WO2019069609A1 - Method for producing cured film, method for producing solid-state imaging element, and method for producing image display device - Google Patents
Method for producing cured film, method for producing solid-state imaging element, and method for producing image display device Download PDFInfo
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- WO2019069609A1 WO2019069609A1 PCT/JP2018/032662 JP2018032662W WO2019069609A1 WO 2019069609 A1 WO2019069609 A1 WO 2019069609A1 JP 2018032662 W JP2018032662 W JP 2018032662W WO 2019069609 A1 WO2019069609 A1 WO 2019069609A1
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- cured film
- curable composition
- nitride
- producing
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- ICWPRFNZEBFLPT-UHFFFAOYSA-N n-(2-hydroxyphenyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=CC=C1O ICWPRFNZEBFLPT-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- HYIMSNHJOBLJNT-UHFFFAOYSA-N nifedipine Chemical compound COC(=O)C1=C(C)NC(C)=C(C(=O)OC)C1C1=CC=CC=C1[N+]([O-])=O HYIMSNHJOBLJNT-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical group 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 229940105570 ornex Drugs 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229940110337 pigment blue 1 Drugs 0.000 description 1
- 229930006728 pinane Natural products 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- KHJHBFLMOSTPIC-UHFFFAOYSA-N prop-2-enylidenechromium Chemical compound C(=C)C=[Cr] KHJHBFLMOSTPIC-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
- GGVMPKQSTZIOIU-UHFFFAOYSA-N quaterrylene Chemical group C12=C3C4=CC=C2C(C2=C56)=CC=C5C(C=57)=CC=CC7=CC=CC=5C6=CC=C2C1=CC=C3C1=CC=CC2=CC=CC4=C21 GGVMPKQSTZIOIU-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- OVTCUIZCVUGJHS-VQHVLOKHSA-N trans-dipyrrin Chemical class C=1C=CNC=1/C=C1\C=CC=N1 OVTCUIZCVUGJHS-VQHVLOKHSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- RSJKGSCJYJTIGS-BJUDXGSMSA-N undecane Chemical group CCCCCCCCCC[11CH3] RSJKGSCJYJTIGS-BJUDXGSMSA-N 0.000 description 1
- PSUYMGPLEJLSPA-UHFFFAOYSA-N vanadium zirconium Chemical compound [V].[V].[Zr] PSUYMGPLEJLSPA-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- 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
- G03F7/004—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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
Definitions
- the present invention relates to a method of manufacturing a cured film, a method of manufacturing a solid-state imaging device, and a method of manufacturing an image display device.
- the method for producing a cured film used for a solid-state imaging device and an image display device is carried out after forming a curable composition layer on a substrate
- the method of hardening this is common.
- the curable composition layer is irradiated with light through a predetermined mask pattern and then developed.
- the optical density (OD: Optical Density) of the curable composition layer with respect to a specific wavelength may be adjusted within a predetermined range.
- Patent Document 1 discloses that when a film having a thickness of 2.0 ⁇ m after drying is formed using a colored photosensitive composition, the film has an optical density of 1.5 or more at a wavelength of 365 nm.
- a photosensitive composition is disclosed (Claim 1).
- the present inventors examined the colored photosensitive composition described in Patent Document 1, and there is room for improvement in rectangularity of the cross-sectional shape of a cured film formed using this colored photosensitive composition. Found out. In addition, it is required that a cured film of stable quality can be produced under various production conditions, and after a curable composition layer is formed, a period (for example, one week) until exposure is left. However, it is also required that the rectangularity of the cross-sectional shape of the obtained cured film be good.
- retention the fact that the object to be treated which has undergone a specific process can be made to stand by until the next process is also referred to as "retention.”
- the present invention can provide a method for producing a cured film capable of producing a cured film excellent in rectangularity of the cross-sectional shape and maintaining excellent rectangularity even when using a drawn curable composition layer. It will be an issue.
- Another object of the present invention is to provide a method of manufacturing a solid-state imaging device and a method of manufacturing an image display device.
- the optical density A at a wavelength of 365 nm per 1.5 ⁇ m of film thickness is 2.60 to 10.00, and the film thickness of 1.5 ⁇ m
- Forming a curable composition layer having an optical density B of 2.00 to 10.00 at a wavelength of 550 nm, and exposing the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume A method for producing a cured film, comprising the steps of: developing the curable composition layer after the exposure to form a cured film.
- the black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, a nitride or oxynitride of niobium, or carbon black
- the manufacturing method of the cured film as described in [1] or [2].
- the black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, or a nitride or oxynitride of niobium [1] ] The manufacturing method of the cured film in any one of-[3]. [5] The method for producing a cured film according to any one of [1] to [4], wherein the black pigment is a nitride or oxynitride of titanium, or a nitride or oxynitride of zirconium.
- [6] The method for producing a cured film according to any one of [1] to [5], wherein the irradiance is from 20000 to 50000 W / m 2 in the exposure.
- [7] The method for producing a cured film according to any one of [1] to [6], wherein the irradiance is 25000 to 40000 W / m 2 in the exposure.
- [8] The cured film according to any one of [1] to [7], wherein the optical density A is 2.80 to 4.00, and the optical density B is 2.50 to 7.00. Production method.
- [9] The method for producing a cured film according to any one of [1] to [8], wherein the ratio of the optical density B to the optical density A is 0.5 to 2.0.
- the curable composition further contains a resin, and the resin contains a resin containing an ethylenically unsaturated group, and the content of the ethylenically unsaturated group with respect to the total mass of the resin Of from 0.10 to 3.00 mmol / g.
- the method for producing a cured film according to any one of [1] to [10] wherein the curable composition further contains a polymerization initiator.
- the cured film which is excellent in the rectangularity of cross-sectional shape can be manufactured, and the manufacturing method of the cured film which can maintain excellent rectangularity even when using the curable composition layer drawn can be provided.
- the present invention can also provide a method of manufacturing a solid-state imaging device and a method of manufacturing an image display device.
- a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
- the notation not describing substitution and non-substitution also includes a group containing a substituent together with a group not containing a substituent.
- the "alkyl group” includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
- active light or “radiation” in the present specification means, for example, far ultraviolet, extreme ultraviolet (EUV), X-ray, electron beam and the like.
- light means actinic rays and radiation.
- exposure in the present specification includes not only exposure by far ultraviolet rays, X-rays, EUV light and the like but also drawing by particle beams such as electron beams and ion beams.
- (meth) acrylate represents acrylate and methacrylate.
- (meth) acryl represents an acryl and a methacryl.
- (meth) acryloyl represents acryloyl and methacryloyl.
- (meth) acrylamide refers to acrylamide and methacrylamide.
- “monomer” and “monomer” are synonymous.
- the weight-average molecular weight (Mw) is a polystyrene conversion value by GPC (Gel Permeation Chromatography) method.
- GPC method uses HLC-8020GPC (made by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ 2000 (made by Tosoh Corp., 4.6 mm ID ⁇ 15 cm) as columns, and THF (tetrahydrofuran as the eluent Based on the method using
- the optical density A at a wavelength of 365 nm per film thickness of 1.5 ⁇ m is 2.60 to 10.00 using a curable composition containing a black pigment and a polymerizable compound, and a film A step of forming a curable composition layer having an optical density B at a wavelength of 550 nm per 1.5 ⁇ m of 2.00 to 10.00, and the curable composition layer having an oxygen concentration of 30 to 50% by volume And exposing the curable composition layer after the exposure to form a cured film.
- the reason why the cured film (patterned cured film) excellent in the rectangularity of the cross-sectional shape can be obtained by using the production method of the present invention is not necessarily clear, but the present inventors are as follows. I am thinking about it. That is, by exposing the curable composition layer exhibiting a predetermined optical density to a specific wavelength under high oxygen concentration, oxygen appropriately inhibits the curing reaction in the surface layer portion, and the curable composition It is believed that this is because curing can proceed in a well-balanced manner in the surface layer portion and the lower layer portion of the object layer.
- the optical density A and the optical density B being within the predetermined range contributes to the improvement of the rectangularity of the cross-sectional shape of the cured film. ing.
- the curable composition layer containing a specific component and exhibiting a predetermined optical density is exposed under a constant oxygen concentration to produce a cured film.
- a curable composition used in the production method of the present invention will be described.
- a curable composition layer is formed using this curable composition, and the method of exposing the said curable composition layer and manufacturing a cured film is demonstrated.
- the use of the cured film obtained using the manufacturing method of this invention is demonstrated.
- the curable composition contains a black pigment.
- the black pigment various known black pigments can be used.
- the black pigment may be an inorganic pigment or an organic pigment.
- Examples of black inorganic pigments include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), cobalt (Co), chromium Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and one or two selected from the group consisting of silver (Ag) Examples thereof include metal oxides, metal nitrides, metal oxynitrides, and the like containing a metal element of a kind or more.
- the inorganic pigment may be subjected to surface modification treatment.
- examples include inorganic particles that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, such as the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
- metal oxides, metal nitrides, and metal oxynitrides may be used as particles in which other atoms are mixed.
- it may be used as a metal nitride-containing particle further containing an atom (preferably an oxygen atom and / or a sulfur atom) selected from periodic table elements 13-17.
- the black pigment also includes carbon black. Specific examples of carbon black include C.I. I. Organic pigments such as C.I. pigment black 1; I. And inorganic pigments such as CI pigment black 7.
- nitrides or oxides of Group 4 metal elements, nitrides or oxynitrides of Group 5 metal elements, or carbon black are preferable, and titanium nitride or oxynitride , Zirconium nitride or oxynitride, vanadium nitride or oxynitride, niobium nitride or oxynitride, or carbon black is more preferable, titanium nitride or oxynitride, zirconium nitride or Oxynitrides, nitrides or oxynitrides of vanadium, or nitrides or oxynitrides of niobium are more preferable, and nitrides or oxynitrides of titanium, or nitrides or oxynitrides of zirconium are particularly preferable.
- the nitride of titanium is titanium nitride
- the nitride of zirconium is zirconium nitride
- the nitride of vanadium is vanadium nitride
- the nitride of niobium is niobium nitride.
- the titanium oxynitride is titanium oxynitride
- the zirconium oxynitride is zirconium oxynitride
- the vanadium oxynitride is vanadium oxynitride
- the niobium oxynitride is oxynitride. It is niobium.
- black pigment a commercially available product "NITRBLACK (night black) UB-1" (manufactured by Mitsubishi Materials Co., Ltd., zirconium nitride powder described in JP-A-2017-222559, and JP-A-4931011)
- black pigments such as particulate low-order zirconium oxide-zirconium nitride composites.
- nitrides or oxynitrides of titanium, nitrides or oxynitrides of zirconium, nitrides or oxynitrides of vanadium, or nitrides or oxynitrides of niobium In the case of using the composition, it is surprising that, after the curable composition is used to form the curable composition layer, the resulting cured film is obtained even if there is a period (eg 1 week) until exposure. Deterioration of the rectangularity of the cross-sectional shape of can be further suppressed.
- the black pigment is preferably as fine as possible.
- the average primary particle size of the black pigment is preferably 0.01 to 0.1 ⁇ m, and more preferably 0.01 to 0.05 ⁇ m.
- the average primary particle size of the black pigment can be measured using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- a transmission electron microscope for example, a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
- Maximum length of particle image obtained using transmission electron microscope (Dmax: maximum length at two points on the contour of particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length When the image is sandwiched, the shortest length connecting two straight lines vertically is measured, and the geometric mean value (Dmax ⁇ DV-max) 1/2 is defined as the particle diameter.
- the particle diameter of 100 particles is measured by this method, and the arithmetic mean value is taken as an average particle diameter to obtain an average primary particle diameter of the black pigment.
- titanium nitride is intended to be TiN, and may contain unavoidable oxygen atoms in production (for example, unintentional oxidation of the surface of TiN particles, etc.).
- titanium nitride means a compound having a diffraction angle 2 ⁇ of 42.5 ° to 42.8 ° of a peak derived from the (200) plane when a CuK ⁇ ray is used as an X-ray source.
- titanium oxynitride means a compound having a diffraction angle 2 ⁇ of a peak derived from the (200) plane in the case of using CuK ⁇ radiation as an X-ray source over 42.8 °.
- the upper limit value of the above-mentioned diffraction angle 2 ⁇ of titanium oxynitride is not particularly limited, but 43.5 ° or less is preferable.
- the titanium nitride for example, include titanium black or the like, more specifically, for example, low-order titanium oxide represented by TiO 2, Ti n O 2n- 1 (1 ⁇ n ⁇ 20), and / or, forms containing TiN x O y titanium oxynitride represented by (0 ⁇ x ⁇ 2.0,0.1 ⁇ y ⁇ 2.0) can be mentioned.
- titanium nitride (the diffraction angle 2 ⁇ is 42.5 ° to 42.8 °) and titanium oxynitride (the diffraction angle 2 ⁇ is more than 42.8 °) are collectively referred to as titanium nitride, The form will be described.
- titanium nitride may be used as particles in which other atoms are further mixed.
- titanium nitride may be used as titanium nitride-containing particles further containing atoms (preferably, sulfur atoms) selected from Periodic Table Group 13-17 elements.
- the metal nitride which is a combination of metal nitride and metal oxynitride may be used as particles in which other atoms are mixed.
- the metal nitride may be used as a metal nitride-containing particle further containing an atom (preferably, a sulfur atom) selected from elements of periodic table 13-17.
