WO2016031442A1 - Coloring composition, color filter, method for forming pattern, method for producing color filter, solid-state imaging element, image display device, and method for producing dye multimer - Google Patents
Coloring composition, color filter, method for forming pattern, method for producing color filter, solid-state imaging element, image display device, and method for producing dye multimer Download PDFInfo
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- 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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- Prior art keywords
- group
- dye
- compound
- general formula
- color filter
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- ZBOYHAZRFJBUEL-UHFFFAOYSA-N n-[2-(4-benzhydryloxypiperidin-1-yl)ethyl]-3-hydroxy-5-(pyridin-3-ylmethoxy)naphthalene-2-carboxamide Chemical compound C1=CC=C2C=C(C(=O)NCCN3CCC(CC3)OC(C=3C=CC=CC=3)C=3C=CC=CC=3)C(O)=CC2=C1OCC1=CC=CN=C1 ZBOYHAZRFJBUEL-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
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- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical compound C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical compound N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 description 1
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- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- XTWQOSYEUVHDIT-CQRHUGCQSA-M sodium 3alpha,7alpha-dihydroxy-5beta-cholane-24-sulfonate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCCS([O-])(=O)=O)C)[C@@]2(C)CC1 XTWQOSYEUVHDIT-CQRHUGCQSA-M 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 230000004304 visual acuity Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
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- 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
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- 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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Abstract
Description
なお、特許文献1は、顔料分散剤に関する発明である。特許文献1には、顔料に対する吸着能を有する部位として、有機色素構造を用いてもよいことが記載されているが、顔料分散剤は、色を持たないことが好ましいため、顔料に対する吸着能を有する部位は、吸光度の小さい構造を選択する必要がある。また、特許文献1には、顔料分散剤を着色剤として用いるという動機づけとなる記載もない。 In the coloring composition used for a color filter etc., further improvement of light resistance, a color transfer property, and flatness is calculated | required.
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.
<1> 一般式(1)で表わされる色素多量体と、重合性化合物とを含む着色組成物;
P-(Q)n ・・・(1)
一般式(1)中、Pはn価の連結基を表し、
Qは色素構造を有する繰り返し単位を含むポリマー鎖を表し、
n個のQの、色素構造を有する繰り返し単位の個数の平均値が2個以上であり、
nは3~10の整数を表す。
<2> 一般式(1)で表わされる色素多量体が、一般式(2)で表される、<1>に記載の着色組成物;
一般式(2)中、A1はn価の連結基を表し、
B1は単結合、-O-、-S-、-CO-、-NR-、-O2C-、-CO2-、-NROC-、または、-CONR-を表し、
Rは、水素原子、アルキル基またはアリール基を表し、
C1は、単結合または2価の連結基を表し、
Sは、硫黄原子を表し、
Qは色素構造を有する繰り返し単位を含むポリマー鎖を表し、
n個のQの、色素構造を有する繰り返し単位の個数の平均値が2個以上であり、
nは3~10の整数を表す。
<3> A1は、主鎖に酸素原子を有しても良い脂肪族炭化水素基、芳香族環基および複素環基から選ばれる1種または2種以上の組み合わせからなる基である、<2>に記載の着色組成物。
<4> 色素多量体は、400nm~800nmでの最大吸収波長における、下記式(Aλ)で表される比吸光度が5以上である、<1>~<3>のいずれかに記載の着色組成物;
E=A/(c×l) ・・・(Aλ)
式(Aλ)中、Eは、400nm~800nmでの最大吸収波長における比吸光度を表し、
Aは、400nm~800nmでの最大吸収波長における吸光度を表し、
lは、単位がcmで表されるセル長を表し、
cは、単位がmg/mlで表される、溶液中の色素多量体の濃度を表す。
<5> 着色組成物の全固形分に対し、色素多量体を1~50質量%含有する、<1>~<4>のいずれかに記載の着色組成物。
<6> 色素多量体は、一般式(3)で表わされる化合物と、色素構造及びラジカル重合性基を有する化合物とをラジカル重合して得られたものである、<1>~<5>のいずれかに記載の着色組成物。
P0-(SH)n ・・・(3)
一般式(3)中、P0はn価の連結基を表し、
SHはチオール基を表し、
nは3~10の整数を表す。
<7> さらに、色素多量体以外の色素を含む<1>~<6>のいずれかに記載の着色組成物。
<8> さらに光重合開始剤を含む<1>~<7>のいずれかに記載の着色組成物。
<9> Qは、トリアリールメタン色素、キサンテン色素、アントラキノン色素、シアニン色素、スクアリリウム色素、キノフタロン色素、フタロシアニン色素、サブフタロシアニン色素、アゾ色素およびジピロメテン色素から選ばれる色素に由来する色素構造を有する、<1>~<8>のいずれかに記載の着色組成物。
<10> Qは、酸基を有する繰り返し単位および重合性基を有する繰り返し単位から選ばれる1種以上を有する、<1>~<9>のいずれかに記載の着色組成物。
<11> Qは、(メタ)アクリル系樹脂、スチレン系樹脂、および、(メタ)アクリル/スチレン系樹脂から選ばれる1種である、<1>~<10>のいずれかに記載の着色組成物。
<12> <1>~<11>のいずれかに記載の着色組成物を用いてなるカラーフィルタ。
<13> <1>~<11>のいずれかに記載の着色組成物を支持体上に適用して着色組成物層を形成する工程と、着色組成物層をパターン状に露光する工程と、パターン状に露光された前記着色組成物層の未露光部を現像除去して着色パターンを形成する工程とを含むパターン形成方法。
<14> <1>~<11>のいずれかに記載の着色組成物を支持体上に適用して着色組成物層を形成し、硬化して着色層を形成する工程と、着色層上にフォトレジスト層を形成する工程と、露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程と、レジストパターンをエッチングマスクとして着色層をドライエッチングして着色パターンを形成する工程とを含む、パターン形成方法。
<15> <13>または<14>に記載のパターン形成方法を含む、カラーフィルタの製造方法。
<16> <12>に記載のカラーフィルタ、または、<15>に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する固体撮像素子。
<17> <12>に記載のカラーフィルタ、または、<15>に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する画像表示装置。
<18> 一般式(3)で表わされる化合物と、色素構造及びラジカル重合性基を有する化合物とをラジカル重合することを含む、色素多量体の製造方法。
P0-(SH)n ・・・(3)
一般式(3)中、P0はn価の連結基を表し、
SHはチオール基を表し、
nは3~10の整数を表す。 As a result of detailed studies, 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.
<1> A colored composition comprising a dye multimer represented by the general formula (1) and a polymerizable compound;
P- (Q) n (1)
In general formula (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.
<2> The coloring composition according to <1>, wherein the dye multimer represented by the general formula (1) is represented by the general formula (2);
In 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.
<3> 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. The coloring composition as described in 2>.
<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 (Aλ) at a maximum absorption wavelength at 400 nm to 800 nm of 5 or more. object;
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the dye multimer in the solution expressed in mg / ml.
<5> The colored composition according to any one of <1> to <4>, which contains 1 to 50% by mass of a dye multimer based on the total solid content of the colored composition.
<6> 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- (SH) n (3)
In general formula (3), P 0 represents an n-valent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10.
<7> The colored composition according to any one of <1> to <6>, further including a dye other than the dye multimer.
<8> The colored composition according to any one of <1> to <7>, further comprising a photopolymerization initiator.
<9> 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. The colored composition according to any one of <1> to <8>.
<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.
<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 unexposed portions of the colored composition layer exposed in a pattern.
<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. A pattern forming method.
<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>.
<17> An image display device having the color filter according to <12> or the color filter obtained by the method for producing a color filter according to <15>.
<18> 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- (SH) n (3)
In general formula (3), P 0 represents an n-valent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10.
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書において光とは、活性光線または放射線を意味する。また、「活性光線」または「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等を意味する。
本明細書において「露光」とは、特に断らない限り、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、X線、EUV光などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も露光に含める。
本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本明細書において、全固形分とは、着色組成物の全組成から溶剤を除いた成分の総質量をいう。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「(メタ)アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「(メタ)アリル」は、アリルおよびメタリルの双方、または、いずれかを表し、「(メタ)アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
本明細書において、重合性化合物とは、重合性官能基を有する化合物のことをいい、モノマーであっても、ポリマーであってもよい。重合性官能基とは、重合反応に関与する基を言う。
本明細書において、化学式中のMeはメチル基を、Etはエチル基を、Prはプロピル基を、Buはブチル基を、Phはフェニル基をそれぞれ示す。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本明細書において、重量平均分子量および数平均分子量は、GPC測定によるポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、例えば、HLC-8220(東ソー(株)製)を用い、カラムとしてTSKgel Super AWM―H(東ソー(株)製、6.0mmID×15.0cm)を、溶離液として10mmol/L リチウムブロミドNMP(N-メチルピロリジノン)溶液を用いることによって求めることができる。 Hereinafter, the contents of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, 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).
In this specification, 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.
In this specification, unless otherwise specified, “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.
In this specification, 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.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ") Allyl" represents both and / or allyl and methallyl, and "(meth) acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, 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.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, 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. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In this specification, 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.
本発明の着色組成物は、後述する一般式(1)で示される色素多量体と、重合性化合物とを含有する。
上記構成とすることにより、耐光性、色移り性ならびに平坦性に優れた着色組成物を提供することができる。
このような効果が得られる理由については、未だ明確ではないが、後述する一般式(1)で表される色素多量体は、n価の連結基に、色素構造を有する繰り返し単位を含むポリマー鎖がn個結合しているので、直鎖構造の色素多量体よりも、色素構造を有するポリマー鎖同士の絡み合いが少なくできたと考えられる。このため、色素多量体が凝集し難くなり、平坦性に優れた膜を得ることができたと考えられる。また、色素構造はポリマー鎖に組み込まれているので、色素が拡散し難く、色移り性にも優れると考えられる。また、色素多量体としたことにより、顔料など他分子との吸着能が向上し、分子間のエネルギー移動が起こりやすくなることで耐光性にも優れると考えられる。
また、例えばフォトリソグラフィ法でパターン形成する場合においては、色素構造を有するポリマー鎖同士の絡み合いが少なくできため、現像液の浸み込みを良好にでき、現像速度が速く、現像残渣を生じにくくすることもできる。以下、本発明について詳細に説明する。 <Coloring composition>
The coloring composition of this invention contains the pigment | dye multimer shown by General formula (1) mentioned later, and a polymeric compound.
By setting it as the said structure, the coloring composition excellent in light resistance, color transfer property, and flatness can be provided.
The reason why such an effect is obtained is not yet clear, but 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. Further, since the dye structure is incorporated in the polymer chain, it is considered that the dye is difficult to diffuse and excellent in color transfer. In addition, it is considered that the dye multimer improves adsorbability with other molecules such as pigments, and facilitates energy transfer between molecules, so that light resistance is also excellent.
In addition, for example, in the case of pattern formation by a photolithography method, 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. Hereinafter, the present invention will be described in detail.
本発明の着色組成物は、下記一般式(1)で表される色素多量体(以下、単に「色素多量体(A)」ということがある。)を含有する。 << Dye Multimer Shown by General Formula (1) >>
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)”).
一般式(1)中、Pはn価の連結基を表し、
Qは色素構造を有する繰り返し単位を含むポリマー鎖を表し、
n個のQの、色素構造を有する繰り返し単位の個数の平均値が2個以上であり、
nは3~10の整数を表す。 P- (Q) n (1)
In general formula (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.
一般式(1)中、Pは、n価の連結基を表す。
n価の連結基としては、1から100個までの炭素原子、0個から10個までの窒素原子、0個から50個までの酸素原子、1個から200個までの水素原子、および0個から20個までの硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。
Pが表すn価の連結基は、1から60個までの炭素原子、0個から10個までの窒素原子、0個から40個までの酸素原子、1個から120個までの水素原子、および0個から10個までの硫黄原子から成り立つ基が好ましい。より好ましくは、1から50個までの炭素原子、0個から10個までの窒素原子、0個から30個までの酸素原子、1個から100個までの水素原子、および0個から7個までの硫黄原子から成り立つ基である。更に好ましくは、1から40個までの炭素原子、0個から8個までの窒素原子、0個から20個までの酸素原子、1個から80個までの水素原子、および0個から5個までの硫黄原子から成り立つ基である。
Pが表すn価の連結基は、多価アルコールから誘導される連結基であることが好ましい。 <<< Linking group P >>>
In general formula (1), 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. 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. It is a group consisting of the sulfur atom. More preferably, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 atoms. It is a group consisting of the sulfur atom.
The n-valent linking group represented by P is preferably a linking group derived from a polyhydric alcohol.
一般式(2)中、A1はn価の連結基を表し、
B1は単結合、-O-、-S-、-CO-、-NR-、-O2C-、-CO2-、-NROC-、または、-CONR-を表し、
Rは、水素原子、アルキル基またはアリール基を表し、
C1は、単結合または2価の連結基を表し、
Sは、硫黄原子を表し、
Qは色素構造を有する繰り返し単位を含むポリマー鎖を表し、
n個のQの、色素構造を有する繰り返し単位の個数の平均値が2個以上であり、
nは3~10の整数を表す。 In the present invention, the dye multimer represented by the general formula (1) is preferably represented by the general formula (2).
In 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.
n価の連結基としては、主鎖に酸素原子を有しても良い脂肪族炭化水素基、芳香族環基および複素環基から選ばれる1種または2種以上の組み合わせからなる基が好ましい。
脂肪族炭化水素基としては、アルキレン基、アルケニレン基が挙げられる。アルキレン基の炭素数は、例えば、1~60が好ましく、1~30がより好ましい。アルケニレン基の炭素数は、例えば、1~60が好ましく、1~30がより好ましい。
主鎖に酸素原子を有する脂肪族炭化水素基としては、-(ORx1)m-、-(Rx1O)m-で表される基が挙げられる。主鎖に酸素原子を有する脂肪族炭化水素基は、直鎖、分岐、環状のいずれであってもよい。なお、主鎖とは、連結基の骨格部分を指し、置換基は含まない。
Rx1は、アルキレン基またはアルケニレン基を表す。mは1以上の整数を表し、mが2以上の場合は、m個のRx1は、同一であってもよく、異なっていてもよい。
Rx1が表すアルキレン基の炭素数は、1~20が好ましく、1~10がより好ましく、1~5が更に好ましい。アルキレン基は直鎖、分岐、環状のいずれでもよい。
Rx1が表すアルケニレン基の炭素数は、2~20が好ましく、2~10がより好ましく、2~5が更に好ましい。アルケニレン基は直鎖、分岐、環状のいずれでもよい。
芳香族環基は、単環であってもよく、多環であってもよい。芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、クリセン環、トリフェニレン環、フルオレン環、ビフェニル環などが挙げられ、ベンゼン環が好ましい。
複素環基は、5員環または6員環が好ましい。複素環基は、単環であってもよく、多環であってもよい。複素環基に含まれるヘテロ原子としては、窒素原子、酸素原子、硫黄原子が例示される。窒素原子が好ましい。ヘテロ原子の数は1~3が好ましい。複素環としては、例えば、シアヌル環、トリアジン環、オキサン環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環、フェナジン環が挙げられ、シアヌル環、トリアジン環、オキサン環が好ましい。
A1が表すn価の連結基は、主鎖に酸素原子を有しても良い炭化水素基、芳香族環基、複素環基、主鎖に酸素原子を有しても良い炭化水素基と芳香族環基との組み合わせ、主鎖に酸素原子を有しても良い炭化水素基と複素環基との組み合わせなどが好ましく挙げられる。
A1が、芳香族環基、複素環基、主鎖に酸素原子を有しても良い炭化水素基と芳香族環基との組み合わせ、または、主鎖に酸素原子を有しても良い炭化水素基と複素環基との組み合わせである場合の連結基P(上記式(2a))としては、例えば以下が挙げられる。
式中、Xは、主鎖に酸素原子を有しても良い炭化水素基を表し、
B1は単結合、-O-、-S-、-CO-、-NR-、-O2C-、-CO2-、-NROC-、または、-CONR-を表し、
Rは、水素原子、アルキル基またはアリール基を表し、
C1は、単結合または2価の連結基を表し、
Sは、硫黄原子を表し、
nは3以上の整数を表し、
*は、Qとの結合位置を表す。 In the general formula (2), 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.
Examples of 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. Examples of the aromatic ring 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. As the 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 phenoxathiin ring, a phenothiazine ring, and a phenazine ring, and a cyanuric ring, a triazine ring, and an oxane ring are preferable.
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.
In the formula, 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,
* Represents a bonding position with Q.
Rは、水素原子、アルキル基またはアリール基を表す。
Rが表すアルキル基の炭素数は、1~30が好ましく、1~10がより好ましい。アルキル基は、直鎖、分岐、環状のいずれであってもよい。
Rが表すアリール基の炭素数は、6~30が好ましく、6~12がより好ましい。
Rは水素原子またはアルキル基が好ましく、水素原子がより好ましい。 In the general formula (2), 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.
2価の連結基としては、アルキレン基、アリーレン基、オキシアルキレン基が好ましく、アルキレン基またはオキシアルキレン基がより好ましい。
アルキレン基、オキシアルキレン基の炭素数は、1~30が好ましく、1~10がより好ましい。アルキル基、オキシアルキレン基は、直鎖、分岐、環状のいずれであってもよい。
アリーレン基の炭素数は、6~30が好ましく、6~12がより好ましい。 In the general formula (2), 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.
Qが表すポリマー鎖は、色素構造を有する繰り返し単位を含むポリマー鎖を表し、n個のQの、色素構造を有する繰り返し単位の個数の平均値が2個以上である。一般式(1)又は(2)に含まれるn個のQについて、このQ1個あたり、色素構造を有する繰り返し単位が2個以上含まれる。一般式(1)又は(2)で表わされる色素多量体は、色素構造を有する繰り返し単位を2n個以上含む。n個のQは、同一であってもよく、異なっていてもよい。
Qが表すポリマー鎖は、色素構造を有する繰り返し単位の平均値が2~20個であることが好ましく、2~15個がより好ましく、2~10個が更に好ましい。
色素構造を有する繰り返し単位の個数の平均値は、NMR(核磁気共鳴)により求めることができる。具体的には例えば、Pで表されるn価の連結基とポリマー鎖Qの繰り返し単位とのピーク面積比から、一般式(1)における繰り返し単位の個数を求める。次に、その値をnで割ることによりポリマー鎖Qにおける繰り返し単位の個数を算出することができる。
ポリマー鎖Qの重量平均分子量は、1,000~100,000が好ましく、1000~30000がより好ましく、1000~10000が特に好ましい。 <<< Polymer chain Q >>>
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. For 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.
