Classifications

• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
• • 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
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
• • 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
• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
  • C09B67/0034—Mixtures of two or more pigments or dyes of the same type
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
  • F21K9/00—Light sources using semiconductor devices as light-generating elements, e.g. using light-emitting diodes [LED] or lasers
  • F21K9/60—Optical arrangements integrated in the light source, e.g. for improving the colour rendering index or the light extraction
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
• • 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
• • 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
• • 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
  • G03F7/0041—Photosensitive materials providing an etching agent upon exposure
• • 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
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • 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

Definitions

• the present invention relates to a colored curable composition for color filter, a colored cured film using the colored curable composition for color filter, a method for producing a color filter, and a color filter provided with the colored cured film,
• the present invention relates to a display device provided with the color filter.
• a back light source is essential, and when using the back light source, a secondary battery serving as a power source of the light source There is a limit due to the electric capacity of the battery and dry cell.
• a coloring material of a color filter used in a display device requiring a backlight source a coloring agent having high luminance and capable of performing color display by well transmitting the bright line of the backlight has been advantageously used.
• an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and other components are further added to the pigment composition in which the particle size of the pigment is further refined to obtain a colored curable composition, which is used
• a color filter in which a coloring pattern of red, green, blue and the like is formed on a transparent substrate such as glass by photolithography is developed and put to practical use.
• a light emitting diode (LED) as a light source for backlight in place of the conventional cold cathode fluorescent tube (CCFL).
• LED light emitting diode
• An LED light source is superior in responsiveness to a CCFL light source, and is also superior in that there is no concern about environmental pollution since it is not necessary to use mercury as a raw material.
• LED light source for example, a white LED in which a blue LED and a YAG-based phosphor are mixed and mixed is proposed (see, for example, JP-A-6-75375 and JP-A-2008-292970).
• LED light sources have been developed that emit various colors using phosphors. Even in the development of such LEDs, high luminance is required to improve color reproducibility and reduce power consumption, but using the color filter used in CCFL, which has been conventionally used, as it is for white LEDs Also, it is difficult to obtain a desired hue in a display device because the characteristics of the light source are different, and therefore, there is currently a need to develop a color filter having a hue matched to a white LED.
• a pigment dispersion composition containing a pigment, a pigment dispersant and a dispersion medium problems such as occurrence of light scattering due to coarse particles of the pigment and increase in viscosity due to poor dispersion stability are more likely to occur. It is difficult to obtain a pigment dispersion composition that achieves an appropriate hue for color filter application when a white LED is used as a backlight, because it is essentially difficult to adjust the hue to obtain the hue of.
• dyes used in colored curable compositions for color filters dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes such as triarylmethane dyes, and compounds having a wide variety of dye bases have been proposed. (For example, see JP 2008-292970, JP 2007-039478, JP 06-230210, JP 2010-256598, etc.).
• the present invention has been made in view of the above-mentioned problems, and the object of the present invention is to colorize a color filter capable of forming a blue pixel having good hue and high luminance even for a white LED light source. It is providing a curable composition.
• another object of the present invention is to provide a colored cured film having good color characteristics and a method for producing the same obtained by using the colored curable composition, a color filter comprising the colored cured film, and the color filter.
• An object of the present invention is to provide a liquid crystal display device provided with a color filter.
• R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an aryl group or R 1 and R 2 present in the molecule may be the same as or different from each other in the molecule
• R 8 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonylamino group, a carbonylamino group, a cyano group, an aryl group or a heteroaryl group; R 5 s present may be the same as or different from each other.
• B Colorant
• the colored curable composition for a color filter according to ⁇ 1> wherein the (B) colorant is a colorant having a maximum absorption peak wavelength in a wavelength range of 380 nm to 800 nm in a range of 500 nm to 800 nm. .
• the colored curable composition for color filters as described in ⁇ 1> or ⁇ 2> whose ⁇ 3> above-mentioned (B) coloring agent is a zinc phthalocyanine compound represented by following General formula (III).
• a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , A 12 , A 13 , A 14 , A 15 and A 16 each independently represent a halogen atom, an alkyl group, an alkoxy group or a thioalkoxy group
• a colorant is a halogenated phthalocyanine zinc complex compound.
• ⁇ 5> The color filter colored curable composition according to any one of ⁇ 1> to ⁇ 4>, further comprising (D) a photopolymerization initiator.
• ⁇ 6> The colored curable composition for a color filter according to ⁇ 5>, wherein the (D) photopolymerization initiator is an oxime compound.
• ⁇ 7> A colored curable composition for a color filter according to any one of ⁇ 1> to ⁇ 6>, further comprising an aliphatic polyfunctional mercapto compound.
• ⁇ 8> The color curability for color filter according to any one of ⁇ 1> to ⁇ 7>, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (IV) Composition.
• R 4, R 5 and R 6 are the respectively the general formula in (II) and R 4, R 5 and R 6 synonymous .
• R 13 and alkyl R 15 are each independently R 14 and R 16 each independently represent a hydrogen atom or an alkyl group.
• the color filter produced by the manufacturing method of the color filter as described in ⁇ 13> ⁇ 11>.
• the display apparatus provided with the color filter as described in ⁇ 14> ⁇ 12> or ⁇ 13>.
• ⁇ 15> The display device according to ⁇ 14>, further including an LED backlight having a peak wavelength of emission intensity in a wavelength range of 430 nm to 470 nm.
• the colored curable composition of the present invention comprises, as a colorant, at least one colorant selected from the compound represented by the general formula (I) and the compound represented by the general formula (II) [hereinafter, And the like) may be referred to as specific colorants.
• the (A) specific colorant according to the present invention has a yellow hue and has a characteristic capable of forming a color filter exhibiting high color purity and luminance because the cut of the absorption spectrum at 450 nm to 500 nm is good. . This property is presumed to be an effect attributed to the high rigidity of the molecular structure of the (A) specific colorant.
• a color filter using a white LED does not have a bright line of 480 nm attributable to a light source, and can express good hue even with a small amount of yellow colorant added to a green pixel.
• A Due to the molecular structure of the specific coloring agent, although the solubility is slightly lower compared to other coloring agents having the same or similar main skeleton, its performance is also excellent in the solubility of the specific coloring agent A color hardening for a color filter which achieves high brightness as well as high color purity even when using the other coloring agent having the same or similar main skeleton having higher solubility because it is sufficiently expressed. It is believed that the membrane can be provided.
• the (A) specific colorant has a steep absorption spectrum derived from its rigid structure, has a low fluorescence intensity, and high contrast can be realized.
• the fluorescence intensity is increased due to the rigidity.
• the (A) specific colorant according to the present invention is sharp because the deactivation of the excitation energy by the thermal vibration of the NN bond can be efficiently generated by having the NN hetero bond in the molecule. It has the characteristics of low fluorescence intensity while having an absorption spectrum, and exhibits excellent performance combining high brightness and high contrast.
• a colored curable composition for a color filter which can form a blue pixel having a good hue and high luminance even for a white LED light source.
• a colored cured film having good color characteristics and a method for producing the same obtained using the colored curable composition, a color filter comprising the colored cured film, and the color filter can provide a liquid crystal display device.
• the colored curable composition the color filter, the method for producing a color filter, and the display device using the color filter of the present invention will be described in detail.
• the notation not describing substitution and non-substitution includes ones further having substitution as well as non-substitution, unless otherwise specified.
• an alkyl group is used by the meaning including an unsubstituted alkyl group and an alkyl group further having a substituent. The same applies to other substituents (atomic groups).