- titanium nitride contains titanium oxide TiO 2
- TiO 2 is white and is a factor to reduce the light shielding property of the light shielding film obtained by curing the curable composition, and therefore, it is preferable to be reduced to such an extent that it is not observed as a peak.
- the crystallite size of titanium nitride can be determined from the half width of the peak obtained by the measurement of the X-ray diffraction spectrum described above.
- the crystallite size can be calculated using Scheller's equation.
- a crystallite size which constitutes titanium nitride 50 nm or less is preferable and 20 nm or more is preferable.
- the cured film formed using the curable composition is likely to have a higher transmittance of ultraviolet light (especially i-line (wavelength 365 nm)), and the photosensitivity is higher. A composition is obtained.
- the specific surface area of titanium nitride is not particularly limited, but can be determined by the BET (Brunauer, Emmett, Teller) method.
- the specific surface area of the titanium nitride is preferably 5 ⁇ 100m 2 / g, more preferably 10 ⁇ 60m 2 / g.
- a well-known manufacturing method can be used, for example, a gas phase reaction method is mentioned.
- the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferable from the viewpoint that the mixing of impurities is small, the particle diameter is easy to be uniform, and the productivity is high.
- the thermal plasma method the method of generating thermal plasma is not particularly limited, and direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, etc. may be mentioned, and contamination with impurities from the electrode is small. High frequency plasma is more preferred.
- a specific method for producing a black pigment by a thermal plasma method is not particularly limited.
- a method for producing a titanium nitride a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 2-22110) Gazette), a method of evaporating titanium powder by high-frequency thermal plasma, introducing nitrogen as a carrier gas, nitriding it in the cooling process (JP-A-61-11140), and ammonia gas at the periphery of plasma And the like (Japanese Patent Application Laid-Open No. 63-85007) and the like.
- the method for producing a black pigment is not limited to the above, and the production method is not limited as long as a black pigment having desired physical properties is obtained.
- the black pigment may contain a layer of a silicon-containing compound (hereinafter referred to as "silicon-containing compound”) on its surface. That is, the (acid) nitride of the metal atom may be coated with a silicon-containing compound to form a black pigment.
- the method for coating the (acid) nitride of the metal atom is not particularly limited, and any known method can be used.
- 40 to 70 mass% is preferable with respect to the total solid of a curable composition, as for content of the black pigment in a curable composition, 45 to 70 mass% is more preferable, and 50 to 65 mass% is still more preferable. .
- the black pigment may be used alone or in combination of two or more. When two or more types of black pigments are used in combination, the total content is preferably in the above range.
- the curable composition may contain a colorant other than the black pigment.
- the colorant is not particularly limited, and known colorants can be used.
- various known pigments (colored pigments), dyes (colored dyes) and the like can be used.
- the content of the colorant in the curable composition is not particularly limited, but is preferably 20 to 99% by mass, and more preferably 20 to 80% by mass, with respect to the total solid content of the curable composition.
- the colorant may be used alone or in combination of two or more. When two or more colorants are used in combination, the total content is preferably within the above range.
- colored dyes include, in addition to colored dyes such as R (red), G (green) and B (blue) (chromatic dyes), those described in paragraphs 0027 to 0200 of JP-A 2014-42375. Colorants can also be used. Also, black dyes can be used. As the color pigment, for example, chromatic color pigments (chromatic color pigments) such as R (red), G (green), and B (blue) can also be used.
- the pigment used as a colorant may be an inorganic pigment or an organic pigment.
- the inorganic pigment is not particularly limited, and known inorganic pigments can be used.
- inorganic pigments include zinc flower, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow 1 type, Zinc yellow 2), ultramarine blue, Prussian blue (ferrous iron potassium) zircon gray, praseodymium yellow, chromium titanium yellow, chromium green, peacock, Victoria green, bitumen blue (independent of Prussian blue), vanadium zirconium blue Chrome tin pink, pottery test pink, and salmon pink etc. are mentioned.
- the inorganic pigment may be surface-modified.
- examples thereof include inorganic pigments that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, such as the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
- Pigments having infrared absorptivity can also be used.
- the pigment having infrared absorptivity tungsten compounds, metal borides and the like are preferable.
- tungsten compounds are preferable from the viewpoint of being excellent in the light shielding property at the wavelength in the infrared region.
- a tungsten compound is preferable from the viewpoint of the excellent light absorption wavelength region of the oxime polymerization initiator related to the curing efficiency by exposure and the light transmittance of the visible light region.
- pigments may be used in combination of two or more, and may be used in combination with the dyes described later.
- pigments having black color or infrared ray shielding property such as red, green, yellow, orange, purple, and blue
- the form which mixes a pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a violet pigment or dye, with the pigment having infrared light shielding properties, and more preferable to mix a red pigment with the pigment having infrared light shielding properties.
- an infrared absorber described later may be added.
- color index (CI) pigment yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,18, for example.
- CI color index
- 20 24, 31, 32, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37, 1, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7, 168, 169, 170, 171, 172, 173, 174, 176, 177, 179, 180, 181,
- pigments may be used alone or in combination of two or more.
- dyes examples include, for example, JP-A 64-90403, JP-A 64-91102, JP-A 1-94301, JP-A 6-11614, JP-B 2592 207, and US Pat. No. 4,808,501.
- the disclosed dyes can be used.
- pyrazole azo compounds When classified as a chemical structure, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, or pyrrolopyrazole azomethines Compounds etc. can be used.
- the dye a dye multimer may be used as the dye. Examples of the dye multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097. Moreover, you may use the polymeric dye which has a polymerizability in a molecule
- the colorant may further contain an infrared absorber.
- the infrared absorber means a compound having absorption in a wavelength range of infrared range (preferably, wavelength of 650 to 1300 nm).
- the infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm.
- Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squalilium compounds, naphthalocyanine compounds, quaterrylene A compound, a dithiol metal complex type compound, and a croconium compound etc.
- phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound
- the compounds disclosed in paragraphs [0010] to [0081] of JP-A-2010-111750 may be used, and the contents of this specification are as described herein. Incorporated into the book.
- the cyanine compound can be referred to, for example, "Functional pigment, Shin Ookawara / Ken Matsuoka / Keijiro Kitao / Tsunehiro Hiraiso, Kodansha Scientific", the contents of which are incorporated herein.
- the compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.
- the infrared absorber is preferably a compound soluble in water at 25 ° C. in 1% by mass or more, and more preferably a compound soluble in water at 25 ° C. in 10% by mass or more. The solvent resistance is improved by using such a compound.
- the pyrrolopyrrole compounds can be referred to paragraphs 0049 to 0062 of JP-A-2010-222557, the contents of which are incorporated herein.
- Cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 in WO 2014/088063, 0053 to 0118 in WO 2014/030628, 0028 to 0074 in JP 2014-59550, WO 2012 / JP-A-2015-147, JP-A-2015-176046, JP-A-2014-63144, JP-A-2014-63144, JP-A-2014-52431, JP-A-2014-523, paragraph Paragraphs 0076 to 0124 of 2014-44301, paragraphs 0045 to 0078 of JP 2012-8532, 0027 to 0067 of JP 2015-172102, 0029 ...
- JP 2015-172004 Paragraph 067 Paragraphs 0029 to 0085 of JP-A-2015-40895, Paragraphs 0022 to 0036 of JP-A-2014-126642, Paragraphs 0011 to 0017 of JP-A-2014-148567, JP-A-2015-157893 Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007, paragraphs 0013 to 0047 of JP 2014-80487, and paragraphs 0007 to 0028 of JP 2013-227403 can be referred to. This content is incorporated herein.
- the curable composition contains a polymerizable compound.
- the term "polymerizable compound” is intended to mean a compound which is polymerized under the action of a polymerization initiator described later, and intends a component different from the dispersant and the alkali-soluble resin described later.
- the content of the polymerizable compound in the curable composition is not particularly limited, but it is preferably 5 to 30% by mass with respect to the total solid content of the curable composition.
- the polymerizable compounds may be used alone or in combination of two or more. When two or more types of polymerizable compounds are used in combination, the total content is preferably in the above range.
- the molecular weight of the polymerizable compound is preferably 2000 or less.
- the polymerizable compound is preferably a compound containing one or more groups containing an ethylenic unsaturated bond (hereinafter, also simply referred to as "ethylenically unsaturated group"), more preferably a compound containing two or more, and three or more.
- the compound to contain is further more preferable, and the compound which contains 5 or more is especially preferable.
- the upper limit is, for example, 15 or less.
- ethylenically unsaturated group a vinyl group, a (meth) allyl group, and a (meth) acryloyl group etc. are mentioned, for example.
- polymerizable compound for example, compounds described in paragraph 0050 of JP-A 2008-260927 and paragraph 0040 of JP-A 2015-68893 can be used, and the above contents are incorporated in the present specification.
- the polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof, and multimers thereof.
- the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
- the polymerizable compound is also preferably a compound having one or more ethylenically unsaturated groups and having a boiling point of 100 ° C. or more under normal pressure.
- the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, the contents of which are incorporated herein.
- the polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), Pentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E; Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol residue or propylene glycol residue (for example, SR454, SR499 commercially available from Sartmar) are preferable.
- NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
- KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd.
- the aspect of a preferable polymeric compound is shown below.
- the polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
- an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a nonaromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to produce an acid.
- a polymerizable compound having a group is more preferable, and in this ester, one in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is more preferable.
- Examples of commercially available products include ALONIX TO-2349, M-305, M-510, and M-520 manufactured by Toa Gosei Co., Ltd.
- the acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mg KOH / g, and more preferably 5 to 30 mg KOH / g.
- the acid value of the polymerizable compound is 0.1 mg KOH / g or more, the developing dissolution property is good, and when it is 40 mg KOH / g or less, it is advantageous in terms of production and / or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
- a compound having a caprolactone structure is also a preferred embodiment.
- the compound having a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentacene.
- ⁇ -caprolactone modified polyfunctional (meth) obtained by esterifying a polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol or trimethylolmelamine with (meth) acrylic acid and ⁇ -caprolactone ) Acrylates.
- a polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol or trimethylolmelamine
- (meth) acrylic acid and ⁇ -caprolactone ) Acrylates Among them, compounds having a caprolactone structure represented by the following formula (Z-1) are preferable.
- 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, and “*” represents a bond.
- a compound represented by the following formula (Z-4) or (Z-5) can also be used.
- E are each independently, - ((CH 2) y CH 2 O) -, or ((CH 2) y CH ( CH 3) O) - a
- y each independently represents an integer of 0 to 10
- each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
- the total of (meth) acryloyl groups is three or four
- m each independently represents an integer of 0 to 10
- the total of each m is an integer of 0 to 40.
- the total of (meth) acryloyl groups is five or six
- n independently represents an integer of 0 to 10
- the sum of each n is an integer of 0 to 60.
- 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 still more preferably an integer of 6 to 12.
- the compounds represented by Formula (Z-4) or Formula (Z-5) may be used alone or in combination of two or more.
- a compound in which all six X's are an acryloyl group in the formula (Z-5) and A preferred embodiment is a mixture with a compound in which at least one hydrogen atom is present. With such a configuration, developability can be further improved.
- the total content of the compound represented by Formula (Z-4) or Formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
- pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
- the polymerizable compound may contain a cardo skeleton.
- the polymerizable compound containing a cardo skeleton is preferably a polymerizable compound containing a 9,9-bisarylfluorene skeleton.
- Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, On Coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
- the polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core.
- NK ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.
- the content of the ethylenically unsaturated group in the polymerizable compound is 5.0 mmol / It is preferably g or more.
- the upper limit is not particularly limited, it is generally 20.0 mmol / g or less.
- the mass ratio of each polymerizable compound in all the polymerizable compounds and the respective polymerizability It is preferable that the sum of the products of the compounds and the double bond equivalents be in the above range.
- the curable composition preferably contains a resin.
- the resin include dispersants and alkali-soluble resins.
- the content of the resin in the curable composition is not particularly limited, but is preferably 3 to 60% by mass, and more preferably 5 to 40% by mass, with respect to the total solid content of the curable composition.
- the resins may be used alone or in combination of two or more. When two or more resins are used in combination, the total content is preferably in the above range.
- the molecular weight of the resin is greater than 2000. When the molecular weight of the resin is polydispersed, the weight average molecular weight is more than 2000.
- the curable composition preferably contains a dispersant.
- the dispersant is intended to be a compound different from the alkali-soluble resin described later.
- the content of the dispersant in the curable composition is not particularly limited, but is preferably 2 to 40% by mass, and more preferably 5 to 30% by mass, relative to the total solid content of the curable composition.
- the dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably in the above range.
- a well-known dispersing agent can be used selecting it suitably, for example. Among these, high molecular compounds are preferable.
- the dispersant polymer dispersants [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, and pigment derivatives.
- the polymer compounds can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.
- Polymer compound The polymer compound is adsorbed on the surface of a material to be dispersed, such as a black pigment and other pigments optionally used in combination (hereinafter, the black pigment and other pigments are collectively referred to simply as “pigments”) , Acts to prevent reaggregation of the material to be dispersed. Therefore, terminal modified polymers, grafted polymers (containing polymer chains), or block polymers containing anchor sites on the pigment surface are preferred.
- the polymer compound may contain a curable group.
- the curable group include ethylenically unsaturated groups (eg, (meth) acryloyl group, vinyl group, and styryl group), and cyclic ether groups (eg, epoxy group, oxetanyl group etc.), etc. But not limited to. Among them, an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by a radical reaction.
