WO2012039286A1 - 染料及び着色感光性組成物 - Google Patents
染料及び着色感光性組成物 Download PDFInfo
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- WO2012039286A1 WO2012039286A1 PCT/JP2011/070456 JP2011070456W WO2012039286A1 WO 2012039286 A1 WO2012039286 A1 WO 2012039286A1 JP 2011070456 W JP2011070456 W JP 2011070456W WO 2012039286 A1 WO2012039286 A1 WO 2012039286A1
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- 0 CC*C(CC)(CC)*C(C(C#N)=C(*)c(c(*)c1*)c(*)c(*)c1N(*)*)=O Chemical compound CC*C(CC)(CC)*C(C(C#N)=C(*)c(c(*)c1*)c(*)c(*)c1N(*)*)=O 0.000 description 3
Classifications
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- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
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- 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
- C09B11/02—Diaryl- or thriarylmethane dyes derived from diarylmethanes
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- 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
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/06—Hydroxy derivatives of triarylmethanes in which at least one OH group is bound to an aryl nucleus and their ethers or esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
- C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
- C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/143—Styryl dyes the ethylene chain carrying a COOH or a functionally modified derivative, e.g.-CN, -COR, -COOR, -CON=, C6H5-CH=C-CN
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- 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
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
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- 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
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- 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
- G02F2202/00—Materials and properties
- G02F2202/04—Materials and properties dye
Definitions
- the present invention relates to a dye designed to have a desired hue and improved heat resistance, and a novel compound suitable for the dye. Furthermore, the present invention relates to a colored photosensitive composition that can be polymerized by energy rays using the dye, and a color filter that uses the colored photosensitive composition.
- Compounds having high intensity absorption for specific light include recording layers of optical recording media such as CD-R, DVD-R, DVD + R, BD-R, liquid crystal display (LCD), plasma display panel (PDP) ), An electroluminescence display (ELD), a cathode ray tube display (CRT), a fluorescent display tube, and an optical display element such as a field emission display.
- optical recording media such as CD-R, DVD-R, DVD + R, BD-R, liquid crystal display (LCD), plasma display panel (PDP) ), An electroluminescence display (ELD), a cathode ray tube display (CRT), a fluorescent display tube, and an optical display element such as a field emission display.
- an optical filter for an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display device (CRT), a fluorescent display tube, a field emission display, etc.
- Various compounds that absorb light having a wavelength of ⁇ 1100 nm are used as light absorbing materials.
- a light absorber that selectively absorbs a wavelength of 380 to 500 nm has been demanded in order to ensure sufficient color purity and color separation of the display element and to improve image quality.
- These light absorbers are required to have particularly steep light absorption, that is, having a small half-value width of ⁇ max and not to lose its function due to light, heat, or the like.
- An optical filter mainly used for a liquid crystal display includes a color filter.
- three primary colors of RGB have been used for a color filter, but it is difficult to have a pure RGB hue with a single color material, and a pure RGB hue using a plurality of color materials. Efforts have been made to get closer to. Therefore, color materials such as yellow, orange and purple are required instead of RGB.
- Organic and / or inorganic pigments have been used as light absorbers for color filters due to their high heat resistance. However, since they are pigments, there is a problem in that the luminance of a display device is lowered. This problem has been solved by increasing the brightness of the.
- Patent Documents 1 to 3 disclose dyes using a compound having a specific structure.
- Patent Document 4 discloses an optical filter using a compound having a specific structure.
- the dyes (compounds) described in these documents are not satisfactory in terms of solubility and heat resistance.
- an object of the present invention is to provide a dye having excellent solubility and heat resistance and a novel compound suitable for the dye, and in particular, a yellow dye having a maximum absorption wavelength in the region of 400 to 450 nm. Is to provide.
- Another object of the present invention is to provide a colored (alkali developable) photosensitive composition using the above dye.
- Another object of the present invention is to provide an optical filter using the above colored (alkali developable) photosensitive composition, particularly a color filter suitable for an image display device such as a liquid crystal display panel without reducing luminance. There is.
- a compound having a specific structure has a maximum absorption wavelength in the region of 400 to 450 nm and that a dye using the compound has excellent solubility and heat resistance.
- a colored (alkali developable) photosensitive composition using the above dye does not decrease the luminance of an optical filter (particularly a color filter) and is suitable for a color filter for an image display device such as a liquid crystal display panel.
- the present invention has been found.
- This invention is made
- R 1 represents a hydrogen atom, a methyl group, a halogen atom, a phenyl group or a cyano group
- R 2 to R 5 each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, an unsubstituted or halogenated alkyl group having 1 to 8 carbon atoms, or an unsubstituted or halogenated carbon.
- R 2 and R 3 , R 4 and R 5 may be linked to form a ring structure
- R 6 and R 7 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms.
- R 3 and R 6 and / or R 5 and R 7 and / or R 6 and R 7 may be linked to form a ring structure
- Q represents —O—, —NR 12 — or —S—
- R 12 represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 8 carbon atoms
- n represents an integer of 2 to 6
- s represents an integer of 0 to 4
- X represents an organic group having 1 to 35 carbon atoms having the same valence as n + s.
- the present invention also provides the dye (A), a polymerizable compound (B) having an ethylenically unsaturated bond, a photopolymerization initiator (C), and, if necessary, an inorganic pigment and / or an organic pigment (D).
- the present invention provides a colored photosensitive composition to be contained.
- the present invention also provides a colored alkali-developable photosensitive composition containing the dye (A), an alkali-developable polymerizable compound (B ′) having an ethylenically unsaturated bond, and a photopolymerization initiator (C). It provides things.
- the present invention also provides a cured product of the colored photosensitive composition or the colored alkali-developable photosensitive composition, a color filter for a display device using the cured product, and a liquid crystal using the color filter for the display device.
- a display panel is provided.
- the present invention also provides a novel compound represented by the following general formula (1 ′).
- R 1 to R 7 , Q, X, and n are the same as those in the general formula (1) and further have any of the following conditions (i) to (v), provided that n is 2)
- n represents 2
- X represents an alkylene group having a side chain of 3 to 35 carbon atoms, and the alkylene group is not further substituted or interrupted.
- n is 2
- X is a linear alkylene group having 4 to 6 carbon atoms
- R 2 to R 5 are hydrogen atoms.
- a dye excellent in solubility and heat resistance and a novel compound suitable for the dye can be provided.
- the colored photosensitive composition (colored alkali-developable photosensitive composition) using the dye and the cured product thereof are suitable for color filters for display devices and liquid crystal display panels.
- the compound used for the dye (A) of the present invention is represented by the general formula (1).
- Examples of the halogen atom represented by R 1 to R 5 in the general formula (1) include fluorine, chlorine, bromine and iodine.
- Examples of the unsubstituted alkyl group having 1 to 8 carbon atoms represented by R 2 to R 5 in the general formula (1) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, and tert-butyl.
- a group halogenated by the halogen atom, and the like examples include methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, amyloxy, iso-amyloxy, tert-amyloxy, hexyl Oxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy, 1-octyloxy, iso -Octyloxy, tert-octyloxy and the like, and examples of the halogenated alkoxy group having 1 to 8 carbon atoms include those exemplified above as the un
- Examples of the ring structure formed by connecting R 2 and R 3 or R 4 and R 5 in the general formula (1) include a cyclopentene ring, a cyclohexene ring, a dihydrofuran ring, and a dihydropyran ring.
- Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by R 6 and R 7 in the general formula (1) include, for example, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, Tertiary butyl, isobutyl, amyl, isoamyl, tertiary amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third Alkyl groups such as heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl; vinyl, 1-methyletheny
- Examples of the aromatic hydrocarbon group having 6 to 35 carbon atoms represented by R 6 and R 7 include arylalkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl and cinnamyl; phenyl, naphthyl and the like
- the methylene group in the arylalkyl group may be interrupted by —O—, —S—, —SO 2 —, —CO—, —OCO— or —COO—.
- heterocyclic group having 2 to 35 carbon atoms represented by R 6 and R 7 examples include pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, Furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4 -Dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl and the like.
- the ring structure formed by linking R 3 and R 6 and / or R 5 and R 7 and / or R 6 and R 7 includes a cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, pyrrolidine ring, pyrrole ring , Piperazine ring, piperidine ring, morpholine ring, thiomorpholine ring, tetrahydropyridine ring, lactone ring, lactam ring and other 5- to 7-membered rings, and condensed rings such as naphthalene ring and anthracene ring.
- Examples of the alkyl group having 1 to 8 carbon atoms represented by R 12 in the general formula (1) include the groups exemplified as the unsubstituted alkyl group having 1 to 8 carbon atoms.
- Aromatic hydrocarbon group in formula (1) aliphatic hydrocarbon group having a carbon number of 1 to 35 represented by R 6 and R 7 in the carbon atom number of 6 to 35 represented by R 6 and R 7
- the heterocyclic group having 2 to 35 carbon atoms represented by R 6 and R 7 may have a substituent, and examples of the substituent include the following.
- R 6 and R 7 are groups containing carbon atoms such as the above-mentioned aliphatic hydrocarbon groups having 1 to 35 carbon atoms, and these groups are carbon atoms among the following substituents. When it has a substituent containing, the total number of carbon atoms including the substituent shall satisfy the specified range.