• a numerical range represented using “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit.
• the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored curable composition.
• (meth) acrylate represents both or either of acrylate and methacrylate
• (meth) acrylic represents both or either of acrylic and methacryl
• ( ) Acryloyl represents both or either of acryloyl and methacryloyl.
• monomer as used herein is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less.
• the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer.
• the polymerizable functional group refers to a group involved in the polymerization reaction.
• process is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process. .
• the colored curable composition of the present invention has at least one colorant selected from (A) a compound represented by the following general formula (I) and a compound represented by the following general formula (II), (B) It comprises the coloring agent which has a hue (structure) different from the (A) coloring agent, and (C) the polymerizable compound.
• A a compound represented by the following general formula (I) and a compound represented by the following general formula (II)
• B) It comprises the coloring agent which has a hue (structure) different from the (A) coloring agent, and (C) the polymerizable compound.
• the colored curable composition of the present invention comprises at least one colorant [(A) specific colorant selected from a compound represented by the following general formula (I) and a compound represented by the following general formula (II)] Contains The (A) specific colorant is a colorant having a yellow hue.
• R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an aryl group or a hetero
• a plurality of R 1 and R 2 in the molecule may be the same as or different from each other.
• R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonylamino group
• R 5 represents a carbonylamino group, a cyano group, an aryl group or a heteroaryl group
• a plurality of R 5 in the molecule may be the same as or different from each other.
• R 1 in General Formula (I) and R 5 in General Formula (II) an alkyl group, an aryl group or a cyano group is preferable, and the alkyl group and the aryl group may further have a substituent .
• transduced into an alkyl group and an aryl group an alkoxy group, a thio alkoxy group, a cyano group, a halogen atom, etc. are mentioned. More preferably, R 1 and R 5 include a t-butyl group, a phenyl group or an o-methylphenyl group.
• R 3 in General Formula (I) is more preferably a hydrogen atom
• R 4 in General Formula (I) and General Formula (II) is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom
• R 2 , R 7 and R 8 each independently represent a hydrogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonylamino group, carbonylamino group, cyano group, aryl group, heteroaryl group Or an alkoxycarbonyl group having a partial structure selected from a substituted alkyl group, a PEO chain (polyethylene glycol), a PPO chain (polypropylene glycol), an ammonium salt, and a polymerizable group in the structure thereof.
• It is preferably a carbamoyl group, a sulfamoyl group, a sulfonylamino group, or a carbonylamino group, and more preferably a sulfonylamino group having the partial structure.
• Plural R 2 in the molecule may be the same as or different from each other, but are preferably the same in terms of synthetic suitability.
• the compound represented by the general formula (I) is a compound represented by the following general formula (IV), and the compound represented by the general formula (II) is It is a more preferred embodiment that the compound is a compound represented by formula (V).
• R 1, R 3 and R 4 are each as R 1, R 3 and R 4 same meaning in the general formula (I), and preferred examples are also the same.
• R 9 and R 11 each independently represent an alkyl group, an aryl group or a heteroaryl group
• R 10 and R 12 each independently represent a hydrogen atom, a methyl group or an ethyl group.
• Each of R 10 and R 12 is preferably a hydrogen atom.
• R 9 and R 11 each represent a substituted or unsubstituted alkyl group, or a moiety selected from PEO chain (polyethylene glycol), PPO chain (polypropylene glycol) chain, ammonium salt, and polymerizable group It is preferably an alkyl group having a structure, an aryl group or a heteroaryl group, more preferably an alkyl group having 2 to 8 carbon atoms or a substituted alkyl group having a (meth) acrylic acid group on the alkyl chain .
• R 4, R 5 and R 6 are each as R 4, R 5 and R 6 same meanings in the general formula (II), and preferred examples are also the same.
• R 13 and R 15 each independently represent an alkyl group, an aryl group or a heteroaryl group
• R 14 and R 16 each independently represent a hydrogen atom, a methyl group or an ethyl group.
• Each of R 14 and R 16 is preferably a hydrogen atom.
• R 13 and R 15 each represent a substituted alkyl group, or an alkyl group having a partial structure selected from PEO chain (polyethylene glycol), PPO chain (polypropylene glycol) chain, ammonium salt, polymerizable group, aryl group, It is preferably a heteroaryl group, more preferably an alkyl group having 2 to 8 carbon atoms, or a substituted alkyl group having a (meth) acrylic acid group on the alkyl chain.
• Examples of the colorant represented by the general formula (I) and the colorant represented by the general formula (IV) which is a preferred embodiment thereof include the following exemplified compounds (B-1) to (B-8) (B-9) to (B-15) can be mentioned as examples of the colorant represented by the general formula (II) or the colorant represented by the general formula (V), which is a preferred embodiment thereof. Although each is mentioned, this invention is not necessarily limited to these.
• the (A) specific colorant may contain only one type, or two or more types may be used in combination.
• the content of the (A) specific colorant in the colored curable composition of the present invention is appropriately selected according to the purpose, but when used for the purpose of forming colored pixels of a color filter
• the solid content is preferably 0.5% by mass to 70% by mass, and more preferably 10% by mass to 40% by mass.
• Colorant having a hue different from that of the specific colorant (A)> in addition to the (A) specific colorant, a colorant different in structure from the (A) specific colorant and having a different hue [hereinafter, appropriately, (B) other colored Referred to as an agent].
• B) Other colorants may be selected from known dyes, dye derivatives, pigments and pigment dispersions that have absorption in the visible light wavelength range.
• the specific colorant has a maximum absorption peak wavelength ( ⁇ max) of 420 nm to 480 nm
• ⁇ max maximum absorption peak wavelength
• B the other colorant, the maximum absorption in the wavelength range of visible light from 380 nm to 800 nm
• the maximum absorption peak wavelength of the coloring agent is a concentration at which the dye solution or pigment dispersion containing the coloring agent to be measured can be measured (for example, a concentration that results in an absorbance of 0.8 to 1.0) It adjusted using a solvent so that it might become, and the value measured using CARY5 / UV-visible spectrophotometer (commercial item: Varian make) is employ
• a dye compound having a different hue and structure from the (A) colorant used as another colorant any structure may be used as long as it does not affect the hue of the colored image.
• anthraquinones for example, anthraquinone compounds described in JP-A-2001-10881
• phthalocyanines for example, phthalocyanine compounds described in US Patent 2008/0076044 A1
• xanthenes for example, C. I. Acid. Red 289 (C.I. Acid Red 289), triarylmethanes (e.g. C. I. Acid Blue 7), C. I. Acid Blue 83 (C. I. Acid Blue 83) , C. I. Acid Blue 90, C. I. Acid Blue 90, C.I. Solvent Blue 38, C.I. Acid Violet 17 (C.I. Acid Violet 17), C. I. Acid Violet 49 (C. I. Acid Violet 49) , C. I. Acid Green 3 and methine dyes.
• xanthenes for example, C. I. Acid. Red 289 (C.I. Acid Red 289)
• triarylmethanes e.g. C. I. Acid Blue 7
• pigment compounds having a different hue from the (A) coloring agent used as another coloring agent include perylene, perinone, quinacridone, quinacridone quinone, anthraquinone, anthantorone, benzimidazolone, disazo condensation, disazo Azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone, isobiolanthrone and the like.