- the ethylenically unsaturated group is more preferably a (meth) acryloyl group.
- the resin containing a curable group preferably contains at least one selected from the group consisting of a polyester structure and a polyether structure.
- the main chain may contain a polyester structure and / or a polyether structure, and as described later, when the resin contains a structural unit containing a graft chain, the above polymer
- the chain may contain a polyester structure and / or a polyether structure.
- the said polymeric chain contains a polyester structure.
- the polymer compound preferably contains a structural unit containing a graft chain.
- structural unit is synonymous with “repeating unit”.
- the polymer compound containing a structural unit containing such a graft chain has an affinity to a solvent by the graft chain, and thus the dispersibility of the pigment etc. and the dispersion stability after aging (stability over time) Excellent. Further, due to the presence of the graft chain, the polymer compound containing a structural unit containing a graft chain has an affinity to a polymerizable compound or other usable resin and the like. As a result, alkaline development is less likely to produce a residue.
- the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and more than 40 atoms excluding hydrogen atoms. More preferably, it is 60 to 500.
- the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.
- the graft chain preferably contains a polymer structure, and as such a polymer structure, for example, poly (meth) acrylate structure (eg, poly (meth) acrylic structure), polyester structure, polyurethane structure, polyurea structure, polyamide And polyether structures and the like.
- the graft chain is selected from the group consisting of a polyester structure, a polyether structure, and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent, thereby enhancing the dispersibility of the pigment etc. It is preferable that it is a graft chain containing at least one, more preferably a graft chain containing at least one of a polyester structure and a polyether structure.
- the macromonomer containing such a graft chain (a monomer having a polymer structure and being bonded to the main chain of the copolymer to constitute the graft chain) is not particularly limited, but a reactive double bondable group may be used.
- the macromonomer contained can be used suitably.
- AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (Trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, produced by Toa Gosei Co., Ltd.), AS-6 (trade name, produced by Toa Gosei Co., Ltd.), AN-6 (trade name, produced by Toa Gosei Co., Ltd.), AW -6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, produced by Toa Gosei Co., Ltd.), AY-707 (trade name, produced by Toa Gosei Co., Ltd.), AY-714 (trade name, produced by Toa Gosei Co., Ltd.
- AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, Toa Gosei Co., Ltd.), AK-32 (trade name, Toa Gosei Co., Ltd.), Blenmer PP-100 (trade name, NOF Corporation) Brenmer PP-500 (trade name, manufactured by NOF Corporation), Brenmer PP-800 Product name, manufactured by NOF Corporation, BLEMMER PP-1000 (trade name, manufactured by NOF Corporation), BLEMMER 55-PET-800 (trade name, manufactured by NOF Corporation), BLEMMER PME-4000 (trade name, manufactured by NOF Corporation) Blemmer PSE-400 (trade name, manufactured by NOF Corporation), Blemmer PSE-1300 (trade name, manufactured by NOF Corporation), or Blemmer 43PAPE-600B (trade name, manufactured by NOF Corporation), etc.
- AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, Toa Gosei Co., Ltd.), AB-6 (trade name, produced by Toa Gosei Co., Ltd.), AS-6 (trade name, Preferably, Toa Gosei Co., Ltd., AN-6 (trade name, Toa Gosei Co., Ltd.), or Blenmer PME-4000 (trade name, NOF Corporation).
- the dispersant preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate and cyclic or chain polyester, and is preferably polymethyl acrylate or polymethacrylic acid. It is more preferable to contain at least one structure selected from the group consisting of methyl and linear polyesters, and a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure More preferably, it contains at least one structure selected from the group consisting of
- the dispersing agent may be a dispersing agent containing the above structure alone in one dispersing agent, or may be a dispersing agent containing a plurality of these structures in one dispersing agent.
- the polycaprolactone structure refers to a structure containing a ring-opened structure of ⁇ -caprolactone as a repeating unit.
- the polyvalerolactone structure refers to a structure containing a ring-opened structure of ⁇ -valerolactone as a repeating unit.
- the dispersing agent containing a polycaprolactone structure the dispersing agent whose j and k in a following formula (1) and a following formula (2) are 5 is mentioned.
- the dispersing agent containing a polyvalerolactone structure the dispersing agent whose j and k in following formula (1) and following formula (2) are 4 is mentioned.
- dispersants containing polymethyl acrylate structure, X 5 in formula (4) is a hydrogen atom
- R 4 can be cited dispersants are methyl groups.
- the polymer compound preferably contains, as a structural unit containing a graft chain, a structural unit represented by any one of the following formulas (1) to (4), and the following formula It is more preferable to contain the structural unit represented by either of (1A), following formula (2A), following formula (3A), following formula (3B), and following (4).
- W 1 , W 2 , W 3 and W 4 each independently represent an oxygen atom or NH.
- W 1 , W 2 , W 3 and W 4 are preferably oxygen atoms.
- X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group.
- Each of X 1 , X 2 , X 3 , X 4 and X 5 independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms), from the viewpoint of the restriction on synthesis
- Y 1 , Y 2 , Y 3 and Y 4 each independently represent a divalent linking group, and the linking group is not particularly restricted in structure.
- Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 and Y 4 include the following linking groups (Y-1) to (Y-21) and the like.
- a and B respectively indicate bonding sites to the left end group and the right end group in the formulas (1) to (4).
- (Y-2) or (Y-13) is more preferable in terms of easiness of synthesis.
- Z 1 , Z 2 , Z 3 and Z 4 each independently represent a monovalent organic group.
- the structure of the organic group is not particularly limited, specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group Etc.
- a group having a steric repulsion effect is particularly preferable from the viewpoint of improving the dispersibility, and each of them independently has carbon number
- An alkyl group or alkoxy group of 5 to 24 is more preferable, and among them, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy having 5 to 24 carbon atoms is particularly independently of each other. Groups are more preferred.
- the alkyl group contained in the alkoxy group may be linear, branched or cyclic.
- n, m, p and q are each independently an integer of 1 to 500.
- j and k each independently represent an integer of 2 to 8.
- J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5 from the viewpoint of the temporal stability and developability of the composition.
- n and m are preferably integers of 10 or more, and more preferably 20 or more.
- the sum of the repeating number of the polycaprolactone structure and the repeating number of the polyvalerolactone is preferably an integer of 10 or more, 20 or more An integer is more preferred.
- R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, plural R 3 s may be the same as or different from each other.
- R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. As R 4 , a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group is preferable, and a hydrogen atom or an alkyl group is more preferable.
- the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
- the linear alkyl group having 1 to 20 carbon atoms is more preferable, and the linear alkyl group having 1 to 6 carbon atoms is further preferable.
- a plurality of X 5 and R 4 in the graft copolymer may be the same or different.
- the polymer compound can contain a graft chain-containing structural unit in which two or more kinds of structures are different. That is, structural units represented by formulas (1) to (4) having mutually different structures may be contained in the molecule of the polymer compound, and n, m, p in formulas (1) to (4) And q each represents an integer of 2 or more, in the formulas (1) and (2), j and k may contain structures different from each other in the side chain, and formulas (3) and (4) In the above, R 3 , R 4 and X 5 which are present in plural in the molecule may be the same as or different from each other.
- the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of the temporal stability of the composition and the developability.
- a structural unit represented by Formula (2) it is more preferable that it is a structural unit represented by following formula (2A) from a time-lapse stability of a composition, and a developability.
- a structural unit represented by Formula (3) it is more preferable that it is a structural unit represented by a following formula (3A) or Formula (3B) from a time-lapse stability of a composition, and a developability viewpoint. .
- the polymer compound more preferably contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
- structural units containing a graft chain are 2 to 90% by mass in terms of mass relative to the total mass of the polymer compound Is preferably contained in the range of 5 to 30% by mass, and more preferably in the range of 5 to 30% by mass.
- the structural unit containing a graft chain is contained in this range, the dispersibility of the pigment is high, and the developability at the time of forming a cured film is good.
- the polymer compound preferably contains a hydrophobic structural unit which is different from the structural unit containing a graft chain (that is, not corresponding to a structural unit containing a graft chain).
- the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).
- the hydrophobic structural unit is preferably a (corresponding) structural unit derived from a compound (monomer) having a C log P value of 1.2 or more, and is a structural unit derived from a compound having a C log P value of 1.2 to 8. Is more preferable. Thereby, the effects of the present invention can be more reliably exhibited.
- ClogP values are from Daylight Chemical Information System, Inc. Is a value calculated by the program "CLOGP” available from This program provides the value of "computed logP” calculated by the fragment approach of Hansch, Leo (see the following document). The fragment approach is based on the chemical structure of the compound, dividing the chemical structure into substructures (fragments) and estimating the logP value of the compound by summing the logP contributions assigned to the fragment. The details are described in the following documents.
- the ClogP value calculated by the program CLOGP v4.82 is used herein. A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P .; G. Sammnens, J.J. B. Taylor and C. A.
- log P means the common logarithm of partition coefficient P (Partition Coefficient), and it quantitatively determines how an organic compound is distributed in the equilibrium of oil (generally 1-octanol) and water. Is a physical property value represented as a numerical value, and is represented by the following equation.
- logP log (Coil / Cwater)
- Coil represents the molar concentration of the compound in the oil phase
- Cwater represents the molar concentration of the compound in the aqueous phase.
- the polymer compound preferably contains, as a hydrophobic structural unit, one or more structural units selected from structural units derived from monomers represented by the following formulas (i) to (iii).
- R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom etc.), or a carbon number Represents an alkyl group of 1 to 6 (eg, a methyl group, an ethyl group, a propyl group, etc.).
- R 1 , R 2 and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
- R 2 and R 3 are more preferably hydrogen atoms.
- X represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.
- L is a single bond or a divalent linking group.
- a divalent aliphatic group for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group
- a divalent aromatic group for example, an arylene group) , substituted arylene group
- a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, wherein R 31 And examples thereof include aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), and combinations thereof.
- the divalent aliphatic group may have a cyclic structure or a branched structure.
- the carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
- the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
- the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.
- the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
- the divalent heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring.
- the heterocycle may be fused to another heterocycle, an aliphatic ring or an aromatic ring.
- L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
- the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
- L may contain a polyoxyalkylene structure containing an oxyalkylene structure repeated two or more times.
- a polyoxyalkylene structure a polyoxyethylene structure or a polyoxypropylene structure is preferable.
- the polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.
- an aliphatic group for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group
- an aromatic group for example, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group
- heterocyclic groups or combinations thereof an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, wherein R 31 is an aliphatic group, an aromatic A group or a heterocyclic group) or a carbonyl group (-CO-) may be included.
- the aliphatic group may have a cyclic structure or a branched structure.
- the carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
- the aliphatic group further includes a ring-aggregated hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the ring-aggregated hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and And-include cyclohexylphenyl and the like.
- bridged cyclic hydrocarbon ring for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) 2 Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredane, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane rings And tetracyclo [4.4.0.1 2,5 .
- [1 7,10 ] dodecane and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring and the like can be mentioned.
- a fused cyclic hydrocarbon ring for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and Also included are fused rings in which a plurality of 5- to 8-membered cycloalkane rings such as perhydrophenalene rings are fused.
- the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
- the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, the aliphatic group does not have an acid group as a substituent.
- the carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups and heterocyclic groups. However, the aromatic group does not have an acid group as a substituent.
- the heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring.
- the heterocycle may be fused to another heterocycle, an aliphatic ring or an aromatic ring.
- the heterocyclic group does not have an acid group as a substituent.
- R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), and an alkyl group having 1 to 6 carbon atoms (Eg, methyl group, ethyl group, propyl group etc.), Z or LZ.
- L and Z are as defined above.
- R 4 , R 5 and R 6 a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.
- R ⁇ 1 >, R ⁇ 2 > and R ⁇ 3 > are a hydrogen atom or a methyl group
- L contains a single bond or an alkylene group or an oxyalkylene structure.
- X is an oxygen atom or an imino group
- Z is an aliphatic group, a heterocyclic group or an aromatic group
- an R 1 is hydrogen atom or a methyl group
- L is an alkylene group
- Z is an aliphatic group, a heterocyclic group, or an aromatic Compounds which are groups are preferred.
- R 4, R 5, and, R 6 is a hydrogen atom or a methyl group
- Z is an aliphatic group, a heterocyclic group, or an aromatic Compounds which are groups are preferred.
- Examples of representative compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes and the like.
- radically polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes and the like.
- the compound as described in stage 0089-0093 of Unexamined-Japanese-Patent No. 2013-249417 can be referred, and these contents are described in this specification. Incorporated into
- the hydrophobic structural unit is preferably contained in a range of 10 to 90%, and more preferably in a range of 20 to 80%, based on the total mass of the polymer compound, in terms of mass. Sufficient pattern formation is obtained in the above range of content.
- the polymer compound can introduce a functional group capable of forming an interaction with the pigment etc.
- the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with a pigment or the like.
- the functional group capable of forming an interaction with the pigment and the like include an acid group, a basic group, a coordinating group, and a functional group having reactivity.
- the polymer compound contains an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit containing an acid group, a structural unit containing a basic group, It is preferable to contain a structural unit containing a reactive group or a structural unit having reactivity.
- the polymer compound when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as the dispersant contributing to the dispersion of the pigment etc. contains alkali solubility by the composition described above. A composition containing such a polymer compound is excellent in the light shielding property of the exposed area, and the alkali developability of the unexposed area is improved.