また、色素構造がカチオンとアニオンとを有する場合、カチオンとアニオンは、ポリマー鎖Qが有する色素構造の同一分子内にあってもよいし、色素構造の分子外にあってもよい。なお、色素構造の同一分子内にカチオンとアニオンとを有するとは、カチオンとアニオンが共有結合を介して結合している場合をいう。また、アニオンを色素構造の分子外に有するとは、カチオンとアニオンが共有結合を介して結合せず、別化合物として存在している場合をいう。以下、色素構造の分子外のアニオンを対アニオンともいう。 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.
When the dye structure has a cation and an anion, 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. In addition, having a cation and an anion in the same molecule | numerator of pigment | dye structure means the case where the cation and an anion are couple | bonded through a covalent bond. Also, 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. Hereinafter, an anion outside the molecule of the dye structure is also referred to as a counter anion.
なお、(メタ)アクリル系樹脂とは、(メタ)アクリル樹脂を主成分として含有する樹脂を意味する。(メタ)アクリル樹脂を主成分として含有するとは、(メタ)アクリル系樹脂中に、(メタ)アクリル樹脂を50質量%以上含有することが好ましく、60質量%以上含有することがより好ましく、70質量%以上含有することが特に好ましい。
また、スチレン系樹脂とは、スチレン樹脂を主成分として含有する樹脂を意味する。スチレン樹脂を主成分として含有するとは、スチレン系樹脂中に、スチレン樹脂を50質量%以上含有することが好ましく、60質量%以上含有することがより好ましく、70質量%以上含有することが特に好ましい。
また、(メタ)アクリル/スチレン系樹脂とは、(メタ)アクリル樹脂およびスチレン樹脂を主成分として含有する樹脂を意味する。(メタ)アクリル樹脂およびスチレン樹脂を主成分として含有するとは、(メタ)アクリル/スチレン系樹脂中に、(メタ)アクリル樹脂およびスチレン樹脂を合計で50質量%以上含有することが好ましく、60質量%以上含有することがより好ましく、70質量%以上含有することが特に好ましい。
以下、ポリマー鎖Qについて詳細に説明する。 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. Preferably there is.
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. When the (meth) acrylic resin and the styrene resin are contained 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.
Hereinafter, the polymer chain Q will be described in detail.
色素構造を有する繰り返し単位の骨格構造としては、特に定めるものではないが、特開2013-28764号の段落番号0276~0304に示される、一般式(A)、一般式(B)、および、一般式(C)で表される構成単位の少なくとも一つを骨格とすることが好ましく、または、一般式(D)で表される色素多量体であることが好ましい。特開2013-28764号の段落番号0276~0304の記載は、本願明細書に組み込まれる。
本発明では、下記一般式(a1-1)で表される繰り返し単位を有することが好ましい。
また、ポリマー鎖Qを構成する全繰り返し単位中における、色素構造を有する繰り返し単位の合計は、5~60モル%であることが好ましく、10~50モル%がより好ましく、20~40モル%がさらに好ましい。 <<<<< skeleton structure of repeating unit having a dye structure >>>>
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.
In the present invention, 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.
Q1としては、公知の重合可能なモノマーから形成される連結基であれば特に制限ないが、特に下記(XX-1)~(XX-24)で表される連結基が好ましく、(XX-1)および(XX-2)で表される(メタ)アクリル系連結鎖、(XX-10)~(XX-17)で表されるスチレン系連結鎖、(XX-18)および(XX-19)、並びに、(XX-24)で表されるビニル系連結鎖から選択されることがより好ましく、(XX-1)および(XX-2)で表される(メタ)アクリル系連結鎖、(XX-10)~(XX-17)で表されるスチレン系連結鎖、(XX-24)で表されるビニル系連結鎖から選択されることがより好ましく、(XX-1)および(XX-2)で表される(メタ)アクリル系連結鎖および(XX-11)で表されるスチレン系連結鎖がより好ましい。
(XX-1)~(XX-24)中、*で示された部位でL1と連結していることを表す。
Meはメチル基を表す。また、(XX-18)および(XX-19)中のRは、水素原子、炭素数1~5のアルキル基またはフェニル基を表す。 In general formula (a1-1), 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. In addition, the site | 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 (XX- (Meth) acrylic linking chain represented by 2) and (XX-11) Styrene linking chain represented is more preferable.
In (XX-1) to (XX-24), it represents that L 1 is linked at the site indicated by *.
Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
2価の連結基としては、炭素数1~30の置換もしくは無置換のアルキレン基(例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、ブチレン基など)、炭素数6~30の置換もしくは無置換のアリーレン基(例えば、フェニレン基、ナフチレン基等)、置換もしくは無置換の複素環基、-CH=CH-、-O-、-S-、-C(=O)-、-CO2-、-NR-、-CONR-、-O2C-、-SO-、-SO2-およびこれらを2個以上連結して形成される連結基を表す。また、L1は、アニオンを含む構成も好ましい。L1は、単結合またはアルキレン基が好ましく、単結合または-(CH2)n-(nは1~5の整数)がより好ましい。ここで、Rは、それぞれ独立に、水素原子、アルキル基、アリール基、またはヘテロアリール基を表す。
D1は、後述する色素化合物に由来する色素構造を表す。 In general formula (a1-1), L 1 each independently represents a single bond or a divalent linking group.
Examples of 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. In addition, 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). Here, 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.
色素構造としては、特に制限はなく、公知の色素構造を含む種々のものを適用することができる。
色素構造を形成しうる具体的な色素化合物については「新版染料便覧」(有機合成化学協会編;丸善、1970)、「カラーインデックス」(The Society of Dyers and colourists)、「色素ハンドブック」(大河原他編;講談社、1986)などに記載されている。
例えば、キノン色素(ベンゾキノン色素、ナフトキノン色素、アントラキノン色素、アントラピリドン色素など)、カルボニウム色素(ジアリールメタン色素、トリアリールメタン色素、キサンテン色素、アクリジン色素など)、キノンイミン色素(オキサジン色素、チアジン色素など)、アジン色素、ポリメチン色素(オキソノール色素、メロシアニン色素、アリーリデン色素、スチリル色素、シアニン色素、スクアリリウム色素、クロコニウム色素など)、キノフタロン色素、フタロシアニン色素、サブフタロシアニン色素、ペリノン色素、インジゴ色素、チオインジゴ色素、キノリン色素、ニトロ色素、ニトロソ色素、ジピロメテン色素、アゾ色素及びそれらの金属錯体色素から選ばれる色素に由来する色素構造などを挙げることができる。
これらの色素構造の中でも、色分離性、耐光性の観点から、トリアリールメタン色素、キサンテン色素、アントラキノン色素、シアニン色素、スクアリリウム色素、キノフタロン色素、フタロシアニン色素、サブフタロシアニン色素、アゾ色素およびジピロメテン色素から選ばれる色素構造が好ましく、トリアリールメタン色素、キサンテン色素、アントラキノン色素、スクアリリウム色素、キノフタロン色素、フタロシアニン色素、サブフタロシアニン色素、アゾ色素およびジピロメテン色素から選ばれる色素構造がより好ましく、トリアリールメタン色素、キサンテン色素が更に好ましい。Qが表すポリマー鎖に含まれる色素構造は、1種のみであってもよいし、2種以上であってもよい。
以下、本発明で好ましく用いられる色素構造について具体的に説明する。 <<<<< Dye Structure >>>>
There is no restriction | limiting in particular as a pigment | dye structure, The various thing containing a well-known pigment | dye structure is applicable.
For specific pigment compounds that can form pigment structures, see "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Dye Handbook" (Okawara et al.) Ed., Kodansha, 1986).
For example, 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. That.
Among these dye structures, 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.
Hereinafter, the dye structure preferably used in the present invention will be described in detail.
本発明における色素構造の好ましい態様は、トリアリールメタン色素(トリアリールメタン化合物)に由来する部分構造を有するものである。トリアリールメタン色素としては、下記式(TP)で表される化合物が挙げられる。トリアリールメタン化合物とは、分子内にトリアリールメタン骨格を含む色素部位を有する化合物を総称するものである。 <<<<<<< Triarylmethane Dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a triarylmethane dye (triarylmethane compound). Examples of the triarylmethane dye include a compound represented by the following formula (TP). A triarylmethane compound is a general term for compounds having a dye moiety containing a triarylmethane skeleton in the molecule.
a、bまたはcは、それぞれ独立に0~4の整数を表す。特にaおよびbは、それぞれ、0または1が好ましく、cは0~2の整数が好ましい。 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. As the substituent represented by Rtp 6 , Rtp 7 and Rtp 8 , the 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. In particular, Rtp 6 and Rtp 8 are preferably alkyl groups having 1 to 5 carbon atoms, and 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; In particular, a and b are each preferably 0 or 1, and c is preferably an integer of 0 to 2.
一般式(P)
一般式(P)中、Lは単結合または2価の連結基を表し、X1は、-SO3 -、-COO-、-PO4 -、下記一般式(A1)で表される構造を含む基および下記一般式(A2)で表される構造を含む基から選択される少なくとも1種から選択される。
一般式(A1)
一般式(A1)中、R1およびR2はそれぞれ独立して-SO2-または-CO-を表す。
一般式(A2)
一般式(A2)中、R3は、-SO2-または-CO-を表す。R4およびR5はそれぞれ独立して-SO2-、-CO-または-CNを表す。 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—.
General formula (A2)
In general formula (A2), R 3 represents —SO 2 — or —CO—. R 4 and R 5 each independently represents —SO 2 —, —CO— or —CN.
-NR10-において、R10は、水素原子または炭素数1~5のアルキル基を表し、水素原子が好ましい。
フッ素置換アルキレン基の炭素数は、1~10が好ましく、1~6がより好ましく、1~3がさらに好ましい。これらのアルキレン基は、パーフルオロアルキレン基がより好ましい。フッ素置換アルキレン基の具体例としては、ジフルオロメチレン基、テトラフルオロエチレン基、ヘキサフルオロプロピレン基などが挙げられる。
フッ素置換フェニレン基の炭素数は、6~20が好ましく、6~14がより好ましく、6~10がさらに好ましい。フッ素置換フェニレン基の具体例としては、テトラフルオロフェニレン基、ヘキサフルオロ-1-ナフチレン基、ヘキサフルオロ-2-ナフチレン基などが挙げられる。 In general formula (P), 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. In particular, 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.
In —NR 10 —, 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. Specific examples of the fluorine-substituted phenylene group include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, and a hexafluoro-2-naphthylene group.
一般式(A1)で表される構造を含む基は、上述した一般式(A1)中、R1およびR2の一方の末端に、フッ素置換アルキル基を有することが好ましく、R1およびR2の一方が直接フッ素置換アルキル基と結合していることがより好ましい。フッ素置換アルキル基の炭素数は、1~10が好ましく、1~6がより好ましく、1~3がさらに好ましく、1または2がよりさらに好ましく、1が特に好ましい。これらのアルキル基は、パーフルオロアルキル基がより好ましい。フッ素置換アルキル基の具体例としては、トリフルオロメチル基が好ましい。
一般式(A2)で表される構造を含む基は、上述した一般式(A2)中、R3~R5の少なくともいずれかの末端に、フッ素置換アルキル基を有することが好ましく、R3~R5の少なくとも2つが直接フッ素置換アルキル基と結合していることがより好ましい。特に、R3~R5の少なくとも2つの末端に、フッ素置換アルキル基を有することが好ましく、R3~R5の少なくとも2つが直接フッ素置換アルキル基と結合していることがより好ましい。フッ素置換アルキル基は、一般式(A1)で表される構造を含む基で説明したものと同義であり、好ましい範囲も同様である。 In general formula (P), 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. As a specific example of the fluorine-substituted alkyl group, a trifluoromethyl group is preferable.
Group containing a structure represented by the general formula (A2), in the above-mentioned general formula (A2), at least either end of R 3 ~ R 5, preferably has a fluorine-substituted alkyl group, R 3 ~ More preferably, at least two of R 5 are directly bonded to a fluorine-substituted alkyl group. In particular, at least two ends of R 3 ~ R 5, preferably has a fluorine-substituted alkyl group, and more preferably at least two of R 3 ~ R 5 are attached directly to a fluorine-substituted alkyl group. 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.
本発明における色素構造の好ましい態様は、キサンテン色素(キサンテン化合物)に由来する部分構造を有するものである。キサンテン色素としては、下記式(J)で表されるキサンテン化合物が挙げられる。 <<<<<< Xanthene Dye >>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a xanthene dye (xanthene compound). Examples of the xanthene dye include xanthene compounds represented by the following formula (J).
式(J)中のR81とR82、R83とR84、およびmが2以上の場合のR85同士は、各々独立に、互いに結合して5員、6員若しくは7員の飽和環、または5員、6員若しくは7員の不飽和環を形成していてもよい。形成される5員、6員または7員の環が、さらに置換可能な基である場合には、R81~R85で説明した置換基で置換されていてもよく、2個以上の置換基で置換されている場合には、それらの置換基は同一であっても異なっていてもよい。
上記式(J)中のR81とR82、R83とR84、およびmが2以上の場合のR85同士は、各々独立に、互いに結合して、置換基を有しない5員、6員並びに7員の飽和環または5員、6員並びに7員の不飽和環を形成する場合、置換基を有しない5員、6員並びに7員の飽和環または5員、6員並びに7員の不飽和環としては、例えば、ピロール環、フラン環、チオフェン環、ピラゾール環、イミダゾール環、トリアゾール環、オキサゾール環、チアゾール環、ピロリジン環、ピペリジン環、シクロペンテン環、シクロヘキセン環、ベンゼン環、ピリジン環、ピラジン環、ピリダジン環が挙げられ、好ましくは、ベンゼン環、ピリジン環が挙げられる。
アニオンとしては、上述したものが挙げられる。 The substituents that can be taken by 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. When the 5-membered, 6-membered or 7-membered ring formed is a further substitutable group, it may be substituted with the substituents described for R 81 to R 85 and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.
In the above formula (J), 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 Examples of 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.
Examples of the anion include those described above.
また、X-が存在せず、R81、R82、R83およびR84の少なくとも1つがアニオンを含む場合、対アニオンが同一構成単位内にある場合の記載を参酌できる。 When X − represents an anion, the description in the case where the counter anion described later is a different molecule can be referred to.
In addition, when X − does not exist and at least one of R 81 , R 82 , R 83 and R 84 contains an anion, the description of the case where the counter anion is in the same structural unit can be referred to.
本発明における色素構造の好ましい態様は、アントラキノン色素に由来する部分構造を有するものである。アントラキノン色素(アントラキノン化合物)としては、下記一般式(AQ-1)~(AQ-3)で表される化合物が好ましい。アントラキノン化合物とは、分子内にアントラキノン骨格を含む色素部位を有する化合物を総称するものである。 <<<<<<< Anthraquinone dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from an anthraquinone dye. As the 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.
一般式(AQ-1)、(AQ-2)及び(AQ-3)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0045~0047を参酌することができ、この内容は本願明細書に組み込まれる。 In general formula (AQ-3), 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).
As preferred ranges of the general formulas (AQ-1), (AQ-2) and (AQ-3), for example, paragraphs 0045 to 0047 of JP-A-2013-29760 can be referred to, and the contents thereof are described in this application. Incorporated in the description.
本発明における色素構造の好ましい態様は、シアニン色素(シアニン化合物)に由来する部分構造を有するものである。シアニン色素としては、下記一般式(PM)で表される化合物(シアニン化合物)が好ましい。本発明においてシアニン化合物とは、分子内にシアニン骨格を含む色素部位を有する化合物を総称するものである。 <<<<<<< cyanine dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a cyanine dye (cyanine compound). As the cyanine dye, a compound represented by the following general formula (PM) (cyanine compound) is preferable. In the present invention, the cyanine compound is a general term for compounds having a dye moiety containing a cyanine skeleton in the molecule.
一般式(PM)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0077~0084を参酌することができ、この内容は本願明細書に組み込まれる。なお、特開2013-29760号公報の段落0077~0084に記載のシアニン色素の具体例において、シアニン色素構造中のいずれかの水素原子が、一般式(1)のR2と結合する。 In general formula (PM), 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.
As a preferable range of the general formula (PM), for example, paragraphs 0077 to 0084 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification. In the specific examples of the cyanine dyes described in paragraphs 0077 to 0084 of JP 2013-29760 A, any hydrogen atom in the cyanine dye structure is bonded to R 2 of the general formula (1).
本発明における色素構造の好ましい態様は、スクアリリウム色素(スクアリリウム化合物)に由来する部分構造を有するものである。スクアリリウム色素としては、下記一般式(K)で表される化合物(スクアリリウム化合物)が好ましい。本発明においてスクアリリウム化合物とは、分子内にスクアリリウム骨格を含む色素部位を有する化合物を総称するものである。 <<<<<<< Squarylium dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from squarylium dye (squarylium compound). As a squarylium pigment | dye, the compound (squarylium compound) represented by the following general formula (K) is preferable. In the present invention, the squarylium compound is a general term for compounds having a dye moiety containing a squarylium skeleton in the molecule.
一般式(K)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0088~0106を参酌することができ、この内容は本願明細書に組み込まれる。
スクアリリウム色素の具体例としては、例えば、特開2013-29760号公報の段落0105を参酌することができる。 In general formula (K), 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.
As a preferable range of the general formula (K), for example, paragraphs 0088 to 0106 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
As specific examples of the squarylium dye, paragraph 0105 of JP 2013-29760 A can be referred to.
本発明における色素構造の好ましい態様は、キノフタロン色素(キノフタロン化合物)に由来する部分構造を有するものである。キノフタロン色素としては、下記一般式(QP)で表される化合物(キノフタロン化合物)が好ましい。本発明においてキノフタロン化合物とは、分子内にキノフタロン骨格を含む色素部位を有する化合物を総称するものである。 <<<<<<< Quinophthalone Dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a quinophthalone dye (quinophthalone compound). As the quinophthalone dye, a compound (quinophthalone compound) represented by the following general formula (QP) is preferable. In the present invention, the quinophthalone compound is a general term for compounds having a dye moiety containing a quinophthalone skeleton in the molecule.
一般式(QP)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0110~0114を参酌することができ、この内容は本願明細書に組み込まれる。
キノフタロン色素の具体例としては、例えば、特開2013-29760号公報の段落0113の記載を参照することができる。 In general formula (QP), 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.
