Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/08—Anhydrides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C09B69/00—Dyes not provided for by a single group of this subclass
  • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
  • C09B69/108—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a phthalocyanine dye
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
  • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
  • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
• • 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, a color filter using the colored curable composition and a method for producing the same, and a display device and a solid-state imaging device provided with the color filter.
• the pigment dispersion method is widely used as one of methods for producing color filters used for display devices such as liquid crystal display devices and organic EL display devices, and solid-state imaging devices and the like.
• a pigment dispersion method there is a method of producing a color filter by a photolithographic method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions.
• the colored radiation-sensitive composition is stable against light and heat because it contains a pigment, and is patterned by the photolithographic method, so that sufficient positional accuracy is ensured, and color filters for color displays, etc. It is considered to be a suitable method for producing
• dye compounds other than pigments have been widely studied as coloring compounds used for the preparation of color filters.
• compounds having a wide variety of dye bases such as pyromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes and the like are known, and a plurality of dyes such as pyromethene dyes and phthalocyanine structures are known.
• a technique for obtaining high color purity by using in combination with a dye having see, for example, JP-A-2008-292970).
• a dye as a coloring compound is considered to be useful in that the hue and brightness of a displayed image when an image is displayed can be enhanced by the color purity of the dye itself and the vividness of the hue.
• color filters using dyes generally have lower storage stability than pigments as colorants, and there is still room for improvement in terms of durability, hue stability at high temperature processing such as post-baking steps, etc. It is the present condition.
• the present invention has been made in view of the above circumstances, and it is possible to form a colored film capable of maintaining excellent hue for a long period of time even when high temperature treatment is performed while maintaining good pattern formability. It is an object of the present invention to provide a curable composition.
• a color filter using the colored curable composition of the present invention which has a good hue and is excellent in durability, a color filter suitable for display devices and solid-state imaging devices, a method for producing the same, and display It is an object of the present invention to provide a display element excellent in color tone of an image and excellent in display characteristics and a solid-state imaging element excellent in color separation.
• R 11 represents a hydrogen atom or a methyl group
• R 12 and R 13 each independently represent a hydrogen atom or a carbonyl group having a carbon number of 3 to 20 containing an unsaturated double bond as a partial structure
• R 12 and R 13 are not both hydrogen atoms.
• at least one of R 12 and R 13 represents a carbonyl group having a carbon number of 3 to 20 containing an unsaturated double bond as a partial structure, it may further contain a carboxy group as a partial structure.
• R 20 represents a hydrogen atom or a methyl group
• R 21 , R 22 , R 23 , R 24 and R 25 each independently represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group Or an aryl group.
• the (A) dye is represented by a metal complex dye (a-1) in which a compound represented by the following general formula (I) is coordinated to a metal atom or a metal compound and the following general formula (II) Colored curable composition as described in ⁇ 1> containing at least 1 type selected from dye (a-2).
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a substituent
• R 7 represents a hydrogen atom, a halogen atom
• an alkyl represents a group, an aryl group or a heterocyclic group.
• R a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R o and R p each independently represent a hydrogen atom or a monovalent substituent, and R a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R o and R p are not all hydrogen atoms or halogen atoms.
• the colored curable composition according to ⁇ 1> or ⁇ 2> which comprises 0.1 to 20 parts by mass of the (B) binder resin relative to 1 part by mass of the (A) dye.
• Structural unit (b-2) having an acidic group and at least one structural unit (b-1) selected from the following general formula (1) and the following general formula (2) in the (B) binder resin.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently And represents a hydrogen atom or a monovalent substituent.
• Each of R 7 and R 14 independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.
• Ma represents a metal atom or a metal compound.
• a color filter comprising: a support; and a colored region provided on the support and formed using the colored curable composition according to any one of ⁇ 1> to ⁇ 7>.
• ⁇ 9> A step of applying the colored curable composition according to any one of ⁇ 1> to ⁇ 7> onto a support to form a colored layer, and exposing the formed colored layer in a pattern. And developing to form a colored area.
• the display element provided with the color filter as described in ⁇ 10> ⁇ 8>, or the color filter manufactured by the method as described in ⁇ 9>.
• the solid-state image sensor provided with the color filter as described in ⁇ 11> ⁇ 8>, or the color filter manufactured by the method as described in ⁇ 9>.
• the action of the present invention is not clear, it is considered as follows. Since the colored curable composition of the present invention contains a binder resin having a specific acid group and a crosslinkable group at a high acid value, an acid group of the binder resin and a dye such as a metal complex dye are preferable. A good interaction is formed between them to improve the storage stability of the dye.
• the dye uniformly fixed in the binder by the interaction is imparted with energy to the colored curable composition, and when cured, is stably contained in the cured film by the function of the crosslinkable group in the binder, for example, Even when a high temperature treatment such as a post-baking process is performed, the change in hue and the decrease in luminance due to the decomposition of the dye are effectively suppressed.
• the said binder resin is high in an acid value, it is considered that it is excellent also in the removability of an unhardened area
• a colored curable composition capable of forming a colored film in which excellent hue is maintained for a long time even when high temperature treatment etc. are performed while maintaining good pattern formability. can do.
• a color filter using the colored curable composition of the present invention which has a good hue and is excellent in durability, and is suitable for a display element or a solid-state imaging element It is also possible to provide a display element excellent in display characteristics with good color tone of a display image and a solid-state imaging element excellent in color separation.
• the colored curable composition of the present invention comprises (A) a dye, (B) a structural unit represented by the following general formula (1), and a structural unit represented by the following general formula (2) Binder resin (having an acid value in the range of 150 mg KOH / g to 300 mg KOH / g) comprising a structural unit (b-1) having at least one crosslinkable group selected and a structural unit (b-2) having an acidic group
• (B) is appropriately referred to as a specific binder
• (C) an organic solvent an organic solvent.
• the colored curable composition of the present invention may further contain, if necessary, a photopolymerization initiator, a polymerizable compound having a structure different from that of the component (B), and the like, and various additives.
• the colored curable composition of the present invention may be simply referred to as “the colored composition of the present invention” or “the colored composition”.
• a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
• alkyl group is a generic term for "linear, branched and cyclic” alkyl groups.
• the substituent (atomic group) in the present specification is used in a meaning that includes an unsubstituted one and one further having a substituent. That is, in the present specification, the term “alkyl group” is used to include unsubstituted alkyl groups and substituted alkyl groups, as well as other substituents.
• the colored curable composition of the present invention contains at least one dye.
• the "dye” in the present invention refers to a colorant which is dissolved in an amount of 1% by mass or more in one kind of organic solvent selected from an alkylene glycol ether solvent, an ester solvent and a ketone solvent. It is distinguished from pigments that are
• the dye used in the present invention is not particularly limited as long as the above physical properties are satisfied, but a metal complex dye is preferably used from the viewpoint of interaction formation with a specific binder (B) described later.
• the metal complex dye in the present invention is a dye complex compound having a metal as a central element, refers to a compound which is dissolved in the organic solvent by 1% by mass or more, and is characterized by being excellent in spectral characteristics and heat resistance. is there.
• a colored curable composition capable of forming a colored cured film excellent in hue and heat resistance by containing (A) a dye as shown below, preferably a metal complex dye, and (B) a binder resin described later You can get it.
• Examples of the metal complex dye in the present invention include complexes in which a dye compound is coordinated with a metal atom or a metal compound, and specific examples include dipyrromethene metal complex compounds, phthalocyanine metal complex compounds, and the like.
