WO2016031442A1 - 着色組成物、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子、画像表示装置および色素多量体の製造方法 - Google Patents

着色組成物、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子、画像表示装置および色素多量体の製造方法 Download PDF

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Publication number
WO2016031442A1
WO2016031442A1 PCT/JP2015/070896 JP2015070896W WO2016031442A1 WO 2016031442 A1 WO2016031442 A1 WO 2016031442A1 JP 2015070896 W JP2015070896 W JP 2015070896W WO 2016031442 A1 WO2016031442 A1 WO 2016031442A1
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WIPO (PCT)
Prior art keywords
group
dye
compound
general formula
color filter
Prior art date
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PCT/JP2015/070896
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English (en)
French (fr)
Japanese (ja)
Inventor
彰宏 原
純一 伊藤
昌之 原田
宏明 出井
賢 鮫島
金子　祐士
和也 尾田
Original Assignee
富士フイルム株式会社
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Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN201580037421.4A priority Critical patent/CN106661343B/zh
Priority to KR1020197008353A priority patent/KR102027797B1/ko
Priority to JP2016545056A priority patent/JP6279745B2/ja
Priority to KR1020177000656A priority patent/KR20170016954A/ko
Publication of WO2016031442A1 publication Critical patent/WO2016031442A1/ja

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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
    • 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
    • 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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • G03F7/09—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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation

Definitions

  • the present invention relates to a coloring composition.
  • the present invention relates to a coloring composition suitable for a color filter used in a solid-state imaging device, an image display device and the like.
  • the present invention also relates to a color filter, a solid-state imaging device, and an image display device using the coloring composition.
  • the present invention also relates to a pattern forming method using a colored composition, a color filter manufacturing method, and a dye multimer manufacturing method.
  • color filters are used as key devices for these displays and optical elements, and there is an increasing demand for higher sensitivity and miniaturization.
  • Such a color filter normally has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and plays a role of separating transmitted light into the three primary colors.
  • Colorants used in color filters are required to have the following properties in common. That is, it is required to have a light absorption characteristic that is favorable for color reproducibility and to have good light resistance.
  • Patent Document 1 discloses a pigment dispersant having 2 to 9 sites having adsorption ability for a pigment in one molecule.
  • site having the ability to adsorb to pigment organic dye structure, heterocyclic structure, acidic group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, hydrocarbon having 4 or more carbon atoms Groups, alkoxysilyl groups, epoxy groups, isocyanate groups, hydroxyl groups, ionic functional groups and the like.
  • Patent Document 1 is an invention related to a pigment dispersant.
  • Patent Document 1 describes that an organic dye structure may be used as a site having an adsorptive capacity for a pigment. However, since the pigment dispersant preferably has no color, the adsorptive capacity for the pigment is determined. It is necessary to select a structure having a low absorbance as the site to have. In addition, Patent Document 1 does not include a motivation to use a pigment dispersant as a colorant.
  • the present invention has been made in view of such a situation, and an object thereof is to provide a coloring composition having excellent light resistance, color transfer and flatness. It is another object of the present invention to provide a color filter, a pattern forming method, a color filter manufacturing method, a solid-state imaging device, an image display device, and a dye multimer manufacturing method.
  • the present inventors have found that light resistance, color transfer and flatness are obtained by using a dye multimer in which n polymer chains including a repeating unit having a dye structure are bonded to an n-valent linking group.
  • the inventors have found that a colored composition excellent in the above can be obtained, and have completed the present invention. Therefore, the present invention provides the following.
  • a colored composition comprising a dye multimer represented by the general formula (1) and a polymerizable compound; P- (Q) n (1)
  • P represents an n-valent linking group
  • Q represents a polymer chain containing a repeating unit having a dye structure
  • the average value of the number of repeating units of n Q having a dye structure is 2 or more
  • n represents an integer of 3 to 10.
  • a 1 represents an n-valent linking group
  • B 1 represents a single bond, —O—, —S—, —CO—, —NR—, —O 2 C—, —CO 2 —, —NROC—, or —CONR—
  • R represents a hydrogen atom, an alkyl group or an aryl group
  • C 1 represents a single bond or a divalent linking group
  • S represents a sulfur atom
  • Q represents a polymer chain containing a repeating unit having a dye structure
  • the average value of the number of repeating units of n Q having a dye structure is 2 or more, n represents an integer of 3 to 10.
  • a 1 is a group composed of one or a combination of two or more selected from an aliphatic hydrocarbon group, an aromatic ring group and a heterocyclic group which may have an oxygen atom in the main chain.
  • ⁇ 4> The coloring composition according to any one of ⁇ 1> to ⁇ 3>, wherein the dye multimer has a specific absorbance represented by the following formula (A ⁇ ) at a maximum absorption wavelength at 400 nm to 800 nm of 5 or more.
  • E A / (c ⁇ l) (A ⁇ )
  • a ⁇ the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm
  • A the absorbance at the maximum absorption wavelength between 400 nm and 800 nm
  • l the cell length in units of cm
  • c the concentration of the dye multimer in the solution expressed in mg / ml.
  • the dye multimer is obtained by radical polymerization of a compound represented by the general formula (3) and a compound having a dye structure and a radical polymerizable group, according to ⁇ 1> to ⁇ 5>.
  • the coloring composition in any one.
  • P 0 represents an n-valent linking group
  • SH represents a thiol group
  • n represents an integer of 3 to 10.
  • ⁇ 8> The colored composition according to any one of ⁇ 1> to ⁇ 7>, further comprising a photopolymerization initiator.
  • Q has a dye structure derived from a dye selected from a triarylmethane dye, a xanthene dye, an anthraquinone dye, a cyanine dye, a squarylium dye, a quinophthalone dye, a phthalocyanine dye, a subphthalocyanine dye, an azo dye, and a dipyrromethene dye.
  • ⁇ 10> The colored composition according to any one of ⁇ 1> to ⁇ 9>, wherein Q has one or more selected from a repeating unit having an acid group and a repeating unit having a polymerizable group.
  • ⁇ 11> The coloring composition according to any one of ⁇ 1> to ⁇ 10>, wherein Q is one selected from a (meth) acrylic resin, a styrene resin, and a (meth) acrylic / styrene resin. object.
  • Q is one selected from a (meth) acrylic resin, a styrene resin, and a (meth) acrylic / styrene resin.
  • Q is one selected from a (meth) acrylic resin, a styrene resin, and a (meth) acrylic / styrene resin.
  • ⁇ 12> A color filter using the colored composition according to any one of ⁇ 1> to ⁇ 11>.
  • ⁇ 13> a step of applying the colored composition according to any one of ⁇ 1> to ⁇ 11> on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, Forming a colored pattern by developing and removing une
  • ⁇ 14> A step of applying the colored composition according to any one of ⁇ 1> to ⁇ 11> on a support to form a colored composition layer and curing to form a colored layer; A step of forming a photoresist layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask to form a colored pattern.
  • ⁇ 15> A method for producing a color filter, comprising the pattern forming method according to ⁇ 13> or ⁇ 14>.
  • ⁇ 16> A solid-state imaging device having the color filter according to ⁇ 12> or the color filter obtained by the method for producing a color filter according to ⁇ 15>.
  • a method for producing a dye multimer comprising radically polymerizing a compound represented by the general formula (3) and a compound having a dye structure and a radical polymerizable group.
  • P 0 represents an n-valent linking group
  • SH represents a thiol group
  • n represents an integer of 3 to 10.
  • a colored composition having excellent light resistance, color transfer and flatness can be provided.
  • the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • light means actinic rays or radiation.
  • Actinic light or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • exposure is not limited to exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. Include drawing in exposure.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
  • “(meth) acrylate” represents both and / or acrylate and methacrylate
  • “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”.
  • Allyl represents both and / or allyl and methallyl
  • “(meth) acryloyl” represents both and / or acryloyl and methacryloyl.
  • 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 that participates in a polymerization reaction.
  • Me in the chemical formula represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes.
  • a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column.
  • 0.0 mm ID ⁇ 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
  • the coloring composition of this invention contains the pigment
  • the coloring composition excellent in light resistance, color transfer property, and flatness can be provided.
  • the dye multimer represented by the general formula (1) described later is a polymer chain containing a repeating unit having a dye structure in an n-valent linking group. It is considered that the entanglement of polymer chains having a dye structure was less than that of a linear dye multimer. For this reason, it is considered that the dye multimer hardly aggregated and a film having excellent flatness could be obtained.
  • the dye structure is incorporated in the polymer chain, it is considered that the dye is difficult to diffuse and excellent in color transfer.
  • the dye multimer improves adsorbability with other molecules such as pigments, and facilitates energy transfer between molecules, so that light resistance is also excellent.
  • entanglement of polymer chains having a dye structure can be reduced, so that the developer can be satisfactorily penetrated, the development speed is high, and development residues are hardly generated. You can also.
  • the present invention will be described in detail.
  • the colored composition of the present invention contains a dye multimer represented by the following general formula (1) (hereinafter sometimes simply referred to as “dye multimer (A)”).
  • the dye multimer (A) preferably has a maximum absorption wavelength in the range of 400 nm to 800 nm.
  • the dye multimer (A) functions as, for example, a colorant in the colored composition of the present invention.
  • P represents an n-valent linking group
  • Q represents a polymer chain containing a repeating unit having a dye structure
  • the average value of the number of repeating units of n Q having a dye structure is 2 or more
  • n represents an integer of 3 to 10.
  • P represents an n-valent linking group.
  • n-valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To 20 sulfur atoms are included, which may be unsubstituted or further substituted.
  • the n-valent linking group represented by P includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and Groups consisting of 0 to 10 sulfur atoms are preferred.
  • the n-valent linking group represented by P is preferably a linking group derived from a polyhydric alcohol.
  • the dye multimer represented by the general formula (1) is preferably represented by the general formula (2).
  • a 1 represents an n-valent linking group
  • B 1 represents a single bond, —O—, —S—, —CO—, —NR—, —O 2 C—, —CO 2 —, —NROC—, or —CONR—
  • R represents a hydrogen atom, an alkyl group or an aryl group
  • C 1 represents a single bond or a divalent linking group
  • S represents a sulfur atom
  • Q represents a polymer chain containing a repeating unit having a dye structure
  • the average value of the number of repeating units of n Q having a dye structure is 2 or more
  • n represents an integer of 3 to 10.
  • a 1 represents an n-valent linking group.
  • the n-valent linking group is preferably a group consisting of one or a combination of two or more selected from an aliphatic hydrocarbon group, an aromatic ring group and a heterocyclic group which may have an oxygen atom in the main chain.
  • the aliphatic hydrocarbon group include an alkylene group and an alkenylene group.
  • the number of carbon atoms of the alkylene group is, for example, preferably 1-60, and more preferably 1-30.