• perylene compound pigments such as, for example, pigment red 190, pigment red 224, pigment violet 29, perinone compound pigments such as pigment orange 43 or pigment red 194, pigment violet 19, pigment violet 42, pigment red 122, pigment red 192, pigment red 202, pigment red 207, or quinacridone compound pigment of pigment red 209, pigment red 206, pigment orange 48, or pigment orange 49, etc.
• quinacridone Anthraquinone compound pigments such as quinone compound pigments, pigment yellow 147, etc., anthanthrone compound pigments such as pigment red 168, pygume Benzimidazolone compound pigments such as To-Brown 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185, Pigment ⁇ 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, pigment red 166, pigment ⁇ Red 220, pigment red 221, pigment red 242, pigment red 248, pigment red 262, or pigment Disazo compound pigments, round 23 such as,
• Disazo compound pigment such as pigment yellow 13, pigment yellow 83 or pigment yellow 188, pigment red 187, pigment red 170, pigment yellow 74, pigment yellow 150, pigment red 48, pigment red 53 Azo compound pigment such as pigment orange 64 or pigment red 247, indanthrone compound pigment such as pigment blue 60, pigment green 7, pigment green 36, pigment green 37, pigment green 58, pigment Phthalocyanine compound pigments such as Blue 16, Pigment Blue 75 or Pigment Blue 15; Tri pigments such as Pigment Blue 56 or Pigment Blue 61 Reel carbonium compound pigment, pigment violet 23 or dioxazine compound pigment such as pigment violet 37, amino red anthraquinone compound pigment such as pigment red 177, pigment red 254, pigment red 255, pigment red 264, pigment ⁇ Diketopyrrolopyrrole compound pigments such as Red 272, Pigment Orange 71 or Pigment Orange 73, Thioindigo compound pigments such as Pigment Red 88, Isoindoline compound pigments such as Pigment Yellow 139, Pigment Orange
• a specific coloring agent having a maximum absorption peak wavelength ( ⁇ max) at 420 nm to 480 nm In the wavelength range of 380 nm to 800 nm, those having the maximum absorption peak wavelength in the wavelength range of 500 nm to 800 nm are preferable, those having the maximum absorption peak wavelength in the wavelength range of 550 nm to 700 nm are more preferable, That is, those having a maximum absorption peak wavelength in a long range of 600 nm to 700 nm are most preferable.
• Specific examples of the colorant having the maximum absorption peak wavelength in the above wavelength range include Pigment Green 36 and Pigment Green 58. Further, focusing on the structure of a preferred pigment, zinc phthalocyanine compounds represented by the following general formula (III) are preferably mentioned as the (B) other colorant.
• a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , A 12 , A 13 , A 14 , a 15, and a 16 each independently represent a halogen atom, an alkyl group, an alkoxy group, or a thioalkoxy group.
• a 1 to A 16 preferably each independently represent a hydrogen atom, a chlorine atom or a bromine atom, and at least eight of them are preferably a bromine atom.
• the zinc phthalocyanine compound when eight or more of A 1 to A 16 are bromine atoms, it exhibits a yellowish green color with high brightness and is most suitable for use in forming a green pixel portion of a color filter. It is.
• the (B) other coloring agent of the present invention a zinc phthalocyanine compound having 10 or more bromine atoms is most preferable.
• the average composition of the zinc phthalocyanine compound can be easily obtained from mass spectrometry based on mass spectroscopy and halogen content analysis by means of a flask combustion ion chromatograph.
• the zinc phthalocyanine compound can be produced, for example, by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, a melting method and the like. More specific manufacturing methods are described in detail in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-70342, and the like. Also, C.I. I.
• the pigment known as Pigment Green 58 is also a pigment included in the brominated phthalocyanine pigment in the present invention.
• the zinc phthalocyanine compound used in the colored curable composition for color filters is preferably one having an average primary particle diameter in the range of 10 nm to 40 nm.
• the color curability for color filters is excellent in dispersibility stability and coloring power, high in luminance and high in contrast.
• a composition can be obtained.
• the average primary particle size refers to the particles in the field of view taken with a transmission electron microscope, and the long primary image per 100 primary particles of the zinc phthalocyanine pigment constituting the aggregate on a two-dimensional image. The average value of the one diameter (long diameter) and the short diameter (short diameter) is determined, and the average value is obtained.
• any of the pigments may be made fine by any method, but crystal growth can be easily suppressed and the average primary particle diameter is relatively large. It is preferable to employ solvent salt milling in that small pigment particles can be obtained.
• a brominated zinc phthalocyanine pigment having an average primary particle diameter in the range of 10 nm to 40 nm is also available as a commercial product, and can also be purchased from DIC Corporation.
• a pigment is used as the other colorant (B)
• a pigment dispersion prepared in advance.
• the pigment dispersion can be prepared, for example, according to the descriptions of JP-A-9-197118 and JP-A-2000-239544.
• the content in the case of using the dye or the pigment as the other coloring agent (B) may be used within the range not impairing the effect of the present invention, relative to the total solid content of the colored curable composition of the present invention The content is preferably 0.5% by mass to 70% by mass.
• (B) another coloring agent is used, (B) the other coloring agent is used in a ratio of 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of (A) the specific coloring agent.
• the colored curable composition of the present invention contains at least one polymerizable compound.
• a polymeric compound the addition polymeric compound which has an at least 1 ethylenically unsaturated double bond can be mentioned, for example.
• the polymerizable compound having at least one ethylenically unsaturated double bond can be selected from known components and used. Specifically, paragraph [0010] to [2006] of JP-A-2006-23696 can be used.
• the components described in [0020] and the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921 can be mentioned.
• the polymerizable compound (C) details of the structure, single use or combined use, details of usage methods such as addition amount 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 more functional is preferable.
• trifunctional or higher functional groups 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) By combining these methods, it is also effective to adjust both the sensitivity and the intensity.
• the selection of the polymerizable compound is also suitable for compatibility and dispersibility with other components (for example, a photopolymerization initiator, a colorant (pigment), a binder polymer, etc.) contained in the colored curable composition.
• the method of use is an important factor, and it may be possible to improve the compatibility, for example, by the use of a low purity compound or a combination of two or more.
• a specific structure may be selected from the viewpoint of improving the adhesion to a hard surface such as a substrate.
• a urethane addition polymerizable compound produced by using an addition reaction of an isocyanate and a hydroxyl group is also suitable, and JP-A-51-37193, JP-B-2-32293 and JP-B 2-16765. JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, JP-B-62-39418 and the like. Urethane compounds having a skeleton are also suitable.
• polyester acrylates as described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490, epoxy resins and (meth) Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting acrylic acid. Furthermore, Japan Adhesiveness Association magazine vol. 20, no. Also those introduced as photocurable monomers and oligomers on pages 7, 300-308 (1984) can be used.
• pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate , Pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc., and as a commercial product, NK ester A-TMMT, NK ester A-TMM-3, NK oligo UA -32P, NK oligo UA-7200 (all, Shin-Nakamura Chemical Co., Ltd.
• two or more kinds of polymerizable compounds may be used in combination.
• dipentaerythritol hexaacrylate pentaerythritol tetra (meth) acrylate EO modified product
• dipentaerythritol diacrylate It is preferable to use in combination with an EO-modified product such as an erythritol hexa (meth) acrylate EO-modified product. The combination of these can further improve the patterning aptitude.
• the polymerizable compound contained in the colored curable composition may be only one type, or as described above, two or more types may be used in combination depending on the purpose.