As a preferable range of the general formula (QP), for example, paragraphs 0110 to 0114 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
As specific examples of the quinophthalone dye, reference can be made to the description in paragraph 0113 of JP2013-29760A, for example.
本発明における色素構造の好ましい態様は、フタロシアニン色素(フタロシアニン化合物)に由来する部分構造を有するものである。フタロシアニン色素としては、下記一般式(F)で表される化合物(フタロシアニン化合物)に由来する部分構造を有するものが好ましい。本発明においてフタロシアニン化合物とは、分子内にフタロシアニン骨格を含む色素部位を有する化合物を総称するものである。 <<<<<<< phthalocyanine dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a phthalocyanine dye (phthalocyanine compound). As the phthalocyanine dye, those having a partial structure derived from a compound represented by the following general formula (F) (phthalocyanine compound) are preferable. In the present invention, the phthalocyanine compound is a general term for compounds having a dye moiety containing a phthalocyanine skeleton in the molecule.
一般式(F)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0118~0124を参酌することができ、この内容は本願明細書に組み込まれる。
フタロシアニン色素の具体例としては、例えば、特開2013-29760号公報の段落0123を参酌することができる。 In the general formula (F), M 1 represents a metal, and 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.
As a preferable range of the general formula (F), for example, paragraphs 0118 to 0124 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
As specific examples of the phthalocyanine dye, for example, paragraph 0123 of JP2013-29760A can be referred to.
本発明における色素構造の好ましい態様は、サブフタロシアニン色素(サブフタロシアニン化合物)に由来する部分構造を有するものである。サブフタロシアニン色素としては、下記一般式(SP)で表される化合物(サブフタロシアニン化合物)が好ましい。本発明においてサブフタロシアニン化合物とは、分子内にサブフタロシアニン骨格を含む色素部位を有する化合物を総称するものである。 <<<<<<< Subphthalocyanine Dye >>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a subphthalocyanine dye (subphthalocyanine compound). As the subphthalocyanine dye, a compound represented by the following general formula (SP) (subphthalocyanine compound) is preferable. In the present invention, the term “subphthalocyanine compound” is a general term for compounds having a dye moiety containing a subphthalocyanine skeleton in the molecule.
一般式(SP)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0128~0133を参酌することができ、この内容は本願明細書に組み込まれる。
サブフタロシアニン色素の具体例としては、例えば、特開2013-29760号公報の段落0132の記載を参照できる。 In the general formula (SP), 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.
As a preferable range of the general formula (SP), for example, paragraphs 0128 to 0133 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
As specific examples of the subphthalocyanine dye, reference can be made to, for example, the description in paragraph 0132 of JP2013-29760A.
本発明における色素構造の好ましい態様は、アゾ色素(アゾ化合物)に由来する部分構造を有するものである。本発明においてアゾ化合物とは、分子内にN=N基を含む色素部位を有する化合物を総称するものである。アゾ色素としては、公知のアゾ色素(例えば、置換アゾベンゼン等)から適宜選択して適用することができる。例えば、アゾ色素としては、特開2013-41097号公報の段落0084~0134の記載、及び特開2011-162760号公報の段落0029~0136の記載を参酌でき、この内容は本明細書に組み込まれる。 <<<<<<< Azo dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from an azo dye (azo compound). In the present invention, the azo compound is a general term for compounds having a dye moiety containing an N = N group in the molecule. As the azo dye, a known azo dye (for example, substituted azobenzene) can be appropriately selected and applied. For example, 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. .
本発明に係る色素構造の態様の一つは、ジピロメテン色素に由来する部分構造を有するものである。ジピロメテン色素としては、ジピロメテン化合物、および、ジピロメテン化合物と金属または金属化合物とから得られるジピロメテン金属錯体化合物が好ましい。例えば、ジピロメテン色素としては、特開2011-95732号公報の段落0033~0136の記載を参酌することができ、この内容は本願明細書に組み込まれる。 <<<<<<< dipyrromethene dye >>>>>>
One of the aspects of the dye structure according to the present invention has a partial structure derived from a dipyrromethene dye. As 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. For example, as 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.
(置換基群A)
色素構造が有してもよい置換基としては、ハロゲン原子(例えば、フッ素原子、塩素原子、臭素原子)、アルキル基(好ましくは炭素数1~48、より好ましくは炭素数1~24の、直鎖、分岐鎖、又は環状のアルキル基で、例えば、メチル、エチル、プロピル、イソプロピル、ブチル基(好ましくは、t-ブチル基)、ペンチル、ヘキシル、ヘプチル、オクチル、2-エチルヘキシル、ドデシル、ヘキサデシル、シクロプロピル、シクロペンチル、シクロヘキシル、1-ノルボルニル、1-アダマンチル)、アルケニル基(好ましくは炭素数2~48、より好ましくは炭素数2~18のアルケニル基で、例えば、ビニル、アリル、3-ブテン-1-イル)、アルキニル基(好ましくは炭素数2~20、より好ましくは炭素数2~12、特に好ましくは炭素数2~8であり、例えばプロパルギル、3-ペンチニル等が挙げられる。)、アリール基(好ましくは炭素数6~48、より好ましくは炭素数6~24のアリール基で、例えば、フェニル、ナフチル)、ヘテロ環基(好ましくは炭素数1~32、より好ましくは炭素数1~18のヘテロ環基で、例えば、2-チエニル、4-ピリジル、2-フリル、2-ピリミジニル、1-ピリジル、2-ベンゾチアゾリル、1-イミダゾリル、1-ピラゾリル、ベンゾトリアゾール-1-イル)、シリル基(好ましくは炭素数3~38、より好ましくは炭素数3~18のシリル基で、例えば、トリメチルシリル、トリエチルシリル、トリブチルシリル、t-ブチルジメチルシリル、t-ヘキシルジメチルシリル)、ヒドロキシル基、シアノ基、ニトロ基、アルコキシ基(好ましくは炭素数1~48、より好ましくは炭素数1~24のアルコキシ基で、例えば、メトキシ、エトキシ、1-ブトキシ、2-ブトキシ、イソプロポキシ、t-ブトキシ、ドデシルオキシ、シクロアルキルオキシ基で、例えば、シクロペンチルオキシ、シクロヘキシルオキシ)、アリールオキシ基(好ましくは炭素数6~48、より好ましくは炭素数6~24のアリールオキシ基で、例えば、フェノキシ、1-ナフトキシ)、ヘテロ環オキシ基(好ましくは炭素数1~32、より好ましくは炭素数1~18のヘテロ環オキシ基で、例えば、1-フェニルテトラゾール-5-オキシ、2-テトラヒドロピラニルオキシ)、シリルオキシ基(好ましくは炭素数1~32、より好ましくは炭素数1~18のシリルオキシ基で、例えば、トリメチルシリルオキシ、t-ブチルジメチルシリルオキシ、ジフェニルメチルシリルオキシ)、アシルオキシ基(好ましくは炭素数2~48、より好ましくは炭素数2~24のアシルオキシ基で、例えば、アセトキシ、ピバロイルオキシ、ベンゾイルオキシ、ドデカノイルオキシ)、アルコキシカルボニルオキシ基(好ましくは炭素数2~48、より好ましくは炭素数2~24のアルコキシカルボニルオキシ基で、例えば、エトキシカルボニルオキシ、t-ブトキシカルボニルオキシ、シクロアルキルオキシカルボニルオキシ基で、例えば、シクロヘキシルオキシカルボニルオキシ)、アリールオキシカルボニルオキシ基(好ましくは炭素数7~32、より好ましくは炭素数7~24のアリールオキシカルボニルオキシ基で、例えば、フェノキシカルボニルオキシ)、 In the dye structure, 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 having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-butene- 1-yl), alkynyl groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, especially Preferably, it has 2 to 8 carbon atoms, such as propargyl, 3-pentynyl, etc.), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, Phenyl, naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1 -Pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, for example, trimethylsilyl , Triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group Nitro group, alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy A cycloalkyloxy group such as cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms such as phenoxy, 1-naphthoxy) A heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), a silyloxy group (Preferably silyloxy having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms. 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) , For example, phenoxycarbonyloxy),
これらの置換基は更に置換されてもよい。また置換基が二つ以上ある場合は、同一でも異なっていても良い。また、可能な場合には互いに連結して環を形成していてもよい。
詳細については、例えば、特開2013-29760号公報の段落0027~0038を参酌することもでき、この内容は本願明細書に組み込まれる。 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 to 32 carbon atoms, more preferably 1 to 2 carbon atoms. 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). 1 to 18 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 to 30 carbon atoms) More preferably an alkyloxycarbonyloxy group having 5 to 10 carbon atoms Etc. The.
These 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.
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.
色素構造が、カチオンと対アニオンとで構成される場合、対アニオンとしては特に制限は無いが、耐熱性の観点で非求核性のアニオンであることが好ましい。非求核性の対アニオンとしては、特開2007-310315号公報の段落番号0075等に記載の公知の非求核性アニオンが好ましい。ここで、非求核性とは、加熱により色素を求核攻撃しない性質を意味する。
対アニオンとしては、スルホン酸アニオン、カルボン酸アニオン、スルホニルイミドアニオン、ビス(アルキルスルホニル)イミドアニオン、トリス(アルキルスルホニル)メチドアニオン、カルボン酸アニオン、テトラアリールボレートアニオン、-CON-CO-、-CON-SO2-、BF4 -、PF6 -、SbF6 -、B-(CN)3OCH3から選ばれる少なくとも一種が好ましい。より好ましくは、スルホン酸アニオン、スルホニルイミドアニオン、ビス(アルキルスルホニル)イミドアニオン、トリス(アルキルスルホニル)メチドアニオン、カルボン酸アニオン、テトラアリールボレートアニオン、BF4 -、PF6 -、およびSbF6 -から選ばれる少なくとも一種である。
これらの中でも、対アニオンとしては、下記(AN-1)~(AN-5)で表される構造を有する非求核性アニオンがより好ましい。 <<<<< Counter Anion >>>>
When the dye structure is composed of a cation and a counter anion, the counter anion is not particularly limited, but is preferably a non-nucleophilic anion from the viewpoint of heat resistance. As the non-nucleophilic counter anion, known non-nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315 are preferable. Here, 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. More preferably, it is selected from sulfonate anion, sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion, carboxylate anion, tetraarylborate anion, BF 4 − , PF 6 − , and SbF 6 −. Is at least one kind.
Among these, as the counter anion, non-nucleophilic anions having structures represented by the following (AN-1) to (AN-5) are more preferable.
X1およびX2は、それぞれ独立に、フッ素原子またはフッ素原子を有する炭素数1~10のアルキル基を表し、フッ素原子またはフッ素原子を有する炭素数1~10のアルキル基が好ましく、炭素数1~10のペルフルオロアルキル基であることがより好ましく、炭素数1~4のペルフルオロアルキル基であることがさらに好ましく、トリフルオロメチル基が特に好ましい。 In formula (AN-1), 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.
X3、X4およびX5は、それぞれ独立に、X1およびX2と同義であり、好ましい範囲も同義である。 In formula (AN-2), 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.
X6は、炭素数1~10のペルフルオロアルキル基であることが好ましく、炭素数1~4のペルフルオロアルキル基であることがさらに好ましい。
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.
X7は、炭素数1~10のペルフルオロアルキレン基であることが好ましく、炭素数1~4のペルフルオロアルキレン基であることがさらに好ましい。 In formula (AN-4), 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.
Ar1、Ar2、Ar3およびAr4は、それぞれ独立に、炭素数6~20のアリール基が好ましく、炭素数6~14のアリール基がより好ましく、炭素数6~10のアリール基がさらに好ましい。
Ar1、Ar2、Ar3およびAr4が表わすアリール基は、置換基を有しても良い。置換基を有する場合、ハロゲン原子、アルキル基、アリール基、アルコキシ基、カルボニル基、カルボニルオキシ基、カルバモイル基、スルホ基、スルホンアミド基、ニトロ基等が挙げられ、ハロゲン原子およびアルキル基が好ましく、フッ素原子、アルキル基がより好ましく、フッ素原子、炭素数1~4のペルフルオロアルキル基がさらに好ましい。
Ar1、Ar2、Ar3およびAr4は、それぞれ独立に、ハロゲン原子および/またはハロゲン原子を有するアルキル基を有するフェニル基がより好ましく、フッ素原子および/またはフッ素原子を有するアルキル基を有するフェニル基がさらに好ましい。 In formula (AN-5), 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. In the case of having 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.
n1は、1~3が好ましく、1~2がより好ましい。 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.
n2は、1~4の整数が好ましく、1または2がより好ましい。 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.
色素多量体(A)は、非求核性対アニオンを1種類のみ含んでいても良いし、2種類以上を含んでいても良い。
以下に、非求核性の対アニオンの具体例を示すが、本発明はこれに限定されるものではない。 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.
ポリマー鎖Qは、上述した色素構造を有する繰り返し単位の他に他の繰り返し単位を含んでいても良い。他の繰り返し単位は、重合性基、酸基等の官能基を含んでいてもよい。官能基を含んでいなくてもよい。酸基を有する繰り返し単位および重合性基を有する繰り返し単位から選ばれる1種以上を有することが好ましく、酸基を有する繰り返し単位を含むことがさらに好ましい。 <<<<< other repeating unit >>>>
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.
ポリマー鎖Qが重合性基を有する繰り返し単位を含む場合、重合性基を有する繰り返し単位の割合は、ポリマー鎖Qの全繰り返し単位100モルに対し、例えば、5~50モルが好ましく、10~40モルがより好ましい。 As the polymerizable group, a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used. For example, 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.
When the polymer chain Q includes a repeating unit having a polymerizable group, 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.
ポリマー鎖Qが酸基を有する繰り返し単位を含む場合、酸基を有する繰り返し単位の割合は、ポリマー鎖Qの全繰り返し単位100モルに対し、例えば、5~50モルが好ましく、10~40モルがより好ましい。 Examples of the acid group 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.
When the polymer chain Q includes a repeating unit having an acid group, 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.
2~20個の無置換のアルキレンオキシ鎖の繰り返しからなる基において、アルキレンオキシ鎖の繰り返しの数は、2~10個が好ましく、2~15個がより好ましく、2~10個がさらに好ましい。1つのアルキレンオキシ鎖は、-(CH2)nO-で表され、nは整数であるが、nは1~10が好ましく、1~5がより好ましく、2または3がさらに好ましい。 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.
In the group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, 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.
色素多量体(A)は、色素構造を含まないポリマー鎖を有していてもよい。
色素構造を含まないポリマー鎖としては、上述したポリマー鎖Qの他の繰り返し単位で説明した繰り返し単位で構成されたポリマー鎖が挙げられる。 <<< Polymer chain containing no dye structure >>>
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.
色素多量体(A)の重量平均分子量は、1000~100000が好ましい。下限は例えば、3000以上がより好ましく、4000以上が更に好ましく、5000以上が一層好ましい。上限は、50000以下がより好ましく、20000以下が更に好ましく、15000以下が一層好ましい。重量平均分子量が上記範囲であれば、色移り性がより良好である。さらには、現像性が向上して、現像残渣の発生をより低減できる。 << Various Properties of Dye Multimer (A) >>
The weight average molecular weight of the dye multimer (A) is preferably from 1,000 to 100,000. For example, 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.
400nm~800nmでの最大吸収波長における、下記式(Aλ)で表される比吸光度は、5以上が好ましく、10以上がより好ましく、20以上が更に好ましく、30以上が特に好ましい。比吸光度が5以上であれば、着色剤として好適に用いることができる。
E=A/(c×l) ・・・(Aλ)
式(Aλ)中、Eは、400nm~800nmでの最大吸収波長における比吸光度を表し、
Aは、400nm~800nmでの最大吸収波長における吸光度を表し、
lは、単位がcmで表されるセル長を表し、
cは、単位がmg/mlで表される、溶液中の色素多量体の濃度を表す。 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. As the solvent for measuring the specific absorbance, 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 (Aλ) 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) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the dye multimer in the solution expressed in mg / ml.
有機溶剤としては、エステル類(例えば、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、乳酸エチル、酢酸ブチル、3-メトキシプロピオン酸メチル等)、エーテル類(例えばメチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等)、ケトン類(メチルエチルケトン、シクロヘキサノン、2-ヘプタノン、3-ヘプタノン等)、芳香族炭化水素類(例えば、トルエン、キシレン等)が挙げられ、これら有機溶剤に対し、1~50質量%溶解することが好ましく、5~40質量%溶解することがより好ましく、10~30質量%溶解することが特に好ましい。この範囲にあることで、本発明の着色組成物をカラーフィルタ等の作製に適用する際に、塗布面状が好適になり、また、他色塗布後の溶出による濃度低下をより低減できる。 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.
Examples of 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). , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), aromatic hydrocarbons (for example, toluene, xylene, etc.) and the like. It is preferable to dissolve 1 to 50% by mass in the solvent, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass. By being in this range, when the colored composition of the present invention is applied to the production of a color filter or the like, the coated surface shape is suitable, and the concentration reduction due to elution after application of other colors can be further reduced.
顔料に対する色素多量体の質量比(色素多量体(A)/顔料)としては、0.1~5が好ましく、0.2~2がより好ましく、0.3~1がさらに好ましい。
本発明の着色組成物における色素多量体(A)の含有量は、着色組成物の全固形分に対して1~50質量%が好ましく、5~30質量%がさらに好ましく、10~25質量%が特に好ましい。 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.
上記一般式(1)で表される色素多量体の製造方法は、特に制限されないが、一分子中に3~10個のチオール基を有する多官能チオール化合物と、色素構造及びラジカル重合性基を有する化合物とをラジカル重合する方法により製造できる。以下、色素構造及びラジカル重合性基を有する化合物を、「ラジカル重合性色素化合物」ともいう。
ラジカル重合性色素化合物において、色素構造としては、上述したものが挙げられる。ラジカル重合性色素化合物において、ラジカル重合性基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基などのエチレン性不飽和結合を含む基が挙げられる。
より具体的には、一般式(3)で表わされる化合物と、ラジカル重合性色素化合物とをラジカル重合する方法が好ましい。
P0-(SH)n ・・・(3)
一般式(3)中、P0はn価の連結基を表し、
SHはチオール基を表し、
nは3~10の整数を表す。 << Synthesis Method of Dye Multimer (A) >>
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. Hereinafter, a compound having a dye structure and a radical polymerizable group is also referred to as a “radical polymerizable dye compound”.