  • the number of carbon atoms of the alkenylene group is, for example, preferably 1-60, and more preferably 1-30.
  • Examples of the aliphatic hydrocarbon group having an oxygen atom in the main chain include groups represented by — (OR x1 ) m — and — (R x1 O) m —.
  • the aliphatic hydrocarbon group having an oxygen atom in the main chain may be linear, branched or cyclic.
  • the main chain refers to a skeleton portion of a linking group and does not include a substituent.
  • R x1 represents an alkylene group or an alkenylene group.
  • m represents an integer of 1 or more. When m is 2 or more, m R x1 s may be the same or different.
  • the alkylene group represented by R x1 preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms.
  • the alkylene group may be linear, branched or cyclic.
  • the carbon number of the alkenylene group represented by R x1 is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 5.
  • the alkenylene group may be linear, branched or cyclic.
  • the aromatic ring group may be monocyclic or polycyclic.
  • the aromatic ring examples include a benzene ring, a naphthalene ring, an anthracene ring, a chrysene ring, a triphenylene ring, a fluorene ring, and a biphenyl ring, and a benzene ring is preferable.
  • the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the heterocyclic group may be monocyclic or polycyclic. Examples of the hetero atom contained in the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. A nitrogen atom is preferred.
  • the number of heteroatoms is preferably 1 to 3.
  • heterocyclic ring for example, cyanuric ring, triazine ring, oxane ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene A ring, a chromene ring, a xanthene ring, a
  • the n-valent linking group represented by A 1 includes a hydrocarbon group that may have an oxygen atom in the main chain, an aromatic ring group, a heterocyclic group, and a hydrocarbon group that may have an oxygen atom in the main chain; Preferred examples include a combination with an aromatic ring group and a combination of a hydrocarbon group that may have an oxygen atom in the main chain and a heterocyclic group.
  • a 1 is an aromatic ring group, a heterocyclic group, a combination of a hydrocarbon group that may have an oxygen atom in the main chain and an aromatic ring group, or a carbon that may have an oxygen atom in the main chain
  • Examples of the linking group P (the above formula (2a)) in the case of a combination of a hydrogen group and a heterocyclic group include the following.
  • X represents a hydrocarbon group which may have an oxygen atom in the main chain
  • B 1 represents a single bond, —O—, —S—, —CO—, —NR—, —O 2 C—, —CO 2 —, —NROC—, or —CONR—
  • R represents a hydrogen atom, an alkyl group or an aryl group
  • C 1 represents a single bond or a divalent linking group
  • S represents a sulfur atom
  • n represents an integer of 3 or more
  • B 1 represents a single bond, —O—, —S—, —CO—, —NR—, —O 2 C—, —CO 2 —, —NROC—, or —CONR—.
  • a single bond, —O—, —CO—, —O 2 C—, —CO 2 —, —NROC—, or —CONR— is preferable.
  • R represents a hydrogen atom, an alkyl group or an aryl group.
  • the alkyl group represented by R preferably has 1 to 30 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched or cyclic.
  • the number of carbon atoms of the aryl group represented by R is preferably 6-30, and more preferably 6-12.
  • R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
  • C 1 represents a single bond or a divalent linking group.
  • the divalent linking group is preferably an alkylene group, an arylene group or an oxyalkylene group, more preferably an alkylene group or an oxyalkylene group.
  • the alkylene group and oxyalkylene group preferably have 1 to 30 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkyl group and oxyalkylene group may be linear, branched or cyclic.
  • the number of carbon atoms in the arylene group is preferably 6 to 30, and more preferably 6 to 12.
  • n-valent linking group represented by P Specific examples of the n-valent linking group represented by P are shown below. However, the present invention is not limited to these.
  • the n-valent linking group is preferably (P-1) to (P-8), (P-16) to (P-20), or (P-22) to (P-32).
  • the polymer chain represented by Q represents a polymer chain containing a repeating unit having a dye structure, and an average value of the number of repeating units of n Qs having a dye structure is 2 or more.
  • n Q contained in the general formula (1) or (2) two or more repeating units having a dye structure are contained per Q1.
  • the dye multimer represented by the general formula (1) or (2) includes 2n or more repeating units having a dye structure.
  • the n Qs may be the same or different.
  • the polymer chain represented by Q preferably has an average value of 2 to 20 repeating units having a dye structure, more preferably 2 to 15 and even more preferably 2 to 10.
  • the average value of the number of repeating units having a dye structure can be determined by NMR (nuclear magnetic resonance). Specifically, for example, the number of repeating units in the general formula (1) is determined from the peak area ratio between the n-valent linking group represented by P and the repeating units of the polymer chain Q. Next, the number of repeating units in the polymer chain Q can be calculated by dividing the value by n.
  • the weight average molecular weight of the polymer chain Q is preferably 1,000 to 100,000, more preferably 1000 to 30,000, and particularly preferably 1,000 to 10,000.
  • the dye structure of each repeating unit may be the same dye structure or the same skeleton, but may be a different dye structure such as a substituent or a central metal, or a dye structure having a different skeleton. May be.
  • the cation and the anion may be in the same molecule of the dye structure that the polymer chain Q has, or may be outside the molecule of the dye structure.
  • dye structure means the case where the cation and an anion are couple
  • having an anion outside the molecule of the dye structure means that the cation and the anion are not bonded via a covalent bond but are present as separate compounds.
  • an anion outside the molecule of the dye structure is also referred to as a counter anion.
  • the polymer chain represented by Q is not particularly defined as long as it contains a dye structure, but is a kind selected from (meth) acrylic resins, styrene resins, and (meth) acrylic / styrene resins.
  • the (meth) acrylic resin means a resin containing a (meth) acrylic resin as a main component. Containing a (meth) acrylic resin as a main component preferably includes (meth) acrylic resin in an amount of 50% by mass or more, more preferably 60% by mass or more in the (meth) acrylic resin. It is particularly preferable to contain at least mass%.
  • the styrene resin means a resin containing a styrene resin as a main component.
  • Containing styrene resin as a main component means that the styrene resin preferably contains 50% by mass or more of styrene resin, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
  • the (meth) acrylic / styrene resin means a resin containing a (meth) acrylic resin and a styrene resin as main components.
  • the (meth) acrylic / styrene resin preferably contains a total of 50% by mass of the (meth) acrylic resin and the styrene resin. % Or more is more preferable, and 70% by mass or more is particularly preferable.
  • the polymer chain Q will be described in detail.
  • the skeleton structure of the repeating unit having a dye structure is not particularly defined, but is represented by general formula (A), general formula (B), and general It is preferable that at least one of the structural units represented by the formula (C) is a skeleton, or a dye multimer represented by the general formula (D) is preferable.
  • the description of paragraph numbers 0276 to 0304 in JP 2013-28764 is incorporated in the present specification.
  • it preferably has a repeating unit represented by the following general formula (a1-1).
  • the total number of repeating units having a dye structure in all repeating units constituting the polymer chain Q is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and 20 to 40 mol%. Further preferred.
  • Q 1 represents a trivalent linking group
  • L 1 represents a single bond or a divalent linking group
  • D 1 represents a dye structure
  • “*” represents a main chain. Represents a bond with
  • Q 1 represents a trivalent linking group.
  • Q 1 is a linking group formed by polymerization and refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction.
  • part represented by two "*" becomes a repeating unit.
  • Q 1 is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but linking groups represented by the following (XX-1) to (XX-24) are particularly preferred, and (XX— 1) (meth) acrylic linking chains represented by (XX-2), styrene linking chains represented by (XX-10) to (XX-17), (XX-18) and (XX-19) ) And a vinyl-based linking chain represented by (XX-24), and (meth) acrylic linking chains represented by (XX-1) and (XX-2), ( More preferably selected from styrene-based connecting chains represented by (XX-10) to (XX-17), and vinyl-based connecting chains represented by (XX-24), (XX-1) and (XXX- (Meth) acrylic linking chain represented by 2) and (XX-11) Styrene linking chain represented is more preferable.
  • L 1 each independently represents a single bond or a divalent linking group.
  • the divalent linking group include substituted or unsubstituted alkylene groups having 1 to 30 carbon atoms (for example, methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted groups having 6 to 30 carbon atoms.
  • a substituted arylene group (for example, a phenylene group, a naphthylene group, etc.), a substituted or unsubstituted heterocyclic group, —CH ⁇ CH—, —O—, —S—, —C ( ⁇ O) —, —CO 2 — , —NR—, —CONR—, —O 2 C—, —SO—, —SO 2 — and a linking group formed by linking two or more thereof.
  • L 1 preferably includes an anion.
  • L 1 is preferably a single bond or an alkylene group, more preferably a single bond or — (CH 2 ) n — (n is an integer of 1 to 5).
  • each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
  • D 1 represents a dye structure derived from a dye compound described later.
  • quinone dye (benzoquinone dye, naphthoquinone dye, anthraquinone dye, anthrapyridone dye, etc.), carbonium dye (diarylmethane dye, triarylmethane dye, xanthene dye, acridine dye, etc.), quinoneimine dye (oxazine dye, thiazine dye, etc.) , Azine dye, polymethine dye (oxonol dye, merocyanine dye, arylidene dye, styryl dye, cyanine dye, squarylium dye, croconium dye, etc.), quinophthalone dye, phthalocyanine dye, subphthalocyanine dye, perinone dye, indigo dye, thioindigo dye, quinoline And dye structures derived from dyes selected from dyes, nitro dyes, nitroso dyes, dipyrromethene dyes, azo dyes and their metal complex dyes.
  • triarylmethane dyes triarylmethane dyes, xanthene dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, azo dyes, and dipyrromethene dyes from the viewpoint of color separation and light resistance.
  • the dye structure selected is preferable, and the dye structure selected from triarylmethane dye, xanthene dye, anthraquinone dye, squarylium dye, quinophthalone dye, phthalocyanine dye, subphthalocyanine dye, azo dye and dipyrromethene dye is more preferable, triarylmethane dye, Xanthene dyes are more preferred.
  • the dye structure contained in the polymer chain represented by Q may be only one type or two or more types.
  • the dye structure preferably used in the present invention will be described in detail.
  • a preferred embodiment of the dye structure in the present invention has a partial structure derived from a triarylmethane dye (triarylmethane compound).
  • triarylmethane compound examples include a compound represented by the following formula (TP).
  • TP triarylmethane compound is a general term for compounds having a dye moiety containing a triarylmethane skeleton in the molecule.
  • Rtp 1 to Rtp 4 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • Rtp 5 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 9 Rtp 10 (Rtp 9 and Rtp 10 represent a hydrogen atom, an alkyl group or an aryl group).
  • Rtp 6 , Rtp 7 and Rtp 8 represent a substituent.
  • a, b and c each represents an integer of 0 to 4. When a, b and c are 2 or more, Rtp 6 , Rtp 7 and Rtp 8 may be linked to each other to form a ring.