• Content of (C) polymerizable compound in total solid content of colored curable composition, (C) total content of plural kinds of (C) polymerizable compounds in the case of containing two or more kinds of polymerizable compounds Is suitably selected without particular limitation, but is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 75% by mass, from the viewpoint that the effects of the present invention are more remarkably exhibited. % To 60% by weight is particularly preferred.
• the colored curable composition of the present invention may further contain, if necessary, a photopolymerization initiator, a coloring compound, an organic solvent, a crosslinking agent, a surfactant, a filler, an antioxidant, an ultraviolet light absorber, an aggregation inhibitor, and the like. You may contain various additives, such as a sensitizer and a light stabilizer.
• 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 above-mentioned polymerizable compound (C), and it is selected in consideration of the characteristics, generation efficiency of initiating species, absorption wavelength, availability, cost and the like. Is preferred.
• the photopolymerization initiator is a compound which is photosensitized by exposure light to initiate and accelerate the polymerization of the polymerizable compound. Among them, preferred is a compound which is sensitive to actinic light having a wavelength of 300 nm or more to initiate and accelerate the polymerization of the polymerizable compound. Further, a photopolymerization initiator which does not directly react to actinic rays having a wavelength of 300 nm or more can also be preferably used in combination with a sensitizer.
• the photopolymerization initiator for example, at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, 3-aryl substituted coumarin compound, lophine dimer, benzophenone compound, acetophenone compound And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, oxime compounds, and the like.
• the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A-2004-295116. Among them, organic halogenated compounds, hexaarylbiimidazole compounds, oxime compounds and the like are preferable, and oxime compounds are preferable from the viewpoint of rapid polymerization reaction and the like.
• the oxime-based compound (hereinafter, also referred to as “oxime-based photopolymerization initiator”) is not particularly limited, and examples thereof include:
• the oxime compound as described is mentioned. Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octaned
• a compound represented by the following general formula (1) and a compound represented by the following general formula (2) As an oxime compound, a compound represented by the following general formula (1) and a compound represented by the following general formula (2)
• the compound selected from is more preferable.
• R and X each represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5) Is)
• R in the general formula (1) an acyl group is preferable from the viewpoint of high sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group and a toluyl group are preferable.
• an alkylene group substituted with an unsubstituted alkylene group or an alkyl group for example, a methyl group, an ethyl group, a tert-butyl group, a dodecyl group from the viewpoint of enhancing sensitivity and suppressing coloring due to heating and aging;
• An alkylene group substituted with an alkenyl group eg, vinyl group, allyl group
• an aryl group eg, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group
• Substituted alkylene groups are preferred.
• Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of enhancing sensitivity and suppressing coloring due to heating and aging.
• a substituted phenyl group as the substituent, for example, a halogen atom group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferable.
• an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkenyl which may have a substituent from the viewpoint of improving the solvent solubility and the absorption efficiency in the long wavelength region Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent
• the arylthioxy group which may have, and the amino group which may have a substituent are preferable.
• n in the general formula (1) is preferably an integer of 0 to 2. More specifically, the compound represented by the general formula (1) is preferably a compound having a structure represented by the following (D-2).
• X 1 , X 2 and X 3 each independently represent a hydrogen atom, a halogen atom or an alkyl group
• R 1 is —R, —OR, —COR, — SR, -CONRR ', or -CN
• R 2 and R 3 each independently represent -R, -OR, -COR, -SR, or -NRR' R and R 'are each independently And an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, which may be substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group, and the alkyl group, and One or more of the carbon atoms constituting the alkyl chain in the aralkyl group may be replaced with an unsaturated bond, an ether bond or an ester bond, and R and R ′ may be combined with each other to form a ring.
• R 1 is —R, —OR,
• organic halogenated compounds include Wakabayashi et al., "Bull Chem. Soc. Japan” 42, 2924 (1969), U.S. Pat. No. 3,905,815 and Japanese Patent Publication No. 46-4605.
• hexaarylbiimidazole compounds include, for example, each of Japanese Patent Publication No. 6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286.
• photopolymerization initiators described in paragraph 0079 of JP-A-2004-295116 may be used.
• the above-mentioned oxime compound can be suitably used, and among them, the compounds represented by the above (D-2) and (D-3) are preferable.
• a photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
• the content (in the case of using two or more photopolymerization initiators, the total content thereof) of the photopolymerization initiator in the total solid content of the colored curable composition obtains the effects of the present invention more significantly.
• the content is preferably 0.5% by mass to 30% by mass, more preferably 3% by mass to 20% by mass, more preferably 4% by mass to 19% by mass, and particularly preferably 5% by mass to 18% by mass preferable.
• the colored curable composition of the present invention may contain a sensitizer.
• Typical sensitizers used in the present invention include those disclosed in Crivello (JVC Crivello, Adv.
• the sensitizer is preferably added in a proportion of 50% by mass to 200% by mass with respect to the photopolymerization initiator.
• the sensitizer improves the sensitivity of the coexisting photopolymerization initiator, but as described above, the photopolymerization initiator which is not directly sensitive to the exposure wavelength by using an appropriate sensitizer in combination, It also has the advantage of becoming applicable to the colored curable composition of the present invention.
• a chain transfer agent may be used in the colored curable composition of the present invention.
• the chain transfer agent used in the present invention for example, N, N-dialkylaminobenzoic acid alkyl ester such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercapto Benzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc.
• Mercapto compounds having the following heterocyclic ring and aliphatic polyfunctional mercapto compounds such as pentaerythritol tetrakis (3-mercaptobutyrate) and 1,4-bis (3-mercaptobutyryloxy) butane.
• aliphatic polyfunctional mercapto compounds are particularly preferable.
• the chain transfer agent may be used alone or in combination of two or more.
• the addition amount of the chain transfer agent is preferably in the range of 0.01 to 15% by mass with respect to the total solid content of the colored curable composition of the present invention, from the viewpoint of reducing the variation in sensitivity. 1 to 10% by mass is more preferable, and 0.5 to 5% by mass is particularly preferable.
• the colored curable composition of the present invention may contain a polymerization inhibitor.
• a polymerization inhibitor is hydrogen donating (or hydrogen donating), energy donating (or energy donating), electron donating (or donating hydrogen) to a polymerization initiating species such as a radical generated in a colored curable composition by light or heat. , Electron transfer, etc., to deactivate the polymerization initiation species and to suppress the unintended initiation of the polymerization.
• the polymerization inhibitor described in paragraphs [0154] to [0173] of JP-A-2007-334322 can be used. Among these, p-methoxyphenol is preferably mentioned as the polymerization inhibitor.
• the content of the polymerization inhibitor in the colored curable composition of the present invention is preferably 0.0001 to 5% by mass, more preferably 0.001 to 5% by mass, with respect to the total mass of the polymerizable compound. Particularly preferred is 001 to 1% 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 the respective components coexisting and the coating property when made into a colored curable composition, and in particular, the solubility of solid components such as a binder, It is preferable to select in consideration of coating property and safety.
• organic solvents examples include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate Alkyl esters of oxyacetic acid (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like).
• esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl
• 3-hydroxypropionic acid alkyl esters eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-) Methyl ethoxypropionate, 3-eth Ethyl cypropionate and the like can be mentioned
• 2-oxypropionic acid alkyl esters eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate etc.
• ethers for example, 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 And propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
• ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like.
• Preferred examples of the aromatic hydrocarbons include toluene and xylene.
• 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 are particularly preferable.
• the content of the organic solvent in the colored curable composition is preferably such that the total solid concentration in the composition is 5% by mass to 80% by mass, and more preferably 5% by mass to 60% by mass. An amount of 10% by mass to 60% by mass is particularly preferable.
