coloring during post-heating.
• R and X each represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n represents an integer of 1 to 5. .
• R is preferably an acyl group from the viewpoint of high sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.
• A is an unsubstituted alkylene group, an alkylene group substituted with an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating,
• An alkylene group substituted with an alkenyl group for example, vinyl group, allyl group
• aryl group for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group
• a substituted alkylene group is preferred.
• Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating.
• the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
• X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region.
• An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable.
• n is preferably an integer of 1 to 2.
• biimidazole compound there is no limitation on the structure as long as it is a dimer of an imidazole ring substituted with three aryl groups.
• general formula (II) or general formula (III) Compounds having the structure represented are preferred.
• 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 1 to 12 carbon atoms.
• a substituted or unsubstituted alkoxy group having the formula: 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 is 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 do not take a hydrogen atom at the same time.
• biimidazole compound examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4- Phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2 , 4-Dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6
• 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (commercially available products are B-CIM, manufactured by Hodogaya Chemical Co., Ltd.).
• 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) biimidazole (HABI1311, Nippon Sebel Hegner)
• 2,2 Examples include '-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole (commercially available from Kurokin Kasei Co., Ltd.).
• a photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
• the content of the photopolymerization initiator in the total solid content of the colored curable composition (total content in the case of two or more types) is 3% by mass to 20% by mass from the viewpoint of more effectively obtaining the effects of the present invention. %, More preferably 4% by mass to 19% by mass, and particularly preferably 5% by mass to 18% by mass.
• the colored curable composition of the present invention can contain at least one organic solvent.
• the organic solvent is basically not particularly limited as long as it can satisfy the solubility of each of the coexisting components and the coating property when the colored curable composition is used, and in particular, the solubility of the binder, the coating property, It is preferable to select in consideration of safety.
• organic solvent examples include esters, ethers, ketones, and aromatic hydrocarbons, and specific examples include those described in paragraph numbers 0161 to 0162 of JP2012-032754A.
• ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether.
• ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
• aromatic hydrocarbons include toluene and xylene.
• organic solvents are preferably mixed in two or more types from the viewpoints of the solubility of each of the above-mentioned components and, when an alkali-soluble polymer is included, the solubility of the components and the improvement of the coated surface.
• the content of the organic solvent in the colored curable composition is preferably such that the total solid concentration in the composition is 10% by mass to 80% by mass, more preferably 15% by mass to 60% by mass. .
• the colored curable composition of the present invention preferably contains an alkali-soluble binder.
• the alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
• the alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent and developable with a weak alkaline aqueous solution.
• linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.
• the alkali-soluble binder in the present invention includes those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth)). Acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers.
• Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include chain butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.
• hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.
• the alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain.
• Polymers and the like are also useful.
• examples of the above-mentioned polymer containing a polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like.
• alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful.
• polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control.
• acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control.
• acrylic resin examples include a copolymer composed of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a commercially available KS resist 106 ( Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (Daicel Chemical Industries, Ltd.) are preferred.
• the alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by the GPC method) of 1000 to 2 ⁇ 10 5 , and a weight of 2000 to 1 ⁇ 10 5 in terms of developability and liquid viscosity. Polymers are more preferred, and polymers of 5000 to 5 ⁇ 10 4 are particularly preferred.
• the blending amount of the alkali-soluble binder is preferably 10 to 80% by mass, more preferably 20 to 60% by mass based on the total solid content.
• the colored curable composition of the present invention can be supplemented with a crosslinking agent to further increase the hardness of the colored cured film obtained by curing the colored curable composition.
• the crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction.
• at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
• the colored curable composition of the present invention may contain a surfactant.
• the surfactant may be any of nonionic, cationic, or anionic, and a fluorine-containing surfactant is preferable.
• JP-A-2-54202 is exemplified.
• the blending amount of the surfactant in the present invention is preferably 0.0001 to 0.1% by mass of the total solid content.
• the colored curable composition of the present invention may further contain various additives such as a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a sensitizer and a light stabilizer, as necessary.
• the colored curable composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
• the components constituting the colored curable composition may be combined at once, or may be sequentially added after each component is dissolved and dispersed in a solvent.