  • X ⁇ represents an anion structure. When X ⁇ is not present, at least one of Rtp 1 to Rtp 7 contains an anion.
  • Rtp 1 to Rtp 6 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group.
  • Rtp 5 is preferably a hydrogen atom or NRtp 9 Rtp 10 , particularly preferably NRtp 9 Rtp 10 .
  • Rtp 9 and Rtp 10 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group.
  • substituents mentioned in the section of Substituent Group A described later can be used, and in particular, a linear or branched alkyl group having 1 to 5 carbon atoms, Preferred is an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group or a sulfo group, a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, phenyl A group or a carboxyl group is more preferable.
  • Rtp 6 and Rtp 8 are preferably alkyl groups having 1 to 5 carbon atoms
  • Rtp 7 is preferably an alkenyl group (particularly a phenyl group in which two adjacent alkenyl groups are linked), a phenyl group or a carboxyl group.
  • a, b or c each independently represents an integer of 0 to 4;
  • a and b are each preferably 0 or 1, and c is preferably an integer of 0 to 2.
  • Rtp 1 to Rtp 7 When at least one of Rtp 1 to Rtp 7 includes an anion, examples of the anion include a structure in which at least one of Rtp 1 to Rtp 7 is substituted with the general formula (P).
  • General formula (P) In the general formula (P), L represents a single bond or a divalent linking group, and X 1 represents —SO 3 ⁇ , —COO ⁇ , —PO 4 ⁇ , a structure represented by the following general formula (A1). It is selected from at least one selected from a group containing and a group containing a structure represented by the following general formula (A2).
  • General formula (A1) In general formula (A1), R 1 and R 2 each independently represents —SO 2 — or —CO—.
  • R 4 and R 5 each independently represents —SO 2 —, —CO— or —CN.
  • L represents a single bond or a divalent linking group.
  • the divalent linking group preferably represents a group consisting of —NR 10 —, —O—, —SO 2 —, a fluorine-substituted alkylene group, a fluorine-substituted phenylene group, or a combination thereof.
  • a group consisting of a combination of —NR 10 —, —SO 2 — and a fluorine-substituted alkylene group a group consisting of a combination of —O— and a fluorine-substituted phenylene group, or —NR 10 — and —SO 2 —
  • a group consisting of a combination with a fluorine-substituted phenylene group is preferred.
  • R 10 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.
  • the fluorine-substituted alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. These alkylene groups are more preferably perfluoroalkylene groups. Specific examples of the fluorine-substituted alkylene group include a difluoromethylene group, a tetrafluoroethylene group, and a hexafluoropropylene group.
  • the number of carbon atoms of the fluorine-substituted phenylene group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.
  • fluorine-substituted phenylene group examples include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, and a hexafluoro-2-naphthylene group.
  • X 1 is an anion, including —SO 3 ⁇ , —COO ⁇ , a group including a structure represented by general formula (A1), and a structure represented by general formula (A2). It is preferably selected from at least one selected from the group.
  • the group including the structure represented by the general formula (A1) preferably has a fluorine-substituted alkyl group at one terminal of R 1 and R 2 in the general formula (A1) described above, and R 1 and R 2 More preferably, one of these is directly bonded to a fluorine-substituted alkyl group.
  • the number of carbon atoms in the fluorine-substituted alkyl group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.
  • These alkyl groups are more preferably perfluoroalkyl groups.
  • a trifluoromethyl group is preferable.
  • a fluorine-substituted alkyl group is synonymous with what was demonstrated by group containing the structure represented by general formula (A1), and its preferable range is also the same.
  • a preferred embodiment of the dye structure in the present invention has a partial structure derived from a xanthene dye (xanthene compound).
  • xanthene compound examples include xanthene compounds represented by the following formula (J).
  • R 81 , R 82 , R 83 and R 84 each independently represent a hydrogen atom or a monovalent substituent
  • R 85 each independently represents a monovalent substituent
  • m Represents an integer of 0 to 5.
  • X ⁇ represents a counter anion. When X ⁇ is not present, at least one of R 81 to R 85 contains an anion.
  • R 81 to R 85 in formula (J) are the same as the substituents mentioned in the section of Substituent group A described later.
  • R 81 and R 82 in formula (J), R 83 and R 84 , and R 85 in the case where m is 2 or more are each independently bonded to each other to form a 5-membered, 6-membered or 7-membered saturated ring. Or a 5-membered, 6-membered or 7-membered unsaturated ring.
  • R 81 and R 82 , R 83 and R 84 , and R 85 in the case where m is 2 or more are each independently bonded to each other, and have no substituent.
  • 5-membered and 7-membered saturated ring or 5-membered, 6-membered and 7-membered unsaturated ring when forming 5-membered, 7-membered saturated ring or 5-membered, 6-membered and 7-membered
  • the unsaturated ring include pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring and pyridine ring.
  • a pyrazine ring and a pyridazine ring preferably a benzene ring and a pyridine ring.
  • the anion include those described above.
  • R 82 and R 83 are preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and R 81 and R 84 are preferably a substituted or unsubstituted alkyl group or a phenyl group.
  • R 85 is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, a carboxyl group, or an amide group. The sulfo group, the sulfonamide group, the carboxyl group, More preferred is an amide group.
  • R 85 is preferably bonded to the adjacent part of carbon linked to the xanthene ring.
  • the substituent that the phenyl group of R 81 and R 84 has is particularly preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group.
  • the compound having a xanthene skeleton represented by the formula (J) can be synthesized by a method described in the literature. Specifically, the methods described in Tetrahedron Letters, 2003, vol. 44, No. 23, pages 4355-4360, Tetrahedron, 2005, vol. 61, No. 12, pages 3097-3106, etc. Can be applied.
  • the cation is delocalized in the dye structure, for example, as shown below, the cation is present on a nitrogen atom or a carbon atom of the xanthene ring.
  • Anthraquinone dye has a partial structure derived from an anthraquinone dye.
  • anthraquinone dye anthraquinone compound
  • compounds represented by the following general formulas (AQ-1) to (AQ-3) are preferable.
  • An anthraquinone compound is a general term for compounds having a dye moiety containing an anthraquinone skeleton in the molecule.
  • a and B each independently represent an amino group, a hydroxyl group, an alkoxy group or a hydrogen atom.
  • Xqa represents ORqa 1 or NRqa 2 Rqa 3.
  • Rqa 1 to Rqa 3 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • Rq 1 to Rq 4 represent a substituent.
  • the substituents that Rq 1 to Rq 4 can take are the same as the substituents mentioned in the section of Substituent group A described later.
  • Ra and Rb each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • C and D have the same meanings as A and B in general formula (AQ-1).
  • Xqb represents ORqb 1 or NRqb 2 Rqb 3.
  • Rqb 1 to Rqb 3 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • Rq 5 to Rq 8 represent a substituent.
  • Rq 5 to Rq 8 have the same meanings as Rq 1 to Rq 4 in formula (AQ-1).
  • Rc has the same meaning as Ra or Rb in formula (AQ-1).
  • E and F have the same meanings as A and B in general formula (AQ-1).
  • Xqc represents ORqc 1 or NRqc 2 Rqc 3.
  • Rqc 1 to Rqc 3 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • Rq 9 to Rq 12 have the same meanings as Rq 1 to Rq 4 in formula (AQ-1).
  • Rd has the same meaning as Ra or Rb in formula (AQ-1).
  • anthraquinone dye for example, paragraphs 0049 to 0050 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • a preferred embodiment of the dye structure in the present invention has a partial structure derived from a cyanine dye (cyanine compound).
  • cyanine dye a compound represented by the following general formula (PM) (cyanine compound) is preferable.
  • the cyanine compound is a general term for compounds having a dye moiety containing a cyanine skeleton in the molecule.
  • ring Z1 and ring Z2 each independently represent a heterocyclic ring which may have a substituent.
  • l represents an integer of 0 or more and 3 or less.
  • X ⁇ represents an anion.
  • paragraphs 0077 to 0084 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
  • any hydrogen atom in the cyanine dye structure is bonded to R 2 of the general formula (1).
  • a preferred embodiment of the dye structure in the present invention has a partial structure derived from squarylium dye (squarylium compound).
  • squarylium compound As a squarylium pigment
  • the squarylium compound is a general term for compounds having a dye moiety containing a squarylium skeleton in the molecule.
  • a and B each independently represent an aryl group or a heterocyclic group.
  • the aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and examples thereof include phenyl and naphthyl.
  • the heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group, and examples thereof include pyroyl, imidazoyl, pyrazoyl, thienyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, furyl, thiadiazoyl and the like.
  • paragraphs 0088 to 0106 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • paragraph 0105 of JP 2013-29760 A can be referred to.
  • a preferred embodiment of the dye structure in the present invention has a partial structure derived from a quinophthalone dye (quinophthalone compound).
  • a compound (quinophthalone compound) represented by the following general formula (QP) is preferable.
  • the quinophthalone compound is a general term for compounds having a dye moiety containing a quinophthalone skeleton in the molecule.
  • Rqp 1 to Rqp 6 each independently represents a hydrogen atom or a substituent. When at least two of Rqp 1 to Rqp 6 are adjacent to each other, they may be bonded to each other to form a ring, and the formed ring may further have a substituent.
  • paragraphs 0110 to 0114 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • specific examples of the quinophthalone dye reference can be made to the description in paragraph 0113 of JP2013-29760A, for example.
  • a preferred embodiment of the dye structure in the present invention has a partial structure derived from a phthalocyanine dye (phthalocyanine compound).
  • phthalocyanine compound those having a partial structure derived from a compound represented by the following general formula (F) (phthalocyanine compound) are preferable.
  • the phthalocyanine compound is a general term for compounds having a dye moiety containing a phthalocyanine skeleton in the molecule.
  • M 1 represents a metal
  • Z 1 , Z 2 , Z 3 , and Z 4 are each independently composed of an atom selected from a hydrogen atom, a carbon atom, and a nitrogen atom. Represents a group of atoms necessary to form a 6-membered ring.
  • paragraphs 0118 to 0124 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • specific examples of the phthalocyanine dye for example, paragraph 0123 of JP2013-29760A can be referred to.
  • a preferred embodiment of the dye structure in the present invention has a partial structure derived from a subphthalocyanine dye (subphthalocyanine compound).
  • a subphthalocyanine dye a compound represented by the following general formula (SP) (subphthalocyanine compound) is preferable.
  • SP general formula
  • the term “subphthalocyanine compound” is a general term for compounds having a dye moiety containing a subphthalocyanine skeleton in the molecule.
  • Z 1 to Z 12 each independently represent a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, a mercapto group, an amino group, an alkoxy group, an aryloxy group, or a thioether group.
  • X represents an anion.
  • paragraphs 0128 to 0133 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • specific examples of the subphthalocyanine dye reference can be made to, for example, the description in paragraph 0132 of JP2013-29760A.