- substituents examples include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, and 3-hexyl.
- Alkyl groups such as cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl Methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, hex Alkoxy groups such as tiloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy,
- Alkylthio group vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl , Alkenyl groups such as 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, tricosenyl; arylalkyls such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl Groups; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; arylthio groups such as phenylthio and naphthylthio; pyri
- the organic group having 1 to 35 carbon atoms having the valence of n + s represented by X in the general formula (1) is divalent (when n is 2), and the following general formula (2) or (3)
- Examples of the trivalent group (when n is 2 or 3) include groups represented by the following general formula (4).
- Examples of the trivalent group (when n is 2 to 4) Are groups represented by the following general formula (5), and pentavalent (when n is 2 to 5) include groups represented by the following general formula (6), and hexavalent (n Is a group represented by the following general formula (7).
- it is assumed that the formula Xn s holds.
- X 1 represents a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, or a disubstituted alicyclic hydrocarbon group having 3 to 20 carbon atoms.
- the alkylidene group may be substituted with a halogen atom, and R 20 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms.
- Z 1 and Z 2 are a direct bond, alkanediyl having 1 to 8 carbon atoms, disubstituted aromatic hydrocarbon having 6 to 20 carbon atoms, —O— or —S -Represents a group of any one of these or a combination thereof, represented by the above general formula (2) or (3).
- Group is in the range of 1 to 25 carbon atoms, and at least one of X 1 , Z 1 and Z 2 is not a direct bond.
- Z 11 represents a hydrogen atom, a phenyl group optionally substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group, or a cycloalkyl group having 3 to 10 carbon atoms
- Y 1 represents a carbon atom.
- D is an integer of 0 to 5.
- Y 2 and Z 12 are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom.
- An arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms that may be substituted with a halogen atom, or a complex having 2 to 20 carbon atoms that may be substituted with a halogen atom represents a cyclic group, or a halogen atom, the alkyl group, the methylene group in the arylalkyl group may be interrupted by an unsaturated bond, -O- or -S
- X 2 is a carbon atom substituted with R 30 , a nitrogen atom, or a trisubstituted chain hydrocarbon having 1 to 20 carbon atoms, or an oil having 3 to 20 carbon atoms.
- Z 1 to Z 3 are the same as the groups represented by Z 1 and Z 2 in the general formula (2), provided that The group represented by the general formula (4) is in the range of 1 to 25 carbon atoms.
- X 3 is a carbon atom, tetrasubstituted chain hydrocarbon having 1 to 20 carbon atoms, alicyclic hydrocarbon having 3 to 20 carbon atoms, or 6 carbon atoms. Represents an aromatic hydrocarbon having ⁇ 20 or a heterocyclic ring having 6 to 20 carbon atoms, and Z 1 to Z 4 are the same as the groups represented by Z 1 and Z 2 in the above general formula (2).
- the group represented by the general formula (5) is in the range of 1 to 25 carbon atoms.
- X 4 is 5-substituted chain hydrocarbon having 1 to 20 carbon atoms, alicyclic hydrocarbon having 3 to 20 carbon atoms, or having 6 to 20 carbon atoms. Represents an aromatic hydrocarbon or a heterocyclic ring having 6 to 20 carbon atoms, and Z 1 to Z 5 are the same as the groups represented by Z 1 and Z 2 in the general formula (2). (The group represented by (6) is in the range of 1 to 35 carbon atoms.)
- Z 1 to Z 6 are the same as the groups represented by Z 1 and Z 2 in the general formula (2), provided that they are represented by the general formula (7).
- the group is in the range of 1 to 35 carbon atoms.
- Examples of the alkylidene group having 1 to 4 carbon atoms represented by X 1 in the general formula (2) include methylidene, ethylidene, propylidene and butylidene.
- the 2 is a substituted alicyclic hydrocarbon radical having 3 to 20 carbon atoms, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethyl cyclobutane, groups such as 4-methylcyclohexane Z 1 And a group substituted with Z 2 (which is disubstituted).
- Examples of the alkyl group having 1 to 8 carbon atoms represented by R 20 as the group in X 1 in the general formula (2) include the groups exemplified in the description of R 2 to R 5 in the general formula (1).
- Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethyl
- alkanediyl having 1 to 8 carbon atoms represented by Z 1 and Z 2 in the general formula (2) or (3) examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, 1 -Methylmethane-1,1-diyl, 1-ethylmethane-1,1-diyl, 1-propylmethane-1,1-diyl, 1-methylethane-1,2-diyl, 1-ethylethane-1,2-diyl 1-propylethane-1,2-diyl, 1-methylpropane-1,3-diyl, 1-ethylpropane-1,3-diyl, 1-propylpropane-1,3-diyl, 2-methylpropane 1,3-diyl, 2-ethylpropane-1,3-diyl, 2-propylpropane-1,3-diy
- Examples of the tri-substituted chain hydrocarbon represented by X 2 in the general formula (4) having 1 to 20 carbon atoms include methane, ethane, propane, iso-propane, butane, sec-butane, tert-butane, iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, iso-heptane, tert-heptane, 1-methyloctane, iso-octane, tert-octane, etc.
- Examples of the trisubstituted alicyclic hydrocarbon having 3 to 20 carbon atoms include the alicyclic hydrocarbon groups exemplified in the description of X 1 in the general formula (2) as Z 1 , Z 2 and Z 3 .
- a substituted (trisubstituted) group examples include groups such as benzene, naphthalene, anthracene, fluorene, biphenylene, and terphenylene substituted with Z 1 , Z 2, and Z 3 (3-substituted Group), and Examples of the trisubstituted heterocyclic ring having 6 to 20 carbon atoms include groups such as pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene, thiophene, and thiolane. And groups substituted with Z 1 , Z 2 and Z 3 (trisubstituted).
- Examples of the alkanediyl having 1 to 8 carbon atoms and the disubstituted aromatic hydrocarbon having 6 to 20 carbon atoms represented by Z 1 to Z 3 in the general formula (4) include the above general formula (2). And the groups exemplified in the description of Z 1 and Z 2 in (3).
- the hydrocarbon or the heterocyclic ring having 6 to 20 carbon atoms the group exemplified in the description of X 2 in the above (4) is substituted with Z 1 , Z 2 , Z 3 and Z 4 (4 substitution). ) Group.
- Examples of the alkanediyl having 1 to 8 carbon atoms and the disubstituted aromatic hydrocarbon having 6 to 20 carbon atoms represented by Z 1 to Z 4 in the general formula (5) include the above general formula (2). And the groups exemplified in the description of Z 1 and Z 2 in (3).
- Examples of the alkanediyl having 1 to 8 carbon atoms and the disubstituted aromatic hydrocarbon having 6 to 20 carbon atoms represented by Z 1 to Z 5 in the general formula (6) include the above general formula (2). And the groups exemplified in the description of Z 1 and Z 2 in (3).
- Examples of the alkanediyl having 1 to 8 carbon atoms and the disubstituted aromatic hydrocarbon having 6 to 20 carbon atoms represented by Z 1 to Z 6 in the general formula (7) include the above general formula (2). And the groups exemplified in the description of Z 1 and Z 2 in (3).
- R 1 is a hydrogen atom
- R 2 to R 5 are hydrogen atoms
- R 6 and R 7 are alkyl groups having 1 to 8 carbon atoms.
- Q is —O— or —NH—
- n 2
- n 3
- XQ moiety is A group selected from group 2
- n 4
- XQ moiety is group 3 group
- n 5, XQ moiety is group 4 group
- n it is more preferable that the XQ moiety is a group 5 group because the raw materials are particularly easily available.
- those in which X in the general formula (1) is an asymmetric group or those having 7 or more carbon atoms are particularly preferable because of excellent solubility.
- R 1 to R 7 and Q may be the same or different.
- Ring A represents an alicyclic hydrocarbon having 3 to 8 carbon atoms
- R represents an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, an alkylene group having 1 to 4 carbon atoms, or a hydroxyl group.
- the manufacturing method of the compound represented by the said General formula (1) is not specifically limited, For example, it can manufacture according to following Reaction formula 1 or 2. That is, in the case of producing according to the following reaction formula 1, the carboxylic acid (10) and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) are reacted in pyridine, and then the polyfunctional alcohol or By reacting the polyfunctional amine (11), a compound represented by the above general formula (1) which is an ester or amide can be obtained.
- the carboxylic acid (10) and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) are reacted in pyridine, and then the polyfunctional alcohol or By reacting the polyfunctional amine (11), a compound represented by the above general formula (1) which is an ester or amide can be obtained.
- cyanoacetic acid ester (13) is reacted with toluene (12) and polyfunctional alcohol or polyfunctional amine (11) in the presence of p-toluenesulfonic acid in toluene.
- the compound represented by the above general formula (1) which is an ester or amide, can be obtained by reacting aldehyde or ketone (14) in toluene in the presence of triethylamine.
- the dye (A) of the present invention only needs to contain at least one compound represented by the general formula (1), and can be used alone or in combination. Moreover, it is also possible to use a well-known dye other than the compound represented by the said General formula (1).
- Known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, Examples thereof include phthalocyanine dyes and cyanine dyes, and a plurality of these may be used in combination.