• Dipyrromethene Metal Complex Compound As a suitable dye contained in the colored photosensitive composition of the present invention, from the viewpoint of the brightness exhibited by a color filter prepared using the colored photosensitive composition, the following general formula (I) And a metal complex compound in which the structure represented by is coordinated to a metal atom or a metal compound (hereinafter appropriately referred to as “dipyrromethene metal complex compound”).
• R 1 to R 6 each independently represent a hydrogen atom or a monovalent substituent
• R 7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group
• metal complex compound dipyrromethene metal complex compound in which the structure represented by the general formula (I) is coordinated to the metal atom or the metal compound will be described in detail.
• the monovalent substituent in the general formula (I) may be a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), an alkyl group (preferably 1 to 48 carbon atoms, more preferably 1 carbon atoms).
• a halogen atom for example, a fluorine atom, a chlorine atom or a bromine atom
• an alkyl group preferably 1 to 48 carbon atoms, more preferably 1 carbon atoms.
• alkenyl group (preferably having 2 to 48 carbon atoms) Preferred is an alkenyl group having a carbon number of 2 to 18, and examples thereof include a vinyl group, an allyl group, and a 3-buten-1-yl group.
• An aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and examples include a phenyl group or a naphthyl group), a heterocyclic group (preferably having a carbon number of 1).
• -32 more preferably a heterocyclic group having 1 to 18 carbon atoms, and examples thereof include 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, or benzotriazol-1-yl group, silyl group (preferably having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms); Trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl or t-hexyldimethylsilyl).
• An oxy group for example, 1-phenyltetrazole-5-oxy group, or 2-tetrahydropyranyl
• a silyloxy group preferably having a carbon number of 1 to 32, more preferably a carbon number of 1 to 18
• a trimethylsilyloxy group preferably having a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, or diphenylmethylsilyl.
• an acyloxy group preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, a pivaloyloxy group, a benzoyloxy group or a dodecanoyloxy group.
• alkoxycarbonyloxy group preferably an alkoxycarbonyloxy group having preferably 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms
• examples thereof include an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and cyclohexyl.
• Oxycarbonyloxy group And aryloxycarbonyloxy groups preferably having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms), and examples thereof include a phenoxy carbonyloxy group.
• Carbamoyloxy group (preferably having a carbon number of 1 to 48, more preferably having a carbon number of 1 to 24), and examples thereof include an N, N-dimethylcarbamoyloxy group and an N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group or N-ethyl-N-phenylcarbamoyloxy group can be mentioned; sulfamoyloxy group (preferably having a carbon number of 1 to 32, more preferably a carbon number of 1 to 24) Group, for example, N, N-diethylsul Amoiruokishi group, or N- propyl-sulfamoyloxy group),
• An alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include a methylsulfonyloxy group, a hexadecylsulfonyloxy group, or a cyclohexylsulfonyloxy group
• An arylsulfonyloxy group preferably an arylsulfonyloxy group having a carbon number of 6 to 32, more preferably a carbon number of 6 to 24, and examples thereof include a phenylsulfonyloxy group), an acyl group (preferably having a carbon number of 1).
• an acyl group having a carbon number of 1 to 24 examples thereof include a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group or a cyclohexanoyl group, an alkoxycarbonyl group (including Preferably, the carbon number is 2 to 48, more preferably Is an alkoxycarbonyl group having a carbon number of 2 to 24, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, or 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl Group, aryloxycarbonyl group (preferably having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonyl group), carbamoyl group
• amino groups include amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, and cyclohexylamino, anilino (preferably, It is an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, and includes, for example, an anilino group or an N-methylanilino group, a heterocyclic amino group (preferably 1 to 32 carbon atoms, more preferably 1)
• To 18 heterocyclic amino groups and examples thereof include a 4-pyridylamino group, and a carbonamido group (preferably Or a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, and includes, for example, an acetamide group, a benzamide group, a tetradecane amide group, a pivaloyl amide group, or a cyclohexan
• a methane sulfonamide group, a butane sulfonamide group, a benzene sulfonamide group, a hexadecane sulfonamide group, or a cyclohexane sulfonamide group is mentioned, a sulfamoyl amino group (preferably having a carbon number of 1 to 48, more preferably Or a sulfamoylamino group having 1 to 24 carbon atoms, and examples thereof include N, N-dipropylsulfamoylamino group, and N-ethyl-N-dodecylsulfamoylamino group;
• An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms and includes, for example, a methylthio group, an ethylthio group, an octylthio group or a cyclohexylthio group), an arylthio group (preferably It is an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and includes, for example, a phenylthio group, a heterocyclic thio group (preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms).
• Heterocyclic thio group examples thereof include a 2-benzothiazolylthio group, a 2-pyridylthio group, or a 1-phenyltetrazolylthio group, an alkylsulfinyl group (preferably having a carbon number of 1 to 32, preferably). Is an alkylsulfinyl group having 1 to 24 carbon atoms, and examples thereof include a dodecanesulfinyl group.
• An arylsulfinyl group (preferably an arylsulfinyl group having a carbon number of 6 to 32, more preferably a carbon number of 6 to 24, and examples thereof include a phenylsulfinyl group), an alkylsulfonyl group (preferably having a carbon number of 1 to 48, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, And an arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms), such as phenylsulfonyl group or 1-nap
• sulfamoyl groups (preferably having a carbon number of 32 or less, more preferably 24 or less), such as sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N.
• -Dodecylsulfamoyl group N-ethyl-N-phenylsulfamoyl group, or N-cyclohexylsulfamoyl group, sulfo group, phosphonyl group (preferably having a carbon number of 1 to 32, more preferably carbon)
• a phosphonyl group of 1 to 24 includes, for example, phenoxyphosphonyl group, octyloxyphosphonyl group or phenylphosphonyl group, phosphinoylamino group (preferably having a carbon number of 1 to 32, more preferably A phosphinoylamino group having 1 to 24 carbon atoms, and examples thereof include And mino or dioctyloxyphosphinoylamino.
• the monovalent substituent described above when it is a substitutable group, it may be further substituted by any of the above-described groups. In addition, when it has 2 or more further substituents, those substituents may be same or different.
• R 1 and R 2 may be combined with each other to form a 5-, 6- or 7-membered ring
• R 2 and R 3 may be combined with each other to be 5-membered, 6 membered, or 7-membered may form a ring
• R 4 and R 5 are 5- bonded to each other, may form a 6-membered, or 7-membered ring
• R 5 and R 6 Each other may form a 5-, 6-, or 7-membered ring.
• any of a saturated ring or an unsaturated ring may be sufficient.
• Examples of the 5-, 6-, or 7-membered saturated or unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, and the like.
• Examples thereof include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
• the formed 5-, 6-, and 7-membered rings are further substitutable groups, they may be substituted by any of the groups exemplified as the monovalent substituent in the general formula (I). When substituted by two or more substituents, those substituents may be the same or different.
• R 7 represents a halogen atom, an alkyl group, an aryl group or a heterocyclic group.
• the halogen atom, alkyl group, aryl group or heterocyclic group represented by R 7 has the same meaning as the halogen atom, alkyl group, aryl group or heterocyclic group as R 1 to R 6 in the general formula (I).
• the preferred range is also the same as the preferred range of the halogen atom, the alkyl group, the aryl group or the heterocyclic group as R 1 to R 6 described above.
• an alkylamino group, an arylamino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, or a sulfonamide group is preferable, and An amido group, a ureido group, an alkoxycarbonylamino group or a sulfonamide group is more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group or a sulfonamide group is more preferable, and a carbonamido group or a ureido group is particularly preferable.
• R 2 and R 5 among the above, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, nitrile group, imide group, or carbamoylsulfonyl group are preferable.