  • a preferred embodiment of the dye structure in the present invention has a partial structure derived from an azo dye (azo compound).
  • a known azo dye for example, substituted azobenzene
  • the description of paragraphs 0084 to 0134 of JP2013-41097A and the description of paragraphs 0029 to 0136 of JP2011-162760A can be referred to as azo dyes, the contents of which are incorporated herein. .
  • dipyrromethene dye >>>>>>>>
  • One of the aspects of the dye structure according to the present invention has a partial structure derived from a dipyrromethene dye.
  • the dipyrromethene dye a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound are preferable.
  • the dipyrromethene dye the description in paragraphs 0033 to 0136 of JP 2011-95732 A can be referred to, and the contents thereof are incorporated in the present specification.
  • a hydrogen atom in the dye structure may be substituted with a substituent selected from the following substituent group A.
  • substituent group A examples of the substituent that the dye structure may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, A chain, branched chain or cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl group (preferably t-butyl group), pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, Cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group (preferably
  • Si group such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy
  • acyloxy group preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms such as acetoxy, Pivaloyloxy, benzoyloxy, dodecanoyloxy
  • an alkoxycarbonyloxy group preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy
  • a cycloalkyloxycarbonyloxy group for example, cyclohexyloxycarbonyloxy
  • an aryloxycarbonyloxy group preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms
  • phenoxycarbonyloxy preferably an aryloxycarbonyloxy group having 7 to
  • a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N- Ethyl-N-phenylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group).
  • a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N- Ethyl-N-phenyl
  • alkylsulfonyloxy groups preferably alkylsulfonyloxy groups having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexyl.
  • arylsulfur Nyloxy groups preferably arylsulfonyloxy groups having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyloxy
  • acyl groups preferably having 1 to 48 carbon atoms, more preferably 1 carbon atom
  • An acyl group having ⁇ 24 for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl
  • an alkoxycarbonyl group preferably having 2 to 48 carbon atoms, more preferably having 2 to 24 carbon atoms
  • aryloxycarbonyl group preferably having 7 to
  • An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), a sulfonamide group (preferably having 1 to 48 carbon atoms, Preferably, it is a sulfonamide group having 1 to 24 carbon atoms, such as methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably carbon A sulfamoylamino group having 1 to 48, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably Has 1
  • An azo group such as a phenylazo group or a 3-pyrazolylazo group
  • an alkylthio group preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylthio, ethylthio, octylthio, cyclohexyl).
  • Thio an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, more preferably an arylthio group having 6 to 24 carbon atoms, such as phenylthio), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a carbon number).
  • heterocyclic thio groups such as 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio
  • alkylsulfinyl groups preferably having 1 to 32 carbon atoms, more preferably having 1 to 32 carbon atoms
  • 24 alkylsulfinyl groups such as dodecanesulfinyl
  • arylsulfinyl Preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfinyl
  • an alkylsulfonyl group preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms).
  • Alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl group (preferably having 6 to 48 carbon atoms, More preferably, it is an arylsulfonyl group having 6 to 24 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably having 32 or less carbon atoms, more preferably 24 or less carbon atoms).
  • Yl groups such as sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo groups, Phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having a carbon number) A phosphinoylamino group having 1 to 32, more preferably 1 to 24 carbon atoms, such as diethoxyphosphinoylamino, dioctyloxyphosphinoylamino), an alkyloxycarbonyloxy group (preferably having 5
  • substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring.
  • substituents for details, for example, paragraphs 0027 to 0038 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • the counter anion is not particularly limited, but is preferably a non-nucleophilic anion from the viewpoint of heat resistance.
  • the non-nucleophilic counter anion known non-nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315 are preferable.
  • the non-nucleophilic property means a property that does not nucleophilic attack the dye by heating.
  • Counter anions include sulfonate anion, carboxylate anion, sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion, carboxylate anion, tetraarylborate anion, —CON ⁇ CO—, —CON ⁇ .
  • At least one selected from SO 2 ⁇ , BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ and B ⁇ (CN) 3 OCH 3 is preferable.
  • sulfonate anion sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion, carboxylate anion, tetraarylborate anion, BF 4 ⁇ , PF 6 ⁇ , and SbF 6 ⁇ .
  • sulfonate anion sulfonylimide anion
  • bis (alkylsulfonyl) imide anion bis (alkylsulfonyl) imide anion
  • tris (alkylsulfonyl) methide anion carboxylate anion, tetraarylborate anion, BF 4 ⁇ , PF 6 ⁇ , and SbF 6 ⁇ .
  • X 1 and X 2 each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom.
  • X 1 and X 2 may be bonded to each other to form a ring.
  • X 1 and X 2 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, More preferred is a perfluoroalkyl group of ⁇ 10, more preferred is a perfluoroalkyl group having 1 to 4 carbon atoms, and a trifluoromethyl group is particularly preferred.
  • X 3 , X 4 and X 5 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms.
  • X 3 , X 4 and X 5 are each independently the same as X 1 and X 2 , and the preferred range is also the same.
  • X 6 represents an alkyl group having a fluorine atom having 1 to 10 carbon atoms.
  • X 6 is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.
  • X 7 represents an alkylene group having 1 to 10 carbon atoms.
  • X 7 is preferably a perfluoroalkylene group having 1 to 10 carbon atoms, and more preferably a perfluoroalkylene group having 1 to 4 carbon atoms.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aryl group.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
  • the aryl group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 may have a substituent.
  • a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group and the like can be mentioned, and a halogen atom and an alkyl group are preferable, A fluorine atom and an alkyl group are more preferable, and a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms are more preferable.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently more preferably a halogen atom and / or a phenyl group having an alkyl group having a halogen atom, and a phenyl group having a fluorine atom and / or an alkyl group having a fluorine atom. More preferred are groups.
  • the non-nucleophilic counter anion is also —B (CN) n1 (OR a ) 4-n1 (R a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents It is preferably an integer of 1 to 4.
  • Ra as the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
  • R a as the aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.
  • n1 is preferably 1 to 3, and more preferably 1 to 2.
  • the non-nucleophilic counter anion is further —PF 6 R P (6-n2) ⁇ (R P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6) It is preferable that R P is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a perfluoroalkyl group having 1 to 3 carbon atoms. n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.
  • the mass per molecule of the non-nucleophilic counter anion is preferably 100 to 1,000, and more preferably 200 to 500.
  • the dye multimer (A) may contain only one kind of non-nucleophilic counter anion, or may contain two or more kinds. Specific examples of the non-nucleophilic counter anion are shown below, but the present invention is not limited thereto.
  • repeating units having a dye structure that are preferably used in the present invention are shown below. Needless to say, the present invention is not limited to these examples.
  • the polymer chain Q may contain other repeating units in addition to the repeating unit having the dye structure described above.
  • Other repeating units may contain a functional group such as a polymerizable group or an acid group. It does not have to contain a functional group. It preferably has at least one selected from repeating units having an acid group and repeating units having a polymerizable group, and more preferably includes a repeating unit having an acid group.
  • the polymerizable group a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used.
  • a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), a methylol group A group containing an ethylenically unsaturated bond is preferable, and a (meth) acryloyl group is more preferable.
  • the (meth) acryloyl group can be introduced, for example, by reacting glycidyl (meth) acrylate with 3,4-epoxycyclohexylmethyl (meth) acrylate.
  • the ratio of the repeating unit having a polymerizable group is preferably, for example, 5 to 50 mol with respect to 100 mol of all the repeating units of the polymer chain Q. Mole is more preferred.
  • the acid group examples include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Only one type of acid group may be included, or two or more types of acid groups may be included.
  • the ratio of the repeating unit having an acid group is preferably, for example, 5 to 50 moles relative to 100 moles of all the repeating units of the polymer chain Q, and 10 to 40 moles. More preferred.
  • Other functional groups include groups consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, development promoting groups such as lactone groups, acid anhydride groups, amide groups and cyano groups, long chain and cyclic alkyl groups, and aralkyls. Groups, aryl groups, polyalkylene oxide groups, hydroxyl groups, maleimide groups, amino group and other affinity control groups, and the like can be introduced as appropriate.
  • the number of repeating alkyleneoxy chains is preferably 2 to 10, more preferably 2 to 15, and even more preferably 2 to 10.
  • One alkyleneoxy chain is represented by — (CH 2 ) n O—, where n is an integer, n is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 or 3.
  • the dye multimer (A) may have a polymer chain that does not contain a dye structure.
  • Examples of the polymer chain not including the dye structure include a polymer chain composed of the repeating units described in the other repeating units of the polymer chain Q described above.
  • the weight average molecular weight of the dye multimer (A) is preferably from 1,000 to 100,000.
  • the lower limit is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more.
  • the upper limit is more preferably 50000 or less, still more preferably 20000 or less, and even more preferably 15000 or less. If the weight average molecular weight is in the above range, the color transfer is better. Furthermore, the developability is improved and the generation of development residues can be further reduced.
  • the acid value of the dye multimer (A) is preferably 10 mgKOH / g or more.
  • the lower limit is more preferably 15 mgKOH / g or more, and still more preferably 20 mgKOH / g or more.
  • the upper limit is more preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less. If the acid value is 10 mgKOH / g or more, the developability is improved and the generation of development residues can be further reduced.
  • the method for measuring the specific absorbance of the dye multimer (A) is, for example, using a solvent having sufficient solubility in the dye multimer (A) so that the maximum absorbance at 400 nm to 800 nm is 1.0. And adjusting the concentration of the solution containing the dye multimer (A) and measuring the absorbance of this solution at 25 ° C. using a cell having an optical path length of 1 cm.
  • a solvent having sufficient solubility for the dye multimer (A) can be appropriately used.
  • Preferred solvents include tetrahydrofuran, methanol, isopropyl alcohol, dimethyl sulfoxide, acetonitrile, ethyl acetate, hexane, toluene, water, concentrated sulfuric acid, methanesulfonic acid and the like.
  • Tetrahydrofuran is used when tetrahydrofuran has sufficient solubility.
  • the specific absorbance represented by the following formula (A ⁇ ) at the maximum absorption wavelength at 400 nm to 800 nm is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and particularly preferably 30 or more. If the specific absorbance is 5 or more, it can be suitably used as a colorant.
  • E A / (c ⁇ l) (A ⁇ )
  • a ⁇ the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm
  • A the absorbance at the maximum absorption wavelength between 400 nm and 800 nm
  • l the cell length in units of cm
  • c the concentration of the dye multimer in the solution expressed in mg / ml.
  • the dye multimer (A) is preferably a dye.
  • the dye refers to a pigment having substantial solubility in water or an organic solvent, and is particularly preferably an organic solvent-soluble dye that is soluble in the following organic solvents.