- the content of the compound represented by the general formula (1) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass.
- the solubility in a solvent may be reduced or the heat resistance may be reduced.
- the dye (A) of the present invention is used as a colored photosensitive composition and a colored alkali-developable photosensitive composition described below, as well as an optical filter used for displays and optical lenses, a silver salt photographic photosensitive material, and a dyed article. , Paints, optical recording dyes and the like.
- the colored photosensitive composition and the colored alkali-developable photosensitive composition of the present invention (hereinafter also simply referred to as a colored composition) will be described.
- the description demonstrated in dye (A) of this invention is applied suitably.
- the coloring composition of the present invention comprises the dye (A) of the present invention, a polymerizable compound (B) having an ethylenically unsaturated bond (a polymerizable compound (B ′) having an ethylenically unsaturated bond and having an ethylenically unsaturated bond). And a photopolymerization initiator (C), and if necessary, an inorganic pigment and / or an organic pigment (D).
- the dye (A) of the present invention is as described above.
- the content of the dye (A) of the present invention is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass in the colored composition of the present invention. . If the content of the dye (A) is less than 0.01% by mass, a desired concentration of color may not be obtained in the cured product of the present invention. If the content is more than 50% by mass, the dye (A A) precipitation may occur.
- the polymerizable compound (B) having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in photosensitive compositions can be used.
- ethylene, propylene, butylene, isobutylene can be used.
- Unsaturated polybasic acids such as polyfunctional (meth) acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate; 121-No.
- Reaction products of polyfunctional isocyanates such as acrylate and tolylene diisocyanate and hexamethylene diisocyanate, hydroxyl-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc.
- the polyfunctional acrylate which has an acid value which is a reaction product of a dibasic acid anhydride is mentioned.
- polymerizable compounds can be used alone or in admixture of two or more, and when used in admixture of two or more, they are copolymerized in advance and used as a copolymer. May be.
- the polymerizable compound (B ′) having an ethylenically unsaturated bond having alkali developability (hereinafter referred to as ethylenic) is used as the polymerizable compound (B) having an ethylenically unsaturated bond.
- ethylenic alkali developability
- the colored photosensitive composition of the present invention becomes a colored alkali-developable photosensitive composition.
- alkali-developable compound (B ′) having an ethylenically unsaturated bond examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylates such as (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; N-vinylpyrroli
- a polyphenylmethane type epoxy resin having a functional epoxy group obtained by allowing an unsaturated monobasic acid to act on an epoxy group such as an epoxy compound represented by the following general formula (I), and further reacting with a polybasic acid anhydride Resins can be used. These monomers can be used individually by 1 type or in mixture of 2 or more types.
- the alkali developing compound having an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.
- X 41 is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, —O—, —S—, —SO 2 —, —SS—, —SO—, —CO—, —OCO— or a substituent represented by the above [Chemical 3A] to [Chemical 3C], wherein the alkylidene group may be substituted with a halogen atom;
- 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom
- the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom
- w is an integer of 0 to
- Examples of the unsaturated monobasic acid that acts on the epoxy group of the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, and the like. Examples thereof include hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, and dicyclopentadiene / malate.
- the polybasic acid anhydride to be acted after the unsaturated monobasic acid is allowed to act is biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride , Pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride Acid, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, trialkyltetra
- the reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group 1 of the epoxy adduct is It is preferable that the ratio of the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0. Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.
- a monofunctional or polyfunctional epoxy compound may be used together with the alkali-developable compound having an ethylenically unsaturated bond. It can.
- the alkali-developable compound having an ethylenically unsaturated bond preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and the use amount of the monofunctional or polyfunctional epoxy compound satisfies the acid value. It is preferable to select as follows.
- Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecy
- the polyfunctional epoxy compound it is preferable to use one or more selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers as the polyfunctional epoxy compound because a colored alkali-developable photosensitive composition with better characteristics can be obtained.
- the bisphenol type epoxy compound an epoxy compound represented by the above general formula (I) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
- glycidyl ethers examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1 , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (g Glycidyl oxymethyl) ethane, 1,1,1-tri (g
- novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl-p-aminophenol and N, N-diglycidylaniline; hetero
- the content of the polymerizable compound (B) having the ethylenically unsaturated bond is the content of the present invention.
- 30 to 99% by mass, particularly 60 to 95% by mass is preferable. If the content of the polymerizable compound (B) having an ethylenically unsaturated bond is less than 30% by mass, the mechanical strength of the cured product is insufficient and cracks occur, or if it has alkali developability, development failure occurs. If it is larger than 99% by mass, curing due to exposure becomes insufficient and tackiness occurs, and if it has alkali developability, the development time becomes long and the cured part may be damaged by alkali. There is a case.
- Photopolymerization initiator (C) As the photopolymerization initiator (C), conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl- 1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl Anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-
- N-1414, N-1717, N-1919, and PZ-4. 8 (manufactured by (Corporation) ADEKA Corporation) NCI-831, NCI-930, IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (BASF (Co.) Co., Ltd.).
- the content of the photopolymerization initiator (C) is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 10% by mass in the colored composition of the present invention.
- the content of the photopolymerization initiator (C) is less than 0.1% by mass, curing by exposure may be insufficient.
- the initiator (C) is contained in the resin composition. May precipitate.
- the coloring composition of the present invention may further contain an inorganic pigment and / or an organic pigment (D). These pigments can be used alone or in admixture of two or more.
- Examples of the inorganic pigment and / or organic pigment (D) include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline.
- inorganic pigment and / or organic pigment (D) a commercially available pigment can also be used, for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41. 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59 , 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137
- the content of the inorganic pigment and / or organic pigment (D) is preferably 0 to 350 with respect to 100 parts by mass of the polymerizable compound (B) having the ethylenically unsaturated bond. Part by mass, more preferably 0 to 250 parts by mass. When it exceeds 350 parts by mass, the light transmittance of the colored composition of the present invention, particularly the cured product using the colored alkali-developable photosensitive composition, and the color filter for display device is lowered, and the luminance of the display device is lowered. Therefore, it is not preferable.
- a solvent (E) can be further added to the colored composition of the present invention.
- a solvent capable of dissolving or dispersing each of the above components (the dye (A) of the present invention) as necessary for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, Ketones such as methyl isobutyl ketone, cyclohexanone, 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, acetic acid Ester solvents such as ethyl, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohex
- Aliphatic hydrocarbon solvents terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Sol Paraffin solvents such as osso # 100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromas such as chlorobenzene Group hydrocarbon solvents; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water, etc.
- terpene hydrocarbon oils such as turpentine oil, D-limonene
- solvents can be used as one or a mixture of two or more.
- ketones, ether ester solvents, and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because the compatibility between the resist and the photopolymerization initiator is good in the photosensitive composition.
- the amount of the solvent (E) used is such that the concentration of the composition other than the solvent (E) is preferably 5 to 30% by mass. It is difficult to increase the thickness and it is not preferable because it cannot sufficiently absorb light of a desired wavelength. When the amount exceeds 30% by mass, the storage stability of the composition due to the precipitation of the composition is decreased, and the viscosity is improved. Is unfavorable because of lowering.
- the coloring composition of the present invention can further contain an inorganic compound.
- the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable.
- the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. It is 20 mass parts, and these inorganic compounds can use 1 type (s) or 2 or more types.
- inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.
- a dispersant can be added.
- any colorant or inorganic compound can be used as long as it can disperse and stabilize, and commercially available dispersants such as BYK series manufactured by BYK Chemie can be used, and polyester having a basic functional group, Polymer dispersant made of polyether, polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / g Those are preferably used.
- the coloring composition of the present invention includes, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; plasticizer; adhesion promoter; filler; Conventional additives such as an agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.
- thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine
- plasticizer such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine
- adhesion promoter such as an agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid
- the colored composition of the present invention optional components other than the dye (A) of the present invention, the polymerizable compound (B) having an ethylenically unsaturated bond, and the photopolymerization initiator (C) (however, inorganic pigment and / or organic)
- the content of the pigment (D) and the solvent (E) is appropriately selected depending on the purpose of use and is not particularly limited, but is preferably 100 masses of the polymerizable compound (B) having an ethylenically unsaturated bond. 50 parts by mass or less in total with respect to parts.
- cured material which consists of a coloring composition of this invention can also be improved by using another organic polymer with the polymeric compound (B) which has the said ethylenically unsaturated bond.
- the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate.
- Copolymer ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenolic resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, and the like.
- polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are included.
- the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound (B) having the ethylenically unsaturated bond.
- a monomer having an unsaturated bond a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, melamine, and the like can be used in combination.
- Examples of the monomer having an unsaturated bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic acid Methoxyethyl, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Tertiary butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, penta Rithritol tetraacrylate, pentaerythr
- a sulfur atom-containing compound is generally used.
- Alkyl compounds trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no.
- aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Karenz MT BD1, PE1, NR1 manufactured by Showa Denko KK and the like.
- the surfactant examples include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.
- fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates
- anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates,
- silane coupling agent for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403 and the like, silane cups having an isocyanate group, a methacryloyl group, and an epoxy group. A ring agent is preferably used.