• a crosslinking agent may be additionally used in the colored curable composition of the present invention 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 it can perform film curing by a crosslinking reaction, and for example, at least at least one selected from (a) epoxy resin, (b) methylol group, alkoxymethyl group, and acyloxymethyl group At least one substituent selected from melamine compounds, guanamine compounds, glycoluril compounds or urea compounds, (c) methylol groups, alkoxymethyl groups, and acyloxymethyl groups, which are substituted by one substituent; A phenol compound, a naphthol compound or a hydroxyanthracene compound is mentioned. Among them, polyfunctional epoxy resins are preferable.
• the description in paragraphs [0134] to [0147] of JP-A-2004-295116 the description in paragraphs [0134] to [0147] of JP-A-
• the colored curable composition of the present invention may contain a surfactant.
• a surfactant any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants.
• nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. .
• the repeating unit A represented by following General formula (1) and the repeating unit B are included, and the weight average molecular weights (Mw) of 1,000 or more of polystyrene conversion measured by gel permeation chromatography are 10 or more. Copolymers having a molecular weight of 1,000 or less can be mentioned as a preferred example.
• R 1 and R 3 each independently represent a hydrogen atom or a methyl group
• R 2 represents a linear alkylene group having 1 to 4 carbon atoms
• R 4 represents a hydrogen atom or carbon atoms
• L represents an alkyl group having 1 to 4 carbon atoms
• L represents an alkylene group having 3 to 6 carbon atoms
• p and q each represent a mass ratio representing a polymerization ratio
• p represents a numerical value of 10 to 80 mass%.
• L in said Formula (1) is a branched alkylene group represented by following formula (2).
• R 5 represents an alkyl group having 1 to 4 carbon atoms, and in view of compatibility and wettability to the surface to be coated, an alkyl group having 1 to 3 carbon atoms is preferable, and the carbon number is An alkyl group of 2 or more and 3 or less is more preferable.
• the weight average molecular weight (Mw) of the copolymer as the surfactant represented by the general formula (1) is more preferably 1,500 or more and 5,000 or less. These surfactants can be used singly or in combination of two or more. It is preferable that the addition amount of (I) surfactant in the photosensitive resin composition of this invention is 10 mass parts or less with respect to 100 mass parts of (A) specific resin, and 0.01 mass part-10 mass. It is more preferably part, and further preferably 0.01 to 1 part by mass.
• the colored curable composition of the present invention may contain an adhesion improver.
• the adhesion improver is a compound that improves the adhesion of the cured film to an inorganic substance to be a base material, for example, a silicon compound such as glass, silicon, silicon oxide, silicon nitride, gold, copper, aluminum and the like.
• silane coupling agents, thiol compounds and the like can be mentioned.
• the silane coupling agent as the adhesion improver is intended to modify the interface, and a known one can be used without particular limitation.
• the silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and in particular, ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable. . These can be used alone or in combination of two or more.
• the content of the adhesion improver in the colored curable composition of the present invention is preferably 0.1% by mass to 20% by mass, and more preferably 0.2% by mass to 5% by mass with respect to the total solid content of the colored curable composition. % Is more preferable.
• a binder polymer In the colored curable composition of the present invention, it is preferable to further use a binder polymer from the viewpoint of film property improvement and the like. It is preferable to contain a linear organic high molecular weight polymer as the binder polymer. Any compound may be used as such a "linear organic polymer", but preferably water or weak alkali water solubility or swelling which enables water development or weak alkali water development A linear organic high molecular weight polymer is selected.
• the linear organic high molecular weight polymer is selected and used not only as a film forming agent of the composition but also according to the use as a water, weak alkaline water or organic solvent developer. For example, use of a water-soluble organic polymer enables water development.
• addition polymers having a carboxylic acid group in the side chain for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-A
• acidic cellulose derivatives having a carboxylic acid group in the side chain for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-A
• methacrylic acid copolymer acrylic acid copolymer Itaconic acid copolymers, crotonic acid copolymers, male
• polyvinyl pyrrolidone, polyethylene oxide and the like are also useful as the water-soluble linear organic polymer.
• alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful for increasing the strength of the cured film.
• These linear organic polymers can be mixed in any amount in the entire composition. From the viewpoint of the image intensity to be formed, it is preferably 30 to 85% by mass. Further, it is preferable to set the polymerizable compound and the linear organic high molecular weight polymer in the range of 1/9 to 7/3 in mass ratio.
• the binder polymer is substantially water-free and alkali-soluble.
• the acid value (the acid content per 1 g of the polymer is represented by the chemical equivalent number) and the molecular weight of the binder polymer are appropriately selected from the viewpoint of image strength and developability.
• the preferred acid value is 3 to 200 mg KOH / g, and the preferred molecular weight is 3,000 to 100,000 in weight average molecular weight, more preferably, the acid number is 50 to 150 mg KOH / g, and the molecular weight is 10,000 to 50,000. It is a range.
• the development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less, or a low molecular weight phenol compound having a molecular weight of 1000 or less.
• aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthate and 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 and the like; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemellitic acid, mesitylene acid; phthalic acid,
• E-10 Other additives
• a filler for example, a filler, a polymer compound other than the above, an ultraviolet absorber, an antioxidant, an aggregation inhibitor, etc. may be blended.
• Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A-2004-295116.
• the colored curable composition of the present invention can contain the light stabilizer described in paragraph [0078] of JP-A-2004-295116 and the thermal polymerization inhibitor described in paragraph [0081] of the same publication. .
• the preparation mode of the colored curable composition of the present invention is not particularly limited, but, for example, (A) specific colorant, (B) other colorant, (C) polymerizable compound, and optionally used in combination (D) It is prepared by mixing a photopolymerization initiator and various additives.
• the filter In the preparation of the colored curable composition of the present invention, it is preferable to filter with a filter after mixing the respective components for the purpose of removing foreign substances, reducing defects and the like.
• a filter those conventionally used for filtration applications and the like are used without particular limitation.
• a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide-based resin such as nylon-6 or nylon-6, 6, a polyolefin resin such as polyethylene or polypropylene (PP)
• PP polypropylene
• the filter formed using the resin raw material chosen from molecular weight etc. etc. is mentioned.
• polyamide resins such as nylon-6 and nylon-6, 6 and polypropylene (including high density polypropylene) are preferable.
• the pore size of the filter is suitably about 0.01 ⁇ m to 7.0 ⁇ m, preferably about 0.01 ⁇ m to 2.5 ⁇ m, and more preferably about 0.01 ⁇ m to 2.0 ⁇ m.
• the filtering using the first filter may be performed only once or may be performed twice or more. Further, it is also possible to combine the filters with different pore sizes within the above-mentioned range, and to set the first filter as a plurality of filters as the first filtering.
• the pore size referred to here can refer to the nominal value of the filter manufacturer.
• the second filter can be formed of the same material as the first filter described above. Also, for example, the filtering with the first filter is performed only on the pigment dispersion, and after mixing the other component with the pigment dispersion to make a colored curable composition, the second filtering is performed. It is also good.
• the colored curable composition of the present invention can be applied to various uses such as color filters for solid-state imaging devices, color filters for liquid crystal display devices, printing inks, and inkjet inks.
• ⁇ Colored cured film> The colored cured film obtained by curing the colored curable composition of the present invention has high color purity, a high absorption coefficient in a thin layer, and good fastness (particularly heat resistance and light resistance).