In the radical polymerizable dye compound, examples of the dye structure include those described above. In the radical polymerizable dye compound, examples of the radical polymerizable group include groups containing an ethylenically unsaturated bond such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
More specifically, a method of radical polymerization of the compound represented by the general formula (3) and a radical polymerizable dye compound is preferable.
P 0- (SH) n (3)
In general formula (3), P 0 represents an n-valent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10.
P0が表すn価の連結基は、1から60個までの炭素原子、0個から10個までの窒素原子、0個から40個までの酸素原子、1個から120個までの水素原子、および0個から10個までの硫黄原子から成り立つ基が好ましい。より好ましくは、1から50個までの炭素原子、0個から10個までの窒素原子、0個から30個までの酸素原子、1個から100個までの水素原子、および0個から7個までの硫黄原子から成り立つ基である。更に好ましくは、1から40個までの炭素原子、0個から8個までの窒素原子、0個から20個までの酸素原子、1個から80個までの水素原子、および0個から5個までの硫黄原子から成り立つ基である。
P0が表すn価の連結基は、多価アルコールから誘導される連結基であることが好ましい。
一般式(3)で表わされる化合物は、一般式(4)で表される化合物が好ましい。
A0-(B0-C0-SH)n ・・・(4)
一般式(4)中、A0はn価の連結基を表し、
B0は単結合、-O-、-S-、-CO-、-NR-、-O2C-、-CO2-、-NROC-、または、-CONR-を表し、
Rは、水素原子、アルキル基またはアリール基を表し、
C0は、単結合または2価の連結基を表し、
SHはチオール基を表し、
nは3~10の整数を表す。
一般式(4)におけるA0、B0およびC0はそれぞれ、一般式(2)におけるA1、B1およびC1について説明した範囲と同義であり、好ましい態様も同様である。
一般式(3)で表わされる化合物の具体的な例としては、以下の化合物が挙げられる。 In the general formula (3), 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. It is a group consisting of the sulfur atom. More preferably, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 atoms. It is a group consisting of the sulfur atom.
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- (B 0 -C 0 -SH) n (4)
In 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.
例えば、メタノール、エタノール、プロパノール、イソプロパノール、1-メトキシ-2-プロパノール、1-メトキシ-2-プロピルアセテート、アセトン、メチルエチルケトン、メチルイソブチルケトン、メトキシプロピルアセテート、乳酸エチル、酢酸エチル、アセトニトリル、テトラヒドロフラン、ジメチルホルムアミド、クロロホルム、トルエンが挙げられる。これらの溶媒は、二種以上を混合して使用してもよい。 Examples of suitable 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.
For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.
本発明の着色組成物は、重合性化合物を含有する。重合性化合物としては、ラジカル、酸、熱により架橋可能な公知の化合物を用いることができる。例えば、エチレン性不飽和結合を有する基、環状エーテル(エポキシ、オキセタン)基、メチロール基等を有する化合物が挙げられる。エチレン性不飽和結合を有する基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基などが挙げられる。本発明において、重合性化合物は、3~6官能の(メタ)アクリレート化合物であることが好ましい。
重合性化合物は、例えば、モノマー、プレポリマー(すなわち2量体、3量体及びオリゴマー)、又はそれらの混合物並びにそれらの多量体などの化学的形態のいずれであってもよい。 << polymerizable compound >>
The coloring composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by a radical, an acid, or heat can be used. For example, 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. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. In the present invention, 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.
これらの具体的な化合物としては、特開2009-288705号公報の段落番号〔0095〕~〔0108〕に記載されている化合物を本発明においても好適に用いることができる。 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. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. In addition, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. 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. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can be preferably used in the present invention.
カプロラクトンに由来する構造を有する化合物としては、分子内にカプロラクトンに由来する構造を有する限り特に限定されるものではないが、例えば、トリメチロールエタンやジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、(メタ)アクリル酸及びε-カプロラクトンと、をエステル化することにより得られる、ε-カプロラクトン変性多官能(メタ)アクリレートを挙げることができる。なかでも下記一般式(Z-1)で表されるカプロラクトンに由来する構造を有する化合物が好ましい。 As the polymerizable compound, a compound having a structure derived from a cyclic ester (for example, caprolactone, valerolactone and the like, and caprolactone is particularly preferable) is also a preferable embodiment.
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. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone-modified polyhydride obtained by esterifying polyhydric alcohols such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone. Mention may be made of functional (meth) acrylates. Of these, compounds having a structure derived from caprolactone represented by the following general formula (Z-1) are preferred.
一般式(Z-4)中、(メタ)アクリロイル基の合計は3個又は4個であり、mは各々独立に0~10の整数を表し、各mの合計は0~40の整数である。但し、各mの合計が0の場合、Xのうちいずれか1つはカルボキシル基である。
一般式(Z-5)中、(メタ)アクリロイル基の合計は5個又は6個であり、nは各々独立に0~10の整数を表し、各nの合計は0~60の整数である。但し、各nの合計が0の場合、Xのうちいずれか1つはカルボキシル基である。 In general formulas (Z-4) and (Z-5), 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, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (Z-4), the total of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40 . However, when the total of each m is 0, any one of X is a carboxyl group.
In general formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60 . However, when the total of each n is 0, any one of X is a carboxyl group.
また、各mの合計は、2~40の整数が好ましく、2~16の整数がより好ましく、4~8の整数が特に好ましい。
一般式(Z-5)中、nは、0~6の整数が好ましく、0~4の整数がより好ましい。
また、各nの合計は、3~60の整数が好ましく、3~24の整数がより好ましく、6~12の整数が特に好ましい。
また、一般式(Z-4)又は一般式(Z-5)中の-((CH2)yCH2O)-又は-((CH2)yCH(CH3)O)-は、酸素原子側の末端がXに結合する形態が好ましい。 In general formula (Z-4), 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.
In general formula (Z-5), 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.
In the general formula (Z-4) or the general formula (Z-5), — ((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.
具体的には、下記式(a)~(f)で表される化合物(以下、「例示化合物(a)~(f)」とも称する。)が挙げられ、中でも、例示化合物(a)、(b)、(e)、(f)が好ましい。 Among the compounds represented by the general formula (Z-4) or the general formula (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)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.
また、エポキシ基は、連結基を介して連結していることが好ましい。連結基としては、アルキレン基、アリーレン基、-O-、-NR’-(R’は、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表し、水素原子が好ましい)で表される構造、-SO2-、-CO-、-O-および-S-から選ばれる少なくとも一つを含む基が挙げられる。 In the present invention, 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.
Moreover, it is preferable that the epoxy group is connected via a connecting group. Examples of 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. And a group containing at least one selected from —SO 2 —, —CO—, —O—, and —S—.
一般式(2a)のR1~R19の詳細は、特開2013-011869号公報の段落番号0036を参酌でき、この内容は本願明細書に含まれることとする。
特に、R1~R19は、それぞれ独立に水素原子、メチル基、エチル基またはメトキシ基のいずれかが好ましい。また、より好ましくは、R13、R18およびR19から選ばれる1以上がメチル基である。更に好ましくは、R13、R18およびR19がメチル基で、R1~R12、R14~R17が水素原子である。
上記一般式(2a)で表される化合物は、特開2013-011869号公報の段落番号0036を参酌して合成できる。市販品としては、株式会社プリンテック製VG-3101L、日本化薬株式会社製NC-6000及びNC-6300等が挙げられる。 In the general formula (2a), 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.
In particular, 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.
QEPは単結合若しくはnEP価の有機基を表す。REP1~REP3は、QEPとも結合して環構造を形成していても良い。
nEPは2以上の整数を表し、好ましくは2~10、更に好ましくは2~6である。但しQEPが単結合の場合、nEPは2である。
REP1~REP3、QEPの詳細について、特開2014-089408号公報の段落番号0087~0088の記載を参酌でき、この内容は本願明細書に組み込まれることとする。 In the formula (EP1), 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.
これらの化合物は、市販品を用いてもよいし、ポリマーの側鎖へエポキシ基を導入することによっても得られる。
市販品としては、例えば、ビスフェノールA型エポキシ樹脂としては、JER827、JER828、JER834、JER1001、JER1002、JER1003、JER1055、JER1007、JER1009、JER1010(以上、ジャパンエポキシレジン(株)製)、EPICLON860、EPICLON1050、EPICLON1051、EPICLON1055(以上、DIC(株)製)等であり、ビスフェノールF型エポキシ樹脂としては、JER806、JER807、JER4004、JER4005、JER4007、JER4010(以上、ジャパンエポキシレジン(株)製)、EPICLON830、EPICLON835(以上、DIC(株)製)、LCE-21、RE-602S(以上、日本化薬(株)製)等であり、フェノールノボラック型エポキシ樹脂としては、JER152、JER154、JER157S70、JER157S65(以上、ジャパンエポキシレジン(株)製)、EPICLON N-740、EPICLON N-770、EPICLON N-775(以上、DIC(株)製)等であり、クレゾールノボラック型エポキシ樹脂としては、EPICLON N-660、EPICLON N-665、EPICLON N-670、EPICLON N-673、EPICLON N-680、EPICLON N-690、EPICLON N-695(以上、DIC(株)製)、EOCN-1020(以上、日本化薬(株)製)等であり、脂肪族エポキシ樹脂としては、ADEKA RESIN EP-4080S、同EP-4085S、同EP-4088S(以上、(株)ADEKA製)、セロキサイド2021P、セロキサイド2081、セロキサイド2083、セロキサイド2085、EHPE3150、EPOLEAD PB 3600、同PB 4700(以上、ダイセル化学工業(株)製)、デナコール EX-212L、EX-214L、EX-216L、EX-321L、EX-850L(以上、ナガセケムテックス(株)製)等である。その他にも、ADEKA RESIN EP-4000S、同EP-4003S、同EP-4010S、同EP-4011S(以上、(株)ADEKA製)、NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502(以上、(株)ADEKA製)、JER1031S(ジャパンエポキシレジン(株)製)等が挙げられる。
また、JER1031S(三菱化学(株)製)、JER1032H60(三菱化学(株)製)、EPICLON HP-4700(DIC(株)社製)、EPICLON N-695(DIC(株)社製)、EPICLON840(DIC(株)社製)、EPICLON N660(DIC(株)社製)、EPICLON HP7200(DIC(株)社製)等も好ましく用いることができる。 As the compound having an epoxy group, 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.
As a commercial product, for example, as 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., and bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835. (Above, manufactured by DIC Corporation), LCE-21, RE-602S (above, Nippon Kayaku) As the phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 The cresol novolac type epoxy resin is EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690. EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc., and 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). In addition, 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.
In addition, 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), and the like can also be preferably used.
また、本発明では重合性化合物としてオキセタン基を有する化合物を用いることもできる。オキセタン基を有する化合物としては、特開2008-224970号公報の段落0134~0145記載の化合物が挙げられ、その内容は本明細書に組み込まれる。具体例としては、アロンオキセタンOXT-121、OXT-221、OX-SQ、PNOX(以上、東亞合成(株)製)を用いることができる。
重合性化合物の市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ社製)、UA-7200(新中村化学社製)、DPHA-40H(日本化薬社製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共栄社製)などが挙げられる。 In the present invention, 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. Thus, a colored composition having an extremely excellent photosensitive speed can be obtained.
In the present invention, a compound having an oxetane group can also be used as the polymerizable compound. Examples of 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. As specific examples, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.
Commercially available 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.
本発明の着色組成物は、重合性化合物の反応を促進させることなどを目的として、分子内に2個以上のメルカプト基を有する多官能チオール化合物を含んでいてもよい。多官能チオール化合物は、2級のアルカンチオール類であることが好ましく、特に下記一般式(T1)で表される構造を有する化合物であることが好ましい。
一般式(T1)
(式(T1)中、nは2~4の整数を表し、Lは2~4価の連結基を表す。) << Polyfunctional thiol compound >>
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).
General formula (T1)
(In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)
本発明の着色組成物は、上述した色素多量体(A)以外の色素(以下、他の色素ともいう)を含んでいてもよい。他の色素は、顔料、染料いずれも好ましく用いることができ、熱や光に対する耐性が高いという理由から顔料がより好ましい。
他の色素は、顔料の含有量が、他の色素の全量に対して95質量%以上であることが好ましく、97質量%以上であることがより好ましく、99質量%以上であることが更に好ましい。この態様によれば、熱や光に対する耐性が高まる効果が得られ易い。
顔料としては、従来公知の種々の無機顔料または有機顔料を用いることができ、有機顔料が好ましい。 << Other dyes >>
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). As the other coloring matter, either a pigment 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.
As the pigment, various conventionally known inorganic pigments or organic pigments can be used, and organic pigments are preferred.
染料としては特に制限はなく、カラーフィルタに使用されている公知の染料が使用できる。例えば特開昭64-90403号公報、特開昭64-91102号公報、特開平1-94301号公報、特開平6-11614号公報、特登2592207号、米国特許4808501号明細書、米国特許5667920号明細書、米国特許505950号明細書、米国特許5667920号明細書、特開平5-333207号公報、特開平6-35183号公報、特開平6-51115号公報、特開平6-194828号公報等に開示されている染料を使用できる。化学構造としては、ピラゾールアゾ系、ピロメテン系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系等の染料を使用できる。 <<< Dye >>>
There is no restriction | limiting in particular as dye, The well-known dye currently used for the color filter can be used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No., US Pat. No. 505950, US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. 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.
無機顔料としては、金属酸化物、金属錯塩等で示される金属化合物又はカーボンブラック(C.I.ピグメントブラック7)を挙げることができる。金属化合物としては、具体的には、鉄、コバルト、アルミニウム、カドミウム、鉛、銅、チタン、マグネシウム、クロム、亜鉛、アンチモン等の金属酸化物、及び金属の複合酸化物を挙げることができる。 <<< Pigment >>>>
Examples of 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.
C.I.ピグメントイエロー11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C.I.ピグメントオレンジ36,38,43,71;
C.I.ピグメントレッド81,105,122,149,150,155,167,171,175,176,177,179,209,220,224,242,254,255,264,270;
C.I.ピグメントバイオレット19,23,32,39;
C.I.ピグメントブルー1,2,15,15:1,15:3,15:6,16,22,60,66;
C.I.ピグメントグリーン7,36,37,58;
C.I.ピグメントブラウン25,28;
C.I.ピグメントブラック1;等を挙げることができる。 As an 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.
例えば、赤の顔料として、アントラキノン系顔料、ペリレン系顔料、ジケトピロロピロール系顔料単独、またはそれらの少なくとも一種と、ジスアゾ系黄色顔料、イソインドリン系黄色顔料、キノフタロン系黄色顔料またはペリレン系赤色顔料との混合などを用いることができる。例えば、アントラキノン系顔料としては、C.I.ピグメントレッド177が挙げられ、ペリレン系顔料としては、C.I.ピグメントレッド155、C.I.ピグメントレッド224が挙げられ、ジケトピロロピロール系顔料としては、C.I.ピグメントレッド254が挙げられ、色分解性の点でC.I.ピグメントイエロー139との混合が好ましい。また、赤色顔料と黄色顔料との質量比は、100:5~100:50が好ましく、100:10~100:30の範囲がより好ましい。赤色顔料同士の組み合わせの場合は、求める分光に併せて調整することができる。
緑色顔料としては、ハロゲン化フタロシアニン系顔料を単独で、または、これとジスアゾ系黄色顔料、キノフタロン系黄色顔料、アゾメチン系黄色顔料若しくはイソインドリン系黄色顔料との混合を用いることができる。例えば、このような例としては、C.I.ピグメントグリーン7、36、37とC.I.ピグメントイエロー83、C.I.ピグメントイエロー138、C.I.ピグメントイエロー139、C.I.ピグメントイエロー150、C.I.ピグメントイエロー180またはC.I.ピグメントイエロー185との混合が好ましい。緑色顔料と黄色顔料との質量比は、100:5~100:150が好ましく、100:30~100:120の範囲がより好ましい。
青色顔料としては、フタロシアニン系顔料を単独で、若しくはこれとジオキサジン系紫色顔料との混合を用いることができる。例えばC.I.ピグメントブルー15:6とC.I.ピグメントバイオレット23との混合が好ましい。青色顔料と紫色顔料との質量比は、100:0~100:100が好ましい。
ブラックマトリックス用の顔料としては、カーボン、チタンブラック、酸化鉄、酸化チタン単独、またはこれらのうち2種類以上の混合が用いられ、カーボンとチタンブラックとの組合せが好ましい。また、カーボンとチタンブラックとの質量比は、100:0~100:60の範囲が好ましい。 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.
For example, as 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. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and 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.
As the green pigment, 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. For example, C.I. I. 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.
As the blue pigment, a phthalocyanine pigment alone or a mixture of this with a dioxazine purple pigment can be used. For example, 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.
As 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.
顔料の一次粒子サイズは、電子顕微鏡等の公知の方法で測定することができる。
中でも、顔料としては、アントラキノン顔料、ジケトピロロピロール顔料、フタロシアニン顔料、キノフタロン顔料、イソインドリン顔料、アゾメチン顔料、およびジオキサジン顔料から選ばれる顔料であることが好ましい。特に、C.I.ピグメントレッド177(アントラキノン顔料),C.I.ピグメントレッド254(ジケトピロロピロール顔料)、C.I.ピグメントグリーン7,36,58、C.I.ピグメントブルー15:6(フタロシアニン顔料)、C.I.ピグメントイエロー138(キノフタロン顔料)、C.I.ピグメントイエロー139,185(イソインドリン顔料)、C.I.ピグメントイエロー150(アゾメチン顔料)、C.I.ピグメントバイオレット23(ジオキサジン顔料)が特に好ましい。 When used for a color filter, 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.
Among these, the pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments. In particular, 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.
本発明の着色組成物は、他の色素を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。 When the coloring composition of the present invention contains other pigments, 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.
本発明の着色組成物は、樹脂を含有することが好ましい。この樹脂としては、顔料を分散させる樹脂(分散樹脂)や、アルカリ可溶性樹脂などが挙げられる。 << Resin >>
The colored composition of the present invention preferably contains a resin. Examples of the resin include a resin (dispersion resin) for dispersing a pigment, an alkali-soluble resin, and the like.
分散樹脂としては、例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ(メタ)アクリレート、(メタ)アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物等の高分子分散剤を挙げることができる。
高分子分散剤は、その構造から更に直鎖状高分子、顔料表面へのアンカー部位を有する末端変性型高分子、顔料表面へのアンカー部位を有するグラフト型高分子、顔料表面へのアンカー部位を有するブロック型高分子に分類することができる。 <<< Dispersed resin >>>
Examples of the dispersion resin 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.