- Examples of the melamine compound include all or part of active methylol groups (CH 2 OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified.
- examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other.
- the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
- an oligomer component may be formed.
- hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.
- alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.
- the coloring composition of the present invention is a known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc. It can be applied on the supporting substrate. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base
- the active light source used for curing the colored composition of the present invention one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, carbon arc. Xenon arc or the like can be used.
- the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy.
- the laser beam light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.
- the colored composition of the present invention (or its cured product) is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, or a color display liquid crystal display such as a color TV, PC monitor, portable information terminal, digital camera, etc.
- a composition for encapsulating resist, electrical and electronic components For manufacturing three-dimensional objects by using resist, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, and stereolithography Materials, holographic recording materials, image recording materials, fine electronic circuits, decoloring materials, decoloring materials for image recording materials, decoloring materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and It can be used for various applications such as photoresist material for visible laser direct image system, photo
- the colored composition of the present invention (particularly the colored alkali-developable photosensitive composition) is used for the purpose of forming pixels of a color filter, and in particular, forms a color filter for a display device for an image display device such as a liquid crystal display panel. It is useful as a photosensitive composition.
- the color filter for display device includes (1) a step of forming a coating film of the colored composition of the present invention (particularly a colored alkali-developable photosensitive composition) on a substrate, and (2) a predetermined pattern shape on the coating film. Preferably formed by a step of irradiating actinic light through a mask having, (3) a step of developing a film after exposure with a developer (particularly an alkali developer), and (4) a step of heating the film after development. Is done.
- the colored composition of the present invention is also useful as an inkjet type colored composition without a development step.
- the novel compound of the present invention corresponds to the compound represented by the general formula (1 ′) among the compounds used in the above-described dye (A) of the present invention. That is, the novel compound of the present invention is a compound that further satisfies any of the following conditions (i) to (v) in addition to the condition defined by the general formula (1).
- n 2 to 6
- R 1 to R 7 and Q may be the same or different.
- n represents 2 and X represents an alkylene group having a side chain having 3 to 35 carbon atoms, and the alkylene group is not further substituted or interrupted.
- (Ii) n is 2, X is a linear alkylene group having 4 to 6 carbon atoms, and R 2 to R 5 are hydrogen atoms.
- (Iii) n is 2, and X is a linear alkylene group having 7 to 10 carbon atoms.
- (Iv) n is 2, and X is a divalent group having a ring structure having 4 to 35 carbon atoms.
- (V) n is 3-6. )
- Examples of the alkylene group having a side chain having 3 to 35 carbon atoms represented by X under the condition (i) include 1-methylethane-1,2-diyl, 1-ethylethane-1,2-diyl, 1-propyl Ethane-1,2-diyl, 1-methylpropane-1,3-diyl, 1-ethylpropane-1,3-diyl, 1-propylpropane-1,3-diyl, 2-methylpropane-1,3- Diyl, 2-ethylpropane-1,3-diyl, 2-propylpropane-1,3-diyl, 1-methylbutane-1,4-diyl, 1-ethylbutane-1,4-diyl, 1-propylbutane-1 , 4-diyl, 2-methylbutane-1,4-diyl, 2-ethylbutane-1,4-diyl, 2-propylbutane-1,
- Examples of the linear alkylene group having 4 to 6 carbon atoms represented by X under the condition (ii) include butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl and the like.
- Examples of the linear alkylene group having 7 to 10 carbon atoms represented by X under the condition (iii) include heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, Decane-1,10-diyl and the like
- Examples of the divalent group having a ring structure having 4 to 35 carbon atoms represented by X under the condition (iv) include cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methyl Cyclohexane, adamantane, benzene, naphthalene, anthracene, fluorene, biphenylene, terphenylene, pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotri
- the dye (A) of the present invention containing the compounds represented by the general formulas (1) and (1 ′) has an appropriate absorption wavelength and a high extinction coefficient. It is clear.