• An alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a nitrile group, an imide group, or a carbamoylsulfonyl group is more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitrile group, an imide group, Or a carbamoylsulfonyl group is more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group is particularly preferable.
• R 3 and R 4 among the above, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group is preferable, and more preferably It is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
• the alkyl group is preferably a linear, branched or cyclic substituted or unsubstituted alkyl having 1 to 12 carbon atoms And more specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group , A cyclohexyl group, and a benzyl group.
• the alkyl group is more preferably a branched chain having 1 to 12 carbon atoms, or a cyclic substituted or unsubstituted alkyl group, and more specifically, for example, an isopropyl group, a cyclopropyl group, an i-butyl group, Examples thereof include t-butyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, and more preferred are secondary or tertiary substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, and more specifically, for example, And isopropyl group, cyclopropyl group, i-butyl group, t-butyl group, cyclobutyl group and cyclohexyl group.
• R 3 and R 4 represent an aryl group
• preferred examples of the aryl group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group, and more preferable Is a substituted or unsubstituted phenyl group.
• the heterocyclic group is preferably a substituted or unsubstituted 2-thienyl group or a substituted or unsubstituted 4-pyridyl group , Substituted or unsubstituted 3-pyridyl group, substituted or unsubstituted 2-pyridyl group, substituted or unsubstituted 2-furyl group, substituted or unsubstituted 2-pyrimidinyl group, substituted or unsubstituted 2-benzothiazolyl group And a substituted or unsubstituted 1-imidazolyl group, a substituted or unsubstituted 1-pyrazolyl group, a substituted or unsubstituted benzotriazol-1-yl group, more preferably a substituted or unsubstituted 2-thienyl group, Examples thereof include a substituted or unsubstituted 4-pyrid
• the metal or metal compound may be any metal atom or metal compound capable of forming a complex, and is a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or Contain metal chloride of For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl, InCl, FeCl, TiCl 2 , SnCl 2 , SiCl 2 Also included are metal chlorides such as GeCl 2 , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) 2 .
• Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoints of stability of the complex, spectral characteristics, heat resistance, light resistance, manufacturing suitability, etc.
• Zn is particularly preferred.
• R 1 and R 6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group , Alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, azo group, alkylthio group, Represented by an aryl
• R 1 and R 6 each independently represent a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, heterocyclic amino group, carbonamide Group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group;
• R 2 and R 5 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an al
• Preferred embodiments of the dipyrromethene metal complex compound in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound include the following general formulas (I-1), (I-2) and (I-3) The complex compound represented by these is mentioned.
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a monovalent substituent.
• R 7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.
• Ma represents a metal atom or a metal compound,
• X 1 represents a group capable of binding to Ma, and
• X 2 represents a group necessary to neutralize the charge of Ma.
• X 1 and X 2 may be bonded to each other to form a 5-, 6-, or 7-membered ring together with Ma.
• R 1 ⁇ R 6 in the general formula (I-1), general formula (I) in a respectively R 1 ⁇ R 6 synonymous, preferred embodiment is also the same.
• Ma in the general formula (I-1) represents a metal atom or a metal compound, and the metal atom or the metal compound in the above-mentioned “complex in which the compound represented by the general formula (I) is coordinated to the metal atom or the metal compound” And their preferred ranges are also the same.
• R 7 in General Formula (I-1) has the same meaning as R 7 in General Formula (I), and preferred embodiments are also the same.
• X 1 in the general formula (I-1) may be any group as long as it is a group capable of binding to Ma, and water, alcohols (eg, methanol, ethanol, propanol), etc., further “metal chelate” [1 ] Groups derived from the compounds described in Takekazu Sakaguchi and Keihei Ueno (Nanegendo, 1995), [2] (1996), and [3] (1997), etc. may be mentioned. Among them, water, a carboxylic acid compound, an alcohol, an amine compound, and an amide compound are preferable, and water, a carboxylic acid compound, and an amide compound are more preferable in terms of production.
• X 2 in the general formula (I-1) represents a group necessary to neutralize the charge of Ma, and for example, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, an aliphatic imide A monovalent group derived from (such as succinimide, maleimide, glutarimide or diacetamide, preferably succinimide or maleimide), an aromatic imide group or a heterocyclic imide (eg, Phthalimide, naphthalimide, 4-bromophthalimide, 4-methylphthalimide, 4-nitrophthalimide, naphthalenecarboximide, tetrabromophthalimide, etc.
• a halogen atom eg, a fluorine atom, a chlorine atom, a bromine atom
• a aliphatic imide A monovalent group derived from such as succinimide, maleimide, glutarimide or di
• a monovalent group derived from aromatic carboxylic acids eg, benzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, or 4
• aromatic carboxylic acids eg, benzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, or 4
• a monovalent group derived from -tert-butylbenzoic acid and the like preferably benzoic acid, 4-methoxybenzoic acid, salicylic acid and the like; aliphatic carboxylic acids (eg, formic acid,
• a monovalent group derived from dithiocarbamic acid for example, including dimethyldithiocarbamic acid, diethyldithiocarbamic acid, or dibenzyldithiocarbamic acid
• sulfonamide for example, benzenesulfonamide, 4-chlorobenzenesulfonamide, 4-methoxybenzenesulfone
• a monovalent group derived from acetohydroxamic acid, octanohydroxamic acid or benzohydroxamic acid, a nitrogen-containing cyclic compound hydantoin, 1-benzyl-5-ethoxyhydantoin, 1-allylhydanto
• X 2 is preferably a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group, or a nitrogen-containing ring compound from the viewpoint of production.
• Aliphatic carboxylic acid groups, aromatic imide groups and nitrogen-containing ring compounds are more preferred.
• X 1 and X 2 in the general formula (I-1) may be combined with each other to form a 5-, 6- or 7-membered ring with Ma.
• the formed 5-, 6-, and 7-membered rings may be saturated or unsaturated rings.
• the 5-, 6-, and 7-membered rings may be composed of only carbon atoms and hydrogen atoms, and are heterocyclic rings having at least one atom selected from nitrogen atoms, oxygen atoms, and sulfur atoms. It may be.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently , A hydrogen atom, or a monovalent substituent.
• Each of R 7 and R 14 independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.
• Ma represents a metal atom or a metal compound.
• R 1 ⁇ R 6 in formula (I-2) the general formula (I) in a respectively R 1 ⁇ R 6 synonymous, preferred embodiment is also the same.
• the monovalent substituents represented by R 8 to R 13 in the general formula (I-2) are the monovalent substituents represented by R 1 to R 6 of the compound represented by the general formula (I) And their preferred embodiments are also the same.
• the monovalent substituent represented by R 8 to R 13 of the compound represented by the general formula (I-2) is a substitutable group, the monovalent substituent in the general formula (I) described above is used. It may be substituted by any of the groups exemplified as the substituent, and in the case of being substituted by two or more substituents, those substituents may be the same or different.
• R 7 in General Formula (I-2) has the same meaning as R 7 in General Formula (I), and preferred embodiments are also the same.
• R 14 in the general formula (I-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the preferred range of R 14 is the same as the preferred range of R 7 above.
• R 14 is a substitutable group, it may be substituted by any of the groups exemplified as the monovalent substituent in the general formula (I) described above, and may be substituted by two or more substituents. Where present, the substituents may be the same or different.
• Ma in the general formula (I-2) represents a metal or a metal compound, and the metal atom or the metal compound in the above-mentioned “complex in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound” It is synonymous, The preferable range is also the same.