• the colored cured film of the present invention colored pixels of a good hue can be formed, so the coloring of the color filter applied to a liquid crystal display device provided with a white LED The effect is remarkable when used for forming a pixel, and in particular, it is suitable for forming a colored pixel in a color filter for a liquid crystal display.
• the colored curable composition is first applied, or the colored curable composition is first dipped by immersing the substrate or the like in the colored curable composition.
• the color curable composition layer may be cured by forming an object layer.
• the colored curable composition may be applied only on the desired area on the substrate by an inkjet recording method, and a known printing method such as printing or offset printing may be applied.
• a known printing method such as printing or offset printing
• the colored curable composition layer may be formed only in the desired region, the colored curable composition layer is formed on the substrate, which will be described later, from the viewpoint that a high definition pattern can be formed. It is preferable to use a method of removing the unexposed area of the colored curable composition layer by development after exposing in the form of a circle.
• step (ii) exposing the colored curable composition layer (colored layer) in a pattern, and then developing and removing the uncured portion with a developer to form a patterned colored cured film
• step (ii) Also referred to as
• the colored curable composition of the present invention is applied onto a substrate such as glass directly or through another layer, for example, by a method such as spin coating, slit coating, cast coating, roll coating, inkjet coating, etc.
• a colored layer Forming a colored layer, exposing the formed colored layer by a method such as exposing through a predetermined mask pattern [step (i)], and developing and removing the uncured portion with a developer after exposure. As a result, a colored cured film is formed [step (ii)].
• the pattern exposure may be performed by scanning exposure as well as exposure through a mask pattern.
• the obtained patterned colored cured film is useful, for example, as a pixel of a color filter.
• the color filter of the present invention is characterized in that a colored cured film formed of the above-mentioned colored curable composition of the present invention is provided on a substrate. That is, the color filter can be most preferably produced by forming a colored cured film (for example, colored pixels) of a pattern of each color (for example, three or four colors) by the method for manufacturing a color filter described below. .
• a colored cured film for example, colored pixels
• each color for example, three or four colors
• step (iii) a step of irradiating the patterned colored area formed in the step (ii) with ultraviolet light [hereinafter, also referred to as step (iii). And / or a step of performing heat treatment on the colored region irradiated with ultraviolet light [hereinafter, referred to as step (iv).
• step (iv) a step of performing heat treatment on the colored region irradiated with ultraviolet light
• the colored curable composition of the present invention described above is applied by a desired method directly on a support or through another layer to obtain a colored curable composition.
• a coated film (colored curable composition layer) is formed, and then, if necessary, precuring (prebaking) is performed to dry the colored curable composition layer.
• the support for example, it is used for non-alkali glass, soda glass, Pyrex (registered trademark) glass used in liquid crystal display devices, quartz glass, those obtained by attaching a transparent conductive film to these, solid-state imaging devices, etc.
• Photoelectric conversion element substrates such as silicon substrates and plastic substrates.
• a black matrix for separating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion or the like.
• a subbing layer may be provided on the support to improve the adhesion with the upper layer, to prevent the diffusion of substances, or to planarize the surface.
• the plastic substrate preferably further has at least one layer selected from a gas barrier layer and a solvent resistant layer on its surface.
• a driving substrate (hereinafter referred to as a "TFT liquid crystal driving substrate") on which thin film transistors (TFTs) of a thin film transistor (TFT) type color liquid crystal display device are disposed as a support is used for the driving.
• TFT liquid crystal driving substrate a driving substrate on which thin film transistors (TFTs) of a thin film transistor (TFT) type color liquid crystal display device are disposed as a support is used for the driving.
• a colored 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, silicon, polycarbonate, polyester, aromatic polyamide, polyamide imide, polyimide and the like. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like, if desired.
• Examples of the method for applying the colored curable composition of the present invention on a support include coating methods 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 on the support in step (i) is not particularly limited, but a slit nozzle such as slit and spin method or spinless coating method is used.
• a method (hereinafter referred to as a slit nozzle coating method) is preferred.
• the slit nozzle coating method although the conditions differ depending on the size of the coated substrate, the slit-and-spin coating method and the spinless coating method are colored and cured on the fifth generation glass substrate (1100 mm ⁇ 1250 mm) by the spinless coating method, for example.
• the discharge rate of the colored curable composition from the slit nozzle is usually 500 microliters / second to 2,000 microliters / second, preferably 800 microliters / second to 1,500 microliters / second.
• the coating speed is usually 50 mm / sec to 300 mm / sec, preferably 100 mm / sec to 200 mm / sec.
• solid content concentration (solid content concentration in colored curable composition coating liquid) of the colored curable composition used at process (i) 10 mass%-20 mass% normally, Preferably 13 mass%- It is 18% by mass.
• a pre-baking treatment is usually performed after the formation of the colored curable composition layer.
• vacuum treatment can be performed before prebaking.
• the conditions for vacuum drying are usually a vacuum of about 13.33 Pa (0.1 torr) to 133.32 Pa (1.0 torr), preferably about 26.66 Pa (0.2 torr) to 66.66 Pa (0.5 torr). It is.
• the pre-baking treatment can be performed using a hot plate, an oven, or the like at a temperature range of 50 ° C. to 140 ° C., preferably at a temperature range of about 70 ° C. to 110 ° C., for 10 seconds to 300 seconds. .
• high-frequency treatment may be used in combination with heat treatment.
• the thickness of the colored curable composition layer formed of the colored curable composition is appropriately selected according to the purpose.
• 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 the most preferable.
• the thickness of the colored curable composition layer is the film thickness after prebaking.
• pattern exposure is performed on the coating film (colored curable composition layer) formed of the colored curable composition formed as described above on the support, and pattern exposure is performed, for example, through a photomask. Exposure is performed.
• As light or radiation applicable to exposure g-ray, h-ray, i-ray, j-ray, KrF light and ArF light are preferable, and i-ray is particularly preferable.
• i-line to the irradiation light is preferably irradiated at an exposure dose of 100mJ / cm 2 ⁇ 10000mJ / cm 2.
• 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 etc. can also be used.
• Exposure process using a laser light source it is preferable to use an ultraviolet light laser as the light source.
• the irradiation light is preferably an ultraviolet light laser having a wavelength in the range of 300 nm to 380 nm, and more preferably an ultraviolet light laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist.
• the third harmonic (355 nm) of a solid laser Nd: YAG laser having a particularly large output and relatively inexpensive, or XeCl (308 nm) or XeF (353 nm) of an excimer laser 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 . It is preferable at the point of productivity of pattern formation that exposure amount is this range.
• the exposure apparatus usable in the present invention is not particularly limited, but commercially available ones include LE 5565A (manufactured by Hitachi High-Technologies Corporation), Callisto (manufactured by Buoy Technology Corporation), EGIS (manufactured by Buoy Technology Corporation) And DF2200G (manufactured by Dainippon Screen Co., Ltd.) can be used. Moreover, apparatuses other than the above are also suitably used. When the production method of the present invention is applied to the production of a color filter for a liquid crystal display device, exposure using mainly h-line or i-line by a proximity exposure machine or a mirror projection exposure machine is preferably used.
• the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). What is provided with a pattern to form is used.
• UV LEDs light emitting diodes
• LDs laser diodes
• UV LEDs and UV LDs can be used.
• Nichia Corporation has marketed purple LEDs whose main emission spectrum has a wavelength between 365 nm and 420 nm. If even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED capable of emitting actinic radiation centered between 300 nm and 370 nm.