- Example 2-1 Colored alkali-developable photosensitive composition No. Preparation of Step 1 ⁇ Step 1> Alkali-developable photosensitive composition No. 1
- ACA Z250 manufactured by Daicel Cytec Co., Ltd.
- Aronix M-450 manufactured by Toagosei Co., Ltd.
- Example 2-2 to 2-20 Colored alkali-developable photosensitive composition No. Preparation of Nos. 2 to 20 Compound No. (A) in Step 2 of Example 2-1 1 was obtained as the compound No. 1 obtained above. 2, 3, 5, 6, 16, 53, 56, 57, 59, 60, 65, 66, 94, or 96 to 101, the color alkali developability feeling was the same as in Example 2-1. Light Composition No. 2 to No. 20 was obtained.
- Comparative colored alkali-developable photosensitive composition No. Preparation of 1 and 2 Compound No. 2 of component (A) in Step 2 of Example 2-1 1 was compared with Comparative Compound No. 1.
- a comparative colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 2-1, except for changing to 1 or 2. 1 and 2 were obtained.
- Example 3 Each of the colored alkali-developable photosensitive compositions obtained in Example 2 was applied to a glass substrate under conditions of 410 rpm ⁇ 7 sec and dried on a hot plate (90 ° C., 90 sec). The obtained coating film was exposed (150 mJ / cm 2 ) with an ultrahigh pressure mercury lamp. The exposed coating film was examined for heat resistance under conditions of 180 ° C. ⁇ 60 min and 230 ° C. ⁇ 30 min. The results are shown in [Table 7].
- the colored alkali-developable photosensitive composition of the present invention has high heat resistance.
- the dye of the present invention has excellent extinction coefficient and heat resistance, and it is clear that the coloring composition using the dye and the cured product thereof have high heat resistance.
- the product is useful for a color filter for a display device and a liquid crystal display panel using the same.
Abstract
Description
更に近年、表示素子の色純度や色分離を十分にし、画像画質を高いものにするために、特に380~500nmの波長を選択的に吸収する光吸収剤が求められている。これらの光吸収剤には、光吸収が特別に急峻であること、即ちλmaxの半値幅が小さいこと、また光や熱等により機能が失われないことが求められている。
カラーフィルタに用いられる光吸収剤には、耐熱性の高さにより有機及び/又は無機顔料が用いられてきたが、顔料であるため表示装置としての輝度を低下させてしまうという問題があり、光源の輝度を高めることでこの問題を解決してきた。しかし、低消費電力化の流れに伴い、溶剤や樹脂組成物に溶解性が優れ、耐熱性の高い染料の開発、該染料を用いたカラーフィルタの開発が盛んになっている。特許文献1~3には、特定の構造を有する化合物を用いた染料が開示されている。特許文献4には、特定の構造を有する化合物を用いた光学フィルタが開示されている。
しかし、これらの文献に記載の染料(化合物)は、溶解性及び耐熱性の点で満足できるものではなかった。
R2~R5は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、無置換若しくはハロゲン化された炭素原子数1~8のアルキル基又は無置換若しくはハロゲン化された炭素原子数1~8のアルコキシ基を表し、R2とR3、R4とR5はそれぞれ連結して環構造を形成してもよく、
R6及びR7は、それぞれ独立に、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香族炭化水素基又は炭素原子数2~35の複素環基を表し、R3とR6及び/又はR5とR7及び/又はR6とR7は、連結して環構造を形成してもよく、
Qは、-O-、-NR12-又は-S-を表し、
R12は、水素原子、フェニル基又は炭素原子数1~8のアルキル基を表し、
nは、2~6の整数を表し、
sは、0~4の整数を表し、
Xは、n+sと同数の価数を有する炭素原子数1~35の有機基を表す。)
(i)nが2であり、Xが炭素原子数3~35の側鎖を有するアルキレン基を表し、該アルキレン基は、更に置換も中断もされていない。
(ii)nが2であり、Xが炭素原子数4~6の直鎖のアルキレン基であり、R2~R5が水素原子である。
(iii)nが2であり、Xが炭素原子数7~10の直鎖のアルキレン基である。
(iv)nが2であり、Xが炭素原子数4~35の環構造を有する2価の基である。
(v)nが3~6である。)
上記一般式(1)におけるR1~R5で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。
上記一般式(1)におけるR2~R5で表される無置換の炭素原子数1~8のアルキル基としては、メチル、エチル、プロピル、iso-プロピル、ブチル、sec-ブチル、tert-ブチル、iso-ブチル、アミル、iso-アミル、tert-アミル、ヘキシル、2-ヘキシル、3-ヘキシル、シクロヘキシル、4-メチルシクロヘキシル、ヘプチル、2-ヘプチル、3-ヘプチル、iso-ヘプチル、tert-ヘプチル、1-オクチル、iso-オクチル、tert-オクチル等が挙げられ、ハロゲン化された炭素原子数1~8のアルキル基としては、上記無置換の炭素原子数1~8のアルキル基として例示した基が、上記ハロゲン原子によりハロゲン化された基等が挙げられ、
無置換の炭素原子数1~8のアルコキシ基としては、メチルオキシ、エチルオキシ、iso-プロピルオキシ、ブチルオキシ、sec-ブチルオキシ、tert-ブチルオキシ、iso-ブチルオキシ、アミルオキシ、iso-アミルオキシ、tert-アミルオキシ、ヘキシルオキシ、2-ヘキシルオキシ、3-ヘキシルオキシ、シクロヘキシルオキシ、4-メチルシクロヘキシルオキシ、ヘプチルオキシ、2-ヘプチルオキシ、3-ヘプチルオキシ、iso-ヘプチルオキシ、tert-ヘプチルオキシ、1-オクチルオキシ、iso-オクチルオキシ、tert-オクチルオキシ等が挙げられ、ハロゲン化された炭素原子数1~8のアルコキシ基としては、上記無置換の炭素原子数1~8のアルコキシ基として例示した基が、上記ハロゲン原子によりハロゲン化された基等が挙げられる。
R6及びR7で表される炭素原子数6~35の芳香族炭化水素基としては、例えば、ベンジル、フェネチル、ジフェニルメチル、トリフェニルメチル、スチリル、シンナミル等のアリールアルキル基;フェニル、ナフチル等のアリール基等が挙げられ、該アリールアルキル基中のメチレン基は、-O-、-S-、-SO2-、-CO-、-OCO-又は-COO-で中断されていても良い。
R6及びR7で表される炭素原子数2~35の複素環基としては、ピリジル、ピリミジル、ピリダジル、ピペリジル、ピラニル、ピラゾリル、トリアジル、ピロリル、キノリル、イソキノリル、イミダゾリル、ベンゾイミダゾリル、トリアゾリル、フリル、フラニル、ベンゾフラニル、チエニル、チオフェニル、ベンゾチオフェニル、チアジアゾリル、チアゾリル、ベンゾチアゾリル、オキサゾリル、ベンゾオキサゾリル、イソチアゾリル、イソオキサゾリル、インドリル、2-ピロリジノン-1-イル、2-ピペリドン-1-イル、2,4-ジオキシイミダゾリジン-3-イル、2,4-ジオキシオキサゾリジン-3-イル等が挙げられる。
R3とR6及び/又はR5とR7及び/又はR6とR7が連結して形成する環構造としては、シクロペンタン環、シクロヘキサン環、シクロペンテン環、ベンゼン環、ピロリジン環、ピロール環、ピペラジン環、ピペリジン環、モルホリン環、チオモルホリン環、テトラヒドロピリジン環、ラクトン環、ラクタム環等の5~7員環及びナフタレン環、アントラセン環等の縮合環が挙げられる。
上記一般式(1)におけるR12で表される炭素原子数1~8のアルキル基としては、上記無置換の炭素原子数1~8のアルキル基として例示した基等が挙げられる。