アルカリ可溶性樹脂としては、(メタ)アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等、並びに側鎖にカルボン酸を有する酸性セルロース誘導体、ヒドロキシル基を有するポリマーに酸無水物を変性した樹脂が挙げられる。特に(メタ)アクリル酸共重合体が好ましい。また、特開平10-300922号公報に記載のN位置換マレイミドモノマー共重合体、特開2004-300204号公報に記載のエーテルダイマー共重合体、特開平7-319161号公報に記載の重合性基を含有するアルカリ可溶性樹脂も好ましい。 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. Particularly preferred is a (meth) acrylic acid copolymer. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300922, an ether dimer copolymer described in JP-A-2004-300204, and a polymerizable group described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.
本発明の着色組成物は、樹脂としてアルカリ可溶性樹脂を含有することができる。アルカリ可溶性樹脂を含有することにより、現像性・パターン形成性が向上する。なお、アルカリ可溶性樹脂は、上述した分散樹脂として用いることもできる。
アルカリ可溶性樹脂の分子量としては、特に定めるものではないが、重量平均分子量(Mw)が5000~100,000であることが好ましい。また、数平均分子量(Mn)は、1000~20,000であることが好ましい。
アルカリ可溶性樹脂としては、線状有機高分子重合体であってもよく、分子(好ましくは、アクリル系共重合体、スチレン系共重合体を主鎖とする分子)中に少なくとも1つのアルカリ可溶性を促進する基を有するアルカリ可溶性樹脂の中から適宜選択することができる。 <<< Alkali-soluble resin >>>
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.
アルカリ可溶性樹脂としては、耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、アクリル系樹脂、アクリルアミド系樹脂、アクリル/アクリルアミド共重合体樹脂が好ましく、現像性制御の観点からは、アクリル系樹脂、アクリルアミド系樹脂、アクリル/アクリルアミド共重合体樹脂が好ましい。
アルカリ可溶性を促進する基(以下、酸基ともいう)としては、例えば、カルボキシル基、リン酸基、スルホン酸基、フェノール性ヒドロキシル基などが挙げられるが、有機溶剤に可溶で弱アルカリ水溶液により現像可能なものが好ましく、(メタ)アクリル酸が特に好ましいものとして挙げられる。これら酸基は、1種のみであってもよいし、2種以上であってもよい。 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.
重合性基を含有するアルカリ可溶性樹脂は、予めイソシアネート基とヒドロキシル基を反応させ、未反応のイソシアネート基を1つ残し、かつ(メタ)アクリロイル基等の重合性基を含む化合物と、カルボキシル基を含むアクリル樹脂とを反応させて得られるウレタン変性したアルカリ可溶性樹脂;カルボキシル基を含むアクリル樹脂と、分子内にエポキシ基及び重合性二重結合を有する化合物との反応によって得られるアルカリ可溶性樹脂;酸ペンダント型エポキシアクリレート樹脂;ヒドロキシル基を含むアクリル樹脂と重合性二重結合を有する2塩基酸無水物を反応させて得られるアルカリ可溶性樹脂;ヒドロキシル基を含むアクリル樹脂と、イソシアネート及び重合性基を有する化合物を反応させて得られるアルカリ可溶性樹脂;特開2002-229207号公報及び特開2003-335814号公報に記載されるα位又はβ位にハロゲン原子或いはスルホネート基などの脱離基を有するエステル基を側鎖に有する樹脂を塩基性処理を行うことで得られるアルカリ可溶性樹脂;などが好ましい。
重合性基を含有するアルカリ可溶性樹脂としては、ダイヤナ-ルNRシリーズ(三菱レイヨン株式会社製)、Photomer6173(COOH含有 polyurethane acrylic oligomer.Diamond Shamrock Co.Ltd.,製)、ビスコートR-264、KSレジスト106(いずれも大阪有機化学工業株式会社製)、サイクロマーPシリーズ、プラクセル CF200シリーズ(いずれもダイセル化学工業株式会社製)、Ebecryl3800(ダイセルユーシービー株式会社製)、アクリキュア-RD-F8(日本触媒社製)などが挙げられる。 Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. As the 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. Urethane-modified alkali-soluble resin obtained by reacting with an acrylic resin containing; an alkali-soluble resin obtained by reacting an acrylic resin containing a carboxyl group with a compound having an epoxy group and a polymerizable double bond in the molecule; acid Pendant-type epoxy acrylate resin; alkali-soluble resin obtained by reacting an acrylic resin containing a hydroxyl group with a dibasic acid anhydride having a polymerizable double bond; an acrylic resin containing a hydroxyl group, an isocyanate and a polymerizable group An alkali-soluble resin obtained by reacting a compound; Basic treatment of a resin having in the side chain an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2002-229207 and JP-A-2003-335814 An alkali-soluble resin obtained by the following:
Examples of the alkali-soluble resin containing a polymerizable group include: Dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (produced by COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., biscort R-264, KS resist). 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure-RD-F8 (Nippon Catalyst) Etc.).
一般式(ED2)
一般式(ED2)中、Rは、水素原子または炭素数1~30の有機基を表す。一般式(ED2)の具体例としては、特開2010-168539号公報の記載を参酌できる。 In general formula (ED), 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.
式(X)において、R1は、水素原子またはメチル基を表し、R2は炭素数2~10のアルキレン基を表し、R3は、水素原子またはベンゼン環を含んでもよい炭素数1~20のアルキル基を表す。nは1~15の整数を表す。 The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).
In formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.
さらに、特開2012-32767号公報に記載の段落番号0029~0063に記載の共重合体(B)および実施例で用いられているアルカリ可溶性樹脂、特開2012-208474号公報の段落番号0088~0098に記載のバインダー樹脂および実施例で用いられているバインダー樹脂、特開2012-137531号公報の段落番号0022~0032に記載のバインダー樹脂および実施例で用いられているバインダー樹脂、特開2013-024934号公報の段落番号0132~0143に記載のバインダー樹脂および実施例で用いられているバインダー樹脂、特開2011-242752号公報の段落番号0092~0098および実施例で用いられているバインダー樹脂、特開2012-032770号公報の段落番号0030~0072に記載のバインダー樹脂を用いることもできる。これらの内容は本願明細書に組み込まれる。 Regarding the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. It is incorporated herein.
Further, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 to 2020 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in Examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP 2012-137531 B, and the binder resin used in Examples, The binder resin described in paragraph Nos. 0132 to 0143 of No. 024934 and the binder resin used in Examples, the binder resin used in paragraph Nos. 0092 to 0098 and Examples of JP 2011-242752 A, Paragraph No. of Kokai 2012-032770 It is also possible to use a binder resin according to 030-0072. These contents are incorporated herein.
本発明の着色組成物は、顔料誘導体を含有することができる。
顔料誘導体とは、顔料の一部分を、酸性基、塩基性基、フタルイミドメチル基などで置換した構造を有する化合物である。顔料誘導体としては、分散性及び分散安定性の観点から、酸性基又は塩基性基を有する顔料誘導体を含有することが好ましい。
顔料誘導体を構成するための顔料としては、ピロロピロール顔料、ジケトピロロピロール顔料、アゾ顔料、フタロシアニン顔料、アントラキノン顔料、キナクリドン顔料、ジオキサジン顔料、ペリノン顔料、ペリレン顔料、チオインジゴ顔料、イソインドリン顔料、イソインドリノン顔料、キノフタロン顔料、スレン顔料、金属錯体顔料等が挙げられる。
顔料誘導体が有する酸性基としては、スルホン酸基、カルボン酸基及びその4級アンモニウム塩が好ましく、カルボン酸基及びスルホン酸基がさらに好ましく、スルホン酸基が特に好ましい。顔料誘導体が有する塩基性基としては、アミノ基が好ましく、特に三級アミノ基が好ましい。
顔料誘導体の含有量は、顔料の全質量に対し、1~50質量%が好ましく、3~30質量%がさらに好ましい。顔料誘導体は、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。 << Pigment derivative >>
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.
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.
本発明の着色組成物は、さらに光重合開始剤を含有してもよい。
光重合開始剤としては、重合性化合物の重合を開始する能力を有する限り、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視の光線に対して感光性を有するものが好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよく、モノマーの種類に応じてカチオン重合を開始させるような開始剤であってもよい。
また、光重合開始剤は、約300nm~800nm(330nm~500nmがより好ましい。)の範囲内に少なくとも約50のモル吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。 << photopolymerization initiator >>
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).
光重合開始剤の具体例としては、例えば、特開2013-29760号公報の段落0265~0268を参酌することができ、この内容は本願明細書に組み込まれる。 In particular, when the colored composition of the present invention is 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. In particular, when a fine pattern is formed in a solid-state image sensor, 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. Considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
ヒドロキシアセトフェノン系開始剤としては、IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959、IRGACURE-127(商品名:いずれもBASF社製)を用いることができる。
アミノアセトフェノン系開始剤としては、市販品であるIRGACURE-907、IRGACURE-369、及び、IRGACURE-379(商品名:いずれもBASF社製)を用いることができる。アミノアセトフェノン系開始剤は、365nm又は405nm等の長波光源に吸収波長がマッチングされた特開2009-191179公報に記載の化合物も用いることができる。
アシルホスフィン系開始剤としては、市販品であるIRGACURE-819やDAROCUR-TPO(商品名:いずれもBASF社製)を用いることができる。 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.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the 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.
As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
オキシム化合物の具体例としては、特開2001-233842号公報記載の化合物、特開2000-80068号公報記載の化合物、特開2006-342166号公報記載の化合物を用いることができる。
本発明において、好適に用いることのできるオキシム化合物としては、例えば、3-ベンゾイロキシイミノブタン-2-オン、3-アセトキシイミノブタン-2-オン、3-プロピオニルオキシイミノブタン-2-オン、2-アセトキシイミノペンタン-3-オン、2-アセトキシイミノ-1-フェニルプロパン-1-オン、2-ベンゾイロキシイミノ-1-フェニルプロパン-1-オン、3-(4-トルエンスルホニルオキシ)イミノブタン-2-オン、及び2-エトキシカルボニルオキシイミノ-1-フェニルプロパン-1-オンなどが挙げられる。
また、J.C.S.Perkin II(1979年)pp.1653-1660、J.C.S.Perkin II(1979年)pp.156-162、Journal of Photopolymer Science and Technology(1995年)pp.202-232、特開2000-66385号公報記載の化合物、特開2000-80068号公報、特表2004-534797号公報、特開2006-342166号公報の各公報に記載の化合物等も挙げられる。
市販品ではIRGACURE-OXE01(BASF社製)、IRGACURE-OXE02(BASF社製)も好適に用いられる。また、TR-PBG-304(常州強力電子新材料有限公司製)、アデカアークルズNCI-831およびアデカアークルズNCI-930(ADEKA社製)も用いることができる。 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.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660, J.A. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can be used.
好ましくは、例えば、特開2013-29760号公報の段落0274~0275を参酌することができ、この内容は本願明細書に組み込まれる。
具体的には、オキシム化合物としては、下記式(OX-1)で表される化合物が好ましい。なお、オキシムのN-O結合が(E)体のオキシム化合物であっても、(Z)体のオキシム化合物であっても、(E)体と(Z)体との混合物であってもよい。 Further, as 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. 7,556,910 contained therein, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, 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. .
一般式(OX-1)中、Rで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
一価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基等が挙げられる。また、これらの基は、1以上の置換基を有していてもよい。また、前述した置換基は、さらに他の置換基で置換されていてもよい。
置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基またはアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、アリール基等が挙げられる。
一般式(OX-1)中、Bで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
一般式(OX-1)中、Aで表される二価の有機基としては、炭素数1~12のアルキレン基、シクロアルキレン基、アルキニレン基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。 In general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of 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. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent 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.
In General Formula (OX-1), 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.
In the general formula (OX-1), 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.
オキシム化合物は、365nm又は405nmにおけるモル吸光係数は、感度の観点から、1,000~300,000であることが好ましく、2,000~300,000であることがより好ましく、5,000~200,000であることが特に好ましい。
化合物のモル吸光係数は、公知の方法を用いることができるが、例えば、紫外可視分光光度計(Varian社製Cary-5 spectrophotometer)にて、酢酸エチル溶媒を用い、0.01g/Lの濃度で測定することが好ましい。
本発明に用いられる光重合開始剤は、必要に応じて2種以上を組み合わせて使用しても良い。 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. For example, in a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), 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.
本発明の組成物は、光重合開始剤を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。 When the colored composition of the present invention contains a photopolymerization initiator, 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.
本発明の着色組成物は、上述の各成分に加えて、本発明の効果を損なわない範囲で、さらに、溶剤、架橋剤、重合禁止剤、界面活性剤、有機カルボン酸、有機カルボン酸無水物などの他の成分を含んでいてもよい。 << other ingredients >>
In addition to the above-mentioned components, 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.
本発明の着色組成物は、溶剤を含有してもよい。
溶剤は、各成分の溶解性や着色組成物の塗布性を満足すれば基本的には特に制限はないが、色素多量体(A)、重合性化合物等の溶解性、塗布性、安全性を考慮して選ばれることが好ましい。 <<< Organic solvent >>>
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.
エステル類として、例えば、酢酸エチル、酢酸-n-ブチル、酢酸イソブチル、酢酸シクロヘキシル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、オキシ酢酸アルキル(例:オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル(例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等))、3-オキシプロピオン酸アルキルエステル類(例:3-オキシプロピオン酸メチル、3-オキシプロピオン酸エチル等(例えば、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル等))、2-オキシプロピオン酸アルキルエステル類(例:2-オキシプロピオン酸メチル、2-オキシプロピオン酸エチル、2-オキシプロピオン酸プロピル等(例えば、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチル、2-メトキシプロピオン酸プロピル、2-エトキシプロピオン酸メチル、2-エトキシプロピオン酸エチル))、2-オキシ-2-メチルプロピオン酸メチルおよび2-オキシ-2-メチルプロピオン酸エチル(例えば、2-メトキシ-2-メチルプロピオン酸メチル、2-エトキシ-2-メチルプロピオン酸エチル等)、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、2-オキソブタン酸メチル、2-オキソブタン酸エチル等、
エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、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、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート等、
ケトン類として、例えば、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、2-ヘプタノン、3-ヘプタノン等、並びに、
芳香族炭化水素類として、例えば、トルエン、キシレン等が好適に挙げられる。 As a solvent,
Examples of the 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. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), 2- Oxypropio Acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid) Propyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2-methylpropionate) Acid methyl, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.
Examples of 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.
Examples of ketones include methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, and the like,
Preferable examples of aromatic hydrocarbons include toluene and xylene.
本発明の着色組成物は、溶剤を、1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。 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. For example, the lower limit is more preferably 5% by mass or more, and still more preferably 10% by mass or more. For example, 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.
本発明の着色組成物は、架橋剤を含有してもよい。架橋剤を含有させることにより、得られる硬化膜の硬度をより高めることもできる。
架橋剤としては、架橋反応により膜硬化を行なえるものであれば、特に限定はない。例えば、(a)エポキシ樹脂、(b)メチロール基、アルコキシメチル基、及びアシロキシメチル基から選ばれる少なくとも1つの置換基で置換された、メラミン化合物、グアナミン化合物、グリコールウリル化合物又はウレア化合物、(c)メチロール基、アルコキシメチル基、及びアシロキシメチル基から選ばれる少なくとも1つの置換基で置換された、フェノール化合物、ナフトール化合物又はヒドロキシアントラセン化合物、が挙げられる。中でも、多官能エポキシ樹脂が好ましい。
架橋剤の具体例などの詳細については、特開2004-295116号公報の段落0134~0147の記載を参照することができ、この内容は本願明細書に組み込まれる。
本発明の着色組成物が架橋剤を含有する場合、架橋剤の含有量は、特に定めるものではないが、着色組成物の全固形分に対し、2~30質量%が好ましく、3~20質量%がより好ましい。
本発明の着色組成物は、架橋剤を、1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。 <<< crosslinking agent >>>
The coloring composition of the present invention may contain 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. 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. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, reference can be made to the description in paragraphs 0134 to 0147 of JP-A No. 2004-295116, the contents of which are incorporated herein.
When 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.
本発明の着色組成物においては、着色組成物の製造中又は保存中において、重合性化合物の不要な熱重合を阻止するために、少量の重合禁止剤を添加することが望ましい。
重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4'-チオビス(3-メチル-6-t-ブチルフェノール)、2,2'-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン第一セリウム塩等が挙げられる。
本発明の着色組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、着色組成物の質量に対して、約0.01~5質量%が好ましい。
本発明の着色組成物は、重合禁止剤を、1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。 <<< Polymerization inhibitor >>>
In the colored composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored composition.
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.
When the coloring composition of the present invention contains a polymerization inhibitor, 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.
本発明の着色組成物には、塗布性をより向上させる観点から、各種の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。 <<< surfactant >>>
Various surfactants may be added to the colored composition of the present invention from the viewpoint of further improving coatability. As the surfactant, 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.
本発明の組成物は、界面活性剤を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。 When the coloring composition of the present invention contains a surfactant, 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.
本発明の着色組成物は、有機カルボン酸、及び/又は、有機カルボン酸無水物を含有していてもよい。有機カルボン酸、有機カルボン酸無水物の分子量は、1000以下が好ましい。有機カルボン酸及び有機カルボン酸無水物の具体例としては、例えば、特開2013-29760号公報の段落0338~0340を参酌することができ、この内容は本願明細書に組み込まれる。
本発明の着色組成物が有機カルボン酸、及び/又は、有機カルボン酸無水物を含有する場合、有機カルボン酸及び/又は有機カルボン酸無水物の含有量は、着色組成物の全固形分に対し0.01~10質量%が好ましく、0.03~5質量%がより好ましく、0.05~3質量%が更に好ましい。
本発明の着色組成物は、有機カルボン酸及び/又は有機カルボン酸無水物を、それぞれ、1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。 <<< 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. As specific examples of the organic carboxylic acid and the organic carboxylic acid anhydride, for example, paragraphs 0338 to 0340 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
When 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.
本発明の着色組成物においては、特開2004-295116号公報の段落0078に記載の増感剤や光安定剤、同公報の段落0081に記載の熱重合防止剤を含有することができる。 Various 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. Examples of 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.