• Other UV LEDs are also available and can emit radiation in different UV bands.
• Particularly preferred actinic radiation sources according to the invention are UV-LEDs, particularly preferably UV-LEDs having a peak wavelength of 340 to 370 m.
• the ultraviolet light laser Since the ultraviolet light laser has a good degree of parallelism, it can be exposed in the form of a pattern without using a mask at the time of exposure. However, when the pattern is exposed using a mask, it is more preferable because the linearity of the pattern is further enhanced.
• the colored curable composition layer exposed as described above can be heated. Further, the exposure can be performed while flowing nitrogen gas into the chamber in order to suppress the oxidative discoloration of the coloring material in the colored curable composition layer.
• the developing solution may be any one as long as it dissolves the coating film (colored curable composition layer) of the colored curable composition in the uncured portion and does not dissolve the cured portion.
• organic solvent used for image development the above-mentioned solvent which can be used when preparing the colored curable composition of this invention is mentioned.
• alkaline aqueous solution examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium borate, sodium metaborate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo- [5,4,0] -7-undecene are used at a concentration of 0.001 to 10% by mass, preferably 0.01 to 10% by mass.
• the alkaline aqueous solution melt
• the alkali concentration is preferably adjusted to be pH 11 to 13, more preferably pH 11.5 to 12.5.
• An appropriate amount of, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline aqueous solution.
• the development temperature is usually preferably carried out using a developer in the temperature range of 20 ° C. to 30 ° C., and the development time is preferably 20 seconds to 90 seconds.
• the developer may be applied by any method such as dip method, shower method and spray method, and any stress is applied to this in a developer solution bath such as swing method, spin method and ultrasonic method Methods may be combined.
• the surface to be developed Before contacting the developing solution, the surface to be developed may be moistened with water or the like in advance to prevent uneven development.
• the substrate provided with the colored curable composition layer after exposure can be inclined and developed.
• paddle development may be used in which development is carried out while stirring the inside of the developing bath.
• Rinse treatment is usually performed with pure water, but pure water is used in the final cleaning, used pure water is used at the initial stage of cleaning, or the substrate is inclined and cleaned for saving liquid. You may use the method of using ultrasonic irradiation together.
• a heat treatment of about 150 ° C. to 250 ° C. is usually performed, as described in detail below.
• this heat treatment post-baking: step (iv)
• the coated film after development is heated using a hot plate, a convection oven (hot air circulating dryer), a high frequency heater, or the like so as to satisfy the above conditions. It can be carried out continuously or batchwise.
• -Process (iv)- It is preferable to further perform a heat treatment on the patterned colored area subjected to the post-exposure by the ultraviolet irradiation as described above.
• the colored region can be further cured by subjecting the formed colored region to heat treatment (so-called post-baking 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., and more preferably 150 ° C. to 250 ° C.
• the heating time is preferably about 10 minutes to 120 minutes.
• the patterned colored area (colored cured film) thus obtained constitutes a pixel in the color filter.
• the steps (i), (ii) and, if necessary, the steps (iii) and (iv) may be repeated according to the desired number of colors. Good.
• at least one step selected from the step (iii) and the step (iv) may be performed collectively. Good.
• the colored cured film obtained by the method for producing a color filter of the present invention, or a color filter provided with a colored cured film formed with the colored curable composition of the present invention (color filter of the present invention) Since the curable composition is used, the color when displaying an image is vivid and the contrast is high, and the fastness (particularly heat resistance and light resistance) is excellent. Furthermore, as described later, even when using a white LED as a backlight as well as a known CCFL, an excellent effect of being able to reproduce a good hue is exhibited.
• the color filter of the present invention can be used for liquid crystal display devices and solid-state imaging devices, and is particularly suitable for use in liquid crystal display devices. When used in a liquid crystal display device, a dye can be used as a colorant to achieve a good hue while achieving display of an image excellent in spectral characteristics and contrast, and further excellent in suitability for white LEDs .
• the application of the colored curable composition of the present invention has mainly been described above mainly for the application of forming a colored pattern of a color filter, but for forming a black matrix which separates the colored pattern (pixel) constituting the color filter Can also be applied.
• the black matrix on the substrate uses a colored curable composition containing a light-shielding pigment of a black pigment such as carbon black or titanium black, passes through the steps of coating, exposure and development, and then, if necessary, post It can be formed by baking.
• the dry thickness of the colored layer is generally 0.3 ⁇ m to 5.0 ⁇ m, preferably 0.5 ⁇ m to 3.5 ⁇ m. And most preferably 1.0 ⁇ m to 2.5 ⁇ m.
• the color filter of the present invention is particularly suitable as a color filter for a display device represented by a liquid crystal display device, an organic EL display device and the like.
• a liquid crystal display device and an organic EL display device provided with such a color filter can display high quality images.
• the color filter of the present invention is particularly effective when used in a color TFT liquid crystal display device.
• the color TFT liquid crystal display device is described, for example, in “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., published in 1996)”.
• the color filter of the present invention may be a liquid crystal display device having an enlarged viewing angle such as a horizontal electric field drive system such as IPS or a pixel division system such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. It can be applied to
• the color filter of the present invention can also be used for a bright and high-definition color-filter on array (COA) system.
• COA color-filter on array
• the required characteristics for the color filter layer are required to have the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance, in addition to the above-described normal required characteristics.
• the color filter of the present invention is considered to enhance the transparency of the ultraviolet light laser as the exposure light by selecting the hue and thickness of the pixel specified by the present invention in addition to the exposure method using the ultraviolet light laser.
• the curability of the colored pixel is improved, and a pixel without chipping, peeling, and blurring can be formed, so that the peeling liquid resistance of the colored layer provided directly or indirectly on the TFT substrate is particularly improved, and the COA method Is useful for liquid crystal display devices.
• a resin film may be further provided on the color filter layer in order to further improve the low dielectric constant requirements.
• the colored layer formed by the COA method has a rectangular shape with a side length of about 1 ⁇ m to 15 ⁇ m in order to electrically connect the ITO electrode disposed on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conductive path such as a through hole or a U-shaped depression, and it is particularly preferable to set the size (that is, the length of one side) of the conductive path to 5 ⁇ m or less. It is also possible to easily form a conductive path of 5 ⁇ m or less by using the color filter of the present invention having The image display method described above is described, for example, on page 43 of "EL, PDP, LCD display-latest trends in technology and market-(Toray Research Center, Research Division, 2001)".
• the liquid crystal display device and the organic EL display device of the present invention are composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle ensuring film, in addition to the color filter of the present invention.
• the color filter of the present invention can be applied to a liquid crystal display device and an organic EL display device composed of these known members.
• these members for example, “'94 Liquid crystal display peripheral materials and chemicals market (Kentaro Shima, Inc., CMSC Co., Ltd. 1994 issue),” “Present state and future prospect of liquid crystal related market in 2003 (second volume) (Yoshikichi Co., Ltd. Fuji Chimera Research Institute, Inc. 2003)).
• the color filter of the present invention When the color filter of the present invention is used in a liquid crystal display device, high contrast can be realized when it is combined with a three-wavelength tube of a cold cathode tube or red, green and blue LED light sources (RGB-LED) as a backlight.
• RGB-LED red, green and blue LED light sources
• a color filter having a colored pixel obtained using the colored curable composition of the present invention has a particularly preferable hue when an LED light source having an emission spectrum at wavelengths around 450 nm and 550 nm is used as a backlight.