- the polymer compound when the polymer compound contains a structural unit containing an acid group, the polymer compound tends to be compatible with the solvent, and the coatability tends to be improved.
- the acid group in the structural unit containing the acid group easily interacts with the pigment and the like, and the polymer compound stably disperses the pigment and the like, and the viscosity of the polymer compound in which the pigment and the like are dispersed decreases. It is presumed that the polymer compound itself is also easily dispersed stably.
- the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the above-mentioned structural unit containing a graft chain, or may be a different structural unit, but an alkali as an acid group
- the structural unit containing a soluble group is a structural unit different from the above-mentioned hydrophobic structural unit (that is, it does not correspond to the above-mentioned hydrophobic structural unit).
- Examples of the acid group that is a functional group capable of forming an interaction with a pigment and the like include, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. And at least one of phosphoric acid groups is preferable, and a carboxylic acid group is more preferable.
- the carboxylic acid group has good adsorptivity to pigments and the like, and has high dispersibility. That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
- the polymer compound may have one or more structural units containing an acid group.
- the polymer compound may or may not contain a structural unit containing an acid group, but when it is contained, the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, the content is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass from the viewpoint of suppressing damage to the image strength due to alkaline development.
- a basic group which is a functional group capable of forming an interaction with a pigment etc. for example, a primary amino group, a secondary amino group, a tertiary amino group, a heterocycle containing N atom, and an amide
- the preferred basic group is a tertiary amino group in that it has a group etc. and is preferable in that it has good adsorptivity to pigments etc and high dispersibility.
- the polymer compound can contain one or more of these basic groups.
- the polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total of the polymer compound in terms of mass. The content is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass from the viewpoint of development inhibition inhibition.
- a coordinating group which is a functional group capable of forming an interaction with a pigment or the like, and as a functional group having reactivity, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acidification Things etc.
- the preferred functional group is an acetylacetoxy group in that it has good adsorptivity to pigments and the like and high dispersibility of pigments and the like.
- the polymer compound may have one or more of these groups.
- the polymer compound may or may not contain a structural unit containing a coordinating group, or a structural unit containing a functional group having reactivity, but when it is contained, the content of these structural units In terms of mass, 10 to 80% by mass is preferable based on the total mass of the polymer compound, and 20 to 60% by mass is more preferable from the viewpoint of development inhibition inhibition.
- the polymer compound may contain a functional group capable of forming an interaction with the various pigments described above, There is no particular limitation on how these functional groups are introduced, but the polymer compound is selected from structural units derived from monomers represented by the following formulas (iv) to (vi). It is preferred to contain more than species of structural units.
- R 11 , R 12 and R 13 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a carbon number of 1 to 6 represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
- R 11 , R 12 and R 13 each independently represent preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently represents a hydrogen atom or methyl More preferred is a group.
- each of R 12 and R 13 is more preferably a hydrogen atom.
- X 1 in the formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.
- Y in Formula (v) represents a methine group or a nitrogen atom.
- L 1 in formulas (iv) to (v) represents a single bond or a divalent linking group.
- the definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in formula (i) described above.
- L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
- the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
- L 1 may also include a polyoxyalkylene structure containing an oxyalkylene structure repeated two or more times.
- a polyoxyalkylene structure a polyoxyethylene structure or a polyoxypropylene structure is preferable.
- the polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.
- Z 1 represents a functional group capable of forming an interaction with a pigment or the like in addition to the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, More preferred is an acid group.
- R 14 , R 15 and R 16 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like), or an alkyl group having 1 to 6 carbon atoms for example, a methyl group, an ethyl group, a propyl group, etc.), - Z 1, or an L 1 -Z 1.
- L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples.
- R 1 As 4 , R 15 and R 16 each independently, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.
- R 11 , R 12 and R 13 each independently represent a hydrogen atom or a methyl group, and L 1 is a divalent having an alkylene group or an oxyalkylene structure.
- Compounds in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group are preferable.
- R 11 is a hydrogen atom or a methyl group
- L 1 is an alkylene group
- Z 1 is a carboxylic acid group
- Y is a methine group Compounds which are preferred.
- R 14 , R 15 and R 16 each independently represent a hydrogen atom or a methyl group, and L 1 represents a single bond or an alkylene group, and Z Compounds in which 1 is a carboxylic acid group are preferred.
- monomers represented by the formulas (iv) to (vi) are shown.
- monomers include methacrylic acid, crotonic acid, isocrotonic acid, and the reaction of succinic anhydride with a compound having an addition-polymerizable double bond and hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate).
- the content of the structural unit containing a functional group capable of forming an interaction with a pigment or the like is the total mass of the polymer compound from the viewpoint of the interaction with the pigment or the like, the temporal stability, and the permeability to the developer.
- 0.05 to 90% by mass is preferable, 1.0 to 80% by mass is more preferable, and 10 to 70% by mass is more preferable.
- the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a pigment as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength.
- other structural units having various functions eg, structural units containing a functional group having an affinity for a solvent described later, etc.
- Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles and the like.
- the polymer compound one or more of these other structural units can be used, and the content thereof is preferably 0 to 80% by mass with respect to the total mass of the polymer compound in terms of mass, 60 mass% or less is more preferable. Sufficient pattern formability is maintained in the above range of content.
- the acid value of the polymer compound is preferably in the range of 0 mg to 250 mg KOH / g, more preferably in the range of 10 to 200 mg KOH / g, and still more preferably in the range of 20 to 120 mg KOH / g.
- the acid value of the polymer compound is 160 mg KOH / g or less, pattern peeling during development when forming a cured film can be more effectively suppressed.
- the acid value of the polymer compound is 10 mg KOH / g or more, the alkali developability becomes better.
- the acid value of the polymer compound is 20 mg KOH / g or more, sedimentation of the pigment and the like can be further suppressed, the number of coarse particles can be further reduced, and the temporal stability of the composition can be further improved.
- the acid value can be calculated, for example, from the average content of acid groups in a compound.
- resin which has a desired acid value can be obtained by changing content of the structural unit containing the acidic radical which is a structural component of resin.
- the weight average molecular weight of the polymer compound is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, and still more preferably 6,000 to 100,000. Particular preference is given to 10,000 to 50,000.
- the polymer compound can be synthesized based on a known method.
- polymer compound examples include “DA-7301” manufactured by Kushimoto Chemical Co., Ltd., “Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (acid group-containing copolymer” manufactured by BYK Chemie ), 111 (phosphate based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer), “BYK-P104, P105 (high molecular weight non-polymer)” Saturated polycarboxylic acid) ", EFKA 4047, 4050 to 4010 to 4165 (polyurethane based), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (manufactured by EFKA) High molecular weight polycarboxylate), 6220 (fatty acid polyaceta) Ter), 6745
- NIKKOL T106 polyoxyethylene sorbitan Monooleate
- MYS-IEX polyoxyethylene monostearate
- Hinoac T-8000 E etc., manufactured by Kawaken Fine Chemicals Co., Ltd., Shin-Etsu Chemical Co., Ltd., organosiloxane polymer, KP-341, Yusho "W 001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene Nonionic surfactants such as glycol distearate, sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", "Morita Sangyo” "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100"
- amphoteric resin containing an acid group and a basic group.
- the amphoteric resin is preferably a resin having an acid value of 5 mg KOH / g or more and an amine value of 5 mg KOH / g or more.
- DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2001, DISPERBYK-2010, manufactured by BIC Chemie Examples include DISPERBYK-2012, DISPERBYK-2025, BYK-9076, and Ajisame Fine Techno Co., Ltd. Ajisper PB 821, Ajisper PB 822, and Ajisper PB 881 and the like.
- One of these polymer compounds may be used alone, or two or more thereof may be used in combination.
- graft copolymers of paragraphs 0037 to 0115 of JP 2010-106268 A (columns 0075 to 0133 of corresponding US 2011/0124824) can be used.
- the contents of are incorporated herein by reference.
- it contains the side chain structure which the acidic group of Unexamined-Japanese-Patent No.2011-153283, Paragraph 0028-0084 (Correspondence US2011 / 02729759 corresponding column 0075-0133 column) joins via a coupling group besides the above.
- Polymer compounds containing the following components can be used, the contents of which can be incorporated and incorporated herein.
- the curable composition preferably contains an alkali soluble resin.
- an alkali-soluble resin is intended to be a resin containing a group that promotes alkali solubility (alkali-soluble group), and is intended to be a resin different from the dispersant described above.
- the content of the alkali-soluble resin in the curable composition is not particularly limited, but is preferably 1 to 30% by mass, and more preferably 1 to 15% by mass with respect to the total solid content of the curable composition.
- the alkali-soluble resin may be used alone or in combination of two or more. When using 2 or more types of alkali-soluble resin together, it is preferable that total content is in the said range.
- alkali-soluble resin examples include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, (meth) Acrylic / (meth) acrylamide copolymer resin, an epoxy resin, and a polyimide resin etc. are mentioned.
- alkali-soluble resin examples include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.
- the unsaturated carboxylic acid is not particularly limited, but monocarboxylic acids such as (meth) acrylic acid, crotonic acid and vinyl acetic acid; itaconic acid, maleic acid and dicarboxylic acids such as fumaric acid or acid anhydride thereof And monohydric carboxylic acid monoesters such as phthalic acid mono (2- (meth) acryloyloxyethyl); and the like.
- Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate and the like. Further, the compounds described in paragraph 0027 of JP-A-2010-97210 and in paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, and the above contents are incorporated in the present specification.
- an ethylenically unsaturated compound which can be copolymerized Comprising: You may use combining the compound containing an ethylenically unsaturated group in a side chain.
- a (meth) acrylic acid group is preferable.
- the acrylic resin containing an ethylenically unsaturated group in the side chain is, for example, an addition reaction of an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group of an acrylic resin containing a carboxylic acid group. You can get it.
- an alkali-soluble resin containing a curable group is also preferable.
- the curable group which the above-mentioned high molecular compound may contain is mentioned similarly, A preferable range is also the same.
- an alkali-soluble resin containing a curable group an alkali-soluble resin having a curable group in a side chain is preferable.
- an alkali-soluble resin containing a curable group Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (containing COOH containing polyurethane acrylic oligomer.
- Diamond Shamrock Co., Ltd. Biscoat R-264, KS resist 106 All of them are Osaka Organic Chemical Industry Co., Ltd., Cyclomer P series (for example, ACA 230 AA), Plaxcel CF 200 series (all of which are manufactured by Daicel), Ebecryl 3800 (manufactured by Daicel Ornex), And the like.
- alkali-soluble resin for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59- Radical polymers containing a carboxylic acid group in the side chain as described in JP-A-59-3836 and JP-A-59-71048; European Patent No. 993966, European Patent No. 1204000, and JP-A No. 2001-318463 Acetal-modified polyvinyl alcohol-based binder resin containing an alkali-soluble group described in each publication such as U.S.
- alkali-soluble resin for example, the compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can also be used, and the above contents are incorporated herein.
- a polyimide precursor can also be used as an alkali soluble resin.
- the polyimide precursor intends a resin obtained by the addition polymerization reaction of a compound containing an acid anhydride group and a diamine compound at 40 to 100 ° C.
- resin containing the repeating unit represented by Formula (1) is mentioned, for example.
- the structure of the polyimide precursor include an amic acid structure represented by the following formula (2), a following formula (3) in which the amic acid structure is partially imide ring-closed, and a following formula (4) in which all imide ring closure
- the polyimide precursor containing the imide structure shown by these) is mentioned.
- a polyimide precursor having an amic acid structure may be referred to as a polyamic acid.
- R 1 represents a tetravalent organic group having 2 to 22 carbon atoms
- R 2 represents a divalent organic group having 1 to 22 carbon atoms
- n is 1 or 2 Represents
- polyimide precursor for example, compounds described in paragraphs 0011 to 0031 of JP 2008-106250 A, compounds described in paragraphs 0022 to 0039 of JP 2016-122101 A, and JP
- the compounds described in paragraphs [0061] to [0092] of 2016-68401, and the like are included, and the above contents are incorporated in the present specification.
- the alkali-soluble resin contains at least one selected from the group consisting of a polyimide resin and a polyimide precursor in that the pattern shape of the cured film in a pattern obtained by using the curable composition is more excellent. Is also preferred.
- the polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include a resin described in paragraph 0050 of JP-A-2014-137523, a resin described in paragraph 0058 of JP-A-2015-187676, and a resin described in JP-A-2014-106326. The resins described in the paragraphs [0012] to [0013] and the like are mentioned, and the above contents are incorporated in the present specification.
- the curable composition used for the manufacturing method of this invention contains resin containing an ethylenically unsaturated group from the point which the rectangularity of the cross-sectional shape of the cured film obtained is more excellent.
- the resin containing an ethylenically unsaturated group may be a dispersant or an alkali soluble resin.
- resin other than a dispersing agent or alkali-soluble resin may be sufficient.
- the lower limit of the content of the resin having an ethylenically unsaturated group in the curable composition is preferably 40% by mass or more, more preferably 45% by mass or more based on the mass of the entire resin contained in the curable composition.
- resin containing an ethylenically unsaturated group in the curable composition is preferably 100% by mass or less based on the total mass of the resin contained in the curable composition.
- resin containing an ethylenically unsaturated group means resin which contains one or more ethylenically unsaturated groups in 1 molecule.