本発明の着色組成物は、前述の成分を混合することで調製される。
着色組成物の調製に際しては、着色組成物を構成する各成分を一括配合してもよいし、各成分を溶剤に溶解・分散した後に逐次配合してもよい。また、配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解・分散して組成物を調製してもよいし、必要に応じては、各成分を適宜2つ以上の溶液・分散液としておいて、使用時(塗布時)にこれらを混合して組成物として調製してもよい。
本発明の着色組成物は、異物の除去や欠陥の低減などの目的で、フィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているものであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン(PTFE)等のフッ素樹脂、ナイロン-6、ナイロン-6,6等のポリアミド系樹脂、ポリエチレン、ポリプロピレン(PP)等のポリオレフィン樹脂(高密度、超高分子量を含む)等によるフィルタが挙げられる。これら素材の中でもポリプロピレン(高密度ポリプロピレンを含む)が好ましい。
フィルタの孔径は、0.01~7.0μm程度が適しており、好ましくは0.01~3.0μm程度、さらに好ましくは0.05~0.5μm程度である。この範囲とすることにより、後工程において均一及び平滑な着色組成物の調製を阻害する、微細な異物を確実に除去することが可能となる。 <Method for preparing colored composition>
The coloring composition of the present invention is prepared by mixing the aforementioned components.
In preparing the colored composition, 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. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, 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. For example, 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. Filter. Among these materials, polypropylene (including high density polypropylene) is preferable.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. 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.
また、上述した範囲内で異なる孔径の第1のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
第2のフィルタは、上述した第1のフィルタと同様の材料等で形成されたものを使用することができる。
例えば、第1のフィルタでのフィルタリングは、分散液のみで行い、他の成分を混合した後で、第2のフィルタリングを行ってもよい。 When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As 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. .
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.
次に、本発明のカラーフィルタ、パターン形成方法およびカラーフィルタについて、その製造方法を通じて詳述する。また、本発明のパターン形成方法を用いたカラーフィルタの製造方法についても説明する。 <Color filter, pattern formation method, color filter manufacturing method>
Next, the color filter, pattern forming method and color filter of the present invention will be described in detail through the manufacturing method. A method for producing a color filter using the pattern forming method of the present invention will also be described.
本発明のパターン形成方法は、本発明の着色組成物を支持体上に適用して着色組成物層を形成し、不要部分を除去して、着色パターンを形成する。
本発明のパターン形成方法は、カラーフィルタの着色パターンの形成に好適に適用することができる。
本発明のパターン形成方法は、いわゆるフォトリソグラフィ法でパターン形成を行ってもよいし、ドライエッチング法によってパターン形成を行ってもよい。
すなわち、本発明のカラーフィルタの製造方法の第一の態様は、本発明の着色組成物を支持体上に適用して着色組成物層を形成する工程と、着色組成物層をパターン状に露光する工程と、未露光部を現像除去して着色パターンを形成する工程と、を含む。必要に応じて、着色組成物層をベークする工程(プリベーク工程)、および、現像された着色パターンをベークする工程(ポストベーク工程)を設けてもよい。
また、本発明のカラーフィルタの製造方法の第二の態様は、本発明の着色組成物を支持体上に適用して着色組成物層を形成し、硬化して着色層を形成する工程と、着色層上にフォトレジスト層を形成する工程と、露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程と、レジストパターンをエッチングマスクとして着色層をドライエッチングして着色パターンを形成する工程とを含む。
本発明のカラーフィルタは、上記製造方法により好適に得ることができる。以下これらの詳細を述べる。 The color filter of the present invention is obtained by using the colored composition of the present invention.
In the pattern forming method 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.
In the pattern forming method of the present invention, 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. And a step of developing and removing the unexposed portion to form a colored pattern. As needed, you may provide the process (prebaking process) of baking a coloring composition layer, and the process (post-baking process) of baking the developed coloring 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.
着色組成物層を形成する工程では、支持体上に、本発明の着色組成物を適用して着色組成物層を形成する。 << Step of Forming Colored Composition Layer >>
In the step of forming the colored composition layer, the colored composition layer is formed by applying the colored composition of the present invention on the support.
本発明における着色パターンは、固体撮像素子用基板の固体撮像素子形成面側(おもて面)に形成してもよいし、固体撮像素子非形成面側(裏面)に形成してもよい。
支持体上には、必要により、上部の層との密着改良、物質の拡散防止或いは基板表面の平坦化のために下塗り層を設けてもよい。 As the support, for example, 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).
If necessary, 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.
<<<露光工程>>>
次に、支持体上に形成した着色組成物層を、パターン状に露光する(露光工程)。例えば、支持体上に形成した着色組成物層に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部分を硬化することができる。
露光に際して用いることができる放射線(光)としては、g線、i線等の紫外線が好ましく(特に好ましくはi線)用いられる。照射量(露光量)は、例えば、30~1500mJ/cm2が好ましく、50~1000mJ/cm2がより好ましく、80~500mJ/cm2が最も好ましい。 << When pattern is formed by photolithography (first aspect) >>
<<< Exposure process >>>
Next, the colored composition layer formed on the support is exposed in a pattern (exposure process). For example, 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.
As 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.
次に、未露光部を現像除去して着色パターンを形成する(パターン形成工程)。未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の着色組成物層が現像液に溶出し、光硬化した部分だけが残る。
現像液としては、下地の固体撮像素子や回路などにダメージを起さない、有機アルカリ現像液が望ましい。
現像液の温度は、例えば、20~30℃が好ましい。現像時間は、20~180秒が好ましい。また、残渣除去性を向上するため、現像液を60秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。 <<< Pattern formation process >>>
Next, 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. Thereby, the coloring composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
As 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. Moreover, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
また、現像液には無機アルカリを用いてもよい。無機アルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、メタ硅酸ナトリウムなどが好ましい。
なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に現像後純水で洗浄(リンス)する。 Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. And organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. An alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer.
Moreover, you may use an inorganic alkali for a developing solution. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
ポストベークは、硬化を完全なものとするための現像後の加熱処理であり、加熱温度は、例えば100~240℃が好ましく、200~240℃がより好ましい。
ポストベーク処理は、現像後の膜を、上記条件になるようにホットプレートやコンベクションオーブン(熱風循環式乾燥機)、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。 It is preferable to perform heat treatment (post-bake) 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.
ドライエッチング法でのパターン形成は、支持体上に形成した着色組成物層を硬化して着色層を形成し、次いで、得られた着色層を、パターニングされたフォトレジスト層をマスクとしてエッチングガスを用いて行うことができる。
具体的には、着色層上にポジ型またはネガ型の感放射線性組成物を塗布し、これを乾燥させることによりフォトレジスト層を形成する。フォトレジスト層の形成においては、さらにプリベーク処理を施すことが好ましい。特に、フォトレジスト層の形成プロセスとしては、露光後の加熱処理、現像後の加熱処理(ポストベーク処理)を実施する形態が望ましい。 << When pattern is formed by dry etching method (second embodiment) >>
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. Can be used.
Specifically, a positive or negative radiation sensitive composition is applied onto the colored layer and dried to form a photoresist layer. In the formation of the 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.
具体的には、ポジ型の感放射線性組成物として、キノンジアジド化合物およびアルカリ可溶性樹脂を含有する組成物が好ましい。キノンジアジド化合物およびアルカリ可溶性樹脂を含有するポジ型の感放射線性組成物は、500nm以下の波長の光照射によりキノンジアジド基が分解してカルボキシル基を生じ、結果としてアルカリ不溶状態からアルカリ可溶性になることを利用するものである。このポジ型フォトレジストは解像力が著しく優れているので、IC(integrated circuit)やLSI(Large Scale Integration)等の集積回路の作製に用いられている。キノンジアジド化合物としては、ナフトキノンジアジド化合物が挙げられる。市販品としては例えば「FHi622BC」(富士フイルムエレクトロニクスマテリアルズ社製)などが挙げられる。 As the photoresist layer, for example, 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.
Specifically, as 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.
フッ素系ガスと酸素ガス(O2)との混合ガスを用い、支持体が露出しない領域(深さ)までエッチングを行なう第1段階のエッチングと、この第1段階のエッチングの後に、窒素ガス(N2)と酸素ガス(O2)との混合ガスを用い、好ましくは支持体が露出する領域(深さ)付近までエッチングを行なう第2段階のエッチングと、支持体が露出した後に行なうオーバーエッチングとを含む形態が好ましい。以下、ドライエッチングの具体的手法、並びに第1段階のエッチング、第2段階のエッチング、およびオーバーエッチングについて説明する。 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.
Using 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. The form containing these is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.
(1)第1段階のエッチングにおけるエッチングレート(nm/min)と、第2段階のエッチングにおけるエッチングレート(nm/min)とをそれぞれ算出する。
(2)第1段階のエッチングで所望の厚さをエッチングする時間と、第2段階のエッチングで所望の厚さをエッチングする時間とをそれぞれ算出する。
(3)上述した(2)で算出したエッチング時間に従って第1段階のエッチングを実施する。
(4)上述した(2)で算出したエッチング時間に従って第2段階のエッチングを実施する。あるいはエンドポイント検出でエッチング時間を決定し、決定したエッチング時間に従って第2段階のエッチングを実施してもよい。
(5)上述した(3)および(4)の合計時間に対してオーバーエッチング時間を算出し、オーバーエッチングを実施する。 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.
(4) 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.
上記のうち、アルキレングリコールモノアルキルエーテルカルボキシレートおよびアルキレングリコールモノアルキルエーテルが好ましい。
これら溶媒は、単独で用いても2種以上を混合して用いてもよい。2種以上を混合する場合、ヒドロキシル基を有する溶剤とヒドロキシル基を有しない溶剤とを混合することが好ましい。ヒドロキシル基を有する溶剤とヒドロキシル基を有しない溶剤との質量比は、1/99~99/1、好ましくは10/90~90/10、さらに好ましくは20/80~80/20である。プロピレングリコールモノメチルエーテルアセテート(PGMEA)とプロピレングリコールモノメチルエーテル(PGME)の混合溶剤で、その比率が60/40であることが特に好ましい。なお、汚染物に対する洗浄液の浸透性を向上させるために、洗浄液には上述した本発明の着色組成物に関する界面活性剤を添加してもよい。 In addition, 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. Is preferably used as the cleaning liquid. Also, JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can be suitably used.
Of the above, 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. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning liquid to contaminants, the above-described surfactant relating to the colored composition of the present invention may be added to the cleaning liquid.
本発明のカラーフィルタは、CCD、CMOS等の固体撮像素子に好適に用いることができ、特に100万画素を超えるような高解像度のCCDやCMOS等に好適である。本発明の固体撮像素子用カラーフィルタは、例えば、CCDまたはCMOSを構成する各画素の受光部と、集光するためのマイクロレンズと、の間に配置されるカラーフィルタとして用いることができる。 Since 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.
また、着色パターン(着色画素)のサイズ(パターン幅)としては、2.5μm以下が好ましく、2.0μm以下がより好ましく、1.7μm以下が特に好ましい。 The film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.7 μm or less.
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.
本発明の固体撮像素子は、上述した本発明のカラーフィルタを備える。本発明の固体撮像素子の構成としては、本発明のカラーフィルタを備え、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。 <Solid-state imaging device>
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.
さらに、デバイス保護層上であってカラーフィルタの下(支持体に近い側)に集光手段(例えば、マイクロレンズ等。以下同じ)を有する構成や、カラーフィルタ上に集光手段を有する構成等であってもよい。 On the support, there are a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon, etc., and the photodiode is placed on the transfer electrode. A light-shielding film made of tungsten or the like that is open only in the light-receiving part, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. Further, the color filter for a solid-state image sensor according to the present invention is provided.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protection layer and under the color filter (on the side close to the support), a structure having the light condensing means on the color filter It may be.
本発明のカラーフィルタは、液晶表示装置や有機エレクトロルミネッセンス表示装置などの、画像表示装置に用いることができる。特に液晶表示装置の用途に好適である。本発明のカラーフィルタを備えた液晶表示装置は、表示画像の色合いが良好で表示特性に優れた高画質画像を表示することができる。 <Image display device>
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.
また、本発明におけるカラーフィルタは、明るく高精細なCOA(Color-filter On Array)方式にも供することが可能である。COA方式の液晶表示装置にあっては、カラーフィルタ層に対する要求特性は、前述のような通常の要求特性に加えて、層間絶縁膜に対する要求特性、すなわち低誘電率および剥離液耐性が必要とされることがある。本発明のカラーフィルタは、耐光性などに優れるので、解像度が高く長期耐久性に優れたCOA方式の液晶表示装置を提供することができる。なお、低誘電率の要求特性を満足するためには、カラーフィルタ層の上に樹脂被膜を設けてもよい。
これらの画像表示方式については、例えば、「EL、PDP、LCDディスプレイ-技術と市場の最新動向-(東レリサーチセンター調査研究部門 2001年発行)」の43ページなどに記載されている。 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.)”. Furthermore, 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.
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, 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. Sometimes. Since 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. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center Research Division)".
バックライトに関しては、SID meeting Digest 1380(2005)(A.Konno et.al)や、月刊ディスプレイ 2005年12月号の18~24ページ(島 康裕)、同25~30ページ(八木隆明)などに記載されている。 In addition to the color filter of the present invention, 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. Regarding 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) ”.
Regarding 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.
3,6-ジクロロスルホフルオラン (DCSF)(中外化成製)31部、2,6-ジイソプロピルアニリン67部、塩化亜鉛17部、スルホラン120部をフラスコへ入れ外温200度にて8時間攪拌した。その後、室温まで放冷し、この反応液を2N塩酸水600部へ滴下し、析出した結晶をろ別した。結晶を、40度のアセトニトリル600部で分散洗浄し、ろ取し、送風乾燥10時間をし、中間体1を42.5部(収率:82%)得た。
<<中間体2の合成>>
中間体1を11部およびオキシ塩化リン50部をフラスコへ入れ60℃で4時間攪拌した。室温まで放冷し、この反応液を氷水150部へ滴下し、30分攪拌した。得られた結晶をろ別し、水20部で洗浄した。その後、得られた結晶をクロロホルム150部に溶かし、セライトろ過を行った。ろ液を5%食塩水100部、15%食塩水100部で分液洗浄した。このろ液を硫酸ナトリウム乾燥した後、減圧濃縮し、中間体2を12.1部(収率:91%)得た。
<<中間体3の合成>>
ペンタフルオロベンゼンスルホニルクロリド15部、テトラヒドロフラン(THF)300部をフラスコに入れ、内温を-10℃に冷却した。そこに28%アンモニア水6.8部を、反応液が0℃以下を維持するように滴下した。滴下後1時間0℃で攪拌したのち、反応液をろ過した。得られたろ液を減圧濃縮し、THFを除いた後、水100部を添加し、攪拌した。得られた固体をろ過し、水洗した後に送風乾燥10時間を行い、中間体3を11.7部(収率:84%)得た。
<<中間体4の合成>>
中間体3を15部、2-メルカプトエタノール4.9部、メタノール100部をフラスコに加え、室温攪拌した。そこにトリエチルアミン6.5部を、反応液の温度が30℃を超えないように滴下した。この反応液を室温で1時間攪拌し、減圧濃縮した後、これに酢酸エチル90部、飽和食塩水80部、飽和重曹水10部を加え、分液操作を行った。水層を酢酸エチル90部で抽出した後、得られた有機層に硫酸マグネシウムを加えた。ろ過した後、ろ液を減圧濃縮し、送風乾燥10時間を行い、中間体4を17部(収率:92%)得た。
<<中間体5の合成>>
中間体4を49部、2-イソシアナトエチルアクリレート(AOI、昭和電工製)25部、ジブチルヒドロキシトルエン(BHT)0.2部、ジメチルアセトアミド95部、ネオスタンU-600(日東化成製)0.1部を添加し、85℃1時間攪拌した。続いて、これに酢酸エチル500部、飽和食塩水500部を添加し分液操作を行った。得られた有機層に硫酸ナトリウムを加えた後、ろ別し、ろ液を減圧濃縮した。得られた固体をクロロホルム170部で懸濁洗浄した後、ろ過し、送風乾燥を行うことで、中間体5を60部(収率:84%)得た。
<<キサンテン化合物(A-xt-1)の合成>>
中間体5を5部、塩化メチレンを50部、トリエチルアミン3.4部をフラスコに加え、室温で攪拌した。そこに中間体2を10.8部加え、室温で2時間攪拌した。反応終了後、クロロホルム200部、純水500部、飽和食塩水200部を加え、分液操作を行った。得られた有機層に硫酸ナトリウムを加え、脱水した後に、ろ別し、ろ液を減圧濃縮した。得られた固体をクロロホルムに溶解し、クロロホルム/酢酸エチル溶媒を用いてカラムクロマトグラフィーにより精製することで、A-xt-1を12.5部(収率:86%)得た。 << Synthesis of Intermediate 1 >>
31 parts of 3,6-dichlorosulfofluorane (DCSF) (manufactured by Chugai Kasei), 67 parts of 2,6-diisopropylaniline, 17 parts of zinc chloride and 120 parts of sulfolane were placed in a flask and stirred at an external temperature of 200 ° C. for 8 hours. . Thereafter, the mixture was allowed to cool to room temperature, the reaction solution was added dropwise to 600 parts of 2N aqueous hydrochloric acid, and the precipitated crystals were filtered off. The crystals were dispersed and washed with 600 parts of acetonitrile at 40 degrees, filtered, and air-dried for 10 hours to obtain 42.5 parts of intermediate 1 (yield: 82%).
<< Synthesis of Intermediate 2 >>
11 parts of Intermediate 1 and 50 parts of phosphorus oxychloride were placed in a flask and stirred at 60 ° C. for 4 hours. The mixture was allowed to cool to room temperature, and the reaction solution was added dropwise to 150 parts of ice water and stirred for 30 minutes. The obtained crystals were filtered off and washed with 20 parts of water. Thereafter, the obtained crystals were dissolved in 150 parts of chloroform and filtered through Celite. The filtrate was separated and washed with 100 parts of 5% saline and 100 parts of 15% saline. The filtrate was dried over sodium sulfate and concentrated under reduced pressure to obtain 12.1 parts of intermediate 2 (yield: 91%).
<< Synthesis of Intermediate 3 >>
15 parts of pentafluorobenzenesulfonyl chloride and 300 parts of tetrahydrofuran (THF) were placed in a flask, and the internal temperature was cooled to -10 ° C. Thereto, 6.8 parts of 28% aqueous ammonia was added dropwise so that the reaction solution maintained at 0 ° C. or lower. After dropping, the reaction solution was filtered after stirring at 0 ° C. for 1 hour. The obtained filtrate was concentrated under reduced pressure to remove THF, and then 100 parts of water was added and stirred. The obtained solid was filtered, washed with water, and then blown and dried for 10 hours to obtain 11.7 parts of intermediate 3 (yield: 84%).