上記置換基としては、例えば、メチル、エチル、プロピル、イソプロピル、シクロプロピル、ブチル、第二ブチル、第三ブチル、イソブチル、アミル、イソアミル、第三アミル、シクロペンチル、ヘキシル、2-ヘキシル、3-ヘキシル、シクロヘキシル、ビシクロヘキシル、1-メチルシクロヘキシル、ヘプチル、2-ヘプチル、3-ヘプチル、イソヘプチル、第三ヘプチル、n-オクチル、イソオクチル、第三オクチル、2-エチルヘキシル、ノニル、イソノニル、デシル等のアルキル基;メチルオキシ、エチルオキシ、プロピルオキシ、イソプロピルオキシ、ブチルオキシ、第二ブチルオキシ、第三ブチルオキシ、イソブチルオキシ、アミルオキシ、イソアミルオキシ、第三アミルオキシ、ヘキシルオキシ、シクロヘキシルオキシ、ヘプチルオキシ、イソヘプチルオキシ、第三ヘプチルオキシ、n-オクチルオキシ、イソオクチルオキシ、第三オクチルオキシ、2-エチルヘキシルオキシ、ノニルオキシ、デシルオキシ等のアルコキシ基;メチルチオ、エチルチオ、プロピルチオ、イソプロピルチオ、ブチルチオ、第二ブチルチオ、第三ブチルチオ、イソブチルチオ、アミルチオ、イソアミルチオ、第三アミルチオ、ヘキシルチオ、シクロヘキシルチオ、ヘプチルチオ、イソヘプチルチオ、第三ヘプチルチオ、n-オクチルチオ、イソオクチルチオ、第三オクチルチオ、2-エチルヘキシルチオ等のアルキルチオ基;ビニル、1-メチルエテニル、2-メチルエテニル、2-プロペニル、1-メチル-3-プロペニル、3-ブテニル、1-メチル-3-ブテニル、イソブテニル、3-ペンテニル、4-ヘキセニル、シクロヘキセニル、ビシクロヘキセニル、ヘプテニル、オクテニル、デセニル、ぺンタデセニル、エイコセニル、トリコセニル等のアルケニル基;ベンジル、フェネチル、ジフェニルメチル、トリフェニルメチル、スチリル、シンナミル等のアリールアルキル基;フェニル、ナフチル等のアリール基;フェノキシ、ナフチルオキシ等のアリールオキシ基;フェニルチオ、ナフチルチオ等のアリールチオ基;ピリジル、ピリミジル、ピリダジル、ピペリジル、ピラニル、ピラゾリル、トリアジル、ピロリル、キノリル、イソキノリル、イミダゾリル、ベンゾイミダゾリル、トリアゾリル、フリル、フラニル、ベンゾフラニル、チエニル、チオフェニル、ベンゾチオフェニル、チアジアゾリル、チアゾリル、ベンゾチアゾリル、オキサゾリル、ベンゾオキサゾリル、イソチアゾリル、イソオキサゾリル、インドリル、2-ピロリジノン-1-イル、2-ピペリドン-1-イル、2,4-ジオキシイミダゾリジン-3-イル、2,4-ジオキシオキサゾリジン-3-イル等の複素環基;フッ素、塩素、臭素、ヨウ素等のハロゲン原子;アセチル、2-クロロアセチル、プロピオニル、オクタノイル、アクリロイル、メタクリロイル、フェニルカルボニル(ベンゾイル)、フタロイル、4-トリフルオロメチルベンゾイル、ピバロイル、サリチロイル、オキザロイル、ステアロイル、メトキシカルボニル、エトキシカルボニル、t-ブトキシカルボニル、n-オクタデシルオキシカルボニル、カルバモイル等のアシル基;アセチルオキシ、ベンゾイルオキシ等のアシルオキシ基;アミノ、エチルアミノ、ジメチルアミノ、ジエチルアミノ、ブチルアミノ、シクロペンチルアミノ、2-エチルヘキシルアミノ、ドデシルアミノ、アニリノ、クロロフェニルアミノ、トルイジノ、アニシジノ、N-メチル-アニリノ、ジフェニルアミノ,ナフチルアミノ、2-ピリジルアミノ、メトキシカルボニルアミノ、フェノキシカルボニルアミノ、アセチルアミノ、ベンゾイルアミノ、ホルミルアミノ、ピバロイルアミノ、ラウロイルアミノ、カルバモイルアミノ、N,N-ジメチルアミノカルボニルアミノ、N,N-ジエチルアミノカルボニルアミノ、モルホリノカルボニルアミノ、メトキシカルボニルアミノ、エトキシカルボニルアミノ、t-ブトキシカルボニルアミノ、n-オクタデシルオキシカルボニルアミノ、N-メチル-メトキシカルボニルアミノ、フェノキシカルボニルアミノ、スルファモイルアミノ、N,N-ジメチルアミノスルホニルアミノ、メチルスルホニルアミノ、ブチルスルホニルアミノ、フェニルスルホニルアミノ等の置換アミノ基;スルホンアミド基、スルホニル基、カルボキシル基、シアノ基、スルホ基、水酸基、ニトロ基、メルカプト基、イミド基、カルバモイル基、スルホンアミド基等が挙げられ、これらの基は更に置換されていてもよい。また、カルボキシル基及びスルホ基は塩を形成していてもよい。
2置換である炭素原子数3~20の脂環式炭化水素基としては、シクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン、2,4-ジメチルシクロブタン、4-メチルシクロヘキサン等の基がZ1及びZ2で置換された(2置換である)基が挙げられる。
炭素原子数6~20のアリール基としては、フェニル、ナフチル、2-メチルフェニル、3-メチルフェニル、4-メチルフェニル、4-ビニルフェニル、3-iso-プロピルフェニル、4-iso-プロピルフェニル、4-ブチルフェニル、4-iso-ブチルフェニル、4-tert-ブチルフェニル、4-ヘキシルフェニル、4-シクロヘキシルフェニル、4-オクチルフェニル、4-(2-エチルヘキシル)フェニル、2,3-ジメチルフェニル、2,4-ジメチルフェニル、2,5-ジメチルフェニル、2,6-ジメチルフェニル、3,4-ジメチルフェニル、3,5-ジメチルフェニル、2,4-ジ-tert-ブチルフェニル、2,5-ジ-tert-ブチルフェニル、2,6-ジ-tert-ブチルフェニル、2,4-ジ-tert-ペンチルフェニル、2,5-ジ-tert-アミルフェニル、2,4,5-トリメチルフェニル等が挙げられ、
炭素原子数7~20のアリールアルキル基としては、ベンジル、フェネチル、2-フェニルプロパン-2-イル、ジフェニルメチル、トリフェニルメチル、スチリル、シンナミル等が挙げられる。
2置換である炭素原子数6~20の芳香族炭化水素としては、フェニレン、ナフチレン、ビフェニルなどが挙げられ、該芳香族炭化水素はハロゲン原子、シアノ基、ニトロ基、上記R2で表される炭素原子数1~8のアルキル基、又は上記R2で表される炭素原子数1~8のアルコキシ基で置換されていてもよい。
3置換である炭素原子数3~20の脂環式炭化水素としては、上記一般式(2)におけるX1で説明で例示した脂環式炭化水素基が、Z1、Z2及びZ3で置換された(3置換である)基が挙げられ、
3置換である炭素原子数6~20の芳香族炭化水素としては、ベンゼン、ナフタレン、アントラセン、フルオレン、ビフェニレン、ターフェニレン等の基が、Z1、Z2及びZ3で置換された(3置換である)基が挙げられ、
3置換である炭素原子数6~20の複素環としては、ピリジン、ピラジン、ピペリジン、ピペラジン、ピリミジン、ピリダジン、トリアジン、ヘキサヒドロトリアジン、フラン、テトラヒドロフラン、クロマン、キサンテン、チオフェン、チオラン等の基が、Z1、Z2及びZ3で置換された(3置換である)基が挙げられる。
また、上記一般式(1)で表される化合物の中でも、nが2の時、X-Qの部分が群1から選ばれる基であるもの;nが3の時、X-Qの部分が群2から選ばれる基であるもの;nが4の時、X-Qの部分が群3の基であるもの;nが5の時、X-Qの部分が群4の基であるもの;nが6の時、X-Qの部分が群5の基であるものは特に原料の入手が容易であるためより好ましい。
また、上記一般式(1)におけるXが非対称の基であるもの又は炭素原子数7以上であるものは溶解性に優れるため特に好ましい。
nが2~6の時、R1~R7及びQはそれぞれ同じでも異なっていてもよい。
即ち、下記反応式1に従って製造する場合は、カルボン酸(10)と1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(EDC)とをピリジン中で反応させ、次いで多官能アルコール又は多官能アミン(11)を反応させることでエステル体又はアミド体である上記一般式(1)で表わされる化合物を得ることができる。
また、下記反応式2に従って製造する場合は、シアノ酢酸とアルコール(12)と多官能アルコール又は多官能アミン(11)とをp-トルエンスルホン酸存在下トルエン中で反応させてシアノ酢酸エステル(13)とし、これに、アルデヒド又はケトン(14)をトリエチルアミン存在下トルエン中で反応させることで、エステル体又はアミド体である上記一般式(1)で表される化合物を得ることができる。
本発明の染料(A)については上述した通りである。本発明の着色組成物において、本発明の染料(A)の含有量は、本発明の着色組成物中、好ましくは0.01~50質量%、より好ましくは0.1~30質量%である。染料(A)の含有量が0.01質量%より小さいと、本発明の硬化物において所望する濃度の色が得られない場合があり、50質量%より大きいと、着色組成物中で染料(A)の析出が起こる場合がある。
上記エチレン性不飽和結合を有する重合性化合物(B)としては、特に限定されず、従来、感光性組成物に用いられているものを用いることができるが、例えば、エチレン、プロピレン、ブチレン、イソブチレン、塩化ビニル、塩化ビニリデン、フッ化ビニリデン、テトラフルオロエチレン等の不飽和脂肪族炭化水素;(メタ)アクリル酸、α―クロルアクリル酸、イタコン酸、マレイン酸、シトラコン酸、フマル酸、ハイミック酸、クロトン酸、イソクロトン酸、ビニル酢酸、アリル酢酸、桂皮酸、ソルビン酸、メサコン酸、コハク酸モノ[2-(メタ)アクリロイロキシエチル]、フタル酸モノ[2-(メタ)アクリロイロキシエチル]、ω-カルボキシポリカプロラクトンモノ(メタ)アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート・マレート、ヒドロキシプロピル(メタ)アクリレート・マレート、ジシクロペンタジエン・マレート或いは1個のカルボキシル基と2個以上の(メタ)アクリロイル基とを有する多官能(メタ)アクリレート等の不飽和多塩基酸;(メタ)アクリル酸-2-ヒドロキシエチル、(メタ)アクリル酸-2-ヒドロキシプロピル、(メタ)アクリル酸グリシジル、下記化合物No.121~No.124、(メタ)アクリル酸メチル、 (メタ)アクリル酸ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸-t-ブチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸ジメチルアミノメチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸アミノプロピル、(メタ)アクリル酸ジメチルアミノプロピル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸ポリ(エトキシ)エチル、(メタ)アクリル酸ブトキシエトキシエチル、(メタ)アクリル酸エチルヘキシル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸テトラヒドロフリル、(メタ)アクリル酸ビニル、(メタ)アクリル酸アリル、(メタ)アクリル酸ベンジル、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリシクロデカンジメチロールジ(メタ)アクリレート、トリ[(メタ)アクリロイルエチル]イソシアヌレート、ポリエステル(メタ)アクリレートオリゴマー等の不飽和一塩基酸及び多価アルコール又は多価フェノールのエステル;(メタ)アクリル酸亜鉛、(メタ)アクリル酸マグネシウム等の不飽和多塩基酸の金属塩;マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、5-(2,5-ジオキソテトラヒドロフリル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸-無水マレイン酸付加物、ドデセニル無水コハク酸、無水メチルハイミック酸等の不飽和多塩基酸の酸無水物;(メタ)アクリルアミド、メチレンビス-(メタ)アクリルアミド、ジエチレントリアミントリス(メタ)アクリルアミド、キシリレンビス(メタ)アクリルアミド、α-クロロアクリルアミド、N-2-ヒドロキシエチル(メタ)アクリルアミド等の不飽和一塩基酸及び多価アミンのアミド;アクロレイン等の不飽和アルデヒド;(メタ)アクリロニトリル、α-クロロアクリロニトリル、シアン化ビニリデン、シアン化アリル等の不飽和ニトリル;スチレン、4-メチルスチレン、4-エチルスチレン、4-メトキシスチレン、4-ヒドロキシスチレン、4-クロロスチレン、ジビニルベンゼン、ビニルトルエン、ビニル安息香酸、ビニルフェノール、ビニルスルホン酸、4-ビニルベンゼンスルホン酸、ビニルベンジルメチルエーテル、ビニルベンジルグリシジルエーテル等の不飽和芳香族化合物;メチルビニルケトン等の不飽和ケトン;ビニルアミン、アリルアミン、N-ビニルピロリドン、ビニルピペリジン等の不飽和アミン化合物;アリルアルコール、クロチルアルコール等のビニルアルコール;ビニルメチルエーテル、ビニルエチルエーテル、n-ブチルビニルエーテル、イソブチルビニルエーテル、アリルグリシジルエーテル等のビニルエーテル;マレイミド、N-フェニルマレイミド、N-シクロヘキシルマレイミド等の不飽和イミド類;インデン、1-メチルインデン等のインデン類;1,3-ブタジエン、イソプレン、クロロプレン等の脂肪族共役ジエン類;ポリスチレン、ポリメチル(メタ)アクリレート、ポリ-n-ブチル(メタ)アクリレート、ポリシロキサン等の重合体分子鎖の末端にモノ(メタ)アクリロイル基を有するマクロモノマー類;ビニルクロリド、ビニリデンクロリド、ジビニルスクシナート、ジアリルフタラート、トリアリルホスファート、トリアリルイソシアヌラート、ビニルチオエーテル、ビニルイミダゾール、ビニルオキサゾリン、ビニルカルバゾール、ビニルピロリドン、ビニルピリジン、水酸基含有ビニルモノマー及びポリイソシアネート化合物のビニルウレタン化合物、水酸基含有ビニルモノマー及びポリエポキシ化合物のビニルエポキシ化合物、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート等の水酸基含有多官能アクリレートとトリレンジイソシアネート、ヘキサメチレンジイソシアネート等の多官能イソシアネートの反応物、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート等の水酸基含有多官能アクリレートと無水コハク酸、無水フタル酸、テトラヒドロ無水フタル酸等の二塩基酸無水物の反応物である酸価を有する多官能アクリレートが挙げられる。