- the content of the resin containing an ethylenically unsaturated group may be calculated from the amount of raw materials charged.
- the content of the ethylenically unsaturated group is not particularly limited, but is preferably 0.001 to 5.00 mmol / g, more preferably 0.10 to 3.00 mmol / g, and the like. More preferred is 26 to 2.50 mmol / g.
- the content of the ethylenically unsaturated group is in the range of 0.10 to 3.00 mmol / g, the rectangularity of the cross-sectional shape of a cured film obtained using the curable composition is more excellent.
- the said resin total mass intends the total mass of resin contained in a curable composition, for example, curable composition of resin containing an ethylenically unsaturated group, and resin which does not contain an ethylenically unsaturated group
- the content of the above-mentioned ethylenically unsaturated group represents the content of the ethylenically unsaturated group in the resin containing the ethylenically unsaturated group with respect to the total mass of the resin.
- resin is a component which is melt
- combining resin containing an ethylenically unsaturated group it can replace with measurement by calculating from the preparation amount of a raw material.
- require C C number of.
- the ethylenically unsaturated group content of the resin when the ethylenically unsaturated group is a (meth) acryloyl group, it is measured by the following method. First, solid components (black pigment and the like) in the curable composition are precipitated by centrifugation, and the remaining liquid component is separated. Further, from the obtained liquid component, a component having a weight average molecular weight of more than 2000 is separated by a GPC method, and this is used as a resin to be measured. Next, 0.25 mg of a resin to be measured is dissolved in 50 mL of THF (tetrahydrofuran), and 15 mL of methanol is further added to prepare a solution.
- THF tetrahydrofuran
- the ethylenically unsaturated group is a combination of a (meth) acryloyl group other than (meth) acryloyl group and a group other than a (meth) acryloyl group and a (meth) acryloyl group
- a method of measuring the bromination of the resin to be measured that has been separated by the above-mentioned method may be mentioned.
- the bromine number is measured in accordance with JIS K2605: 1996.
- bromine was added to the resin 100g of measurements obtained in bromine number (Br 2) grams of (gBr 2 / 100g), the resin per 1g It is a value converted to the number of moles of added bromine (Br 2 ).
- the curable composition preferably contains a polymerization initiator.
- the polymerization initiator is not particularly limited, and known polymerization initiators can be used.
- a polymerization initiator a photoinitiator, a thermal-polymerization initiator etc. are mentioned, for example, A photoinitiator is preferable.
- a photoinitiator is preferable.
- a polymerization initiator what is called a radical polymerization initiator is preferable.
- the content of the polymerization initiator in the curable composition is not particularly limited, but it is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition.
- the polymerization initiator may be used alone or in combination of two or more. When two or more polymerization initiators are used in combination, the total content is preferably in the above range.
- thermal polymerization initiator As a thermal polymerization initiator, for example, 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, and dimethyl- (2,2 ′)-azobis (2) Azo compounds such as -methyl propionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
- AIBN 2,2′-azobisisobutyronitrile
- 3-carboxypropionitrile 3-carboxypropionitrile
- azobismaleonitrile azobismaleonitrile
- dimethyl- (2,2 ′)-azobis (2) Azo compounds such as -methyl propionate) [V-601]
- organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
- organic peroxides such as benzoyl peroxide, lauroyl per
- the curable composition preferably contains a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited as long as polymerization of the polymerizable compound can be initiated, and known photopolymerization initiators can be used.
- a photopolymerization initiator having photosensitivity to an ultraviolet light region to a visible light region is preferable.
- it may be an activator that produces an action with photoexcited sensitizers to generate active radicals, and may be an initiator that initiates cationic polymerization depending on the type of the polymerizable compound.
- the photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least 50 in the range of 300 to 800 nm (more preferably 330 to 500 nm).
- the content of the photopolymerization initiator in the curable composition is not particularly limited, but it is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition.
- the photopolymerization initiator may be used singly or in combination of two or more. When using 2 or more types of photoinitiators together, it is preferable that total content is in the said range.
- the photopolymerization initiator for example, a halogenated hydrocarbon derivative (for example, one containing a triazine skeleton, one containing an oxadiazole skeleton, etc.), an acylphosphine compound such as an acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.
- paragraphs 0265 to 0268 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.
- the photopolymerization initiator for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.
- the hydroxyacetophenone compound for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Corporation) can be used.
- the aminoacetophenone compound for example, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade name: all manufactured by BASF Corp.) can be used.
- aminoacetophenone compound a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long wave light source having a wavelength of 365 nm or a wavelength of 405 nm can also be used.
- an acyl phosphine compound IRGACURE-819 which is a commercial item, or IRGACURE-TPO (trade name: all manufactured by BASF Corporation) can be used.
- an oxime ester-type polymerization initiator (oxime compound) is more preferable.
- oxime compounds are preferable because they have high sensitivity and high polymerization efficiency, and the black pigment content in the curable composition is easily designed to be high.
- compounds described in JP-A-2001-233842 compounds described in JP-A-2000-80068, or compounds described in JP-A-2006-342166 can be used.
- Examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentan-3-one.
- 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy Examples include carbonyloxyimino-1-phenylpropan-1-one and the like. Also, J.J. C. S. Perkin II (1979) pp. 1653-1660), J.F. C. S.
- IRGACURE-OXE01 manufactured by BASF
- IRGACURE-OXE02 manufactured by BASF
- IRGACURE-OXE03 manufactured by BASF
- IRGACURE-OXE04 manufactured by BASF
- TR-PBG-304 made by Changzhou Strong Electronic New Materials Co., Ltd.
- Adeka Akuls NCI-831 Adeka Ark's NCI-930
- N-1919 carboxylic acid
- An initiator made by ADEKA
- 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. Compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced at a dye site; a ketoxime compound described in WO 2009-131189; and a triazine skeleton and an oxime skeleton
- US Pat. No. 7,556,910 contained in the same molecule; the compound described in JP-A 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source; etc. Good.
- oxime compound a compound represented by the following formula (OX-1) is preferable. Whether the N-O bond of the oxime compound is an oxime compound of (E) form, an oxime compound of (Z) form, or a mixture of (E) form and (Z) form Good.
- 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 nonmetal atomic group.
- the monovalent nonmetal atom 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 the other substituent.
- substituents examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group and the like.
- a halogen atom an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group
- an acyloxy group an acyl group, an alkyl group, an aryl group and the like.
- OX-1 as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group is preferable, and an aryl group or a heterocyclic group is preferable. preferable.
- These groups may have one or more substituents.
- the substituent the above-mentioned substituents can be exemplified.
- 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. As the substituent, the above-mentioned substituents can be exemplified.
- the oxime compound containing a fluorine atom can also be used.
- the oxime compound containing a fluorine atom compounds described in JP-A-2010-262028; Compounds 24 and 36 to 40 described in JP-A-2014-500852; and JP-A-2013-164471 Compounds (C-3); and the like. This content is incorporated herein.
- R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or R 7 represents an arylalkyl group having 7 to 30 carbon atoms, and when R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to form a fluorene group, and R 3 and R 4 are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or carbonyl Indicates a group.
- R 1, R 2, R 3 and, R 4 is, R 1, R 2, R 3 in the formula (1), and has the same meaning as R 4,
- R 5 are, -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6
- R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 4 to carbon atoms 20 heterocyclic groups
- X represents a direct bond or a carbonyl group
- a represents an integer of 0 to 4.
- R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl having 7 to 30 carbon atoms.
- R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon And represents a heterocyclic group of 4 to 20, and X represents a direct bond or a carbonyl group.
- R 1, R 3 and, R 4 is, R 1, R 3 in the formula (3), and has the same meaning as R 4,
- R 5 are, -R 6, -OR 6, -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, a halogen atom
- R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms
- X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
- R 1 and R 2 are each independently preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group.
- R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
- R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
- R 1 is preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group.
- R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
- R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
- X is preferably a direct bond.
- Specific examples of the compounds represented by the formulas (1) and (2) include, for example, compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein by reference.
- oxime compound preferably used for the said curable composition is shown below.
- the compounds described in Table 1 of WO 2015-036910 can also be used, and the above contents are incorporated herein.
- the oxime compound preferably has a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a maximum absorption wavelength in a wavelength range of 360 to 480 nm, and still more preferably a high absorbance at 365 nm and 405 nm.
- the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, 5,000 to 200, More preferably, it is 000.
- the molar absorptivity of the compound can be measured by a known method, for example, using an ethyl acetate solvent at a concentration of 0.01 g / L with an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian). Is preferred. You may use a photoinitiator in combination of 2 or more types as needed.
- the curable composition preferably contains a polymerization inhibitor.
- the polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used.
- the polymerization inhibitor include phenolic polymerization inhibitors (eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4-methoxynaphthol etc .; hydroquinone polymerization inhibitors (eg Hydroquinone, 2,6-di-tert-butyl hydroquinone, etc .; quinone type polymerization inhibitors (eg, benzoquinone etc.); free radical polymerization inhibitors (eg, 2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, 4-hydroxy-2,2,6,6
- the effect of the polymerization inhibitor is remarkable when used together with a resin containing a curable group.
- the content of the polymerization inhibitor in the curable composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, and more preferably 0.001 to 0.2%, based on the total solid content of the curable composition. % By mass is more preferred.
- the polymerization inhibitor may be used alone or in combination of two or more. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
- the curable composition may contain a surfactant.
- the surfactant contributes to the improvement of the coatability of the curable composition.
- the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
- the surfactant may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total amount is preferably in the above range.
- surfactant examples include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
- liquid properties (in particular, fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorine-based surfactant, the wettability to the surface to be coated is improved by reducing the interfacial tension between the surface to be coated and the coating liquid. The coating property on the surface to be coated is improved. For this reason, even in the case where a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that film formation with uniform thickness with small thickness unevenness can be more suitably performed.
- the content of fluorine in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass.
- the fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and / or the liquid saving property, and the solubility in the curable composition is also good. .
- fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like.
- the same F482, the same F554, and the same F780 (above, DIC Corporation); Florard FC430, the same FC431, and the same FC171 (above, Sumitomo 3M Co., Ltd.); Surfron S-382, the same SC-101 , SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by Asahi Glass Co., Ltd.) And PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA Corporation).
- a block polymer can also be used as the fluorine-based surfactant, and as a specific example, for example, compounds described in JP-A No.
- the curable composition may contain a UV absorber.
- a UV absorber UV absorbers of salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type and triazine type can be used.
- the compounds of paragraphs 0137 to 0142 of JP 2012-068418 A (corresponding to paragraphs 0251 to 0254 of corresponding US 2012/0068292) can be used, and the contents thereof can be incorporated and incorporated herein. .
- diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Industries, trade name: UV-503) is preferably used.
- the ultraviolet absorber include compounds exemplified in paragraphs [0134] to [0148] of JP-A-2012-32556.
- the content of the UV absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.1 to 5% by mass, based on the total solid content of the curable composition. preferable.
- the curable composition may contain a silane coupling agent.
- the silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule.
- hydrolysable groups such as an alkoxy group, are couple
- the hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis reaction and / or condensation reaction.
- a hydrolysable group a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned, for example.
- the hydrolyzable group contains a carbon atom
- the carbon number thereof is preferably 6 or less, more preferably 4 or less.
- an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
- the silane coupling agent improves the adhesion between the substrate and the cured film, so fluorine atoms and silicon atoms (but excluding silicon atoms to which a hydrolyzable group is bonded) It is preferable not to contain, and a fluorine atom, a silicon atom (but excluding a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, It is desirable not to include a branched alkyl group having 3 or more carbon atoms.
- the content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, and more preferably 0.5 to 8% by mass, relative to the total solid content in the curable composition. 1.0 to 6% by mass is more preferable.
- the said curable composition may contain the silane coupling agent individually by 1 type, and may contain 2 or more types. When a curable composition contains 2 or more types of silane coupling agents, the sum total should just be in the said range.
- silane coupling agent for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Vinyl trimethoxysilane, and vinyl triethoxysilane etc. are mentioned.
- the curable composition preferably contains a solvent.
- the solvent is not particularly limited and known solvents can be used. Although the content of the solvent in the curable composition is not particularly limited, it is preferably adjusted so that the solid content of the curable composition is 10 to 90% by mass, and is 15 to 90% by mass. It is more preferable to be adjusted.
- the solvents may be used alone or in combination of two or more. When using 2 or more types of solvents together, it is preferable to adjust so that the total solid of a curable composition may become in the said range.
- a solvent water and an organic solvent are mentioned, for example.
- the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone , Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Ethyl ether, diethylene glycol monoethyl ether, diethylene glycol dio
- the curable composition it is preferable to first prepare a dispersion composition in which a black pigment and a colorant are dispersed, and further mix the obtained dispersion composition with other components to obtain a curable composition.
- the dispersion composition is preferably prepared by mixing a black pigment, a colorant, a resin (preferably a dispersant), and a solvent. It is also preferable to incorporate a polymerization inhibitor in the dispersion composition.
- the dispersion composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high pressure emulsifying device, a wet crusher, a wet dispersing machine or the like).
- a known mixing method for example, a mixing method using a stirrer, a homogenizer, a high pressure emulsifying device, a wet crusher, a wet dispersing machine or the like.
- each component may be blended at one time, or each component may be sequentially blended after being dissolved or dispersed in a solvent.
- the order of introduction and working conditions at the time of blending are not particularly limited.