<< Synthesis of Intermediate 4 >>
15 parts of Intermediate 3, 4.9 parts of 2-mercaptoethanol and 100 parts of methanol were added to the flask and stirred at room temperature. Thereto, 6.5 parts of triethylamine was added dropwise so that the temperature of the reaction solution did not exceed 30 ° C. After stirring this reaction liquid at room temperature for 1 hour and concentrating under reduced pressure, 90 parts of ethyl acetate, 80 parts of saturated salt solution, and 10 parts of saturated sodium hydrogen carbonate solution were added thereto, and liquid separation operation was performed. After extracting the aqueous layer with 90 parts of ethyl acetate, magnesium sulfate was added to the obtained organic layer. After filtration, the filtrate was concentrated under reduced pressure and blown and dried for 10 hours to obtain 17 parts (yield: 92%) of Intermediate 4.
<< Synthesis of Intermediate 5 >>
49 parts of Intermediate 4, 25 parts of 2-isocyanatoethyl acrylate (AOI, Showa Denko), 0.2 part of dibutylhydroxytoluene (BHT), 95 parts of dimethylacetamide, Neostan U-600 (manufactured by Nitto Kasei) 1 part was added and it stirred at 85 degreeC for 1 hour. Subsequently, 500 parts of ethyl acetate and 500 parts of saturated saline were added thereto to carry out a liquid separation operation. Sodium sulfate was added to the obtained organic layer, followed by filtration, and the filtrate was concentrated under reduced pressure. The obtained solid was suspended and washed with 170 parts of chloroform, filtered, and blown and dried to obtain 60 parts of intermediate 5 (yield: 84%).
<< Synthesis of Xanthene Compound (A-xt-1) >>
5 parts of Intermediate 5, 50 parts of methylene chloride and 3.4 parts of triethylamine were added to the flask and stirred at room temperature. Thereto was added 10.8 parts of Intermediate 2 and stirred at room temperature for 2 hours. After completion of the reaction, 200 parts of chloroform, 500 parts of pure water and 200 parts of saturated saline were added to carry out a liquid separation operation. Sodium sulfate was added to the obtained organic layer and dehydrated, followed by filtration, and the filtrate was concentrated under reduced pressure. The obtained solid was dissolved in chloroform and purified by column chromatography using a chloroform / ethyl acetate solvent to obtain 12.5 parts (yield: 86%) of A-xt-1.
キサンテン化合物(A-xt-2)、(A-xt-4)、(A-xt-6)、(A-xt-7)、(A-xt-9)、(A-xt-12)、(A-xt-15)を、上記キサンテン化合物(A-xt-1)にならって合成した。 <Xanthene compounds (A-xt-2), (A-xt-4), (A-xt-6), (A-xt-7), (A-xt-9), (A-xt-12) Synthesis Example of (A-xt-15)>
Xanthene compounds (A-xt-2), (A-xt-4), (A-xt-6), (A-xt-7), (A-xt-9), (A-xt-12), (A-xt-15) was synthesized following the xanthene compound (A-xt-1).
[色素多量体S-1の合成]
[Synthesis of Dye Multimer S-1]
色素多量体S-1の重量平均分子量(ポリスチレン換算値)は14500であり、0.1N水酸化ナトリウム水溶液を用いた滴定により、酸価は40mgKOH/gであった。
また、NMR(核磁気共鳴)測定でのポリマー鎖Qの色素構造を有する繰り返し単位の数は、平均4.5と計算された。また、テトラヒドロフラン(THF)に溶解させて色素多量体S-1を0.01mg/ml含む溶液を調製し(最大吸光度が1.0になるように調節した濃度)、かかる溶液の25℃での吸光度を、光路長1cmのセルを用いて測定したところ、最大吸収波長(λmax)は535nmで、最大吸収波長(λmax)の比吸光度は44であった。 1.0 part of polyfunctional thiol (compound having the above structure (SH-1), manufactured by SC Organic Chemical Industry Co., Ltd.), 13.7 parts of xanthene compound (A-xt-1), 2. methacrylic acid (MAA) 2. A mixed solution of 1 part and 9.0 parts of cyclohexanone was heated to 80 ° C. under a nitrogen stream. To this, 0.254 parts of 2,2′-azobis (isobutyric acid) dimethyl [V-601; manufactured by Wako Pure Chemical Industries, Ltd.] was added, and the mixture was heated and stirred at 80 ° C. for 2 hours. Further, 0.254 part of V-601 was added, and the mixture was stirred with heating at 80 ° C. for 2 hours, and further stirred with heating at 90 ° C. for 2 hours. After cooling to room temperature, 30.7 parts of cyclohexanone, 0.32 part of tetrabutylammonium bromide (TBAB), and 1.8 parts of glycidyl methacrylate (GMA) were added, and the mixture was heated and stirred at 80 ° C. for 18 hours. After cooling to room temperature, the reaction solution was dropped into a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate and reprecipitated to obtain Dye Multimer S-1.
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. Also, 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). When the absorbance was measured using a cell having an optical path length of 1 cm, the maximum absorption wavelength (λmax) was 535 nm, and the specific absorbance at the maximum absorption wavelength (λmax) was 44.
多官能チオール、各種モノマーの種類及び量、V-601の量、GMAの量、TBABの量を下記表に変更した以外は、色素多量体S-1の合成方法にならって、色素多量体S-2~S-52を得た。 [Synthesis of Dye Multimer S-2 to 52]
According to the synthesis method of dye multimer S-1, except that the types and amounts of polyfunctional thiols, various monomers, the amount of V-601, the amount of GMA, and the amount of TBAB were changed to the following table, -2 to S-52 were obtained.
各色素多量体をテトラヒドロフラン(THF)に溶解させて、波長400nm~800nmでの最大吸光度が1.0となる濃度に調整し、かかる溶液の25℃での吸光度を、光路長1cmのセルを用い、下記式(Aλ)に基づき算出した。
E=A/(c×l) ・・・(Aλ)
式(Aλ)中、Eは、400nm~800nmでの最大吸収波長における比吸光度を表し、
Aは、400nm~800nmでの最大吸収波長における吸光度を表し、
lは、単位がcmで表されるセル長を表し、
cは、単位がmg/mlで表される、溶液中の色素多量体の濃度を表す。 <Measurement of specific absorbance>
Each dye multimer is dissolved in tetrahydrofuran (THF) to adjust the concentration so that the maximum absorbance at a wavelength of 400 nm to 800 nm is 1.0, and the absorbance of this solution at 25 ° C. is measured using a cell having an optical path length of 1 cm. , Based on the following formula (Aλ).
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the dye multimer in the solution expressed in mg / ml.
特開2000-162429号公報に記載の方法に準じてトリアリールメタン化合物(A-tp-101)を合成した。
トリアリールメタン化合物(A-tp-101)(15g)、ヒドロキシエチルメタクリレート(10g)、メタクリル酸(5.5g)、及びアゾビスイソブチロニトリル(5g)を、N-エチルピロリドン(70g)に加え、室温で30分攪拌し溶解させた(滴下用重合溶液)。
別途、トリアリールメタン化合物(A-tp-101)(15g)、ヒドロキシエチルメタクリレート(10g)、及びメタクリル酸(5.5g)を容器に入れ溶解させ、80℃で攪拌した。そこに調製した滴下用重合溶液を3時間かけて滴下し、1時間攪拌した後、アゾイソブチロニトリル(2.5g)を添加し、さらに2時間反応させ停止した。室温まで冷却後、溶媒を留去し、比較色素3を得た。比較色素3の重量平均分子量(Mw)は18000、0.1N水酸化ナトリウム水溶液を用いた滴定により、酸価は1.81mgKOH/gであった。 (Synthesis of comparative dye (S'-3))
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). In addition, the mixture was stirred and dissolved at room temperature for 30 minutes (polymerization solution for dropping).
Separately, 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.
1.レジスト液の調製
下記組成の成分を混合して溶解した後、0.45μmナイロンフィルタでろ過することにより下塗り層用レジスト液を調製した。
下塗り層用レジスト液の組成
・溶剤:プロピレングリコールモノメチルエーテルアセテート 19.20部
・溶剤:乳酸エチル 36.67部
・アルカリ可溶性樹脂:メタクリル酸ベンジル/メタクリル酸/メタクリル酸-2-ヒドロキシエチル共重合体(モル比=60/22/18、重量平均分子量15,000、数平均分子量9,000)の40%PGMEA溶液 30.51部
・重合性化合物:ジペンタエリスリトールヘキサアクリレート(KAYARAD DPHA(日本化薬社製)) 12.20部
・重合禁止剤:p-メトキシフェノール 0.0061部
・フッ素系界面活性剤:F-475、DIC(株)製 0.83部
・光重合開始剤:トリハロメチルトリアジン系の光重合開始剤(TAZ-107、みどり化学社製) 0.586部 <Example 1>
1. Preparation of Resist Solution After the components having the following composition were mixed and dissolved, the resist solution for undercoat layer was prepared by filtering with a 0.45 μm nylon filter.
Composition of resist solution for undercoat layer: Solvent: propylene glycol monomethyl ether acetate 19.20 parts Solvent: ethyl lactate 36.67 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (Molar ratio = 60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) 40% PGMEA solution 30.51 parts Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA (Nippon Kayaku) 12.20 parts ・ Polymerization inhibitor: 0.0061 part ・ Fluorosurfactant: F-475, 0.83 part by DIC Corporation ・ Photopolymerization initiator: Trihalomethyltriazine -Based photopolymerization initiator (TAZ-107, manufactured by Midori Chemical Co., Ltd.) 0.586
6インチ(inch)シリコンウエハをオーブン中で200℃のもと30分加熱処理した。次いで、このシリコンウエハ上に、下塗り層用レジスト液を乾燥膜厚が1.5μmになるように塗布し、更に220℃のオーブン中で1時間加熱乾燥させて下塗り層を形成し、下塗り層付シリコンウエハ基板を得た。 2. Preparation of silicon wafer substrate with undercoat layer A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, an undercoat layer resist solution is applied onto this silicon wafer so that the dry film thickness is 1.5 μm, and further dried by heating in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate was obtained.
3-1.青色顔料分散液の調製
(顔料分散液P1(C.I.Pigment Blue15:6分散液)の調製)
以下のようにして、顔料分散液P1(C.I.Pigment Blue15:6分散液)を調製した。
即ち、C.I.Pigment Blue15:6(青色顔料;以下、「PB15:6」とも称する)を19.4質量部(平均一次粒子径55nm)、及び分散樹脂BY-161(BYK社製)を2.95質量部、アルカリ可溶性樹脂J1(メタクリル酸ベンジル/メタクリル酸の共重合体、30%PGMEA溶液)を固形分換算で2.95質量部(溶液9.93質量部)、PGMEAを165.3質量部混合した混合液を、ビーズミル(beads mill)(ジルコニアビーズ0.3mm径)により3時間混合・分散した。その後、さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、顔料分散液として、C.I.Pigment Blue15:6分散液を得た。得られたC.I.Pigment Blue15:6分散液について、顔料の平均一次粒子径を動的光散乱法(Microtrac Nanotrac UPA-EX150(日機装社(Nikkiso Co.,Ltd.)製))により測定したところ、24nmであった。 3. 3. Preparation of coloring composition 3-1. Preparation of blue pigment dispersion (preparation of pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion))
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. Mixing which mixed alkali-soluble resin J1 (copolymer of benzyl methacrylate / methacrylic acid, 30% PGMEA solution) 2.95 parts by mass (solution 9.93 parts by mass) and 165.3 parts by mass of PGMEA The liquid was mixed and dispersed for 3 hours by a beads mill (zirconia beads 0.3 mm diameter). Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain C.I. I. Pigment Blue 15: 6 dispersion was obtained. The obtained C.I. I. With respect to Pigment Blue 15: 6 dispersion, the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 24 nm.
下記の各成分を混合して分散、溶解し、0.45μmナイロンフィルタでろ過することにより着色組成物を得た。
・有機溶剤(シクロヘキサノン):17.12部
・アルカリ可溶性樹脂1(下記J1):1.23部(固形分0.37部、固形分濃度30%)
・アルカリ可溶性樹脂2(アクリキュア-RD-F8(日本触媒社製)):0.23部
・光重合開始剤I-2(IRGACURE OXE-02):0.975部
・色素多量体のシクロヘキサノン溶液(固形分濃度12.3%):24.57部
・顔料分散液P1(C.I.Pigment Blue15:6分散液、PGMEA溶液、固形分濃度12.8%):51.40部
・重合性化合物Z-1(エチレンオキシ変性ジペンタエリスリトールヘキサアクリレート、NKエステル A-DPH-12E(新中村化学社製)):1.96部
・重合禁止剤(p-メトキシフェノール):0.0007部
・フッ素系界面活性剤(DIC社製F475、1%PGMEA溶液):2.50部 3-2. Preparation of coloring composition The following components were mixed, dispersed and dissolved, and filtered through a 0.45 µm nylon filter to obtain a coloring composition.
Organic solvent (cyclohexanone): 17.12 parts Alkali-soluble resin 1 (J1 below): 1.23 parts (solid content 0.37 parts, solid content concentration 30%)
Alkali-soluble resin 2 (Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)): 0.23 part Photopolymerization initiator I-2 (IRGACURE OXE-02): 0.975 part A cyclohexanone solution of dye multimer ( (Solid content concentration 12.3%): 24.57 parts pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion, PGMEA solution, solid concentration 12.8%): 51.40 parts polymerizable compound Z-1 (ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)): 1.96 parts, polymerization inhibitor (p-methoxyphenol): 0.0007 parts, fluorine Surfactant (DIC, F475, 1% PGMEA solution): 2.50 parts
4-1:フォトリソグラフィ法による着色組成物を用いたカラーフィルタの作製
上記で調製された着色組成物を、上記で作製された下塗り層付シリコンウエハの下塗り層上に塗布し、着色層(塗布膜)を形成した。そして、この塗布膜の乾燥膜厚が1μmになるように、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行なった。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して365nmの波長でパターンが1.0μm四方のIslandパターンマスクを通して50~1200mJ/cm2の露光量で露光した。
その後、照射された塗布膜が形成されているシリコンウエハ基板をスピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、CD-2000(富士フイルムエレクトロニクスマテリアルズ(株)製)を用いて23℃で60秒間パドル現像を行ない、下塗り層付シリコンウエハの下塗り層上に着色パターンを形成した。
着色パターンが形成されたシリコンウエハを、真空チャック方式で水平回転テーブルに固定し、回転装置によってシリコンウエハを回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行なった。その後スプレー乾燥し、200℃で300秒間、ホットプレートでポストベークを行い、シリコンウエハ上の膜厚1μmの着色パターン(カラーフィルタ)を得た。
以上により、下塗り層付シリコンウエハの下塗り層上に着色パターン(カラーフィルタ)が設けられた構成の着色パターン付シリコンウエハを得た。
その後、測長SEM「S-9260A」(日立ハイテクノロジーズ(株)製)を用いて、着色パターンのサイズを測定した。
パターンサイズが1.0μmとなる露光量の着色パターンを用い、現像残渣の評価を行った。 4). 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 μm.
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 μm square at a wavelength of 365 nm.
Thereafter, 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. Thereafter, it was spray-dried and post-baked on a hot plate at 200 ° C. for 300 seconds to obtain a colored pattern (color filter) having a film thickness of 1 μm 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 μm in pattern size.
シリコンウエハにおける着色パターンの形成領域外(未露光部)を走査式電子顕微鏡を用いて、倍率30000倍にて観察し、下記評価基準に従って評価した。
A:着色パターン形成領域外(未露光部)には残渣が全く確認されなかった。
B:着色パターン形成領域外(未露光部)に、残渣がわずかに確認されたが、実用上問題のない程度であった。
C:着色パターン形成領域外(未露光部)に残渣が確認された。現像条件を23℃で60秒間パドル現像から23℃で180秒間パドル現像に変更することで、実用上問題のない程度となった。
D:着色パターン形成領域外(未露光部)に残渣が著しく確認された。 << Evaluation of development residue >>
The outside of the colored pattern formation region (unexposed portion) on the silicon wafer was observed at a magnification of 30000 using a scanning electron microscope, and evaluated according to the following evaluation criteria.
A: No residue was observed outside the colored pattern formation region (unexposed area).
B: A small amount of residue was confirmed outside the colored pattern formation region (unexposed area), but was practically unproblematic.
C: A residue was confirmed outside the colored pattern formation region (unexposed portion). By changing the development condition from paddle development at 23 ° C. for 60 seconds to paddle development at 23 ° C. for 180 seconds, there was no practical problem.
D: Residue was remarkably confirmed outside the colored pattern formation region (unexposed portion).
各カラーフィルタにおける着色パターンの吸光度を、MCPD-3000(大塚電子(株)製)にて測定した(吸光度A)。
カラーフィルタの着色パターン形成面に、乾燥膜厚が1μmとなるようにCT-2000L溶液(富士フイルムエレクトロニクスマテリアルズ(株)製;透明下地剤)を塗布し、乾燥させて、透明膜を形成した後、280℃で5分間加熱処理を行なった。
加熱終了後、着色パターンに隣接する透明膜の吸光度を、MCPD-3000(大塚電子(株)製)にて測定した(吸光度B)。
得られた透明膜の吸光度Bの値について、加熱前に測定した着色パターンの吸光度Aの値に対する割合[%]を算出した〔下記(式A)〕。これを隣接ピクセルへの色移りを評価する指標とした。
(式A) 色移り(%)=(吸光度B/吸光度A)×100
A:1%未満
B:1%以上3%未満
C:3%以上10%未満
D:10%以上 << Evaluation of color transfer >>
The absorbance of the colored pattern in each color filter was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance A).
A transparent film was formed by applying a CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd .; transparent base material) so that the dry film thickness was 1 μm on the color pattern forming surface of the color filter. Thereafter, heat treatment was performed at 280 ° C. for 5 minutes.
After heating, the absorbance of the transparent film adjacent to the colored pattern was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance B).
With respect to the value of absorbance B of the obtained transparent film, the ratio [%] to the value of absorbance A of the colored pattern measured before heating was calculated [the following (formula A)]. This was used as an index for evaluating the color transfer to adjacent pixels.