• R 8 and R 9 in the general formula (I-2) may combine with each other to form a 5-, 6-, or 7-membered saturated ring or an unsaturated ring
• R 9 and R 10 May be combined with each other to form a 5-, 6-, or 7-membered saturated ring or unsaturated ring
• R 11 and R 12 are combined with each other to be 5-, 6-, or 7
• R 12 and R 13 may be combined with each other to form a 5-, 6-, or 7-membered saturated ring or unsaturated ring. It is also good.
• the saturated ring or unsaturated ring to be formed is the same as the saturated ring or unsaturated ring formed by R 1 and R 2 , R 2 and R 3 , R 4 and R 5 , or R 5 and R 6. Preferred examples are also the same.
• R 2 , R 3 , R 4 and R 5 each independently represent a hydrogen atom or a monovalent substituent, and R 7 represents a hydrogen atom, a halogen atom, an alkyl Represents a group, an aryl group or a heterocyclic group.
• R 8 and R 9 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group.
• Ma represents a metal atom or a metal compound.
• Each of X 3 and X 4 independently represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group), an oxygen atom, or Represents a sulfur atom.
• Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group
• an oxygen atom or Represents a sulfur atom.
• Y 1 and Y 2 each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group), an oxygen atom, Represents a sulfur atom or a carbon atom.
• X 5 represents a group capable of binding to Ma, and a represents 0, 1 or 2.
• R 8 and Y 1 may be combined with each other to form a 5-, 6-, or 7-membered ring, and R 9 and Y 2 may be combined with each other to be 5, 6, or 7-membered May form a ring of
• Ma in the general formula (I-3) represents a metal or a metal compound, and has the same meaning as a metal atom or a metal compound in a complex in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound The preferred range is also the same.
• each of R 8 and R 9 independently represents an alkyl group (preferably having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, and is a linear, branched or cyclic alkyl group
• alkyl group preferably having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, and is a linear, branched or cyclic alkyl group
• an alkenyl group preferably an alkenyl group having a carbon number of 2 to 24, more preferably 2 to 12
• examples thereof include a vinyl group, an allyl group, and a
• An aryl group (preferably having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms), and examples thereof include a phenyl group and a naphthyl group.
• a heterocyclic group (preferably having a carbon number of 1 to 24, more preferably 1 to 12), for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1- A pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, or benzotriazol-1-yl group may be mentioned, an alkoxy group (preferably having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms) A methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, a dodecyloxy group or a cyclohexyloxy group
• Alkylamino group (preferably having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms), such as methylamino group, ethylamino group, propylamino group, butylamino group, Hexylamino group, 2-ethylhexylamino group, isopropylamino group, t-butylamino group, t-octylamino group, cyclohexylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N- A dibutylamino group or an N-methyl-N-ethylamino group, an arylamino group (preferably having a carbon number of 6 to 36, more preferably 6 to 18), for example, a phenylamino group, Naphthylamino group, N, N-diphenylamino group, or N-ethyl-N-phenylamino group can
• R 8 and R 9 When it is a further substitutable group, it may be substituted by any of the aforementioned groups represented by R 8 or R 9 , and when it is substituted by two or more substituents, And their substituents may be the same or different.
• X 3 and X 4 each independently represent NRa, an oxygen atom, or a sulfur atom.
• Ra is a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36, more preferably 1 to 12 carbon atoms), and examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group , Butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl or 1-adamantyl), alkenyl (preferably having carbon atoms) It is an alkenyl group of 2 to 24, more preferably 2 to 12, and examples thereof include a vinyl group, an allyl group or a 3-buten-1-yl group, an aryl group (preferably having a carbon number of 6 to 36, Prefer
• heterocyclic groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl Group, 1-pyrazolyl group, or benzotriazol-1-yl group, acyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms), for example, acetyl group, pivaloyl group And an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms), such as a methylsulfonyl group, Ethylsulfonyl group, isopropylsulfonyl group or cyclohexylsulfonyl group can be mentioned), aryl Ruhoniru group (preferably having 6 carbon atoms 24, more preferably 6 to 18 arylsulfonyl group, for example, a
• Ra when substitutable, it may be further substituted by each group mentioned above, and when it is substituted by two or more substituents, those substituents may be the same or different. It is also good.
• Each of X 3 and X 4 is preferably, independently, an oxygen atom or a sulfur atom, and particularly preferably, both of X 3 and X 4 are an oxygen atom.
• Y 1 and Y 2 each independently represent NR b, a sulfur atom, or a carbon atom, and R b has the same meaning as Ra in X 3 .
• Y 1 and Y 2 are preferably each independently NRb (Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and Y 1 and Y 2 are particularly preferably both NH. .
• R 8 and Y 1 are bonded to each other to form a 5-membered ring (for example, cyclopentane, pyrrolidine, tetrahydrofuran, etc.) together with R 8 , Y 1 and carbon atoms adjacent thereto.
• a 5-membered ring for example, cyclopentane, pyrrolidine, tetrahydrofuran, etc.
• 6-membered ring eg cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine Or pyridazine, quinoline
• R 9 and Y 2 bond to each other to form a 5-, 6-, or 7-membered ring together with R 9 , Y 2 and a carbon atom adjacent thereto. It may be done.
• Examples of the formed 5-, 6-, and 7-membered rings include rings in which one bond in the ring formed by R 8 , Y 1 and carbon atoms is changed to a double bond.
• X 5 represents a group capable of binding to Ma, and examples thereof include the same groups as X 2 in the general formula (I-1).
• a represents 0, 1 or 2;
• R 2 to R 5 , R 7 and Ma each represent the same as a preferred embodiment of a complex (dipyrromethene metal complex compound) containing a structure represented by general formula (I) and a metal atom or a metal compound
• 3 and X 4 each independently represent NRa (wherein Ra represents a hydrogen atom, an alkyl group or a heterocyclic group), or an oxygen atom
• Y 1 and Y 2 each independently represent NRb (Rb represents a hydrogen atom, Or an alkyl group is mentioned)
• X 5 is a group bonded via an oxygen atom or a nitrogen atom
• R 8 and R 9 are each independently an alkyl group or an aryl group
• Group represents a group, a heterocyclic group, an alkoxy group, or an alkylamino group
• R 2 to R 5 , R 7 and Ma are respectively the same as the preferred embodiments of the complex (dipyrromethene metal complex compound) containing the structure represented by the general formula (I) and a metal atom or a metal compound;
• X 3 And X 4 is an oxygen atom;
• Y 1 is NH;
• Y 2 is a nitrogen atom;
• X 5 is an oxygen atom or a group bonded via a nitrogen atom;
• R 8 and R 9 are each independently represent an alkyl group, an aryl group, a heterocyclic group, or an alkoxy group, or an alkylamino group, bonded with R 8 and Y 1 are each other to form a 5-membered or 6-membered ring,
• R 9 and Y And a is an embodiment represented by 0 or 1 in which 2 is bonded to each other to form a
• the above general formulas (I-1), (I-2) and (I-3) are preferred embodiments of the dipyrromethene metal complex compound in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound.
• the complex compounds represented by the general formula (I-3) are particularly preferable embodiments.
• metal complex compound dipyrromethene metal complex compound in which the compound represented by the general formula (I) used in the present invention is coordinated to a metal atom or a metal compound.
• the present invention is not limited to these.
• Exemplified compounds (1) to (30) are shown.
• the exemplified compounds (1) to (30) can be represented by R 101 , R 102 , R 103 , X 101 and M 1 in the general formula (I-4) Is a compound which is a combination shown below.
• Examples of the compound represented by the general formula (I-4) also include the following exemplified compounds (31) to (45).