- the curable composition is preferably filtered through a filter for the purpose of removing foreign matter and reducing defects.
- a filter if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular.
- a filter made of a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP) can be mentioned. .
- a filter made of a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP)
- PP polypropylene
- nylon are preferable.
- the pore size of the filter is preferably 0.1 to 7.0 ⁇ m, more preferably 0.2 to 2.5 ⁇ m, still more preferably 0.2 to 1.5 ⁇ m, and particularly preferably 0.3 to 0.7 ⁇ m. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filter clogging of the pigment (including the black pigment).
- different filters may be combined. At this time, the filtering with the first filter may be performed only once or may be performed twice or more. When different filters are combined to perform filtering twice or more, it is preferable that the second and subsequent pore sizes be the same or larger than the pore size of the first filtering.
- the pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it is possible to select from, for example, various filters provided by Nippon Pall Co., Advantec Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like.
- the second filter can use a filter formed of the same material as the first filter described above.
- the pore size of the second filter is preferably 0.2 to 10.0 ⁇ m, more preferably 0.2 to 7.0 ⁇ m, and still more preferably 0.3 to 6.0 ⁇ m.
- the curable composition is preferably free of impurities such as metals, metal salts containing halogen, acids, alkalis and the like.
- the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially not including (less than detection limit of measuring device Is most preferred.
- the above impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
- the curable composition layer (composition layer) formed using the above-mentioned photocurable composition can be cured to obtain a cured film in a pattern. More specifically, the production method of the present invention makes it possible to obtain an optical density A of 2.60 to 10.00 at a wavelength of 365 nm per 1.5 ⁇ m of film thickness using the above-described curable composition, and Forming a curable composition layer having an optical density B at a wavelength of 550 nm per 1.5 ⁇ m of 2.00 to 10.00 (curable composition layer forming step), Exposing the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume (exposure step); Developing the curable composition layer after the exposure to form a cured film (developing step); Contains Also, if desired, post-baking may be performed after the developing step.
- each of the above steps will be described.
- the curable composition layer forming step prior to exposure, the curable composition is applied on a support or the like to form a layer of the curable composition (curable composition layer).
- a support for example, a substrate for a solid-state imaging device in which an imaging device (light receiving device) such as a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS) is provided on a substrate (for example, a silicon substrate) it can.
- CMOS complementary metal-oxide semiconductor
- a subbing layer may be provided on the support for the purpose of improving adhesion with the upper layer, preventing diffusion of substances, flattening of the substrate surface, and the like.
- the curable composition layer is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and still more preferably 0.2 to 3 ⁇ m. Drying (pre-baking) of the curable composition layer coated on the support can be carried out at a temperature of 50 to 140 ° C. for 10 to 300 seconds with a hot plate, an oven or the like.
- the curable composition layer (preferably a dried (prebaked) curable composition layer or a naturally dried curable composition layer) has an optical density A of 2.60 to 10 It is preferably 2.00 to 4.00, and more preferably 2.90 to 3.50 from the viewpoint that the rectangularity of the cross-sectional shape of the resulting cured film is further improved.
- the optical density B is from 2.00 to 10.00, and it is preferably 2.50 to 7.00, and 2.80 to 6 from the viewpoint that the rectangularity of the cross-sectional shape of the obtained cured film is more excellent. 50 is more preferred.
- the ratio of optical density B to optical density A is preferably 0.3 to 3.5, more preferably 0.5 to 2.0, and 0.8 to 1.2. More preferable.
- a curable composition layer dried on a glass substrate is formed, and a transmission densitometer (X-rite 361 T (visual) is provided.
- the film thickness is also measured using a densitometer, and the optical density per 1.5 ⁇ m of film thickness is calculated.
- the value measured with the transmission densitometer can be used as it is.
- the curable composition layer may be exposed under conditions of an oxygen concentration of 30 to 50% by volume.
- the curable composition may be through a mask having a predetermined mask pattern.
- the aspect which pattern-exposes a layer is mentioned.
- Examples of light at the time of exposure include light selected from g-rays, h-rays, i-rays, KrF rays (excimer laser rays), and ArF rays (excimer laser rays).
- Irradiance is preferably 20000 ⁇ 50000W / m 2, more preferably 25000 ⁇ 40000W / m 2.
- the exposure step is performed under the conditions of an oxygen concentration of 30 to 50% by volume.
- an oxygen concentration of 30 to 50% by volume.
- Control of this oxygen concentration can be performed by a usual method.
- the apparatus chamber containing the exposure apparatus has a sealed structure, and oxygen gas and nitrogen gas in a desired ratio can be supplied to adjust the oxygen concentration in the room.
- oxygen gas and nitrogen gas of predetermined flow rates may be circulated in the chamber of the exposure apparatus so that the exposure atmosphere has a predetermined oxygen concentration.
- the optical density A is X
- the oxygen concentration (volume fraction) at the time of exposure is Y
- the irradiance (W / m 2 ) is Z
- the value to be set is preferably 1.60 ⁇ 10 ⁇ 5 to 10.00 ⁇ 10 ⁇ 5, and more preferably 2.80 ⁇ 10 ⁇ 5 to 5.20 ⁇ 10 ⁇ 5 .
- Curing if the value calculated by the equation (1) in which X, Y and Z are combined, which is closely related to the progress of curing of these curable composition layers, falls within the above-mentioned range
- the rectangularity of the film is good.
- the rectangularity of the cross-sectional shape of the cured film does not easily deteriorate.
- the developing step is a step of developing the curable composition layer after exposure to form a cured film.
- the curable composition layer in the non-light-irradiated portion in the exposure step is eluted, and only the light-cured portion remains, and a patterned cured film is obtained.
- the type of developing solution used in the developing step is not particularly limited, but an alkaline developing solution which does not cause damage to the underlying imaging device and circuit is desirable.
- the development temperature is, for example, 20 to 30.degree.
- the developing time is, for example, 20 to 90 seconds. In order to remove more residue, it may be carried out for 120 to 180 seconds in recent years. Furthermore, in order to further improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
- the alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water so that the concentration is 0.001 to 10% by mass (preferably 0.01 to 5% by mass).
- the alkaline compound is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium borate, sodium metaborate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl Ammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo [5.4.0] -7-undecene etc. (of which the organic alkali is preferable.).
- washing processing is generally performed by water after image development.
- Post-bake After the exposure step, heat treatment (post-baking) is preferably performed.
- Post-baking is a heat treatment after development to complete curing. 240 degrees C or less is preferable and, as for the heating temperature, 220 degrees C or less is more preferable. There is no particular lower limit, but in consideration of efficient and effective treatment, 50 ° C. or higher is preferable, and 100 ° C. or higher is more preferable.
- Post-baking can be performed by a continuous system or a batch system using heating means, such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater.
- the above post-baking is preferably performed in an atmosphere of low oxygen concentration.
- the oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, still more preferably 10% by volume or less, particularly preferably 7% by volume or less, 3 volumes Most preferably, it is at most%. There is no particular lower limit, but 10 ppm by volume or more is practical.
- the curable composition described above preferably further contains a UV curing agent.
- the UV curing agent is preferably a UV curing agent that can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for the lithography process by ordinary i-ray exposure.
- UV curing agents include Ciba Irgacure 2959 (trade name).
- the curable composition layer is preferably a material that cures at a wavelength of 340 nm or less.
- the exposure dose of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and still more preferably 800 to 3500 mJ.
- This UV curing step is preferably performed after the lithography step in order to perform low temperature curing more effectively.
- the exposure light source is preferably an ozoneless mercury lamp.
- the cured film obtained by the production method of the present invention preferably has an optical density at a wavelength of 365 nm per 1.5 ⁇ m of film thickness of 2.60 to 10.00, more preferably 2.80 to 4.00, 2.90 -3.50 is more preferable.
- the optical density at a wavelength of 550 nm per 1.5 ⁇ m of film thickness of the cured film obtained by the production method of the present invention is preferably 2.00 to 10.00, more preferably 2.50 to 7.00, 2.80 To 6.50 is more preferable.
- the cured film preferably has an optical density of more than 2.00 per 1.5 ⁇ m in the wavelength region of 400 to 1200 nm, since the cured film has better performance when used as a light shielding film described later. More than 3.00 is more preferable. Although the upper limit value is not particularly limited, it is preferably 10 or less. Such a cured film can be preferably used as a light shielding film.
- a method of measuring the optical density of a cured film first, a cured film on a glass substrate is formed, and measurement is performed using a transmission densitometer (X-rite 361 T (visual) densitometer). The film thickness of the portion is also measured, and the optical density per predetermined film thickness is calculated.
- an optical density of 1.5 ⁇ m or more in the wavelength range of 400 to 1200 nm means an optical density of 1.5 ⁇ m or more in the entire wavelength range of 400 to 1200 nm. Intended to be over 2.00.
- the said cured film has a surface asperity structure.
- the reflectance of the cured film can be reduced when the cured film is a light shielding film.
- another layer may be provided on a cured film and a concavo-convex structure may be given.
- the shape of the surface asperity structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 ⁇ m to 1.5 ⁇ m. 5% or less is preferable, as for the reflectance of a cured film, 3% or less is more preferable, and 2% or less is still more preferable.
- the method for producing the surface concavo-convex structure is not particularly limited, a method including an organic filler and / or an inorganic filler in a cured film or other layers, a lithography method using exposure and development, or an etching method, a sputtering method and nanoimprinting
- the surface of the cured film or other layers may be roughened by a method or the like.
- a method of providing a low refractive index layer on the cured film a method of providing a plurality of layers having different refractive indexes (for example, high refractive index layers), and a method of reducing the reflectance of the cured film And a method of forming a low optical density layer and a high optical density layer, as described in JP-A-2015-1654.
- the cured film is a portable computer such as a personal computer, a tablet, a cellular phone, a smart phone, and a digital camera; a printer complex machine, an OA (Office Automation) equipment such as a scanner; a surveillance camera, a barcode reader, cash Industrial equipment such as an automated teller machine (ATM), a high speed camera, and a device having an identity authentication function using face image authentication; automotive camera devices; endoscopes, capsule endoscopes, And medical camera devices such as catheters; and bio-sensors, biosensors, cameras for military reconnaissance, cameras for stereoscopic maps, cameras for weather and ocean observation, land resource exploration cameras, astronomy for space and deep space targets Space equipment such as exploration cameras; etc.
- Light blocking member and the light-shielding film of the optical filter and the module is used, yet is suitable for anti-reflection member and the antireflection film.
- the said cured film can be used also for uses, such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode).
- the said cured film is suitable for the member which provides a light shielding function or an antireflection function other than the optical filter and optical film which are used for micro LED and micro OLED.
- micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.
- the cured film is also suitable as an optical filter and an optical film used for a quantum dot sensor and a quantum dot solid-state imaging device. Moreover, it is suitable as a member which provides a light shielding function and a reflection preventing function. Examples of the quantum dot sensor and the quantum dot solid-state imaging device include those described in U.S. Patent Application Publication 2012/37789 and WO 2008/131313.
- a light shielding film is one of the preferable uses in the cured film obtained by the manufacturing method of this invention, Comprising:
- the manufacturing method of the light shielding film of this invention is similarly the method demonstrated as the manufacturing method of the above-mentioned cured film. It can do. Specifically, the curable composition is applied to a substrate to form a curable composition layer, and the light shielding film can be produced by exposure and development.
- a method of manufacturing a solid-state imaging device includes a step of manufacturing a cured film (light shielding film) through the above-described manufacturing method of the present invention, the solid-state imaging device having the cured film (light shielding film) It is a method of manufacturing.
- the solid-state imaging device according to the manufacturing method of the present invention contains the cured film (light shielding film).
- the form in which the solid-state imaging device contains a cured film (light-shielding film) is not particularly limited.
- a plurality of photodiodes constituting the light receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate And a light receiving element made of polysilicon or the like, and having a cured film on the light receiving element forming surface side of the support (for example, a portion other than the light receiving portion and / or a pixel for color adjustment) It can be mentioned.
- the solid-state imaging device contains the above-described solid-state imaging device.
- the solid-state imaging device 100 includes a rectangular solid-state imaging device 101, and a transparent cover glass 103 held above the solid-state imaging device 101 and sealing the solid-state imaging device 101. There is. Furthermore, on the cover glass 103, a lens layer 111 is provided so as to overlap via a spacer 104.
- the lens layer 111 is composed of a support 113 and a lens material 112.
- the lens layer 111 may have a configuration in which the support 113 and the lens material 112 are integrally formed.
- a light shielding film 114 is provided to shield the peripheral region of the lens layer 111 from light.
- the cured film obtained by the manufacturing method of the present invention can also be used as the light shielding film 114.
- the solid-state imaging device 101 photoelectrically converts an optical image formed by the imaging unit 102 serving as the light receiving surface and outputs the image as an image signal.
- the solid-state imaging device 101 includes a laminated substrate 105 in which two substrates are laminated.
- the laminated substrate 105 is composed of a rectangular chip substrate 106 and a circuit substrate 107 of the same size, and the circuit substrate 107 is laminated on the back surface of the chip substrate 106.
- the material of the substrate used as the chip substrate 106 is not particularly limited, and known materials can be used.
- An imaging unit 102 is provided at the center of the surface of the chip substrate 106.
- a dark current (noise) is generated from the circuit in the peripheral region, and the peripheral region is shielded by the light shielding film 115 provided.
- the cured film obtained by the production method of the present invention is preferably used as the light shielding film 115.