また、上記不飽和一塩基酸を作用させた後に作用させる上記多塩基酸無水物としては、ビフェニルテトラカルボン酸二無水物、テトラヒドロ無水フタル酸、無水コハク酸、無水マレイン酸、トリメリット酸無水物、ピロメリット酸無水物、2,2'-3,3'-ベンゾフェノンテトラカルボン酸無水物、エチレングリコールビスアンヒドロトリメリテート、グリセロールトリスアンヒドロトリメリテート、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ナジック酸無水物、メチルナジック酸無水物、トリアルキルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、5-(2,5-ジオキソテトラヒドロフリル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸-無水マレイン酸付加物、ドデセニル無水コハク酸、無水メチルハイミック酸等が挙げられる。
上記エポキシ化合物、上記不飽和一塩基酸及び上記多塩基酸無水物の反応は、常法に従って行なうことができる。
その他、フェノールノボラック型エポキシ化合物、ビフェニルノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビスフェノールAノボラック型エポキシ化合物、ジシクロペンタジエンノボラック型エポキシ化合物等のノボラック型エポキシ化合物;3,4-エポキシ-6-メチルシクロヘキシルメチル-3,4-エポキシ-6-メチルシクロヘキサンカルボキシレート、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、1-エポキシエチル-3,4-エポキシシクロヘキサン等の脂環式エポキシ化合物;フタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ダイマー酸グリシジルエステル等のグリシジルエステル類;テトラグリシジルジアミノジフェニルメタン、トリグリシジル-p-アミノフェノール、N,N-ジグリシジルアニリン等のグリシジルアミン類;1,3-ジグリシジル-5,5-ジメチルヒダントイン、トリグリシジルイソシアヌレート等の複素環式エポキシ化合物;ジシクロペンタジエンジオキシド等のジオキシド化合物;ナフタレン型エポキシ化合物、トリフェニルメタン型エポキシ化合物、ジシクロペンタジエン型エポキシ化合物等を用いることもできる。
上記光重合開始剤(C)としては、従来既知の化合物を用いることが可能であり、例えば、ベンゾフェノン、フェニルビフェニルケトン、1-ヒドロキシ-1-ベンゾイルシクロヘキサン、ベンゾイン、ベンジルジメチルケタール、1-ベンジル-1-ジメチルアミノ-1-(4'-モルホリノベンゾイル)プロパン、2-モルホリル-2-(4'-メチルメルカプト)ベンゾイルプロパン、チオキサントン、1-クロル-4-プロポキシチオキサントン、イソプロピルチオキサントン、ジエチルチオキサントン、エチルアントラキノン、4-ベンゾイル-4'-メチルジフェニルスルフィド、ベンゾインブチルエーテル、2-ヒドロキシ-2-ベンゾイルプロパン、2-ヒドロキシ-2-(4'-イソプロピル)ベンゾイルプロパン、4-ブチルベンゾイルトリクロロメタン、4-フェノキシベンゾイルジクロロメタン、ベンゾイル蟻酸メチル、1,7-ビス(9'-アクリジニル)ヘプタン、9-n-ブチル-3,6-ビス(2'-モルホリノイソブチロイル)カルバゾール、2-メチル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-ナフチル-4,6-ビス(トリクロロメチル)-s-トリアジン、2,2-ビス(2-クロロフェニル)-4,5,4’,5’-テトラフェニル-1-2’-ビイミダゾール、4、4-アゾビスイソブチロニトリル、トリフェニルホスフィン、カンファーキノン、過酸化ベンゾイル等が挙げられ、市販品としては、N-1414、N-1717、N-1919、PZ-408、NCI-831、NCI-930((株)ADEKA社製)、IRGACURE369、IRGACURE907、IRGACURE OXE 01、IRGACURE OXE 02(BASF(株)社製)等が挙げられる。
本発明の着色組成物には、更に無機顔料及び/又は有機顔料(D)を含有させてもよい。これらの顔料は、単独で又は2種以上を混合して用いることができる。
本発明の着色組成物には、更に溶媒(E)を加えることができる。該溶媒としては、通常、必要に応じて上記の各成分(本発明の染料(A)等)を溶解又は分散しえる溶媒、例えば、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン、メチルイソブチルケトン、シクロヘキサノン、2-ヘプタノン等のケトン類;エチルエーテル、ジオキサン、テトラヒドロフラン、1,2-ジメトキシエタン、1,2-ジエトキシエタン、ジプロピレングリコールジメチルエーテル等のエーテル系溶媒;酢酸メチル、酢酸エチル、酢酸-n-プロピル、酢酸イソプロピル、酢酸n-ブチル、酢酸シクロヘキシル、乳酸エチル、コハク酸ジメチル、テキサノール等のエステル系溶媒;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のセロソルブ系溶媒;メタノール、エタノール、イソ-又はn-プロパノール、イソ-又はn-ブタノール、アミルアルコール等のアルコール系溶媒;エチレングリコールモノメチルアセテート、エチレングリコールモノエチルアセテート、プロピレングリコール-1-モノメチルエーテル-2-アセテート(PGMEA)、ジプロピレングリコールモノメチルエーテルアセテート、3-メトキシブチルアセテート、エトキシエチルプロピオネート等のエーテルエステル系溶媒;ベンゼン、トルエン、キシレン等のBTX系溶媒;ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素系溶媒;テレピン油、D-リモネン、ピネン等のテルペン系炭化水素油;ミネラルスピリット、スワゾール#310(コスモ松山石油(株))、ソルベッソ#100(エクソン化学(株))等のパラフィン系溶媒;四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン、1,2-ジクロロエタン等のハロゲン化脂肪族炭化水素系溶媒;クロロベンゼン等のハロゲン化芳香族炭化水素系溶媒;カルビトール系溶媒、アニリン、トリエチルアミン、ピリジン、酢酸、アセトニトリル、二硫化炭素、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン、ジメチルスルホキシド、水等が挙げられ、これらの溶媒は1種又は2種以上の混合溶媒として使用することができる。これらの中でもケトン類、エーテルエステル系溶媒等、特にプロピレングリコール-1-モノメチルエーテル-2-アセテート、シクロヘキサノン等が、感光性組成物においてレジストと光重合開始剤の相溶性がよいので好ましい。
他の有機重合体を使用する場合、その使用量は、上記エチレン性不飽和結合を有する重合性化合物(B)100質量部に対して、好ましくは10~500質量部である。
(i)nが2であり、Xが炭素原子数3~35の側鎖を有するアルキレン基を表し、該アルキレン基は、更に置換も中断もされていない。
(ii)nが2であり、Xが炭素原子数4~6の直鎖のアルキレン基であり、R2~R5が水素原子である。
(iii)nが2であり、Xが炭素原子数7~10の直鎖のアルキレン基である。
(iv)nが2であり、Xが炭素原子数4~35の環構造を有する2価の基である。
(v)nが3~6である。)
上記(ii)の条件におけるXで表わされる炭素原子数4~6の直鎖のアルキレン基としては、ブタン-1,4-ジイル、ペンタン-1,5-ジイル、ヘキサン-1,6-ジイル等が挙げられ、
上記(iii)の条件におけるXで表わされる炭素原子数7~10の直鎖のアルキレン基としては、ヘプタン-1,7-ジイル、オクタン-1,8-ジイル、ノナン-1,9-ジイル、デカン-1,10-ジイル等が挙げられ、
上記(iv)の条件におけるXで表される炭素原子数4~35の環構造を有する2価の基としては、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン、2,4-ジメチルシクロブタン、4-メチルシクロヘキサン、アダマンタン、ベンゼン、ナフタレン、アントラセン、フルオレン、ビフェニレン、ターフェニレン、ピリジン、ピラジン、ピペリジン、ピペラジン、ピリミジン、ピリダジン、トリアジン、ヘキサヒドロトリアジン、フラン、テトラヒドロフラン、クロマン、キサンテン、チオフェン、チオラン等の基が上記一般式(2)におけるZ1及びZ2で置換された(2置換である)基又は下記[化29]から選ばれる基等が挙げられる。
300ml四つ口フラスコにカルボン酸及びピリジンを入れ溶解させ、アルゴン雰囲気下に置換した後、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(以後、EDCと呼ぶ)を添加し、1.5時間反応させた。反応後、多官能アルコール又は多官能アミンのピリジン溶液を滴下し、滴下終了後、75℃で3時間反応させた。60℃まで冷却してメタノールを滴下した。その後室温まで冷却し、析出した結晶をろ別、洗浄後、乾燥してエステル体又はアミド体である一般式(1)で表される化合物をそれぞれ得た。
得られた固体が目的物であることは1H-NMR及びIRにて確認した。また、得られた化合物の溶解度を測定した。溶解度は、化合物0.1gに対しPGMEAを撹拌しながら滴下し完全に溶解したときの濃度とした。これらの結果を[表1]~[表4]に示す。
300ml四つ口フラスコにシアノ酢酸と多官能アルコール又は多官能アミン、p-トルエンスルホン酸及びトルエンを入れ混合し、還流脱水しながら110℃で2時間反応させた。室温まで冷却し、水中に反応液を滴下して析出した固体をろ別、洗浄後、乾燥してシアノ酢酸エステルを得た。
得られたシアノ酢酸エステルとアルデヒド又はケトン、トリエチルアミン及びトルエンを入れて混合し、還流脱水しながら110℃で2時間反応させた。80℃まで冷却してイソプロパノールを滴下した。その後室温まで冷却し、析出した固体をろ別、洗浄、乾燥してエステル体又はアミド体である一般式(1)で表される化合物をそれぞれ得た。