• the exemplified compounds (40) to (44) have the general formula (I) It is also an exemplified compound of -1), exemplified compound (45) is also exemplified compound of general formula (I-2), and exemplified compounds (1) to (39) are also exemplified compounds of general formula (I-3) .
• dipyrromethene metal complex compounds As the dipyrromethene metal complex compounds, exemplified compounds (Ia-3) to (Ia-83) and (Ia-1) to (IIa-20) described in JP-A-2008-292970, in addition to the above exemplified compounds, Exemplary Compounds (I-1) to (I-1) to (I-36) (II-1) to (II-11), and (III-1) to (III-103), Patent No. 3324279 Examples (I-1) to (I-13) described in Japanese Patent No. 3279035, and Example Compounds (2-1) to (2) described in Japanese Patent Application Laid-Open No. 11-256057.
• Phthalocyanine Metal Complex compound As the phthalocyanine metal complex compound, a compound represented by the following general formula (II) is preferable.
• R a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R o and R p each independently represent a hydrogen atom, a halogen atom or a monovalent substituent, and R a , R b , R c , R d , R e , R f , R g , R h , R At least one of i , R j , R k , R l , R m , R n , R o , and R p represents a monovalent substituent.
• M represents a metal or a metal compound.
• the metal or metal compound may be any metal or metal compound capable of forming a complex, and may be a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or Contain metal chloride of M in the general formula (II) is, for example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, etc., and AlCl, InCl, FeCl, etc.
• Metal chlorides such as TiCl 2 , SnCl 2 , SiCl 2 and GeCl 2 , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) 2 are included.
• the maximum absorption wavelength ⁇ max of the raphthalocyanine metal complex in the present invention is preferably 580 nm to 700 nm, and more preferably 600 nm to 680 nm, from the viewpoint of improving color purity.
• the maximum absorption wavelength was measured in the same manner as the dipyrromethene metal complex compound in the present invention.
• R a to R p each represents a monovalent substituent
• R 1 to R 6 in the general formula (I) described above It is synonymous with the illustration of group, The preferable aspect is also the same.
• all of the 16 substituents R a to R p are not all hydrogen atoms or halogen atoms, and at least one of these is a monovalent substituent as described above other than hydrogen atoms and halogen atoms. Need to be When the monovalent substituent represented by R a to R p of the compound represented by the general formula (II) is a substitutable group, it is substituted by the substituent described in R 1 to R 6 above. When substituted by two or more substituents, those substituents may be the same or different.
• T-1 to T141 examples (T-1 to T141) of a halogen atom and a monovalent substituent which can be taken by R a to R p in the general formula (II) are shown.
• the present invention is not limited to these.
• R a to R p each represents a monovalent substituent
• a halogen atom an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a carboxyl group is exemplified.
• M examples include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, TiO, VO and the like, and more preferably Cu, Zn, Co, TiO, VO, Mg, etc. may be mentioned, and particularly preferably Cu, Zn, Co, TiO, VO.
• xanthene dyes for example, xanthene dyes, anthraquinone dyes, porphyrin dyes, cyanine dyes and methine dyes may be used in combination as the (A) dye in the present invention.
• the colored curable composition of the present invention may contain only one kind of the (A) dye, and may be used in combination of two or more kinds according to the purpose. Usually, in order to achieve a desired hue, two or more are used in combination. Moreover, depending on the purpose, a pigment may be used in combination.
• the content of the (A) dye in the colored curable composition of the present invention is preferably 1 to 50% by mass, and more preferably 5 to 40% by mass, with respect to the solid content of the composition.
• Favorable spectral characteristics and heat resistance are obtained as content of a metal complex pigment
• dye is 1 mass% or more, and it is advantageous at the point of a hue as it is 50 mass% or less.
• solid content refers to the total amount of all the components except the solvent in a coloring curable composition here.
• a binder resin having an acid value in the range of 150 mg KOH / g to 300 mg KOH / g a binder resin having an acid value in the range of 150 mg KOH / g to 300 mg KOH / g
• the specific binder (B) contains a crosslinkable group having a specific structure and an acidic group in the molecule, and the acid value is required to be in the range of 150 mg KOH / g to 300 mg KOH / g.
• the (B) specific binder of the present invention comprises at least one structural unit (b-1) selected from monomers represented by the following general formula (1) and monomers represented by the following general formula (2) And the like.
• structural unit (b-1) is a monomer which has a crosslinkable group so that it may become clear from the following structure
• (B) specific binder is a crosslinkable group derived from these structural units (b-1) In the molecule.
• R 11 represents a hydrogen atom or a methyl group
• R 12 and R 13 each independently represent a hydrogen atom or a carbonyl group having a carbon number of 3 to 20 containing an unsaturated double bond as a partial structure
• R 12 and R 13 are not both hydrogen atoms.
• R 11 represents a hydrogen atom or a methyl group, preferably a methyl group.
• R 12 and R 13 each independently represent a hydrogen atom or a carbonyl group having a carbon number of 3 to 20 containing an unsaturated double bond as a partial structure, and when R 12 and R 13 each represent the carbonyl group, a partial structure And may contain a carboxyl group, and preferably represents an ⁇ , ⁇ -unsaturated carbonyl group having a carbon number of 3 to 4.
• R 20 represents a hydrogen atom or a methyl group
• R 21 , R 22 , R 23 , R 24 and R 25 each independently represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group Or an aryl group.
• R 20 represents a hydrogen atom or a methyl group, preferably a methyl group.
• Specific examples of the halogen atom when R 21 to R 25 represent a halogen atom include, for example, Cl, Br, I and the like.
• Examples of the alkyl group when R 21 to R 25 represent an alkyl group include linear And may be any of branched and cyclic, and specific examples thereof include methyl, n-propyl, iso-propyl and tert-butyl groups, and the like, and alkyl having 1 to 7 carbon atoms Groups are preferred.
• Specific examples of the aryl group when R 21 to R 25 represent an aryl group include, for example, a phenyl group, a furyl group, and a naphthyl group.
• Each of R 21 , R 22 , R 23 , R 24 and R 25 is preferably a hydrogen atom, and more preferably all hydrogen atoms.
• Specific examples of the structural unit (b-2) include the following structures, but the present invention is not limited thereto.
• the (B) specific binder of the present invention is a copolymer further comprising a structural unit derived from the monomer (b-2) having an acidic group.
• a structural unit derived from the monomer (b-2) having an acidic group As an acidic group in the monomer used for this invention and which has an acidic group, a carboxy group, a sulfoxy group, etc. are mentioned.
• acrylic acid, methacrylic acid, a sulfonic acid, a phosphoric acid etc. are mentioned, Especially, acrylic acid and methacrylic acid are preferable.
• (B) A monomer having at least one crosslinkable group selected from the monomer represented by the general formula (1) and the monomer represented by the general formula (2) in a specific binder (b-1
• the molar ratio of the structural unit derived from (a) (structural unit: b-1) to the structural unit (a structural unit: b-2) derived from the monomer (b-2) having an acidic group is 1: 0.3. It is preferably in the range of ⁇ 1: 2, and more preferably in the range of 1: 0.3 to 1: 1.
• the (B) specific binder may further include another structural unit having a structure different from that of the structural unit: (b-1) and the structural unit: (b-2).
• the monomer giving (B) another structural unit usable for the specific binder include benzyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, isobutyl methacrylate, styrene and the like.
• the content of the other structural unit is preferably 0 to 40 mol%, and more preferably 30 mol% or less.