- a plurality of electrode pads 108 are provided at the surface edge of the chip substrate 106.
- the electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (not shown) (which may be a bonding wire) provided on the surface of the chip substrate 106.
- each external connection terminal 109 is connected to the electrode pad 108 through the penetration electrode 110 which penetrates the lamination substrate 105 perpendicularly. Further, each external connection terminal 109 is connected to a control circuit that controls the driving of the solid-state imaging device 101, an image processing circuit that performs image processing on an imaging signal output from the solid-state imaging device 101, etc. It is done.
- the imaging unit 102 includes components provided on the substrate 204 such as the light receiving element 201, the color filter 202, and the microlens 203.
- the color filter 202 includes a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm.
- the cured film obtained by the production method of the present invention can also be used as a black matrix 205bm.
- a material of the substrate 204 As a material of the substrate 204, the same material as the above-described chip substrate 106 can be used.
- a p well layer 206 is formed on the surface of the substrate 204.
- light receiving elements 201 which are n-type layers and generate and accumulate signal charges by photoelectric conversion are arranged and formed in a square lattice shape.
- a vertical transfer path 208 formed of an n-type layer is formed on one side of the light receiving element 201 via the readout gate portion 207 on the surface layer of the p well layer 206. Further, on the other side of the light receiving element 201, a vertical transfer path 208 belonging to an adjacent pixel is formed via an element isolation region 209 formed of a p-type layer.
- the read gate unit 207 is a channel region for reading out the signal charge stored in the light receiving element 201 to the vertical transfer path 208.
- a gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204.
- a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed on the gate insulating film 210 so as to cover the vertical transfer path 208, the read gate portion 207, and the element isolation region 209 almost immediately.
- the vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to perform charge transfer, and a read electrode that drives the read gate unit 207 to read a signal charge.
- the signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path and an output unit (floating diffusion amplifier) not shown, and then output as a voltage signal.
- a light shielding film 212 is formed on the vertical transfer electrode 211 so as to cover the surface thereof.
- the light shielding film 212 has an opening at a position immediately above the light receiving element 201, and shields the other regions.
- the cured film obtained by the manufacturing method of the present invention can also be used as the light shielding film 212.
- a transparent intermediate layer formed of an insulating film 213 made of borophospho silicate glass (BPSG), an insulating film (passivation film) 214 made of P-SiN, and a planarizing film 215 made of a transparent resin or the like is provided on the light shielding film 212.
- BPSG borophospho silicate glass
- passivation film insulating film
- planarizing film 215 made of a transparent resin or the like
- the image display manufactured by the manufacturing method of this invention contains the cured film obtained by the manufacturing method of this invention.
- a method of producing an image display device of the present invention is a method of producing an image display device having the above-mentioned cured film, including the step of producing a cured film through the above-mentioned production method of the present invention.
- an image display apparatus has a cured film
- a form in which a cured film is contained in a black matrix, and the color filter containing such a black matrix is used for an image display apparatus is mentioned, for example.
- a black matrix and a color filter containing the black matrix will be described, and a liquid crystal display device containing such a color filter will be described as a specific example of the image display device.
- the cured film obtained by the production method of the present invention is contained in a black matrix.
- the black matrix may be contained in an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.
- an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.
- black matrix those already described above; black edges provided at the periphery of an image display device such as a liquid crystal display device; grids between red, blue and green pixels, and / or stripes Black portions; dot-like and / or linear black patterns for light shielding of TFT (thin film transistor); and the like.
- the black matrix has a high light-shielding property (optical density OD) in order to improve the display contrast, and in the case of an active matrix drive liquid crystal display device using thin film transistors (TFTs), to prevent image quality deterioration due to light current leakage. It is preferable to have three or more.
- the method for producing the black matrix is not particularly limited, but it can be produced by the same method as the method for producing a cured film described above.
- a curable composition can be applied to a substrate to form a curable composition layer, exposed, and developed to produce a patterned cured film (black matrix).
- the thickness of the cured film used as the black matrix is preferably 0.1 to 4.0 ⁇ m.
- the material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more to visible light (wavelength 400 to 800 nm).
- a material specifically, for example, glass such as soda lime glass, non-alkali glass, quartz glass, and borosilicate glass; plastics such as polyester resin and polyolefin resin; From the viewpoint of chemical resistance and heat resistance, alkali-free glass, quartz glass and the like are preferable.
- the cured film obtained by the production method of the present invention is contained in a color filter.
- a color filter provided with a board
- the color filter containing the black matrix (cured film) can be produced, for example, by the following method.
- a coating (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in the opening of a pattern-like black matrix formed on a substrate.
- a resin composition for each color Although a well-known resin composition can be used, In the curable composition demonstrated in this specification, the black pigment was substituted to the coloring agent corresponding to each pixel It is preferred to use one.
- the resin composition layer is exposed to light through a photomask having a pattern corresponding to the opening of the black matrix.
- a color filter having red, green and blue pixels can be produced by performing a series of operations using, for example, resin compositions for each color containing red, green and blue pigments.
- the cured film obtained by the production method of the present invention is contained in a liquid crystal display device.
- the form in which the liquid crystal display device contains the cured film is not particularly limited, but the form containing the color filter containing the black matrix (cured film) described above can be mentioned.
- liquid crystal display device As a liquid crystal display device concerning this embodiment, a form provided with a pair of substrates arranged facing, and a liquid crystal compound enclosed between those substrates is mentioned, for example.
- the substrate is as described above for the black matrix.
- liquid crystal display device for example, from the user side, polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) A laminate including an element / substrate / polarizer / backlight unit in this order may be mentioned.
- the liquid crystal display device is not limited to the above, and, for example, “Electronic display device (authored by Akio Sasaki, published by Industry Research Association 1990)”, “Display device (authored by Ibuki Osamu, Industrial Books (stock) The liquid crystal display device described in the Heisei 1st year publication etc. is mentioned. In addition, for example, a liquid crystal display device described in “Next-Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Inc., Industrial Research Association, Inc. 1994)” may be mentioned.
- the cured film obtained by the production method of the present invention is contained in an infrared sensor.
- the infrared sensor according to the above embodiment will be described with reference to FIG.
- reference numeral 310 denotes a solid-state imaging device.
- the imaging region provided on the solid-state imaging device 310 is configured by combining the infrared absorption filter 311 and the color filter 312.
- the infrared absorption filter 311 transmits light in the visible light range (for example, light with a wavelength of 400 to 700 nm) and light in the infrared range (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm)
- it is a film that shields light having a wavelength of 900 to 1000 nm, and a cured film containing an infrared ray absorbent (as described in the form of the infrared ray absorbent as described above) as a colorant can be used.
- the color filter 312 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed, and for example, red (R), green (G), and blue (B) pixels are formed.
- the color filter or the like is used, and the form is as described above.
- a resin film 314 (for example, a transparent resin film or the like) capable of transmitting light of the wavelength transmitted through the infrared transmission filter 313 is disposed between the infrared transmission filter 313 and the solid-state imaging device 310.
- the infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light of a specific wavelength, and is a colorant (for example, a perylene compound and / or bisbenzo) that absorbs light in the visible light range.
- a cured film obtained by the production method of the present invention, which contains a furanone compound and the like) and an infrared absorber for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound
- an infrared absorber for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound
- the infrared transmission filter 313 shields light having a wavelength of 400 to 830 nm and transmit light having a wavelength of 900 to 1300 nm.
- a microlens 315 is disposed on the incident light h ⁇ side of the color filter 312 and the infrared transmission filter 313.
- a planarization film 316 is formed to cover the microlenses 315.
- the resin film 314 is disposed in the embodiment shown in FIG. 3, the infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared ray transmission filter 313 may be formed on the solid-state imaging device 310.
- the film thickness of the color filter 312 and the film thickness of the infrared rays permeable filter 313 are the same, the film thickness of both may be different.
- the color filter 312 is provided closer to the incident light h ⁇ than the infrared absorption filter 311, but the infrared absorption filter 311 and the color filter 312 are interchanged in order and the infrared absorption filter 311 may be provided closer to the incident light h ⁇ than the color filter 312.
- the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other, but the two filters do not necessarily have to be adjacent to each other, and another layer may be provided between them. Good.
- the cured film obtained by the manufacturing method of the present invention can be used as a light shielding film for the edge and / or the side of the surface of the infrared absorption filter 311, and by using for the inner wall of the infrared sensor, internal reflection and / or light reception. Unintended light can be prevented from entering the unit and sensitivity can be improved.
- this infrared sensor it is possible to simultaneously capture image information, so that it is possible to perform motion sensing in which an object whose motion is to be detected is recognized. Furthermore, since distance information can be acquired, it is also possible to capture an image including 3D information.
- the solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like. Note that, regarding each configuration of the solid-state imaging device, paragraphs 0032 to 0036 in JP-A-2011-233983 can be referred to, and the contents thereof are incorporated in the present specification.
- Dispersion Composition A dispersion composition was prepared which was used to prepare a curable composition. Table 1 below shows the composition ratio (parts by mass) of each component in each dispersion composition.
- the dispersion compositions 1, 13 and 14 have the same composition.
- ⁇ Pigment> The pigment shown below was used.
- Ti, Zr, V, Nb, and CB, inorganic black pigment (A), inorganic black pigment (B), inorganic black pigment (C) are black pigments, and PG58 and PY185 are pigments other than black pigments. .
- Ti titanium nitride-containing particles produced by the method for producing metal nitride-containing particles shown below.
- metal nitride-containing particles titanium nitride-containing particles
- the apparatus described in paragraph 0042 of JP-A-2005-343784 and FIG. 1 was used.
- metal nitride is used with an apparatus (hereinafter referred to as “nanoparticle manufacturing apparatus”) in which the discharge vessel 1 in FIG. 1 of the above publication is a stainless steel vacuum chamber (manufactured by Fukushin Kogyo Co., Ltd.). Containing particles (titanium nitride containing particles) were produced.
- the air in the vacuum chamber was exhausted by the exhaust pump.
- a tungsten rod having a length of 500 mm, a diameter of 12 mm, and a rod shape of a hollow structure having a hollow diameter of 6 mm was used as a discharge electrode of the nano-particle production apparatus.
- the arrangement of the discharge electrodes was the same as that of FIG. 1 of JP-A-2005-343784. Specifically, 12 discharge electrodes were arranged in two stages of six each. The distance between the upper and lower portions was about 160 mm.
- the hollow discharge electrode was connected to the raw material supply device so that the raw material gas could be supplied into the vacuum chamber from the hollow portion of the discharge electrode.
- the discharge starts in a state where the tips of the discharge electrodes are in contact with each other while applying an alternating current (voltage: 20 to 40 V, current: 70 to 100 A) having a phase difference to each discharge electrode.
- an alternating current voltage: 20 to 40 V, current: 70 to 100 A
- the tips of the discharge electrodes were moved outward so as to separate them, and the distance between the tips of the adjacent discharge electrodes was set to a position of 5 to 10 mm to continue the arc discharge .
- the feed tank of the raw material feeder was heated to introduce the raw material gas into the vacuum chamber.
- NH 3 gas liquefied ammonium ECOAN, manufactured by Showa Denko KK
- H 2 gas hydrogen gas, Showa Denko gas products
- Ar gas argon gas, Taiyo Nichi acid
- the supply tank was heated to 210 ° C.
- TiCl 4 gas TiCl 4 gas (TLT-1, manufactured by Toho Titanium Co., Ltd.) was introduced from the discharge electrode at 600 atm.
- sulfur fine powder fine powder sulfur 325 mesh, manufactured by Tsurumi Chemical Industry Co., Ltd.
- a powder supply device TP-99010 FDR manufactured by JEOL
- the feed rate is determined by X-ray fluorescence analysis using the content by mass of sulfur atoms detected by X-ray photoelectron spectroscopy in the obtained metal nitride-containing particles (particles containing titanium nitride) as T E (mass%).
- T E / T X The ratio (T E / T X ) of the two was set to be less than 1.1, where T X (mass%) was the content by mass of sulfur atoms detected by After introducing TiCl 4 gas and nitrogen gas mixed with sulfur fine powder into the vacuum chamber for 1 hour, voltage application from the AC power supply was stopped, and the supply of the gas was stopped. Next, particles attached to the inner wall of the vacuum chamber were recovered.
- the obtained particles were placed in a closed vessel into which nitrogen (N 2 ) gas having an O 2 content and a water content controlled to 100 ppm or less, respectively, was introduced and allowed to stand for 24 hours.
- nitrogen (N 2 ) gas having an O 2 content and a water content controlled to 100 ppm or less, respectively, was introduced and allowed to stand for 24 hours.
- the particles obtained above were heated at 200 ° C. using a vacuum oven VAC-101P (manufactured by ESPEC) to obtain metal nitride-containing particles (titanium nitride-containing particles).
- the internal pressure of the decompression oven during heating was 1.0 ⁇ 10 3 Pa.
- zirconium powder zirconium powder manufactured by Wako Pure Chemical Industries, Ltd.
- powder feeder TP-99010 FDR powder feeder TP-99010 FDR (manufactured by JEOL Ltd.) instead of Zr: TiCl 4 gas.
- V Similar to the titanium nitride-containing particles described above, except that vanadium powder (Vanadium metal powder VHO manufactured by Taiyo Mining Co., Ltd.) was introduced by a powder supply device TP-99010FDR (manufactured by JEOL Ltd.) instead of the introduction of TiCl 4 gas. Vanadium nitride-containing particles produced by the method.