• the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
• the colored curable composition prepared as described above is preferably filtered using a filter having a pore size of about 0.01 ⁇ m to 3.0 ⁇ m, more preferably about 0.05 ⁇ m to 0.5 ⁇ m. Can be used for use.
• the colored curable composition of the present invention can form a colored cured film excellent in hue and contrast
• a color filter used in a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.) It can be suitably used for forming colored pixels such as printing inks, inkjet inks, and paints. In particular, it is suitable for use in forming colored pixels for liquid crystal display devices.
• the color filter of the present invention is configured by providing a substrate and a colored region containing the colored curable composition of the present invention on the substrate.
• the colored region on the substrate is composed of colored films such as red (R), green (G), and blue (B) that form each pixel of the color filter.
• the color filter of the present invention may be formed by any method as long as it can form a colored region (colored pattern) cured by applying the colored curable composition of the present invention onto a substrate. Preferably, it is produced using the colored curable composition of the present invention.
• the above-described colored curable composition is applied (preferably applied) on a substrate to form a colored layer (also referred to as a colored curable composition layer) (A And a step (B) of curing the colored curable composition layer formed in the step (A).
• the curing step is preferably performed in a pattern (preferably through a mask), and the uncured portion of the coating film is developed and removed with a developer to form a colored region (colored pattern).
• a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained.
• the step (C) of irradiating the colored pattern formed in the step (B) with ultraviolet rays and the colored pattern irradiated with the ultraviolet rays in the step (C) are applied.
• the aspect which further provided the process (D) which heat-processes is preferable.
• the substrate for example, alkali-free glass, sodium glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, solid-state imaging elements, and the like are used.
• the photoelectric conversion element substrate include a silicone substrate and a plastic substrate. On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. Further, if necessary, an undercoat layer may be provided on the substrate in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface.
• the plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.
• a driving substrate on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed (hereinafter referred to as “TFT type liquid crystal driving substrate”) is used as the substrate.
• TFT type liquid crystal driving substrate a driving substrate on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed
• a color pattern formed using the colored curable composition of the present invention can be formed to produce a color filter.
• the substrate in the TFT type liquid crystal driving substrate include glass, silicone, 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.
• the colored curable composition of the present invention is applied to the substrate directly or via another layer.
• coating is preferable, and coating is preferably performed by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, and inkjet.
• the method for applying the colored curable composition of the present invention to the 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, Slit nozzle coating method) is preferable.
• a slit nozzle coating method such as a slit-and-spin method or a spinless coating method (hereinafter, Slit nozzle coating method) is preferable.
• the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm ⁇ 1250 mm) is coated by the spinless coating method.
• the discharge amount of the colored curable composition from the slit nozzle is usually 500 microliters / second to 2000 microliters / second, preferably 800 microliters / second to 1500 microliters / second.
• the speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
• the solid content of the colored curable composition used in the coating step is usually 10% to 20%, preferably 13% to 18%.
• the thickness of the coating film is generally 0.3 ⁇ m to 5.0 ⁇ m, preferably 0.5 ⁇ m to 4 ⁇ m. It is 0.0 ⁇ m, and most desirably 0.5 ⁇ m to 3.0 ⁇ m.
• the thickness of the coating film is preferably in the range of 0.5 ⁇ m to 5.0 ⁇ m.
• a pre-bake treatment is performed after application.
• vacuum treatment can be performed before pre-baking.
• the vacuum drying conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
• the pre-bake treatment is performed in a temperature range of 50 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C., using a hot plate, an oven, etc., and can be performed under conditions of 10 seconds to 300 seconds.
• high-frequency treatment or the like may be used in combination with the pre-bake treatment.
• the high frequency treatment can be used alone.
• Examples of the pre-baking condition include a condition of heating at 70 to 130 ° C. for about 0.5 to 15 minutes using a hot plate or an oven.
• the thickness of the colored curable composition layer formed from the colored curable composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, the range of 0.2 ⁇ m to 5.0 ⁇ m is preferable, the range of 1.0 ⁇ m to 4.0 ⁇ m is more preferable, and the range of 1.5 ⁇ m to 3.5 ⁇ m is most preferable.