• the synthesis of the specific binder (B) used in the present invention can be carried out by a conventional method. Below, the synthesis example of the exemplary compounds 1 and 6 is shown. Other exemplified compounds can be synthesized by similar methods. Synthesis of Exemplified Compound 1 Methacrylic acid (55 parts by weight), cyclohexyl methacrylate (61 parts by weight), 1-methoxy-2-propanol (175 parts by weight), V-601 (trade name: manufactured by Wako Pure Chemical Industries, Ltd., polymerization start A mixed solution of 6.8 parts by weight of an agent (Dimethyl 2,2'-azobis (2-methylpropionate)) was polymerized at 90.degree. C. for 4 hours under a nitrogen stream.
• an agent Dimethyl 2,2'-azobis (2-methylpropionate
• Exemplified Compound 1 was synthesized by adding glycidyl methacrylate (37 parts by weight), tetraethylammonium bromide (0.6 parts by weight) and methyl ethyl ketone (40 parts by weight) to the reaction mixture solution, and reacting at 100 ° C. for 4 hours. .
• the weight average molecular weight (GPC, in terms of polystyrene) of the obtained polymer was 30,000.
• the weight average molecular weight of the obtained polymer was 33,000.
• the content of the (B) specific binder in the colored curable composition of the present invention is preferably in the range of 0.1 parts by mass to 20 parts by mass with respect to 1 part by mass of the dye (A).
• the colored curable composition of the present invention contains an 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 the solid content, the coating property It is preferable to be selected in consideration of 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 And oxyacetic acid alkyl esters (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate etc., more specifically methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Etc., 3-hydroxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyru
• ethers used as an organic solvent 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 mono Butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl-n-propyl ether, propylene Glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate
• ketones used as the organic solvent include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like.
• aromatic hydrocarbon used as an organic solvent toluene, xylene etc. are mentioned suitably, for example.
• 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 an amount that the total solid concentration in the colored curable composition is 10% by mass to 80% by mass, and is preferably 15% by mass to 60% by mass. More preferable.
• the colored curable composition of the present invention may contain various compounds according to the purpose as long as the effects of the present invention are not impaired. It may be Polymerizable Compound
• the colored curable composition of the present invention may contain at least one kind of polymerizable compound having a structure different from that of the (B) specific binder. By containing the polymerizable compound, the curability of the colored curable composition can be improved.
• a photopolymerizable compound can be mentioned as a polymerizable compound.
• the photopolymerizable compound is preferably a compound having a boiling point of 100 ° C. or more under normal pressure and having at least one addition polymerizable ethylenic unsaturated group.
• Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tritriol (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Those obtained by adding ethylene oxide or propylene oxide to a
• thermally polymerizable compound in addition to the above-mentioned photopolymerizable compound, a thermally polymerizable compound can also be contained as a polymeric compound.
• the thermally polymerizable compound include epoxy compounds, oxetane compounds, 1,2-halohydrin compounds, etc. More specifically, Patent 3599866, Patent 4459651, Patent 3850756, Patent 4185245, etc. The compound as described in is mentioned.
• an alkali-soluble resin having a polymerizable group can be mentioned.
• the alkali-soluble resin having a polymerizable group include alkali-soluble resins having a (meth) acryloyl group and a glycidyl group, and specific examples thereof include JP 2007-233184 A and JP 2005-326507 A. The resin as described in etc. is mentioned.
• an alkali-soluble resin having a polymerizable group in the side chain may be used, and a polymer having an allyl group, a (meth) acrylic group, an allyloxyalkyl group or the like in the side chain is also useful.
• the polymer having such a polymerizable group include KS Resist-106 (trade name, manufactured by Osaka Organic Chemical Industry Ltd.), Cyclomer P series (trade name, manufactured by Daicel Chemical Industries, Ltd.), etc. It can be mentioned.
• the content in the colored curable composition in the case of using a polymerizable compound is preferably 0.1 to 90% by mass, and more preferably 1.0 to 80% by mass with respect to the solid content in the colored curable composition. Preferably, 2.0% by mass to 70% by mass is particularly preferable.
• the colored curable composition of the present invention preferably contains at least one radiation-sensitive initiator.
• a photopolymerization initiator is a compound capable of causing a chemical reaction such as radical generation, acid generation or base generation for ultraviolet (UV) light of 400 nm or less, and (B) a specific binder or a polymerizing material optionally used Insolubilizing a coating film in an alkali developer by causing the compound to be insolubilized by a reaction such as crosslinking or polymerization, or causing polymerization of a polymerizable monomer or oligomer coexistent in the coating film, or crosslinking of a crosslinking agent.
• UV ultraviolet
• 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 for example, at least one active halogen compound selected from halomethyl oxadiazole compounds, halomethyl-s-triazine compounds, 3-aryl substituted coumarin compounds, rhofin dimers, benzophenone compounds, acetophenone compounds And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.
• active halogen compound selected from halomethyl oxadiazole compounds, halomethyl-s-triazine compounds, 3-aryl substituted coumarin compounds, rhofin dimers, benzophenone compounds, acetophenone compounds And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.
• active halogen compound selected from halomethyl oxadiazole compounds, halomethyl-s-triazine compounds, 3-aryl substituted coumarin compounds, rhofin dim
• the oxime-based compound (hereinafter, also referred to as an oxime-based photopolymerization initiator) is not particularly limited, and, for example, the oximes described in JP-A-2000-80068, WO02 / 100903 A1, JP-A-2001-233842, etc. There is a series of compounds.
• an oxime-O-acyl compound such as oxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, specifically, for example, CGI- 124, CGI-242, Irgacure OXE01 (trade names, manufactured by Ciba Japan KK) and the like.
• a compound represented by the following general formula (3) or (4) is more preferable as the oxime-based compound.
• R and X each independently represent a monovalent substituent
• A represents a divalent organic group
• Ar represents an aryl group.
• n is an integer of 0 to 5. When n is an integer of 2 to 5, plural X's may be the same or different.
• an acyl group is preferable from the viewpoint of sensitization, and specifically, an acetyl group, a propionyl group, a benzoyl group, or a toluyl group is preferable.
• unsubstituted alkylene group alkyl group (for example, methyl group, ethyl group, tert-butyl) Group, or an alkylene group substituted by dodecyl group, an alkylene group substituted by alkenyl group (eg, vinyl group or allyl group), an aryl group (eg, phenyl group, p-tolyl group, xylyl group, cumenyl group)
• an alkylene group substituted with a naphthyl group, anthryl group, phenanthryl group or styryl group is preferable.
• a substituted or unsubstituted phenyl group is preferable from the viewpoint of enhancing sensitivity and suppressing coloring due to heating and aging.
• a substituted phenyl group for example, a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferable.
• X in the general formula (3) and the general formula (4) it may have an alkyl group which may have a substituent, and a substituent from the viewpoint of improving the solvent solubility and the absorption efficiency in the long wavelength region.
• the alkylthioxy group which may have, the arylthioxy group which may have a substituent, and the amino group which may have a substituent are preferable.
• n in the general formula (3) and the general formula (4) is preferably an integer of 01 to 2.
• the radiation sensitive compounds can be contained singly or in combination of two or more.
• the content (total content in the case of two or more types) of the photopolymerization initiator in the colored curable composition is 0.01 to the total solid content of the polymerizable compound. 50% by mass is preferable, 1 to 30% by mass is more preferable, and 1 to 20% by mass is particularly preferable. If the content is in the above range, polymerization proceeds well and the film strength is excellent.
• a sensitizer and a light stabilizer can be used in combination with the photopolymerization initiator.
• Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (di
• thermal polymerization inhibitor for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone 4,
• thermal polymerization inhibitor for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone 4
• 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like.
• the colored curable composition of the present invention may contain a binder (referred to as another binder) having no crosslinkable group, which is different in structure from (B) the specific binder.