得られた固体が目的物であることは1H-NMR及びIRにて確認した。また、得られた化合物の溶解度を測定した。溶解度は、化合物0.1gに対しPGMEAを撹拌しながら滴下し完全に溶解したときの濃度とした。これらの結果を[表1]~[表4]に示す。
上記特許文献4(特開2007-286189号公報)の段落〔0046〕に記載の方法により、下記の比較化合物No.1を得た。
4’-(N,N-ジエチルアミノ)アセトフェノン(3.55g、20mmol)と2-エトキシエチルシアノアセテート(3.77g、24mmol)をエタノール(6.33g)中に分散し、撹拌しながら50℃まで加温した。そこにトリエチルアミン(0.2g、2mmol)を滴下し、70℃で3hr反応させた。冷却後、酢酸エチル/イオン交換水で油水分離し、得られた有機相を減圧留去して粗生成物4.3gを得た。粗生成物を酢酸エチル/ヘキサンの混合溶液で再結晶し、乾燥させて、下記の比較化合物No.2(橙色結晶、収量2.2g及び収率34.8%)を得た。
上記で得られた化合物No.1~7、16、26、43、52~62、65、66、69、70及び94~102並びに比較化合物No.1及び2の吸収波長特性をCHCl3溶液で評価した。結果を[表5]に示す。
上記で得られた化合物No.1~7、16、26、43、52~62、65、66、69、70及び94~102並びに比較化合物No.1及び2をTG-DTAにて分析し、融点及び10%重量減少の温度を測定した。結果を[表6]に示す。
<ステップ1>アルカリ現像性感光性組成物No.1の調製
(B)成分としてACA Z250(ダイセルサイテック社製)を30.33g並びにアロニックスM-450(東亜合成社製)を11.04g、(C)成分としてイルガキュア907(BASF社製)を1.93g、(E)成分としてPGMEAを36.60g並びにシクロヘキサノンを20.08g、及び、その他成分としてFZ2122(東レ・ダウコーニング社製)を0.01g混合し、不溶物が無くなるまで撹拌し、アルカリ現像性感光性組成物No.1を得た。
<ステップ2>染料液No.1
(A)成分として上記で得られた化合物No.1の0.10gに、ジメチルアセトアミド1.90gを加え、撹拌して溶解させた。
<ステップ3>着色アルカリ現像性感光性組成物No.1の調製
ステップ1で得られたアルカリ現像性感光性組成物No.1を5.0gとステップ2で得られた染料液No.1を1.0gとを混合して均一になるまで撹拌し、本発明の着色アルカリ現像性感光性組成物No.1を得た。
実施例2-1のステップ2における(A)成分の化合物No.1を上記で得られた化合物No.2、3、5、6、16,53,56、57、59、60、65、66、94又は96~101に変更した以外は、実施例2-1と同様の手法で、着色アルカリ現像性感光性組成物No.2~No.20を得た。
実施例2-1のステップ2における(A)成分の化合物No.1を比較化合物No.1又は2に変更した以外は、実施例2-1と同様の手法で、比較着色アルカリ現像性感光性組成物No.1及び2を得た。
実施例2で得られた着色アルカリ現像性感光性組成物を各々ガラス基板に410rpm×7secの条件で塗工し、ホットプレートで乾燥(90℃、90sec)させた。得られた塗膜に超高圧水銀ランプで露光(150mJ/cm2)した。露光後の塗膜を、180℃×60minと230℃×30minの条件で耐熱性を調べた。結果を[表7]に示す。
評価例3と同様の手法で、実施例2-2~2-20並びに比較例2-1及び2-2で得られた着色アルカリ現像性感光性組成物を用いて耐熱性を調べた。結果を[表7]に示す。
Claims (8)
- 下記一般式(1)で表される化合物を少なくとも一種含有してなる染料。
R2~R5は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、無置換若しくはハロゲン化された炭素原子数1~8のアルキル基又は無置換若しくはハロゲン化された炭素原子数1~8のアルコキシ基を表し、R2とR3、R4とR5はそれぞれ連結して環構造を形成してもよく、
R6及びR7は、それぞれ独立に、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香族炭化水素基又は炭素原子数2~35の複素環基を表し、R3とR6及び/又はR5とR7及び/又はR6とR7は、連結して環構造を形成してもよく、
Qは、-O-、-NR12-又は-S-を表し、
R12は、水素原子、フェニル基又は炭素原子数1~8のアルキル基を表し、
nは、2~6の整数を表し、
sは、0~4の整数を表し、
Xは、n+sと同数の価数を有する炭素原子数1~35の有機基を表す。) - 下記一般式(1)で表される化合物を少なくとも一種含有してなる染料(A)、エチレン性不飽和結合を有する重合性化合物(B)及び光重合開始剤(C)を含有する着色感光性組成物。
R2~R5は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、無置換若しくはハロゲン化された炭素原子数1~8のアルキル基又は無置換若しくはハロゲン化された炭素原子数1~8のアルコキシ基を表し、R2とR3、R4とR5はそれぞれ連結して環構造を形成してもよく、
R6及びR7は、それぞれ独立に、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香族炭化水素基又は炭素原子数2~35の複素環基を表し、R3とR6及び/又はR5とR7及び/又はR6とR7は、連結して環構造を形成してもよく、
Qは、-O-、-NR12-又は-S-を表し、
R12は、水素原子、フェニル基又は炭素原子数1~8のアルキル基を表し、
nは、2~6の整数を表し、
sは、0~4の整数を表し、
Xは、n+sと同数の価数を有する炭素原子数1~35の有機基を表す。) - 更に無機顔料及び/又は有機顔料(D)を含有する請求項2に記載の着色感光性組成物。
- 下記一般式(1)で表される化合物を少なくとも一種含有してなる染料(A)、アルカリ現像性を有するエチレン性不飽和結合を有する重合性化合物(B')及び光重合開始剤
(C)を含有する着色アルカリ現像性感光性組成物。
R2~R5は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、無置換若しくはハロゲン化された炭素原子数1~8のアルキル基又は無置換若しくはハロゲン化された炭素原子数1~8のアルコキシ基を表し、R2とR3、R4とR5はそれぞれ連結して環構造を形成してもよく、
R6及びR7は、それぞれ独立に、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香族炭化水素基又は炭素原子数2~35の複素環基を表し、R3とR6及び/又はR5とR7及び/又はR6とR7は、連結して環構造を形成してもよく、
Qは、-O-、-NR12-又は-S-を表し、
R12は、水素原子、フェニル基又は炭素原子数1~8のアルキル基を表し、
nは、2~6の整数を表し、
sは、0~4の整数を表し、
Xは、n+sと同数の価数を有する炭素原子数1~35の有機基を表す。) - 請求項2若しくは3に記載の着色感光性組成物又は請求項4に記載の着色アルカリ現像性感光性組成物の硬化物。
- 請求項5に記載の硬化物を用いてなる表示デバイス用カラーフィルタ。
- 請求項6に記載の表示デバイス用カラーフィルタを用いてなる液晶表示パネル。
- 下記一般式(1’)で表される化合物。
R2~R5は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、無置換若しくはハロゲン化された炭素原子数1~8のアルキル基又は無置換若しくはハロゲン化された炭素原子数1~8のアルコキシ基を表し、R2とR3、R4とR5はそれぞれ連結して環構造を形成してもよく、
R6及びR7は、それぞれ独立に、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香族炭化水素基又は炭素原子数2~35の複素環基を表し、R3とR6及び/又はR5とR7及び/又はR6とR7は、連結して環構造を形成してもよく、
Qは、-O-、-NR12-又は-S-を表し、
R12は、水素原子、フェニル基又は炭素原子数1~8のアルキル基を表し、
nは、2~6の整数を表し、
sは、0~4の整数を表し、
Xは、n+sと同数の価数を有する炭素原子数1~35の有機基を表し、
更に以下の(i)~(v)の何れかの条件を満足する。但し、nが2~6の時、R1~R7及びQはそれぞれ同じでも異なっていてもよい。
(i)nが2であり、Xが炭素原子数3~35の側鎖を有するアルキレン基を表し、該アルキレン基は、更に置換も中断もされていない。
(ii)nが2であり、Xが炭素原子数4~6の直鎖のアルキレン基であり、R2~R5が水素原子である。
(iii)nが2であり、Xが炭素原子数7~10の直鎖のアルキレン基である。
(iv)nが2であり、Xが炭素原子数4~35の環構造を有する2価の基である。
(v)nが3~6である。)
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US9334270B2 (en) | 2011-04-20 | 2016-05-10 | Adeka Corporation | Polymerizable (photosensitive or reactive) cyano-containing compound, a dye, and colored photosensitive composition |
JP2015532667A (ja) * | 2012-08-31 | 2015-11-12 | エルジー・ケム・リミテッド | スチリル系化合物、前記スチリル系化合物を含む色材、これを含む感光性樹脂組成物、前記感光性樹脂組成物で製造された感光材、これを含むカラーフィルタおよび前記カラーフィルタを含むディスプレイ装置 |
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KR20210156873A (ko) | 2013-12-05 | 2021-12-27 | 가부시키가이샤 아데카 | 신규 화합물 및 상기 화합물을 함유하는 조성물 |
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Also Published As
Publication number | Publication date |
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KR20130108499A (ko) | 2013-10-04 |
TWI546344B (zh) | 2016-08-21 |
TW201237108A (en) | 2012-09-16 |
US20130041062A1 (en) | 2013-02-14 |
CN102858884B (zh) | 2015-10-21 |
CN102858884A (zh) | 2013-01-02 |
US8664289B2 (en) | 2014-03-04 |
KR101908363B1 (ko) | 2018-10-16 |
JPWO2012039286A1 (ja) | 2014-02-03 |
EP2620476A4 (en) | 2016-11-16 |
EP2620476A1 (en) | 2013-07-31 |
JP5844267B2 (ja) | 2016-01-13 |
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