• the range of 0.2 ⁇ m to 5.0 ⁇ m is preferable, the range of 0.3 ⁇ m to 2.5 ⁇ m is more preferable, and the range of 0.3 ⁇ m to 1.5 ⁇ m is most preferable.
• the thickness of the colored curable composition layer is a film thickness after pre-baking.
• the film (colored curable composition layer) formed of the colored curable composition formed on the substrate as described above is exposed through, for example, a photomask. Is done.
• a photomask As light or radiation applicable to exposure, g-line, h-line, i-line, j-line, KrF light and ArF light are preferable, and i-line is particularly preferable.
• i-line is particularly preferable.
• the i-line to the irradiation light is preferably irradiated at an exposure dose of 100mJ / cm 2 ⁇ 10000mJ / cm 2.
• exposure rays include ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light or the like can also be used.
• an ultraviolet laser is used as the light source.
• the irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist. Is preferable.
• the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
• the exposure amount of the object to be exposed is in the range of 1 mJ / cm 2 to 100 mJ / cm 2 , and more preferably in the range of 1 mJ / cm 2 to 50 mJ / cm 2 . An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.
• a color filter for a liquid crystal display device exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine. Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine.
• the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.
• the colored curable composition layer exposed as described above can be heated.
• the exposure can be performed while flowing nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the colored curable composition layer.
• the colored curable composition layer after exposure is developed with a developer.
• a negative type or positive type coloring pattern (resist pattern) can be formed.
• the uncured portion of the coating film after exposure is eluted in the developer, and only the cured portion remains on the substrate.
• Any developer can be used as long as it dissolves the coating film (colored curable composition layer) of the colored curable composition in the uncured portion while not dissolving the cured portion.
• combinations of various organic solvents and alkaline aqueous solutions can be used.
• the organic solvent used for development include the above-described solvents that can be used when preparing the colored curable composition of the present invention.
• alkaline aqueous solution examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl.
• An alkaline compound such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is used at a concentration of 0.001% by mass to 10% by mass, preferably 0.01%.
• Examples thereof include an alkaline aqueous solution dissolved so as to have a mass% to 1 mass%.
• the alkali concentration is preferably adjusted to pH 11 to 13, more preferably pH 11.5 to 12.5.
• 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 temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
• Development 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. It is also possible to prevent development unevenness by previously moistening the surface to be developed with water or the like before touching the developer. It is also possible to develop with the substrate tilted. Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.
• a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
• the rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning, or the substrate is inclined and cleaned. Alternatively, a method of using ultrasonic irradiation together may be used.
• a heat treatment at about 200 ° C. to 250 ° C. is usually performed.
• 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 color filter of the present invention has high contrast, small color density unevenness, and good color characteristics, it can be suitably used for a solid-state imaging device or a liquid crystal display device.
• a post-exposure by ultraviolet irradiation can be performed on a colored pattern (pixel) formed using a colored curable composition.
• the colored pattern can be further cured by subjecting the formed colored pattern to heat treatment (so-called post-bake treatment).
• This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
• the temperature during the heat treatment is preferably 100 ° C. to 300 ° C., more preferably 150 ° C. to 250 ° C.
• the heating time is preferably about 10 minutes to 120 minutes.
• the colored pattern thus obtained constitutes a pixel in the color filter.
• the above steps (A), (B), and if necessary, the steps (C) and (D) are repeated according to the desired number of colors. Good.
• the process (C) and / or the process (D) may be performed every time the formation, exposure, and development of the monochromatic colored curable composition layer is completed (for each color), or a desired color. After the formation, exposure, and development of all the colored curable composition layers are completed, the step (C) and / or the step (D) may be performed collectively.
• the color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in hue and contrast since the colored curable composition of the present invention is used.
• the color filter of the present invention can be used for a liquid crystal display element or a solid-state image sensor, and is particularly suitable for use in a liquid crystal display device. When used in a liquid crystal display device, it is possible to display an image excellent in spectral characteristics and contrast while achieving a good hue using a dye as a colorant.