• the binder can be selected from those having alkali solubility. In this case, it is not particularly limited as long as it has alkali solubility, but it is preferably selected from the viewpoints of heat resistance, developability, availability and the like.
• the alkali-soluble binder is preferably a linear organic high molecular weight polymer which is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.
• linear organic high molecular weight polymers polymers having a carboxylic acid in the side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54- No.
• methacrylic acid copolymer acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid Copolymers, partially esterified maleic acid copolymers and the like can be mentioned.
• alkali-soluble binder particularly, an acidic cellulose derivative having a carboxylic acid in its side chain is useful.
• monomers having a hydrophilic group may be copolymerized, and examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylol acrylamide.
• Secondary and tertiary alkyl acrylamides dialkylaminoalkyl (meth) acrylates, morpholino (meth) acrylates, N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl triazole, methyl (meth) acrylate, ethyl (meth) Acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate and the like can be mentioned.
• monomers having a hydrophilic group tetrahydrofurfuryl group, phosphoric acid site, phosphoric acid ester site, quaternary ammonium salt site, ethylene oxy chain, propylene oxy chain, sulfonic acid and its salt site, morpholinoethyl group etc. Monomers, etc. contained are also useful.
• alcohol-soluble nylon, polyether of 2,2-bis (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful to increase the strength of the cured film.
• binders are preferably polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins. Further, from the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.
• the acrylic resin is preferably a copolymer comprising a monomer selected from benzyl (meth) acrylate, (meth) acrylic, hydroxyethyl (meth) acrylate, (meth) acrylamide and the like.
• the other binder is preferably a polymer having a mass average molecular weight (in terms of polystyrene measured by GPC method) of 1000 to 2 ⁇ 10 5 , more preferably a polymer of 2000 to 1 ⁇ 10 5 , still more preferably 5000 to 5 ⁇ 10 5
• the polymer of 4 is particularly preferred.
• 10 to 90 mass% is preferable with respect to the total solid of a composition, and, as for content in the colored curable composition in the case of using another binder, 20 to 80 mass% is more preferable, and 30 to 70 mass% Is particularly preferred.
• additives such as fillers, polymer compounds other than the above, surfactants, adhesion accelerators, antioxidants, UV absorbers, if necessary, Or an aggregation inhibitor etc. can be mix
• Examples of the various additives include those described in paragraph Nos. [0275] to [0276] of JP-A-2008-292970.
• the coloring component may further contain a pigment or the like as long as the effects of the present invention are not impaired. By containing various combinations of pigments, it is possible to achieve the desired hue and color purity.
• the colored curable composition of the present invention is used for forming colored pixels such as color filters used in liquid crystal display devices (LCD) and solid-state imaging devices (for example, CCD, CMOS etc.), and also for printing ink, inkjet ink, It can be used suitably as preparation applications, such as paints. In the present invention, in particular, it can be suitably used for applications of color filters for liquid crystal display elements.
• the color filter of the present invention contains at least the dye (A), the specific binder (B), and the specific solvent (C), and may optionally contain other components.
• the color filter of the present invention contains the specific binder of the present invention (B) together with the dye (A), so that the stability of the dye (A) is improved, and the dye is exposed to a high temperature atmosphere by post-baking process. Even in the case of (A), discoloration or decoloration resulting from the decomposition of the dye is suppressed, and excellent hue is maintained for a long time. Therefore, it is possible to display an image with good color tone over a long period of time.
• the color filter of the present invention may be formed by any method as long as it can form a colored film (colored pattern) cured using the colored curable composition of the present invention.
• the color filter of the present invention comprises the steps of applying the colored curable composition of the present invention on a support to form a colored layer, exposing the formed colored layer in a pattern and developing the colored region And the forming step can be suitably prepared by the method provided. Specifically, after the colored curable composition of the present invention is applied onto a support by a coating method such as spin coating, cast coating, roll coating, etc. to form a radiation sensitive composition layer, this layer is A desired colored area which is a colored pattern constituting a color filter can be formed by exposing in a predetermined pattern through a mask pattern and developing with a developer. By repeating these operations in accordance with the desired number of colors, it is possible to obtain a color filter configured to have the desired number of hues.
• a coating method such as spin coating, cast coating, roll coating, etc.
• a light source used for exposure a light source having a wavelength of 400 nm or less is preferable.
• light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, etc., described in paragraph No. [0278] of JP 2008-292970A. Can be mentioned. From the viewpoint of cost and exposure energy, preferred is ultraviolet light, and further i-ray.
• the pattern formed by exposure and development may be further provided with a curing step of heating and / or exposing for more curing, if necessary.
• a curing step of heating and / or exposing for more curing, if necessary.
• radiation such as i-line is preferable.
• the support examples include soda glass, Pyrex (registered trademark) glass and quartz glass used for liquid crystal display devices and the like, those obtained by attaching a transparent conductive film to these, photoelectric conversion device substrates used for imaging devices and the like, For example, a silicon substrate etc., a complementary metal oxide semiconductor (CMOS) etc. are mentioned. These supports may be provided with black stripes separating the respective pixels. In addition, a subbing layer may be provided on the support in order to improve the adhesion between the layer provided thereon, if necessary, to prevent the diffusion of substances, or to flatten the surface of the support.
• CMOS complementary metal oxide semiconductor
• the developer used for development is particularly limited as long as it dissolves a region (uncured portion) to be developed and removed of the colored curable composition but does not dissolve the other region (cured portion).
• a combination of various organic solvents and an alkaline aqueous solution can be used as the developer.
• the organic solvent include the aforementioned solvents used when preparing the composition.
• an alkaline aqueous solution an alkaline aqueous solution in which an alkaline compound is dissolved to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass can be used.
• alkaline compound examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium borate, sodium metaborate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and the like can be mentioned.
• an alkaline aqueous solution washing with water is generally performed after development.
• the color filter of the present invention can be used for organic EL display devices, liquid crystal display devices and solid-state imaging devices, and is particularly suitable for use in liquid crystal display devices.
• a dye excellent in spectral characteristics and heat resistance preferably a metal complex dye as a colorant, the change in hue due to heat treatment or the like is small, and the tint of a displayed image is Good and excellent in display characteristics.
• the color filter of the present invention is particularly suitable as a color filter for a display device such as an organic EL display device or a liquid crystal display device because it has colored pixels excellent in hue and light resistance.
• a display device provided with such a color filter can display a high-quality image with excellent color tone of a display image and excellent display characteristics for a long time. That is, the display device of the present invention is provided with a color filter using the colored curable composition of the present invention or a color filter obtained by the method of producing a color filter of the present invention.
• the color filter of the present invention is particularly effective for a color TFT liquid crystal display device, among others.
• 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 present invention relates to a liquid crystal display device in which the viewing angle is expanded, such as a horizontal electric field drive method such as IPS (In-plane Switching) or a pixel division method such as MVA (Multi-domain Vertical Alignment), or STN (Super Twisted Nematic) And TN (Twisted Nematic), VA (Vertical Alignment), OCS (Optically Compensated Splay), FFS (Fringe Field Switching), R-OCB (Reflective Optically Compensated Bend), and the like.
• a horizontal electric field drive method such as IPS (In-plane Switching) or a pixel division method such as MVA (Multi-domain Vertical Alignment), or STN (Super Twisted Nematic) And TN (Twisted Nematic), VA (Vertical Alignment), OCS (Optically Compensated Splay), FFS (Fringe Field Switching), R-OCB (Reflective Optically Compensated Bend), and the like.
• 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-mentioned normal requirements.