• Particularly preferred backlights include LED light sources having a peak wavelength of emission intensity in the range of 430 nm to 470 nm.
• a liquid crystal display device comprising: a color filter having colored pixels obtained using the colored curable composition of the present invention; and an LED backlight having a peak wavelength of emission intensity in the range of 430 nm to 470 nm
• the liquid crystal display device can provide particularly good images.
• an organic EL display device comprising: a color filter having colored pixels obtained using the colored curable composition of the present invention; and a phosphor having a peak wavelength of emission intensity in the range of 430 nm to 470 nm,
• the display device can provide an image with high luminance and good color reproducibility.
• Y phosphor YAG phosphor, TAG phosphor, ⁇ -sialon phosphor, G phosphor: ⁇ -sialon phosphor,
• a silicate type fluorescent substance, BSS fluorescent substance, BSON fluorescent substance, R fluorescent substance: CASN fluorescent substance, SCASN fluorescent substance, etc. are mentioned, and all can be applied to the display apparatus of this invention.
• a solution containing the colorant represented by the formula 1 is adjusted to a concentration of 0.8 to 1.0 using PGMEA, and a CARY 5 / UV-visible spectrophotometer (commercially available: manufactured by Varian) is used. As a result of measurement, the maximum absorption peak wavelength was 450 nm.
• B1 C.I. I. Pigment Green 58, 14.9 parts, and 7.1 parts of an acrylic pigment dispersant (methyl methacrylate / methacrylic acid (80/20) [mass ratio] copolymer (weight average molecular weight: 12,000)], A pigment dispersion obtained by mixing 78.0 parts of propylene glycol monomethyl ether acetate, and sufficiently dispersing the pigment using a bead mill.
• Component (B) The C.I. I.
• the pigment dispersion of Pigment Green 58 is further diluted with propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) to adjust the concentration to an absorbance of 0.8 to 1.0, and the CARY 5 / UV-visible spectrophotometer ( When measured using a commercially available product: manufactured by Varian, the maximum absorption peak wavelength was 661 nm.
• PGMEA propylene glycol monomethyl ether acetate
• the maximum absorption peak wavelength was 661 nm.
• E1 Propylene glycol monomethyl ether acetate (solvent)
• E2) Ethyl 3-ethoxypropionate (solvent)
• E3) Pentaerythritol tetrakis (3-mercaptobutyrate) [polyfunctional mercapto compound]
• Binder resin allyl methacrylate / methacrylic acid (80: 20 (molar ratio)
• Example 1 Formation of Colored Cured Film
• the colored curable composition of Example 1 obtained above was applied by spin coating onto glass (manufactured by Corning; product name: EAGLE-XG (trade name: thickness 0.7 mm)).
• the volatile component was volatilized at 80 ° C. for 2 minutes to form a coated film 1.
• the coating film 1 was exposed by irradiation with i-rays [wavelength 365 nm].
• An ultra-high pressure mercury lamp was used as a light source of i-line, and it was irradiated as parallel light. The irradiation light amount was 50 mJ / cm 2 .
• post-baking was performed at 230 ° C.
• a coating film is similarly formed and exposed for each of the colored curable compositions of Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Examples 4 to 7.
• the cured film 2 to the colored cured film 9 were produced. That is, the colored cured film 2 and the colored cured film 3 according to the colored curable compositions of Example 2 and Example 3 and the colored cured film 4 and the colored cured film 5 according to the colored curable compositions of Comparative Examples 1 and 2
• a colored cured film 6 to a colored cured film 9 were produced from the colored curable composition of Examples 4 to 7, respectively.
• the obtained colored cured film is sandwiched between two polarizing films, and the brightness values of the two polarizing films when the polarization axes are parallel or perpendicular are measured with a color brightness meter (TOPCON ( Ltd., model number: BM-5A), and the obtained value is obtained as the contrast by dividing the luminance when the polarization axes of the two polarizing films are parallel by the luminance when it is perpendicular. (Described as CR in Tables 2 to 4). The higher the value described in the column of contrast (CR), the better the performance as a color filter for liquid crystal displays. 4. Measurement of heat resistance The sample used for the measurement of the contrast was forcibly heat treated in an oven at 230 ° C.
• the chromaticity is measured by a microspectrophotometer (manufactured by OLYMPUS OPTICAL CO., LTD .; OSP 100 or 200), calculated as a result of an F10 light source field of view 2 degrees, and represented by xyY values of the xyz colorimetric system. Further, the difference in chromaticity is represented by the color difference of the La * b * color system. The smaller the color difference, the higher the heat resistance. 5.
• the colored curable composition was exposed by irradiating i-rays [wavelength 365 nm] under the same conditions as described above through a mask on which a pattern with a line width of 20 ⁇ m was formed. Then, after developing with a developer (aqueous solution of sodium carbonate / sodium hydrogen carbonate (concentration: 2.4%)) and washing with water, the pattern-like colored cured film thus formed was fine-lined with an optical microscope at a magnification of 200 times. It observed, and the following criteria evaluated whether the pattern as the design value was formed.
• C rank is a level which poses a problem in practical performance as a color filter resist.
• AA Line width of 19 ⁇ m or more.
• A The line width is 17 ⁇ m or more and less than 19 ⁇ m.
• C The line width is less than 15 ⁇ m.
• the colored cured film 1 to the colored cured film 3 and the colored cured film 6 to the colored cured film 9 obtained by the colored curable composition of Examples 1 to 7 of the present invention are any of Also, in combination with the CCFL backlight, the G color of the HDTV standard is obtained, the luminance at that time is high, the contrast is excellent, and the patterning suitability is also good. Among them, Example 1 becomes G chromaticity of the HDTV standard in combination with the LED backlight, and in particular, the patterning suitability is also excellent. This is presumed to be due to the low concentration of colorant required to achieve good brightness and hue.
• the colored cured film 4 obtained by the colored curable composition of Comparative Example 1 using the known yellow coloring agent (B2) without using the specific coloring agent according to the present invention (A) is an LED backlight
• the combination results in the G color of the HDTV standard the luminance at that time is low.
• the patterning suitability is better.
• the combined use of the polyfunctional mercapto compound is more excellent in the patterning aptitude and further improves the contrast and the luminance.
• the color filter which uses the colored curable composition of this invention as a whole has high heat resistance, and the (DELTA) Eab value is low.
• Example 8 to Example 10 in the same manner as in Example 1 to Example 3 except that the specific colorant (A) used in Example 1 to Example 3 was changed to a compound represented by the following formula 2
• the colored curable composition of the above was obtained, and the same evaluation was performed.
• the results are shown in Table 3 below.
• the maximum peak wavelength of the compound represented by the following formula 2 was measured in the same manner as the compound represented by the above formula 1 to be 460 nm.
• the colored cured films using the colored curable compositions of Examples 8 to 10 all have G color in the HDTV standard in combination with the CCFL backlight, in that case The brightness was high, the contrast was excellent, and the patterning aptitude was also at a level that causes no practical problems.
• the (A) specific coloring agent shown by said Formula 1 which is excellent in solubility is used, it is shown by said Formula 2 ( A) It is understood that the patterning aptitude and the heat resistance are better as compared with the case where a specific coloring agent is used.
• the color filter using the (A) specific coloring agent according to the present invention as a yellow coloring agent has higher contrast and higher compared to the case where other yellow dyes or yellow pigments are used as a coloring agent. It has been confirmed that a very excellent characteristic is realized that luminance is realized and heat resistance is also good.

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• 2012
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