  • the organic solvent include esters (eg, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate), ethers (eg, methyl cellosolve acetate, ethyl cellosolve acetate).
  • the dye multimer (A) may be used alone or in combination of two or more.
  • the content of the dye multimer (A) in the colored composition of the present invention is set in consideration of the content ratio with other dyes (preferably pigments) described later.
  • the mass ratio of the dye multimer to the pigment (dye multimer (A) / pigment) is preferably from 0.1 to 5, more preferably from 0.2 to 2, even more preferably from 0.3 to 1.
  • the content of the dye multimer (A) in the colored composition of the present invention is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and more preferably 10 to 25% by mass with respect to the total solid content of the colored composition. Is particularly preferred.
  • the method for producing the dye multimer represented by the general formula (1) is not particularly limited. It can manufacture by the method of radical-polymerizing the compound which has.
  • a compound having a dye structure and a radical polymerizable group is also referred to as a “radical polymerizable dye compound”.
  • examples of the dye structure include those described above.
  • examples of the radical polymerizable dye compound include groups containing an ethylenically unsaturated bond such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • P 0- (SH) n (3) P 0 represents an n-valent linking group, SH represents a thiol group, n represents an integer of 3 to 10.
  • P 0 is 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And groups consisting of 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.
  • the n-valent linking group represented by P 0 is 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And groups consisting of 0 to 10 sulfur atoms are preferred. More preferably, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 atoms.
  • the n-valent linking group represented by P 0 is preferably a linking group derived from a polyhydric alcohol.
  • the compound represented by the general formula (3) is preferably a compound represented by the general formula (4).
  • a 0 represents an n-valent linking group
  • B 0 represents a single bond, —O—, —S—, —CO—, —NR—, —O 2 C—, —CO 2 —, —NROC—, or —CONR—
  • R represents a hydrogen atom, an alkyl group or an aryl group
  • C 0 represents a single bond or a divalent linking group
  • SH represents a thiol group
  • n represents an integer of 3 to 10.
  • a 0 , B 0 and C 0 in the general formula (4) are respectively synonymous with the ranges described for A 1 , B 1 and C 1 in the general formula (2), and preferred embodiments are also the same.
  • Specific examples of the compound represented by the general formula (3) include the following compounds.
  • (SH-1) to (SH-8), (SH-16) to (SH—) are particularly preferred compounds from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents. 20) and (SH-22) to (SH-32) are preferable.
  • the radical polymerization of the polyfunctional thiol compound and the radical polymerizable dye compound is performed by, for example, dissolving the polyfunctional thiol compound and the radical polymerizable dye compound in an appropriate solvent, adding a radical generator to the solution, The addition can be carried out at a temperature of about 50 ° C. to 100 ° C. (thiol-ene reaction method).
  • solvents used in the thiol-ene reaction method can be arbitrarily selected depending on the solubility of the polyfunctional thiol compound and the radical polymerizable dye compound.
  • Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.
  • radical generators 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate Azo compounds such as benzoyl peroxide, peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.
  • the coloring composition of the present invention contains a polymerizable compound.
  • a polymerizable compound a known compound that can be crosslinked by a radical, an acid, or heat can be used.
  • a compound having a group having an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane) group, a methylol group and the like can be mentioned.
  • the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound is preferably a tri- to hexafunctional (meth) acrylate compound.
  • the polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer (ie, a dimer, a trimer and an oligomer), or a mixture thereof and a multimer thereof.
  • Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof.
  • unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable.
  • the polymerizable compound is also preferably a compound having one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure.
  • compounds described in paragraph 0227 of JP 2013-29760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, the contents of which are incorporated herein.
  • Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.) , Dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues (for example, SR454,
  • the polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
  • an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • An ester having a group is more preferable, and particularly preferable is an ester in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.
  • Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
  • a compound having a structure derived from a cyclic ester for example, caprolactone, valerolactone and the like, and caprolactone is particularly preferable
  • the compound having a structure derived from caprolactone is not particularly limited as long as it has a structure derived from caprolactone in the molecule.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” represents a bond
  • R 1 represents a hydrogen atom or a methyl group
  • “*” represents a bond
  • polymerizable compound a compound represented by the following general formula (Z-4) or (Z-5) can also be used.
  • each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O).
  • — Each independently represents an integer of 0 to 10
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
  • the total of (meth) acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40 .
  • any one of X is a carboxyl group.
  • the total number of (meth) acryloyl groups is 5 or 6
  • each n independently represents an integer of 0 to 10
  • the total of each n is an integer of 0 to 60 .
  • any one of X is a carboxyl group.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents oxygen
  • a form in which the end on the atom side is bonded to X is preferred.
  • the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
  • a form in which all six Xs are acryloyl groups is preferable.
  • the total content of the compound represented by the general formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • the compound represented by the general formula (Z-4) or (Z-5) has a ring-opening skeleton bonded to pentaerythritol or dipentaerythritol by ring-opening addition reaction of ethylene oxide or propylene oxide. And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).
  • a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available polymerizable compounds represented by general formula (Z-4) or general formula (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Japan. Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
  • a compound having an epoxy group can also be used as the polymerizable compound.
  • the compound having an epoxy group one having two or more epoxy groups in one molecule is preferable. By using a compound having two or more epoxy groups in one molecule, the effect of the present invention can be achieved more effectively.
  • the number of epoxy groups is preferably 2 to 10, more preferably 2 to 5, and particularly preferably 3 in one molecule.
  • the compound having an epoxy group preferably has a structure in which two benzene rings are connected by a hydrocarbon group.
  • the hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.
  • the epoxy group is connected via a connecting group.
  • the linking group include an alkylene group, an arylene group, —O—, —NR ′ — (R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • the said effect is acquired by making the upper limit of the epoxy equivalent of the compound which has an epoxy group into 500 g / eq or less.
  • the lower limit of the epoxy equivalent of the compound which has an epoxy group shall be 100 g / eq or more.
  • the compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or a molecular weight of less than 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more).
  • the weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
  • a compound represented by the following general formula (2a) is preferably used as the compound having an epoxy group having a structure in which two benzene rings are linked by a hydrocarbon group.
  • R 1 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. Details of R 1 to R 19 in the general formula (2a) can be referred to paragraph number 0036 of JP2013-011869A, the contents of which are included in the present specification.
  • R 1 to R 19 are preferably each independently a hydrogen atom, a methyl group, an ethyl group or a methoxy group. More preferably, at least one selected from R 13 , R 18 and R 19 is a methyl group. More preferably, R 13 , R 18 and R 19 are methyl groups, and R 1 to R 12 and R 14 to R 17 are hydrogen atoms.
  • the compound represented by the general formula (2a) can be synthesized in consideration of paragraph number 0036 of JP2013-011869A.
  • Examples of commercially available products include VG-3101L manufactured by Printec Co., Ltd., NC-6000 and NC-6300 manufactured by Nippon Kayaku Co., Ltd.
  • R EP1 to R EP3 each represent a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and may have a substituent. Also good. R EP1 and R EP2 and R EP2 and R EP3 may be bonded to each other to form a ring structure.
  • QEP represents a single bond or an nEP- valent organic group.
  • R EP1 ⁇ R EP3 combines with Q EP may form a ring structure.
  • nEP represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. However, n EP is 2 when Q EP is a single bond. Details of R EP1 to R EP3 and Q EP can be referred to the descriptions in paragraph numbers 0087 to 0088 of Japanese Patent Application Laid-Open No. 2014-089408, the contents of which are incorporated herein.
  • an oligomer or polymer having an epoxy group in the side chain can also be preferably used.
  • examples of such compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aliphatic epoxy resins. These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.
  • bisphenol A type epoxy resin JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc.
  • bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835.
  • EPICLON N-695 manufactured by DIC Corporation
  • EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.
  • aliphatic epoxy resins include ADEKA RESIN EP-4080S, E -4085S, EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation).
  • ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
  • JER1031S manufactured by Mitsubishi Chemical Corporation
  • JER1032H60 manufactured by Mitsubishi Chemical Corporation
  • EPICLON HP-4700 manufactured by DIC Corporation
  • EPICLON N-695 manufactured by DIC Corporation
  • EPICLON840 DIC Corporation
  • EPICLON N660 DIC Corporation
  • EPICLON HP7200 DIC Corporation
  • the like can also be preferably used.
  • examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used.
  • a compound having an oxetane group can also be used as the polymerizable compound.
  • the compound having an oxetane group include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein.
  • Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX can be used.
  • polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
  • the content of the polymerizable compound is preferably 0.1 to 30% by mass with respect to the total solid content of the colored composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 20% by mass or less, and further preferably 15% by mass or less.
  • One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
  • the coloring composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound.
  • the polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).
  • T1 In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.
  • the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
  • Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable. These polyfunctional thiols can be used alone or in combination.
  • the content of the polyfunctional thiol is preferably 0.3 to 8.9% by mass with respect to the total solid content of the coloring composition, and preferably 0.8 to 6 More preferably, 4% by mass.
  • Polyfunctional thiols may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
  • the coloring composition of the present invention may contain a dye other than the above-described dye multimer (A) (hereinafter also referred to as other dye).
  • a dye or a dye can be preferably used, and a pigment is more preferred because of its high resistance to heat and light.
  • the content of other pigments is preferably 95% by mass or more, more preferably 97% by mass or more, and still more preferably 99% by mass or more with respect to the total amount of other pigments. . According to this aspect, it is easy to obtain an effect of increasing resistance to heat and light.
  • the pigment various conventionally known inorganic pigments or organic pigments can be used, and organic pigments are preferred.
  • ⁇ Dye >>>
  • the well-known dye currently used for the color filter can be used.
  • the chemical structure includes pyrazole azo, pyromethene, anilinoazo, triarylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, etc. Dyes can be used.
  • inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like, or carbon black (CI Pigment Black 7).
  • specific examples of the metal compound include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and metal composite oxides.
  • organic pigment for example, C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199; C. I. Pigment orange 36, 38, 43, 71; C. I. Pigment red 81,105,122,149,150,155,167,171,175,176,177,179,209,220,224,242,254,255,264,270; C. I. Pigment violet 19, 23, 32, 39; C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; C. I. Pigment green 7, 36, 37, 58; C. I. Pigment brown 25, 28; C. I. Pigment black 1; and the like.
  • the organic pigments can be used alone or in various combinations in order to adjust the spectrum and increase the color purity. Specific examples of preferred combinations are shown below.
  • a red pigment an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them and a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment And the like can be used.
  • an anthraquinone pigment C.I. I. Pigment red 177
  • perylene pigments include C.I. I. Pigment red 155, C.I. I.
  • Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred.
  • the mass ratio of the red pigment to the yellow pigment is preferably from 100: 5 to 100: 50, and more preferably from 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the desired spectrum.
  • a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used.
  • Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
  • the mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150, and more preferably 100: 30 to 100: 120.