• the color filter of the present invention is obtained by curing a curable composition comprising the (B) dye and the (B) specific binder together with the (A) dye. It is considered that the stability is dramatically improved and the deterioration of the display characteristics is eliminated. Accordingly, since the color purity and the like are good and the color tone is excellent, it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability.
• a resin film may be provided on the color filter layer in order to satisfy the required characteristics.
• one side has a 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 under the colored layer. It is necessary to form a conducting path such as a rectangular through hole or a U-shaped (U-shaped) recess, and the dimension of the conducting path (that is, the length of one side) is preferably 5 ⁇ m or less. By using the present invention, it is also possible to form a conduction path of 5 ⁇ m or less.
• the display device of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle ensuring film, etc., 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 element 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, published in 2003).
• For backlight see SID meeting Digest 1380 (2005) (A. Konno et. Al), pages 18 to 24 of Monthly Display December 2005 (Yasuhiro Shima), pages 25 to 30 (Takaaki Yagi), etc. Have been described.
• the color filter of the present invention When the color filter of the present invention is used for a liquid crystal display element, high contrast can be realized when it is combined with a conventionally known cold cathode tube three wavelength tube, but red, green and blue LED light sources (RGB-LED) By using as a backlight, it is possible to provide a liquid crystal display device having high luminance and high color purity and good color reproducibility.
• RGB-LED red, green and blue LED light sources
• the solid-state imaging device of the present invention comprises the color filter of the present invention described above.
• the configuration of the solid-state imaging device according to the present invention is a configuration provided with the color filter according to the present invention, and is not particularly limited as long as it functions as a solid-state imaging device. .
• a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like, and on the photodiodes and the transfer electrodes It has a light shielding film made of tungsten or the like in which only the light receiving portion of the photodiode is opened, and has a device protective film made of silicon nitride or the like formed on the light shielding film to cover the entire light shielding film and the photodiode light receiving portion It is a structure which has a color filter for solid-state image sensors of this invention on a device protective film.
• Synthesis Example 1 Synthesis of Exemplified Compound 1 Methacrylic acid (55 parts by weight), cyclohexyl methacrylate (61 parts by weight), 1-methoxy-2-propanol (175 parts by weight), V-601 (trade name: Wako Pure Chemical Industries, Ltd.) A mixed solution of 6.8 parts by weight) was polymerized at 90 ° C. for 4 hours under a nitrogen stream. Furthermore, Exemplified Compound 1 was synthesized by adding glycidyl methacrylate (37 parts by weight), tetraethylammonium bromide (0.6 parts by weight) and methyl ethyl ketone (40 parts by weight) to the reaction mixture solution, and reacting at 100 ° C. for 4 hours. . The weight average molecular weight (GPC, in terms of polystyrene) of the obtained polymer was 30,000.
• GPC weight average molecular weight
• Synthesis Example 2 Synthesis of Exemplified Compound 6 Allyl methacrylate (79 parts by weight), methacrylic acid (32 parts by weight), 1-methoxy-2-propanol (140 parts by weight), V-65 (polymerization initiator, trade name: A mixed solution of Wako Pure Chemical Industries, Ltd .: 0.6 parts by weight) was polymerized at 70 ° C. for 8 hours under a nitrogen stream. The reaction solution was cooled to room temperature, water (200 parts by weight) was added, and reprecipitation treatment was performed. The aggregated polymer was filtered, washed with water and then dried to synthesize Example Compound 6. The weight average molecular weight of the obtained polymer (GPC method, in terms of polystyrene) was 33,000.
• Example 1 Preparation of Colored Photosensitive Composition
• Organic solvent 1 (propylene glycol monomethyl ether acetate) 5.1 g -Organic solvent 2 (diethylene glycol ethyl methyl ether) 17.1 g ⁇
• Binder resin (exemplified compound 1) 12.2 g -Polymerizable compound 1 (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 4.0 g -Polymerizable compound 2 (manufactured by Toagosei Co., Ltd., ALONIX TO-2349) 1.3 g ⁇ 0.003 g of polymerization inhibitor (p-methoxyphenol) ⁇ Photopolymerization initiator 1 (1- (O-acetyloxime) -1- [9-ethyl-6-) 0.39 g of (thiophenoyl) -9H-c
• Blue pigment dispersion 1 was prepared as follows. C. I. 12.8 parts of pigment blue 15: 6 and 7.2 parts of dispersant (trade name: Solsparse 5500, manufactured by Nippon Lubrizol) with 80.0 parts of propylene glycol monomethyl ether acetate and using a bead mill The pigment was well dispersed to prepare a blue pigment dispersion.
• Dye solution 1 was prepared by mixing and dissolving the following components.
• Organic solvent 1 (propylene glycol monomethyl ether acetate) 4.23 g ⁇ Dye (B-1) 0.47 g
• Dye solution 2 was prepared by mixing and dissolving the following components.
• Organic solvent 1 (propylene glycol monomethyl ether acetate) 23.84 g -Dye (A-1) 1.26 g
• the dye (A-1) used in the preparation of the colored photosensitive composition of Example 1 below is an exemplified compound (11) of a pyrromethene metal complex dye.
• the dye (B-1) is an anthraquinone compound (a compound having an anthracene-9,10-dione skeleton) of the following structure.
• the photosensitive colored curable composition prepared above is applied on a glass (# 1737; manufactured by Corning) by spin coating, and then heated at 100 ° C. for 80 seconds.
• the volatile component was volatilized to form a photosensitive colored film.
• the photosensitive colored film was irradiated with i-ray (wavelength 365 nm) to be cured.
• An ultra-high pressure mercury lamp was used as a light source of the i-line, and at this time, the irradiation light amount was 40 mJ / cm 2 .
• development was carried out at 25 ° C. for 40 seconds with a 0.05% KOH solution, and then the developing solution was washed away by rinsing with pure water.
• post-baking treatment was performed on this colored film at 230 ° C. for 60 minutes to obtain a colored film having a thickness of 2 ⁇ m.
• Example 2 to Example 9 A photosensitive colored curable composition is prepared and a colored film is formed in the same manner as in Example 1 except that (B) the specific binder in Example 1 is changed to one shown in Table 1, and evaluation is made I did. The evaluation results are shown in Table 1 below.
• Comparative Examples 1 to 3 A photosensitive colored curable composition was prepared in the same manner as in Example 1 except that the comparative binder (comparative compounds 1 to 3) shown in Table 1 was used in place of the specific binder (B) in Example 1. The evaluation was performed while forming a colored film. The evaluation results are shown in Table 1 below.
• Comparative Example 1 using the comparative compound 1 whose acid value is out of the scope of the present invention, and the structural unit (b-1), which contain the structural unit derived from the monomer according to the present invention
• the decrease in luminance in the post-baking step can not be suppressed, and the displayed image has poor color tone, and the display characteristics It was inferior to.

Landscapes

• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• General Physics & Mathematics (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Structural Engineering (AREA)
• Architecture (AREA)
• Materials For Photolithography (AREA)
• Liquid Crystal (AREA)
• Electroluminescent Light Sources (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Optical Filters (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=47995650

Family Applications (1)

Country Status (3)

Families Citing this family (4)

Citations (4)

• 2011
  • 2011-09-30 JP JP2011218597A patent/JP2013080010A/ja active Pending
• 2012
  • 2012-09-26 WO PCT/JP2012/074787 patent/WO2013047619A1/ja not_active Ceased
  • 2012-09-27 TW TW101135447A patent/TW201319741A/zh unknown

Patent Citations (4)

Also Published As

Similar Documents

Legal Events