(Formula A) Color transfer (%) = (absorbance B / absorbance A) × 100
A: Less than 1% B: 1% or more and less than 3% C: 3% or more and less than 10% D: 10% or more
上記で調製された着色感光性組成物をガラス基板にスピンコーター(ミカサ(株)社製)を用いて塗布し、塗膜を形成した。そして、この塗膜の乾燥膜厚が0.6μmになるように、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行った。次いで200℃で5分間の加熱を行い、塗布膜の硬化を行って着色層を形成した。
着色層を形成したガラス基板を、耐光試験装置(スガ試験機社製SX-75)を用いてブラックパネル温度63℃、石英インナーフィルター、275nmカットアウターフィルター、照度75mw/m2(300~400nm)、湿度50%の条件下で10時間、耐光性試験を実施した。
耐光性試験前後の色差(ΔE*ab)を分光光度計MCPD-3000(大塚電子(株)社製)で測定した。測定された色差(ΔE*ab)に基づき、下記評価基準に従って耐光性を評価した。この数値が小さいほど、耐光性が良好であるといえる。評価結果を下記表に示す。AおよびBが実際の使用に問題のないレベルである。 << Light resistance evaluation >>
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.
Using a light resistance tester (SX-75 manufactured by Suga Test Instruments Co., Ltd.), 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 (ΔE * 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 (ΔE * 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.
A:ΔE*abが3以下
B:ΔE*abが3より大きく5以下
C:ΔE*abが5より大きく10以下
D:ΔE*abが10より大きい <Evaluation criteria>
A: ΔE * ab is 3 or less B: ΔE * ab is greater than 3 and less than 5 C: ΔE * ab is greater than 5 and less than 10 D: ΔE * ab is greater than 10
上記で調製された着色組成物1.0mLを4インチシリコンウエハーにスピンコーター(ミカサ(株)社製)を用いて塗布し、塗膜を形成した。そして、この塗膜の中心部の乾燥膜厚が0.60μmになるように、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行い着色層を形成した。
光学式膜厚計(フィルメトリクス(株)F20)を用い、着色層の膜厚を測定した。膜厚の一番薄い部分(中心部)と一番厚部分(周辺部)の差が小さいほど良好であるといえる。評価結果を下記表に示す。AおよびBが実際の使用に問題のないレベルである。 << Evaluation of flatness >>
The coloring composition 1.0mL prepared above was apply | coated to the 4-inch silicon wafer using the spin coater (made by Mikasa Co., Ltd.), and the coating film was formed. And the heat treatment (prebaking) was performed for 120 seconds using a 100 degreeC hotplate so that the dry film thickness of the center part of this coating film might be 0.60 micrometer, and the colored layer was formed.
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.
A:膜厚の差が0.02μm以下である
B:膜厚の差が0.02μmより大きく0.05μm以下である
C:膜厚の差が0.05μmより大きい。 <Evaluation criteria>
A: The difference in film thickness is 0.02 μm or less B: The difference in film thickness is greater than 0.02 μm and 0.05 μm or less C: The difference in film thickness is greater than 0.05 μm.
なお、比較例1~3は、色素多量体として、上述した比較色素S’-1~S’-3を使用した。 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.
一方、比較例1~3は、色移り性または平坦性のいずれかが劣るものであった。 From the above results, the colored compositions of Examples 1 to 52 were excellent in color transfer, light resistance and flatness. Furthermore, there was very little development residue and it was excellent in developability.
On the other hand, Comparative Examples 1 to 3 were inferior in either color transfer or flatness.
下記の各成分を混合して分散、溶解し、0.45μmナイロンフィルタでろ過することにより着色組成物を得た。
次に、得られた着色組成物を、7.5cm×7.5cmのガラス基板上に膜厚が0.5μmになるようにスピンコーターを用いて塗布し、ホットプレートを使用して、200℃で5分間、加熱を行い、塗布膜の硬化を行って着色層を作製した。この着色層の膜厚は、0.5μmであった。
次いで、ポジ型フォトレジスト「FHi622BC」(富士フイルムエレクトロニクスマテリアルズ社製)を塗布し、90℃で1分間、プリベーク処理を実施し、膜厚0.8μmのフォトレジスト層を形成した。
続いて、フォトレジスト層を、i線ステッパー(Canon(株)製)を用い、350mJ/cm2の露光量でパターン露光し、フォトレジスト層の温度又は雰囲気温度が90℃となる温度で1分間、加熱処理を行なった。その後、現像液「FHD-5」(富士フイルムエレクトロニクスマテリアルズ社製)で1分間の現像処理を行ない、さらに110℃で1分間のポストベーク処理を実施して、レジストパターンを形成した。このレジストパターンのサイズは、エッチング変換差(エッチングによるパターン幅の縮小)を考慮して、一辺1.0μmで形成した。
次に、フォトレジスト層を形成したガラス基板を8inchシリコンウェハに貼り付け、ドライエッチング装置(U-621、日立ハイテクノロジーズ社製)にて、RFパワー:800W、アンテナバイアス:400W、ウエハバイアス:200W、チャンバーの内部圧力:4.0Pa、基板温度:50℃、混合ガスのガス種及び流量をCF4:80mL/分、O2:40mL/分、Ar:800mL/min.として、80秒の第1段階のエッチング処理を実施した。
次いで、同一のエッチングチャンバーにて、RFパワー:600W、アンテナバイアス:100W、ウエハバイアス:250W、チャンバーの内部圧力:2.0Pa、基板温度:50℃、混合ガスのガス種及び流量をN2:500mL/分、O2:50mL/分、Ar:500mL/分とし(N2/O2/Ar=10/1/10)、28秒の第2段階のエッチング処理を実施した。
上記条件でドライエッチングを行った後、フォトレジスト剥離液「MS230C」(富士フイルムエレクトロニクスマテリアルズ社製)を使用して、50℃で120秒間、剥離処理を実施してレジストを除去し、着色パターンを形成した。更に純水による洗浄、スピン乾燥を実施し、その後、100℃で2分間の脱水ベーク処理を行った。以上により、カラーフィルタを得た。
得られたカラーフィルタについて、実施例1と同様にして色移り性、耐光性、平坦性を評価した。
<着色組成物の組成>
・有機溶剤(シクロヘキサノン):17.12部
・エポキシ樹脂JER1031S(三菱化学(株)製、エポキシ当量:180-220(g/eq.)):4.395部
・色素多量体のシクロヘキサノン溶液(固形分濃度12.3%):24.57部
・顔料分散液(下記表参照):51.40部
・重合禁止剤(p-メトキシフェノール):0.0007部
・フッ素系界面活性剤(DIC社製F475、1%PGMEA溶液):2.50部 <Examples 53 and 54>
The following components were mixed, dispersed and dissolved, and filtered through a 0.45 μm 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 μm. 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 μm.
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 μm-thick photoresist layer.
Subsequently, 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 μm in consideration of etching conversion difference (pattern width reduction by etching).
Next, 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. As a result, the first stage etching process of 80 seconds was performed.
Next, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., gas mixture type and flow rate of N 2 : The second stage etching process was performed for 28 seconds at 500 mL / min, O 2 : 50 mL / min, Ar: 500 mL / min (N 2 / O 2 / Ar = 10/1/10).
After performing dry etching under the above conditions, a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is used to perform stripping treatment at 50 ° C. for 120 seconds to remove the resist. Formed. Further, washing with pure water and spin drying were performed, and then a dehydration baking process was performed at 100 ° C. for 2 minutes. As a result, a color filter was obtained.
The resulting color filter was evaluated for color transfer, light resistance and flatness in the same manner as in Example 1.
<Composition of coloring composition>
Organic solvent (cyclohexanone): 17.12 parts Epoxy resin JER1031S (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 180-220 (g / eq.)): 4.395 parts (Concentration 12.3%): 24.57 parts • Pigment dispersion (see table below): 51.40 parts • Polymerization inhibitor (p-methoxyphenol): 0.0007 parts • Fluorosurfactant (DIC) F475, 1% PGMEA solution): 2.50 parts
Z-1:エチレンオキシ変性ジペンタエリスリトールヘキサアクリレート、NKエステル A-DPH-12E(新中村化学社製)
Z-2:ジペンタエリスリトールヘキサアクリレート、KAYARAD DPHA(日本化薬社製)
Z-3:エトキシ化(4)ペンタエリスリトールテトラアクリレート、SR494(サートマー社製)
Z-4:エトキシ化(3)トリメチロールプロパントリアクリレート、SR454(サートマー社製)
Z-5:エトキシ化(6)トリメチロールプロパントリアクリレート、SR499(サートマー社製)
Z-6:KAYARAD DPCA-60(日本化薬社製)
Z-7:トリス(2-ヒドロキシエチル)イソシアヌレートトリアクリレート、SR368(サートマー社製) 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-hydroxyethyl) isocyanurate triacrylate, SR368 (manufactured by Sartomer)
顔料分散液P2(C.I.Pigment Blue15:6分散液:
顔料分散液P1の調製において、分散樹脂BY-161の代わりに、下記分散樹脂D1を用いる以外は同様の操作により顔料分散液P2を調製した。
Mw=20000、x/y=50/50(質量比)、n=20、酸価=100mgKOH/g
顔料分散液P3(C.I.Pigment Blue15:6分散液):
顔料分散液P1の調製において、分散樹脂BY-161の代わりに、下記分散樹脂D2を用いる以外は同様の操作により顔料分散液P3を調製した。
Mw=20000、x/y=15/85(質量比)、n=20、酸価=100mgKOH/g
顔料分散液P4(C.I.Pigment Violet23分散液):
顔料分散液P1の調製において、顔料としてPB15:6の代わりに、C.I.Pigment Violet23を使用する以外は顔料分散液P1の調製と同様にして顔料分散液P4を調製した。
顔料分散液P5(C.I.Pigment Red254分散液):
顔料分散液P1の調製において、顔料としてPB15:6の代わりに、C.I.Pigment Red254を使用する以外は顔料分散液P1の調製と同様にして顔料分散液P5を調製した。
顔料分散液P6(C.I.Pigment Green58分散液):
顔料分散液P1の調製において、顔料としてPB15:6の代わりに、C.I.Pigment Green58を使用する以外は顔料分散液P1の調製と同様にして顔料分散液P6を調製した。
顔料分散液P7(C.I.Pigment Yellow139分散液):
顔料分散液P1の調製において、顔料としてPB15:6の代わりに、C.I.Pigment Yellow139を使用する以外は顔料分散液P1の調製と同様にして顔料分散液P7を調製した。 Pigment Dispersion Pigment Dispersion P2 (CI Pigment Blue 15: 6 Dispersion:
Pigment dispersion P2 was prepared in the same manner as in the preparation of pigment dispersion P1, except that the following dispersion resin D1 was used instead of dispersion resin BY-161.
Mw = 20000, x / y = 50/50 (mass ratio), n = 20, acid value = 100 mgKOH / g
Pigment dispersion P3 (CI Pigment Blue 15: 6 dispersion):
A pigment dispersion P3 was prepared in the same manner as the pigment dispersion P1, except that the following dispersion resin D2 was used instead of the dispersion resin BY-161.
Mw = 20000, x / y = 15/85 (mass ratio), n = 20, acid value = 100 mgKOH / g
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.
Claims (18)
- 一般式(1)で表わされる色素多量体と、重合性化合物とを含む着色組成物;
P-(Q)n ・・・(1)
一般式(1)中、Pはn価の連結基を表し、
Qは色素構造を有する繰り返し単位を含むポリマー鎖を表し、n個のQの、色素構造を有する繰り返し単位の個数の平均値が2個以上であり、
nは3~10の整数を表す。 A coloring composition comprising a dye multimer represented by the general formula (1) and a polymerizable compound;
P- (Q) n (1)
In general formula (1), P represents an n-valent linking group,
Q represents a polymer chain including a repeating unit having a dye structure, and the average value of the number of n repeating units having a dye structure is 2 or more,
n represents an integer of 3 to 10. - 前記色素多量体が、一般式(2)で表される、請求項1に記載の着色組成物;
一般式(2)中、A1はn価の連結基を表し、
B1は単結合、-O-、-S-、-CO-、-NR-、-O2C-、-CO2-、-NROC-、または、-CONR-を表し、Rは、水素原子、アルキル基またはアリール基を表し、
C1は、単結合または2価の連結基を表し、
Sは、硫黄原子を表し、
Qは色素構造を有する繰り返し単位を含むポリマー鎖を表し、n個のQの、色素構造を有する繰り返し単位の個数の平均値が2個以上であり、
nは3~10の整数を表す。 The coloring composition according to claim 1, wherein the dye multimer is represented by the general formula (2);
In 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—, and R represents a hydrogen atom Represents 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 including a repeating unit having a dye structure, and the average value of the number of n repeating units having a dye structure is 2 or more,
n represents an integer of 3 to 10. - 前記A1は、主鎖に酸素原子を有しても良い脂肪族炭化水素基、芳香族環基および複素環基から選ばれる1種または2種以上の組み合わせからなる基である、請求項2に記載の着色組成物。 The A 1 is 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 coloring composition as described in.
- 前記色素多量体は、400nm~800nmでの最大吸収波長における、下記式(Aλ)で表される比吸光度が5以上である、請求項1~3のいずれか1項に記載の着色組成物;
E=A/(c×l) ・・・(Aλ)
式(Aλ)中、Eは、400nm~800nmでの最大吸収波長における比吸光度を表し、
Aは、400nm~800nmでの最大吸収波長における吸光度を表し、
lは、単位がcmで表されるセル長を表し、
cは、単位がmg/mlで表される、溶液中の色素多量体の濃度を表す。 The colored composition according to any one of claims 1 to 3, wherein the dye multimer has a specific absorbance represented by the following formula (Aλ) at a maximum absorption wavelength at 400 nm to 800 nm of 5 or more;
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the dye multimer in the solution expressed in mg / ml. - 前記着色組成物の全固形分に対し、前記色素多量体を1~50質量%含有する、請求項1~4のいずれか1項に記載の着色組成物。 The colored composition according to any one of claims 1 to 4, comprising 1 to 50% by mass of the dye multimer based on the total solid content of the colored composition.
- 前記色素多量体は、一般式(3)で表わされる化合物と、色素構造及びラジカル重合性基を有する化合物とをラジカル重合して得られたものである、請求項1~5のいずれか1項に記載の着色組成物。
P0-(SH)n ・・・(3)
一般式(3)中、P0はn価の連結基を表し、
SHはチオール基を表し、
nは3~10の整数を表す。 6. The dye multimer according to claim 1, wherein 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. The coloring composition as described in.
P 0- (SH) n (3)
In general formula (3), P 0 represents an n-valent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10. - さらに、前記色素多量体以外の色素を含む請求項1~6のいずれか1項に記載の着色組成物。 The colored composition according to any one of claims 1 to 6, further comprising a dye other than the dye multimer.
- さらに、光重合開始剤を含む請求項1~7のいずれか1項に記載の着色組成物。 The colored composition according to any one of claims 1 to 7, further comprising a photopolymerization initiator.
- 前記Qは、トリアリールメタン色素、キサンテン色素、アントラキノン色素、シアニン色素、スクアリリウム色素、キノフタロン色素、フタロシアニン色素、サブフタロシアニン色素、アゾ色素およびジピロメテン色素から選ばれる色素に由来する色素構造を有する、請求項1~8のいずれか1項に記載の着色組成物。 The 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. The coloring composition according to any one of 1 to 8.
- 前記Qは、酸基を有する繰り返し単位および重合性基を有する繰り返し単位から選ばれる1種以上を有する、請求項1~9のいずれか1項に記載の着色組成物。 The colored composition according to any one of claims 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.
- 前記Qは、(メタ)アクリル系樹脂、スチレン系樹脂、および、(メタ)アクリル/スチレン系樹脂から選ばれる1種である、請求項1~10のいずれか1項に記載の着色組成物。 The colored composition according to any one of claims 1 to 10, wherein Q is one selected from a (meth) acrylic resin, a styrene resin, and a (meth) acrylic / styrene resin.
- 請求項1~11のいずれか1項に記載の着色組成物を用いてなるカラーフィルタ。 A color filter using the colored composition according to any one of claims 1 to 11.
- 請求項1~11のいずれか1項に記載の着色組成物を支持体上に適用して着色組成物層を形成する工程と、
前記着色組成物層をパターン状に露光する工程と、
パターン状に露光された前記着色組成物層の未露光部を現像除去して着色パターンを形成する工程と、
を含むパターン形成方法。 Applying the colored composition according to any one of claims 1 to 11 on a support to form a colored composition layer;
Exposing the colored composition layer in a pattern;
Developing and removing unexposed portions of the colored composition layer exposed in a pattern to form a colored pattern; and
A pattern forming method including: - 請求項1~11のいずれか1項に記載の着色組成物を支持体上に適用して着色組成物層を形成し、硬化して着色層を形成する工程と、
前記着色層上にフォトレジスト層を形成する工程と、
露光および現像することにより前記フォトレジスト層をパターニングしてレジストパターンを得る工程と、
前記レジストパターンをエッチングマスクとして前記着色層をドライエッチングして着色パターンを形成する工程と、
を含む、パターン形成方法。 Applying the colored composition according to any one of claims 1 to 11 on a support to form a colored composition layer and curing to form a colored layer;
Forming a photoresist layer on the colored layer;
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; and
A pattern forming method. - 請求項13または14に記載のパターン形成方法を含む、カラーフィルタの製造方法。 A method for producing a color filter, comprising the pattern forming method according to claim 13 or 14.
- 請求項12に記載のカラーフィルタ、または、請求項15に記載のカラーフィルタの製造方法により得られたカラーフィルタ、を有する固体撮像素子。 A solid-state imaging device having the color filter according to claim 12 or the color filter obtained by the method for producing a color filter according to claim 15.
- 請求項12に記載のカラーフィルタ、または、請求項15に記載のカラーフィルタの製造方法により得られたカラーフィルタ、を有する画像表示装置。 An image display device comprising the color filter according to claim 12 or a color filter obtained by the method for producing a color filter according to claim 15.
- 一般式(3)で表わされる化合物と、色素構造及びラジカル重合性基を有する化合物とをラジカル重合することを含む、色素多量体の製造方法。
P0-(SH)n ・・・(3)
一般式(3)中、P0はn価の連結基を表し、
SHはチオール基を表し、
nは3~10の整数を表す。 A method for producing a dye multimer, comprising radical polymerization of a compound represented by the general formula (3) and a compound having a dye structure and a radical polymerizable group.
P 0- (SH) n (3)
In general formula (3), P 0 represents an n-valent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10.
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