  • a phthalocyanine pigment alone or a mixture of this with a dioxazine purple pigment can be used.
  • C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred.
  • the mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100.
  • the pigment for the black matrix carbon, titanium black, iron oxide, titanium oxide alone, or a mixture of two or more of these is used, and a combination of carbon and titanium black is preferable.
  • the mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.
  • the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast. Moreover, it is preferable that it is 5 nm or more from a viewpoint of dispersion stability.
  • the primary particle size of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
  • the primary particle size of the pigment can be measured by a known method such as an electron microscope.
  • the pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments.
  • C.I. I. Pigment red 177 anthraquinone pigment
  • C.I. I. Pigment red 254 diketopyrrolopyrrole pigment
  • C.I. I. Pigment green 7, 36, 58 C.I. I. Pigment Blue 15: 6 (phthalocyanine pigment), C.I. I. Pigment yellow 138 (quinophthalone pigment), C.I. I. Pigment yellow 139,185 (isoindoline pigment), C.I. I. Pigment yellow 150 (azomethine pigment), C.I. I. Pigment violet 23 (dioxazine pigment) is particularly preferred.
  • the content of the other pigments is preferably 10 to 70% by mass, more preferably 25 to 65% by mass with respect to the total solid content of the coloring composition. 35 to 55% by mass is more preferable.
  • the coloring composition of the present invention may contain only one type of other pigment or two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the colored composition of the present invention preferably contains a resin.
  • the resin include a resin (dispersion resin) for dispersing a pigment, an alkali-soluble resin, and the like.
  • Dispersed resin examples include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalene.
  • examples thereof include polymer dispersants such as sulfonic acid formalin condensate. From the structure, the polymer dispersant further comprises a linear polymer, a terminal-modified polymer having an anchor site to the pigment surface, a graft polymer having an anchor site to the pigment surface, and an anchor site to the pigment surface. It can be classified into a block type polymer having.
  • Examples of the terminal-modified polymer having an anchor site to the pigment surface include polymers having a phosphate group at the terminal described in JP-A-3-112992 and JP-T-2003-533455, and the like. Examples thereof include polymers having a sulfonic acid group at the terminal end described in JP-A-273191 and the like, and polymers having a partial skeleton of an organic dye and a heterocyclic ring described in JP-A-9-77994. In addition, polymers having two or more pigment surface anchor sites (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) introduced at the polymer ends described in JP-A-2007-277514 are also available. It is preferable because of excellent dispersion stability.
  • polyester resins examples include polyester resins. Specifically, reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, etc.
  • the amphoteric resin having a basic group and an acid group described in JP-A-2009-203462 has the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion. Particularly preferable from the viewpoint.
  • Macromonomer AA-6 manufactured by Toa Gosei Co., Ltd. Acid-6
  • AS-6 polystyrene whose terminal group is a methacryloyl group
  • AN-6S a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group
  • AB-6 polyyester whose terminal group is a methacryloyl group
  • Placel FM5 manufactured by Daicel Chemical Industries, Ltd.
  • polyesters described in JP-A-2-272009 System macromonomer and the like a polyester-based macromonomer that is particularly excellent in flexibility and solvent affinity is preferable from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion.
  • Polyester macromonomers represented by polyester macromonomers described in Japanese Utility Model Laid-Open No. 2-272009 are particularly preferred.
  • block polymers having an anchor site to the pigment surface block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
  • the resin is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, and 107 (carboxylic acid ester).
  • Solsperse 5000 phthalocyanine derivative
  • 22000 azo pigment derivative
  • 13240 polyyesteramine 3000
  • 17000 polymer having a functional part at the end
  • 24000, 28000, 32000, 38500 graft type polymer
  • Nikkor T106 polyoxyethylene sorbitan monooleate
  • MYS manufactured by Nikko Chemical Co., Ltd.
  • Polymer dispersants such as “Perth Aid 9100”, manufactured by ADEKA Corporation “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108 , L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like.
  • Resin may be used independently and may be used in combination of 2 or more type.
  • the resin is described later together with a terminal-modified polymer having an anchor site to the pigment surface, a graft polymer having an anchor site to the pigment surface, and a block polymer having an anchor site to the pigment surface.
  • An alkali-soluble resin may be used in combination.
  • Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples thereof include an acidic cellulose derivative having a resin and a resin having a hydroxyl group modified with an acid anhydride.
  • a (meth) acrylic acid copolymer Particularly preferred is a (meth) acrylic acid copolymer.
  • An alkali-soluble resin containing is also preferred.
  • the content of the dispersion resin is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment.
  • the lower limit is more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more.
  • the upper limit is more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, and still more preferably 60 parts by mass or less.
  • the coloring composition of this invention can contain alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formation are improved. In addition, alkali-soluble resin can also be used as a dispersion resin mentioned above.
  • the molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably 5000 to 100,000.
  • the number average molecular weight (Mn) is preferably 1000 to 20,000.
  • the alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having groups to promote.
  • the alkali-soluble resin will be described.
  • the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance.
  • Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
  • Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What can be developed is preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
  • a known radical polymerization method can be applied.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.
  • the alkali-soluble resin a polymer having a carboxylic acid in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used.
  • a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used.
  • examples thereof include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group added with an acid anhydride.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
  • examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
  • alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate,
  • vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfury
  • an alkali-soluble resin having a polymerizable group may be used.
  • the polymerizable group include a (meth) allyl group and a (meth) acryloyl group.
  • an alkali-soluble resin having a polymerizable group an alkali-soluble resin containing a polymerizable group in a side chain is useful.
  • the alkali-soluble resin containing a polymerizable group is prepared by reacting an isocyanate group and a hydroxyl group in advance, leaving one unreacted isocyanate group and containing a polymerizable group such as a (meth) acryloyl group, and a carboxyl group.
  • Diamond Shamrock Co. Ltd. biscort R-264, KS resist
  • 106 all manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • Cyclomer P series all manufactured by Daicel Chemical Industries, Ltd.
  • Ebecryl 3800 manufactured by Daicel UCB Co., Ltd.
  • Acrycure-RD-F8 Nippon Catalyst Etc.
  • Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used.
  • the alkali-soluble resin is a monomer containing a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer (a) obtained by polymerizing the components.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • General formula (ED2) In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description in JP 2010-168539 A can be referred to.
  • the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited, and examples thereof include methyl, ethyl, n Linear or branched alkyl groups such as -propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as;
  • ether dimers include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di ( n-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (tert-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (steary
  • dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.
  • These ether dimers may be only one kind or two or more kinds.
  • the structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.
  • the alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or a benzene ring that may contain a benzene ring.
  • n represents an integer of 1 to 15.
  • the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
  • the alkyl group of R 3 has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and the alkyl group of R 3 may contain a benzene ring.
  • Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
  • the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
  • the lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.
  • the upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and even more preferably 120 mgKOH / g or less.
  • the content of the alkali-soluble resin is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, with respect to the total solid content of the coloring composition. 10 mass% is still more preferable.
  • the coloring composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the coloring composition of the present invention can contain a pigment derivative.
  • the pigment derivative is a compound having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a phthalimidomethyl group, or the like.
  • the pigment derivative preferably contains a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.
  • Examples of the pigment for constituting the pigment derivative include pyrrolopyrrole pigment, diketopyrrolopyrrole pigment, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, Indolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments and the like can be mentioned.
  • a sulfonic acid group As an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its quaternary ammonium salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable.
  • the basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
  • the content of the pigment derivative is preferably 1 to 50% by mass, and more preferably 3 to 30% by mass with respect to the total mass of the pigment.
  • the pigment derivative may contain only one type, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the colored composition of the present invention may further contain a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
  • the photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives.
  • Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
  • trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums
  • compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.
  • trihalomethyltriazine compound More preferred are trihalomethyltriazine compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, ⁇ -aminoketone
  • the colored composition of the present invention when used for the production of a color filter for a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it be developed. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator.
  • an oxime compound as the photopolymerization initiator.
  • stepper exposure is used for curing exposure. This exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of the photopolymerization initiator low.
  • an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device.
  • oxime compound can improve the color transfer.
  • paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
  • acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
  • More preferred examples of the photopolymerization initiator include oxime compounds.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • J.H. C. S. Perkin II (1979) pp. 1653-1660
  • oxime compounds other than those described above compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in US Pat. No.
  • the oxime compound is preferably a compound represented by the following formula (OX-1).
  • the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
  • these groups may have one or more substituents.
  • the substituent mentioned above may be further substituted by another substituent.
  • the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
  • the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
  • the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
  • the oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
  • For the molar extinction coefficient of the compound a known method can be used.
  • an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure. You may use the photoinitiator used for this invention in combination of 2 or more type as needed.
  • the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5%, based on the total solid content of the colored composition. -30% by mass, more preferably 1-20% by mass. Within this range, better sensitivity and pattern formability can be obtained.
  • the composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the coloring composition of the present invention is a range that does not impair the effects of the present invention. And other components may be included.
  • the coloring composition of the present invention may contain a solvent.
  • the solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied, but the solubility, coating property, and safety of the dye multimer (A), the polymerizable compound, etc. are improved. It is preferable to select in consideration.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate ( Examples: methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (example: Methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
  • 2- Oxypropio Acid alkyl esters eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.
  • ketones include methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, and the like
  • aromatic hydrocarbons include toluene and xylene.
  • solvents are also preferably mixed in two or more types from the viewpoints of solubility of the dye multimer (A), polymerizable compound, etc., and improvement of the coated surface.
  • a mixed solution composed of two or more selected from butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
  • the content of the solvent is preferably such that the total solid concentration of the colored composition is 5 to 80% by mass from the viewpoint of applicability.
  • the lower limit is more preferably 5% by mass or more, and still more preferably 10% by mass or more.
  • the upper limit is more preferably 60% by mass or less, and still more preferably 50% by mass or less.
  • the colored composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the coloring composition of the present invention may contain a crosslinking agent.
  • a crosslinking agent By containing a crosslinking agent, the hardness of the cured film obtained can be further increased.
  • the crosslinking agent is not particularly limited as long as it can cure the film by a crosslinking reaction.
  • an epoxy resin for example, (a) an epoxy resin, (b) a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, c) A phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
  • polyfunctional epoxy resins are preferred.
  • the coloring composition of the present invention contains a crosslinking agent
  • the content of the crosslinking agent is not particularly defined, but is preferably 2 to 30% by mass with respect to the total solid content of the coloring composition, and 3 to 20% by mass. % Is more preferable.
  • the coloring composition of the present invention may contain only one type of crosslinking agent or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
  • the content of the polymerization inhibitor is preferably about 0.01 to 5% by mass relative to the mass of the coloring composition.