• the use of the colored curable composition of the present invention has been described mainly focusing on the formation of the color filter color pattern.
• the color curable composition of the present invention is used to form a black matrix that isolates the color pattern (pixels) constituting the color filter. Can also be applied.
• the black matrix on the substrate is a colored curable composition containing a black pigment processed pigment such as carbon black, titanium black, etc., and is subjected to coating, exposure, and development steps. It can be formed by baking.
• the liquid crystal display element and the solid-state image sensor of the present invention are provided with the color filter of the present invention. More specifically, for example, by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and filling the gap with liquid crystal and sealing, a panel which is the liquid crystal display element of the present invention is obtained. .
• the solid-state image sensor of this invention is obtained by forming a color filter on a light receiving element.
• liquid crystal display devices For the definition of liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Sangyo Tosho) Issued in 1989).
• the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
• the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”.
• the color filter of the present invention is particularly effective for a color TFT liquid crystal display device.
• the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
• the present invention is applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
• the color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) system.
• COA Color-filter On Array
• the color filter of the present invention When the color filter of the present invention is used for a liquid crystal display element, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue LED light sources (RGB-LED).
• RGB-LED red, green and blue LED light sources
• Example 1 Each component used for preparation of a colored curable composition is shown below.
• (Y-1) C.I. I. Pigment Yellow 150 (12.8 parts) and methyl methacrylate / methacrylic acid (80/20) [mass ratio] copolymer (weight average molecular weight: 12,000) (7.2 parts) are mixed with propylene glycol monomethyl ether acetate (80.0).
• a pigment dispersion (Y-2) C. obtained by sufficiently dispersing the pigment using a bead mill.
• Photopolymerizable compound Kayalad DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
• ⁇ Preparation of colored film> Preparation of colored curable composition (coating liquid) Components in the following composition were mixed to prepare a colored curable composition 1.
• ⁇ Composition> Exemplary Compound A-1 ... 6.9 parts by mass-(T-1) ... 103.4 parts by mass-(U-1) ... 212.2 parts by mass (in terms of solid content) (Value: 84.9 parts by mass) ⁇ (V-1) ⁇ ⁇ ⁇ 21.2 parts by mass ⁇ (W-1) ⁇ ⁇ ⁇ 3.5 parts by mass ⁇ ⁇ (X-1) ⁇ ⁇ ⁇ 71.9 parts by mass ⁇ (X-2) ... 3.6 parts by mass, (Z-1) ... 0.06 parts by mass
• the colored curable composition (color resist solution) obtained above is placed on a 100 mm ⁇ 100 mm glass substrate (1737, manufactured by Corning) so that the maximum absorbance at 600 to 700 nm is 1.5 to 2.0. And dried in an oven at 100 ° C. for 180 seconds to produce a colored film on the substrate.
• Example 101 Preparation of green colored film (Preparation of colored curable composition (coating solution)) Components in the following composition were mixed to prepare a colored curable composition.
• ⁇ Composition> Exemplified Compound A-1 ... 6 parts by mass Yellow colored substance ((Y-2)) ...
• Absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05 The amount of yellow coloring was adjusted and added to fit.
• -(T-1) 103.4 parts by mass-(U-1) ...
• ⁇ Light resistance> The colored film was irradiated with a xenon lamp at 200,000 lux for 10 hours (equivalent to 2 million lux ⁇ h), and then the chromaticity change, that is, ⁇ Eab value was measured. A smaller ⁇ Eab value indicates better light resistance.
• a colored film was prepared in the same manner as in Example 1, then immersed in a sodium bicarbonate / sodium carbonate aqueous solution adjusted to 23 ° C. and pH 12.0 as a developer for 60 seconds, and then washed with ion-exchanged water at 23 ° C. Then, a substrate for residue evaluation was produced.
• the developed substrate was measured with an ultraviolet-visible spectrophotometer (UV2400-PC, manufactured by Shimadzu Corporation), and the residue was evaluated by the maximum absorbance at 400 nm to 700 nm as follows. 2: Maximum absorbance less than 0.05 1: Maximum absorbance 0.05 or more
• the said phthalocyanine compound respond corresponds to the number of the above-mentioned exemplary compound.

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