  • the coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • ⁇ surfactant Various surfactants may be added to the colored composition of the present invention from the viewpoint of further improving coatability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. That is, in the case of forming a film using a coloring composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, The coating property to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored composition.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like.
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.001% by mass with respect to the total mass of the coloring composition. 005 to 1.0% by mass.
  • the composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.
  • Organic carboxylic acid, organic carboxylic acid anhydride >>>
  • the coloring composition of the present invention may contain an organic carboxylic acid and / or an organic carboxylic acid anhydride.
  • the molecular weight of the organic carboxylic acid or organic carboxylic acid anhydride is preferably 1000 or less.
  • paragraphs 0338 to 0340 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
  • the coloring composition of the present invention contains an organic carboxylic acid and / or an organic carboxylic acid anhydride
  • the content of the organic carboxylic acid and / or the organic carboxylic acid anhydride is based on the total solid content of the coloring composition. 0.01 to 10% by mass is preferable, 0.03 to 5% by mass is more preferable, and 0.05 to 3% by mass is still more preferable.
  • the colored composition of the present invention may contain only one type of organic carboxylic acid and / or organic carboxylic acid anhydride, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • additives for example, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like can be blended with the colored composition of the present invention as necessary.
  • these additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
  • the coloring composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the same publication.
  • the coloring composition of the present invention is prepared by mixing the aforementioned components.
  • the components constituting the colored composition may be blended together, or may be blended sequentially after each component is dissolved and dispersed in a solvent.
  • the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
  • the colored composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
  • any filter can be used without particular limitation as long as it has been conventionally used for filtration.
  • fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc.
  • PTFE polytetrafluoroethylene
  • polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight)
  • PP polypropylene
  • the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, more preferably about 0.05 to 0.5 ⁇ m. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of the uniform and smooth coloring composition in a post process.
  • the filtering by the first filter may be performed only once or may be performed twice or more.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
  • the second filter a filter formed of the same material as the first filter described above can be used.
  • the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.
  • the colored composition of the present invention can be suitably used for forming a colored layer of a color filter because it can form a cured film having good light resistance, color transfer and flatness.
  • the colored composition of the present invention is a colored pattern such as a color filter used in a solid-state imaging device such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS), or an image display device such as a liquid crystal display device. It can be suitably used for forming. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. Especially, it can use suitably for manufacture of the color filter for solid-state image sensors, such as CCD and CMOS.
  • the color filter of the present invention is obtained by using the colored composition of the present invention.
  • the colored composition of the present invention is applied onto a support to form a colored composition layer, and unnecessary portions are removed to form a colored pattern.
  • the pattern forming method of the present invention can be suitably applied to the formation of a colored pattern of a color filter.
  • pattern formation may be performed by a so-called photolithography method, or pattern formation may be performed by a dry etching method. That is, the first aspect of the method for producing a color filter of the present invention includes a step of applying the colored composition of the present invention on a support to form a colored composition layer, and exposing the colored composition layer in a pattern.
  • the second aspect of the method for producing a color filter of the present invention includes a step of applying the colored composition of the present invention on a support to form a colored composition layer and curing to form a colored layer; A step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and forming a colored pattern by dry etching the colored layer using the resist pattern as an etching mask Including the step of.
  • the color filter of the present invention can be suitably obtained by the above production method. These details are described below.
  • the colored composition layer is formed by applying the colored composition of the present invention on the support.
  • a solid-state image sensor substrate in which a solid-state image sensor (light receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
  • the colored pattern in the present invention may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface).
  • an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.
  • various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be used.
  • the drying (pre-baking) of the colored composition layer applied on the support can be performed at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, an oven or the like.
  • the colored composition layer formed on the support is exposed in a pattern (exposure process).
  • pattern exposure can be performed by exposing the colored composition layer formed on the support using a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
  • radiation (light) that can be used for exposure ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line).
  • Irradiation dose (exposure dose) for example, preferably 30 ⁇ 1500mJ / cm 2, more preferably 50 ⁇ 1000mJ / cm 2, and most preferably 80 ⁇ 500mJ / cm 2.
  • the thickness of the cured film is preferably 1.0 ⁇ m or less, more preferably 0.1 to 0.9 ⁇ m, and further preferably 0.2 to 0.8 ⁇ m. By setting the film thickness to 1.0 ⁇ m or less, high resolution and high adhesion can be easily obtained.
  • Pattern formation process the unexposed portion is developed and removed to form a colored pattern (pattern forming step).
  • the development removal of the unexposed portion can be performed using a developer.
  • the coloring composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
  • the developer an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable.
  • the temperature of the developer is preferably 20 to 30 ° C., for example.
  • the development time is preferably 20 to 180 seconds.
  • the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide.
  • organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene.
  • the inorganic alkali for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
  • a developer composed of such an alkaline aqueous solution it is generally washed (rinsed) with pure water after development.
  • post-bake heat treatment after development and drying. If a multicolor coloring pattern is formed, a cured film can be produced by sequentially repeating the process for each color. Thereby, a color filter is obtained.
  • the post-baking is a heat treatment after development for complete curing, and the heating temperature is preferably, for example, 100 to 240 ° C, more preferably 200 to 240 ° C.
  • the post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so that the film after development is in the above condition. it can.
  • the pattern formation by the dry etching method is performed by curing the colored composition layer formed on the support to form a colored layer, and then using the patterned photoresist layer as a mask to etch the obtained colored layer.
  • a positive or negative radiation sensitive composition is applied onto the colored layer and dried to form a photoresist layer.
  • it is preferable to further perform a pre-bake treatment in particular, as a process for forming the photoresist layer, a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable.
  • a positive radiation sensitive composition sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), excimer lasers, far ultraviolet rays, electron beams, ion beams and X rays. Is preferably used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is more preferable.
  • the positive radiation sensitive composition a composition containing a quinonediazide compound and an alkali-soluble resin is preferable.
  • a positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to produce a carboxyl group, resulting in alkali-solubility from an alkali-insoluble state. It is what you use. Since this positive photoresist has remarkably excellent resolving power, it is used for manufacturing integrated circuits such as IC (integrated circuit) and LSI (Large Scale Integration). Examples of the quinonediazide compound include a naphthoquinonediazide compound. As a commercial item, "FHi622BC" (made by FUJIFILM Electronics Materials) etc. are mentioned, for example.
  • the thickness of the photoresist layer is preferably from 0.1 to 3 ⁇ m, more preferably from 0.2 to 2.5 ⁇ m, still more preferably from 0.3 to 2 ⁇ m.
  • the application method of a positive type radiation sensitive composition can be suitably performed using the application method in the above-mentioned colored layer.
  • the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with resist through-hole groups.
  • the formation of the resist pattern is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique.
  • a resist through hole group in the photoresist layer By providing a resist through hole group in the photoresist layer by exposure and development, a resist pattern as an etching mask used in the next etching is provided on the colored layer.
  • the exposure of the photoresist layer is performed by exposing the positive-type or negative-type radiation-sensitive composition with g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. Can do. After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.
  • Any developer can be used as long as it does not affect the colored layer and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist.
  • a combination of various solvents or an alkaline aqueous solution can be used.
  • an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable.
  • alkaline compound examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene. When an alkaline aqueous solution is used, a washing treatment with water is generally performed after development.
  • the resist pattern as an etching mask, patterning is performed by dry etching so that a through hole group is formed in the colored layer. Thereby, a colored pattern is formed.
  • the through-hole group is preferably provided in a checkered pattern, for example, in the colored layer. Therefore, the first colored pattern in which the through hole group is provided in the colored layer has a plurality of square-shaped first colored pixels in a checkered pattern.
  • the dry etching is preferably performed in the following manner from the viewpoint of forming the pattern cross section closer to a rectangle and reducing the damage to the support.
  • a mixed gas of fluorine-based gas and oxygen gas (O 2 ) the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N 2 ) and oxygen gas (O 2 ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed.
  • N 2 nitrogen gas
  • O 2 oxygen gas
  • a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed.
  • the form containing these is preferable.
  • a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.
  • Dry etching is performed by obtaining etching conditions in advance by the following method.
  • (1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
  • (2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
  • (3) The first-stage etching is performed according to the etching time calculated in (2) above.
  • the second-stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
  • (5) The overetching time is calculated with respect to the total time of (3) and (4) described above, and overetching is performed.
  • the mixed gas used in the first-stage etching process preferably contains a fluorine-based gas and an oxygen gas (O 2 ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape.
  • the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed.
  • the second stage etching process and the over etching process after the etching is performed up to the region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first stage etching process, damage to the support is avoided. From the viewpoint, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.
  • the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable.
  • the etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.
  • the etching preferably includes an over-etching process.
  • the overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first.
  • the over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.
  • the resist pattern that is, the etching mask
  • the removal of the resist pattern preferably includes a step of applying a stripping solution or a solvent on the resist pattern so that the resist pattern can be removed, and a step of removing the resist pattern using cleaning water.
  • Examples of the step of applying a stripping solution or solvent on the resist pattern so that the resist pattern can be removed include, for example, a step of applying a stripping solution or solvent on at least the resist pattern and stagnating for a predetermined time to perform paddle development Can be mentioned.
  • time to make stripping solution or a solvent stagnant It is preferable that it is several dozen seconds to several minutes.
  • examples of the step of removing the resist pattern using the cleaning water include a step of removing the resist pattern by spraying the cleaning water onto the resist pattern from a spray type or shower type spray nozzle.
  • the washing water pure water can be preferably used.
  • examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the resist pattern is more effectively removed by moving the support pattern from the center of the support to the end of the support more than twice during the process of removing the resist pattern and spraying the cleaning water. be able to.
  • the stripping solution generally contains an organic solvent, but may further contain an inorganic solvent.
  • organic solvents include 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, and 6) ester compounds.
  • the stripping solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.
  • the acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group.
  • Specific examples include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine.
  • Preferred are monoethanolamine, diethanolamine, and triethanolamine, and more preferred is monoethanolamine (H 2 NCH 2 CH 2 OH).
  • cyclic nitrogen-containing compounds include isoquinoline, imidazole, N-ethylmorpholine, ⁇ -caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2- Preferred examples include pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, and 2,6-lutidine.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • the stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.
  • acyclic nitrogen-containing compound at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic
  • the nitrogen-containing compound preferably includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably includes monoethanolamine and N-methyl-2-pyrrolidone.
  • a deposit means an etching product deposited and deposited on the side wall of a colored layer.
  • the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.
  • the method for producing a color filter of the present invention may have a step known as a method for producing a color filter for a solid-state imaging device as a step other than the above, if necessary.
  • a curing step of curing the formed colored pattern by heating and / or exposure may be included as necessary.
  • the solvent for the colored composition of the present invention is used to efficiently clean the nozzles and pipes of the discharge unit of the coating apparatus, contamination due to adhesion, sedimentation, and drying of the colored composition and pigment in the coating machine.
  • the cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can be suitably used.
  • alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred. These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group.
  • the mass ratio of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • the ratio is particularly preferably 60/40.
  • the above-described surfactant relating to the colored composition of the present invention may be added to the cleaning liquid.
  • the color filter of the present invention uses the colored composition of the present invention, the color filter is excellent in light resistance, color transfer and flatness.
  • the color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels.
  • the color filter for a solid-state imaging device of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.
  • the film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, and even more preferably 0.7 ⁇ m or less. Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and particularly preferably 1.7 ⁇ m or less.
  • the solid-state imaging device of the present invention includes the above-described color filter of the present invention.
  • the configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration that includes the color filter of the present invention and functions as a solid-state imaging device.
  • a solid-state imaging device CCD image sensor, CMOS image sensor, etc.
  • a transfer electrode made of polysilicon, etc.
  • the photodiode is placed on the transfer electrode.
  • the color filter for a solid-state image sensor according to the present invention is provided.
  • a configuration having a light condensing means for example, a microlens, etc., the same applies hereinafter
  • a structure having the light condensing means on the color filter It may be.
  • the color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device. It is particularly suitable for liquid crystal display devices.
  • the liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.
  • display devices For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year).
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • the color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device.
  • the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
  • the present invention is applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
  • the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system.
  • COA Color-filter On Array
  • the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above.
  • the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided.
  • a resin film may be provided on the color filter layer.
  • the liquid crystal display device provided with the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film.
  • the color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
  • these components for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
  • backlighting SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.
  • the color filter according to the present invention When the color filter according to the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue light emitting diode (LED) light sources are used.
  • LED light emitting diode
  • a backlight By using a backlight, a liquid crystal display device having high luminance and high color purity and excellent color reproducibility can be provided.
  • the weight average molecular weight (polystyrene equivalent value) of the dye multimer S-1 was 14500, and the acid value was 40 mgKOH / g by titration with a 0.1N sodium hydroxide aqueous solution.
  • the number of repeating units having a dye structure of the polymer chain Q in NMR (nuclear magnetic resonance) measurement was calculated to be an average of 4.5.
  • a solution containing 0.01 mg / ml of the dye multimer S-1 was prepared by dissolving in tetrahydrofuran (THF) (concentration adjusted so that the maximum absorbance was 1.0).
  • THF tetrahydrofuran
  • E A / (c ⁇ l) (A ⁇ )
  • a ⁇ the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm
  • A the absorbance at the maximum absorption wavelength between 400 nm and 800 nm
  • l the cell length in units of cm
  • c the concentration of the dye multimer in the solution expressed in mg / ml.
  • a triarylmethane compound (A-tp-101) was synthesized according to the method described in JP-A No. 2000-162429.
  • Triarylmethane compound (A-tp-101) (15 g), hydroxyethyl methacrylate (10 g), methacrylic acid (5.5 g), and azobisisobutyronitrile (5 g) were converted into N-ethylpyrrolidone (70 g).
  • the mixture was stirred and dissolved at room temperature for 30 minutes (polymerization solution for dropping).
  • a triarylmethane compound (A-tp-101) (15 g), hydroxyethyl methacrylate (10 g), and methacrylic acid (5.5 g) were placed in a container and dissolved, and stirred at 80 ° C.
  • the polymer solution for dripping prepared there was dripped over 3 hours, and after stirring for 1 hour, azoisobutyronitrile (2.5g) was added, and it was made to react for 2 hours, and was stopped. After cooling to room temperature, the solvent was distilled off to obtain comparative dye 3.
  • the weight average molecular weight (Mw) of the comparative dye 3 was 18000, and the acid value was 1.81 mgKOH / g by titration using a 0.1N sodium hydroxide aqueous solution.
  • a pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion) was prepared as follows. That is, C.I. I. Pigment Blue 15: 6 (blue pigment; hereinafter also referred to as “PB15: 6”) 19.4 parts by mass (average primary particle diameter 55 nm), and dispersion resin BY-161 (manufactured by BYK) 2.95 parts by mass, 2.
  • Pigment Blue 15: 6 dispersion was obtained.
  • Production of color filter (colored pattern) 4-1 Production of color filter using colored composition by photolithography method The colored composition prepared above is applied to the undercoat layer of the silicon wafer with an undercoat layer prepared above. To form a colored layer (coating film). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 1 ⁇ m. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure dose of 50 to 1200 mJ / cm 2 through an Island pattern mask having a pattern of 1.0 ⁇ m square at a wavelength of 365 nm.
  • FPA-3000i5 + manufactured by Canon Inc.
  • the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the undercoat layer of the silicon wafer with the undercoat layer.
  • the silicon wafer on which the colored pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and pure water is sprayed from the jet nozzle from above the rotation center while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device. The rinsing process was performed.
  • a colored pattern (color filter) having a film thickness of 1 ⁇ m on the silicon wafer As described above, a silicon wafer with a colored pattern having a structure in which a colored pattern (color filter) was provided on the undercoat layer of the silicon wafer with an undercoat layer was obtained. Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The development residue was evaluated using a colored pattern having an exposure amount of 1.0 ⁇ m in pattern size.
  • the colored photosensitive composition prepared above was applied to a glass substrate using a spin coater (manufactured by Mikasa Co., Ltd.) to form a coating film. And heat processing (prebaking) was performed for 120 second using a 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 0.6 micrometer. Next, heating was performed at 200 ° C. for 5 minutes, and the coating film was cured to form a colored layer.
  • prebaking heat processing
  • the glass substrate on which the colored layer is formed is black panel temperature 63 ° C., quartz inner filter, 275 nm cut outer filter, illuminance 75 mw / m 2 (300 to 400 nm)
  • the light resistance test was conducted for 10 hours under the condition of 50% humidity.
  • the color difference ( ⁇ E * ab) before and after the light resistance test was measured with a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). Based on the measured color difference ( ⁇ E * ab), light resistance was evaluated according to the following evaluation criteria. It can be said that the smaller this value, the better the light resistance.
  • the evaluation results are shown in the following table. A and B are levels at which there is no problem in actual use.
  • ⁇ E * ab is 3 or less
  • the coloring composition 1.0mL prepared above was apply
  • the thickness of the colored layer was measured using an optical film thickness meter (Filmetrics F20). It can be said that the smaller the difference between the thinnest part (center part) and the thickest part (peripheral part), the better.
  • the evaluation results are shown in the following table. A and B are levels at which there is no problem in actual use.
  • Example 1 Except for changing the pigment dispersion, the dye multimer (dye), the photopolymerization initiator, the alkali-soluble resin, and the polymerizable compound in “3-2. Preparation of colored composition” in Example 1, as shown in the following table. A colored composition was prepared in the same manner as in Example 1, and the development residue, color transfer, light resistance and flatness were evaluated in the same manner as in Example 1. In Comparative Examples 1 to 3, the above-mentioned comparative dyes S′-1 to S′-3 were used as the dye multimer.
  • Examples 53 and 54 The following components were mixed, dispersed and dissolved, and filtered through a 0.45 ⁇ m nylon filter to obtain a colored composition. Next, the obtained colored composition was applied onto a 7.5 cm ⁇ 7.5 cm glass substrate using a spin coater so as to have a film thickness of 0.5 ⁇ m. Then, heating was performed for 5 minutes to cure the coating film to prepare a colored layer. The thickness of this colored layer was 0.5 ⁇ m. Next, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) was applied and prebaked at 90 ° C. for 1 minute to form a 0.8 ⁇ m-thick photoresist layer.
  • FHi622BC positive photoresist
  • the photoresist layer was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.) with an exposure amount of 350 mJ / cm 2 , and the temperature of the photoresist layer or the ambient temperature was 90 ° C. for 1 minute The heat treatment was performed. Thereafter, development processing was performed with a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials) for 1 minute, and further post-baking processing was performed at 110 ° C. for 1 minute to form a resist pattern.
  • the resist pattern was formed with a side of 1.0 ⁇ m in consideration of etching conversion difference (pattern width reduction by etching).
  • a glass substrate on which a photoresist layer is formed is attached to an 8-inch silicon wafer, and RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W using a dry etching apparatus (U-621, manufactured by Hitachi High-Technologies Corporation).
  • the internal pressure of the chamber 4.0 Pa
  • the substrate temperature 50 ° C.
  • the gas type and flow rate of the mixed gas are CF 4 : 80 mL / min
  • O 2 40 mL / min
  • Ar 800 mL / min.
  • the colored compositions of Examples 53 and 54 were excellent in color transfer, light resistance and flatness.
  • Alkali-soluble resin the following structure
  • Polymerizable compound Z-1 Ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Z-2 Dipentaerythritol hexaacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
  • Z-3 Ethoxylation (4) Pentaerythritol tetraacrylate, SR494 (manufactured by Sartomer)
  • Z-4 Ethoxylation (3) Trimethylolpropane triacrylate, SR454 (manufactured by Sartomer)
  • Z-5 Ethoxylation (6) Trimethylolpropane triacrylate, SR499 (manufactured by Sartomer)
  • Z-6 KAYARAD DPCA-60 (Nippon Kayaku Co., Ltd.)
  • Z-7 Tris (2-hydroxyethy
  • Pigment dispersion P4 (CI Pigment Violet 23 dispersion): In the preparation of the pigment dispersion P1, C.I. I. A pigment dispersion P4 was prepared in the same manner as the pigment dispersion P1 except that Pigment Violet 23 was used.
  • Pigment dispersion P5 (CI Pigment Red254 dispersion): In the preparation of the pigment dispersion P1, C.I. I. A pigment dispersion P5 was prepared in the same manner as the pigment dispersion P1 except that Pigment Red254 was used.
  • Pigment dispersion P6 (CI Pigment Green 58 dispersion): In the preparation of the pigment dispersion P1, C.I. I. A pigment dispersion P6 was prepared in the same manner as the pigment dispersion P1 except that Pigment Green 58 was used.
  • Pigment dispersion P7 (CI Pigment Yellow 139 dispersion): In the preparation of the pigment dispersion P1, C.I. I. A pigment dispersion P7 was prepared in the same manner as the pigment dispersion P1, except that Pigment Yellow 139 was used.

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PCT/JP2015/070896 2014-08-29 2015-07-23 着色組成物、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子、画像表示装置および色素多量体の製造方法 WO2016031442A1 (ja)

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KR1020177000656A KR20170016954A (ko) 2014-08-29 2015-07-23 착색 조성물, 컬러 필터, 패턴 형성 방법, 컬러 필터의 제조 방법, 고체 촬상 소자, 화상 표시 장치 및 색소 다량체의 제조 방법

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KR102325836B1 (ko) 2018-11-06 2021-11-11 삼성에스디아이 주식회사 감광성 수지 조성물, 이를 이용하여 제조된 감광성 수지막 및 컬러필터
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