- Niobium powder Niobium (powder) ⁇ 100-325 mesh> manufactured by Mitsuwa Chemical Co., Ltd.
- niobium powder Niobium (powder) ⁇ 100-325 mesh> manufactured by Mitsuwa Chemical Co., Ltd.
- a powder feeder TP-99010 FDR manufactured by JEOL Ltd.
- TiCl 4 gas Niobium nitride-containing particles produced by the same method as titanium-containing particles.
- T E / T X of each metal nitride containing particle (a titanium nitride containing particle, a zirconium nitride containing particle, a vanadium nitride containing particle, and a niobium nitride containing particle) mentioned above was measured by the following method.
- Each metal nitride-containing particle was formed into a pellet by using a press to obtain a sample.
- grains was measured on the following measurement conditions using a X-ray-photoelectron-spectroscopic-analysis apparatus and a fluorescent-X-ray-analysis apparatus.
- X-ray photoelectron spectrometer Measurement of T E
- Quantera-SXM (trade name) device manufactured by PHI
- X-ray source monochromatized Al K ⁇ ray (1486.6 ev, 25 W, 15 kV, beam diameter 200 ⁇ m ⁇ )
- Measurement area 200 ⁇ m ⁇
- Measurement method The sample was set in the apparatus, and the photoelectron extraction angle was measured at 10 degrees.
- X-ray fluorescence analyzer (measurement of T X ) Equipment Rigaku ZSM Primus II XRF X-ray Rh 30-50 kV, 48-80 mA Measurement area 10 ⁇ m ⁇ Measurement time 10-240 deg / min
- transition metal atoms (titanium, zirconium, vanadium, or nitride) contained in each metal nitride-containing particle (titanium nitride-containing particle, zirconium nitride-containing particle, vanadium nitride-containing particle, and niobium nitride-containing particle) Containing atom number ratio X of content of nitrogen atom to content of niobium), contained atom number ratio Y of content of oxygen atom to content of transition metal atom contained in nitride, and transition contained in nitride
- each metal nitride-containing particle as a sample was formed into a pellet by using a press, and the sample was measured using the fluorescent X-ray analyzer under the following conditions.
- the average primary particle diameter of each of the metal nitride-containing particles was less than 80 nm.
- PG58 and PY185 are used together to make it green as a whole.
- Dispersant A (resin having no ethylenically unsaturated group): Synthesized by the method shown below.
- Synthesis Example A1 Synthesis of Macromonomer A-1 In a three-necked flask with a volume of 3000 mL, ⁇ -caprolactone (1044.2 g), ⁇ -valerolactone (184.3 g), and 2-ethyl-1-hexanol (71.6 g) were introduced to obtain a mixture. The mixture was then stirred while blowing with nitrogen. Next, Disperbyk 111 (12.5 g, manufactured by Bick Chemie, phosphoric acid resin) was added to the mixture, and the resulting mixture was heated to 90 ° C. After 6 hours, the mixture was heated to 110 ° C.
- Dispersant B (resin having an ethylenically unsaturated group): Synthesized by the method shown below.
- V-601 (1.48 g) was added to the mixture. After further reacting for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation. After completion of the reaction, tetrabutylammonium bromide (TBAB, 7.5 g) and p-methoxyphenol (MEHQ, 0.13 g) were added under air, and then glycidyl methacrylate (hereinafter also referred to as "GMA", 66.1 g) ) was added dropwise. After completion of the dropwise addition, the reaction was continued under air for 7 hours, and the completion of the reaction was confirmed by acid value measurement. A 20% by mass solution of Dispersant B was obtained by adding PGMEA (643.6 g) to the obtained mixture. The weight average molecular weight of the resulting dispersant B was 35,000, and the acid value was 50 mg KOH / mg.
- TBAB tetrabutylammonium bromide
- MEHQ
- Dispersant C (resin having an ethylenically unsaturated group): Synthesized by the method shown below.
- C C number was calculated
- Dispersion composition The dispersion composition prepared by the method described above was used. For each numbered curable composition, the corresponding numbered dispersion composition was used.
- ⁇ A-1 (resin containing an ethylenically unsaturated group): Acrycure RD-F8, manufactured by Nippon Shokuhin Co., Ltd., solid content 40%, (solvent: propylene glycol monomethyl ether)
- the alkali-soluble resin A-1 was used as a resin-containing solution (resin solution).
- PGMEA Propylene glycol monomethyl ether acetate
- An i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.) is used for the dried curable composition layer with a film thickness of 1.5 ⁇ m to form a 3.0 ⁇ m-square pattern at a wavelength of 365 nm. It exposed through an Island pattern mask.
- the exposure was performed at the optimum exposure dose with the oxygen concentration at the time of exposure set in the range of 25 to 55% by volume and the irradiance set in the range of 15,000 to 55,000 W / m 2 . The exposure was performed within 10 minutes after prebaking.
- the silicon wafer on which the curable composition layer that has been exposed is formed is placed on the horizontal rotation table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (organic alkali) Paddle development was carried out at 23 ° C. for 60 seconds using a developer, manufactured by Fujifilm Electronics Materials. In this way, a pattern (a cured film in the form of a square pixel pattern of 3.0 ⁇ m square) was formed on the undercoating silicon wafer.
- DW-30 type manufactured by Chemitronics
- CD-2000 (organic alkali) Paddle development was carried out at 23 ° C. for 60 seconds using a developer, manufactured by Fujifilm Electronics Materials.
- a silicon wafer on which a pattern is formed is fixed to a horizontal rotation table by a vacuum chuck method, and while rotating this silicon wafer at a rotation speed of 50 rpm by a rotation device, pure water is showered from above the rotation center from a spray nozzle It was supplied and rinsed. Thereafter, the silicon wafer was dried. The obtained silicon wafer was further heated (post-baked) at 200 ° C. for 300 seconds to obtain a silicon wafer with a patterned cured film.
- AA angle of side wall 80 ° to 100 °
- A angle of side wall 75 ° to less than 80 °, or 100 ° to less than 105 °
- B angle of side wall 70 ° to 75 °
- C angle of sidewall 60 ° or more and less than 70 °, or 110 ° or more but less than 120 °
- D angle of sidewall 50 ° or more and less than 60 ° or 120 ° or more and less than 130 °
- E Sidewall angle is less than 50 ° or 130 ° or more
- the column “Disperser Mill Peripheral Speed” means the mill peripheral speed when preparing the dispersion composition used to make the curable composition.
- the column of “Expression (1) value” is a value obtained by applying each test condition to the above-mentioned Expression (1) (X ⁇ Y ⁇ Z). The calculation method is as described above.
- a cured film (patterned cured film) excellent in rectangularity of the cross-sectional shape can be produced, and even in the case where the drawn curable composition layer is used.
- the tendency to maintain excellent rectangularity (the evaluation of rectangularity is C or higher) was confirmed.
- the drawing period should be Also in this case, it was confirmed that the rectangularity of the obtained pattern did not easily deteriorate (comparison of Example 10 with other Examples).
- Example 1, 2 and 6 The tendency which can acquire the outstanding cured film was confirmed (result of Example 1, 2 and 6).
- the irradiance at the time of exposure is from 20000 to 50000 W / m 2
- a cured film having more rectangularity is obtained
- the irradiance at the exposure is from 25000 to 40000 W / m 2
- the cured film is more excellent in rectangularity.
- Tend to be obtained Results of Examples 1, 4, 5, 11 and 12
- inorganic black pigments (A), (B) and (C) were used as the black pigment, it was confirmed that a cured film having more excellent rectangularity could be obtained as in Example 1 (Example 1, 18, 19 and 20 results).
- solid-state imaging device 101 solid-state imaging device 102: imaging unit 103: cover glass 104: spacer 105: laminated substrate 106: chip substrate 107: circuit substrate 108 ... electrode pad 109 ... external connection terminal 110 ... penetrating electrode 111 ... lens layer 112 ... lens material 113 ... support 114, 115 ... cured film 201 ... light receiving element 202: color filter 201: light receiving element 202: color filter 203: microlens 204: substrate 205b: blue pixel 205r: red pixel 205g: green pixel 205bm,. Black matrix 206 p well layer 207 read gate portion 208 vertical transfer path 209 element isolation region 210 Insulating film 211 ...
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Abstract
Description
また、形成する硬化膜の性能改善のために、特定の波長に対する硬化性組成物層の光学濃度(OD:Optical Density)を所定の範囲に調整する場合がある。 The method for producing a cured film used for a solid-state imaging device and an image display device (for example, a liquid crystal display device, an organic EL (electro luminescence) device, etc.) is carried out after forming a curable composition layer on a substrate The method of hardening this is common. Here, it is typical that the curable composition layer is irradiated with light through a predetermined mask pattern and then developed.
Moreover, in order to improve the performance of the cured film to be formed, the optical density (OD: Optical Density) of the curable composition layer with respect to a specific wavelength may be adjusted within a predetermined range.
また、多様な製造条件に対して、安定した品質の硬化膜を製造できることが求められており、硬化性組成物層を形成した後、露光するまで期間(例えば1週間)が空いた場合であっても、得られる硬化膜の断面形状の矩形性が良好であることも求められている。
以下、特定の工程を経た処理対象物が、次の工程まで待機させられることを「引き置き」ともいう。 The present inventors examined the colored photosensitive composition described in Patent Document 1, and there is room for improvement in rectangularity of the cross-sectional shape of a cured film formed using this colored photosensitive composition. Found out.
In addition, it is required that a cured film of stable quality can be produced under various production conditions, and after a curable composition layer is formed, a period (for example, one week) until exposure is left. However, it is also required that the rectangularity of the cross-sectional shape of the obtained cured film be good.
Hereinafter, the fact that the object to be treated which has undergone a specific process can be made to stand by until the next process is also referred to as "retention."
〔2〕 上記黒色顔料が、第4族の金属元素の窒化物若しくは酸窒化物、第5族の金属元素の窒化物若しくは酸窒化物、又は、カーボンブラックである、〔1〕に記載の硬化膜の製造方法。
〔3〕 上記黒色顔料が、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、ニオブの窒化物若しくは酸窒化物、又は、カーボンブラックである、〔1〕又は〔2〕に記載の硬化膜の製造方法。
〔4〕 上記黒色顔料が、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、又は、ニオブの窒化物又は酸窒化物である、〔1〕~〔3〕のいずれかに記載の硬化膜の製造方法。
〔5〕 上記黒色顔料が、チタンの窒化物若しくは酸窒化物、又は、ジルコニウムの窒化物若しくは酸窒化物である、〔1〕~〔4〕のいずれかに記載の硬化膜の製造方法。
〔6〕 上記露光における、放射照度が20000~50000W/m2である、〔1〕~〔5〕のいずれかに記載の硬化膜の製造方法。
〔7〕 上記露光における、放射照度が25000~40000W/m2である、〔1〕~〔6〕のいずれかに記載の硬化膜の製造方法。
〔8〕 上記光学濃度Aが2.80~4.00となり、かつ、上記光学濃度Bが2.50~7.00となる、〔1〕~〔7〕のいずれかに記載の硬化膜の製造方法。
〔9〕 上記光学濃度Aに対する上記光学濃度Bの比が0.5~2.0である、〔1〕~〔8〕のいずれかに記載の硬化膜の製造方法。
〔10〕 上記硬化性組成物が、更に、樹脂を含有し、上記樹脂が、エチレン性不飽和基を含有する樹脂を含有し、上記樹脂の合計質量に対する、上記エチレン性不飽和基の含有量が、0.10~3.00mmol/gである、〔1〕~〔9〕のいずれかに記載の硬化膜の製造方法。
〔11〕 上記硬化性組成物が、更に、重合開始剤を含有する、〔1〕~〔10〕のいずれかに記載の硬化膜の製造方法。
〔12〕 上記硬化性組成物が、更に、重合禁止剤を含有する、〔1〕~〔11〕のいずれかに記載の硬化膜の製造方法。
〔13〕 上記光学濃度AをX、上記露光時の酸素濃度をY、上記放射照度をZとした場合に、後述する式(1)で計算される値が2.80×10-5~5.20×10-5となる、〔1〕~〔12〕のいずれかに記載の硬化膜の製造方法。
〔14〕 上記硬化膜が遮光膜である、〔1〕~〔13〕のいずれかに記載の硬化膜の製造方法。
〔15〕 〔1〕~〔14〕のいずれかに記載の製造方法を介して、硬化膜を有する固体撮像素子の製造を行う、固体撮像素子の製造方法。
〔16〕 〔1〕~〔14〕のいずれかに記載の製造方法を介して、硬化膜を有する画像表示装置の製造を行う、画像表示装置の製造方法。 [1] Using a curable composition containing a black pigment and a polymerizable compound, the optical density A at a wavelength of 365 nm per 1.5 μm of film thickness is 2.60 to 10.00, and the film thickness of 1.5 μm Forming a curable composition layer having an optical density B of 2.00 to 10.00 at a wavelength of 550 nm, and exposing the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume A method for producing a cured film, comprising the steps of: developing the curable composition layer after the exposure to form a cured film.
[2] The cured material according to [1], wherein the black pigment is a nitride or oxynitride of a metal element of Group 4, a nitride or oxynitride of a metal element of Group 5 or carbon black Method of producing a membrane
[3] The black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, a nitride or oxynitride of niobium, or carbon black The manufacturing method of the cured film as described in [1] or [2].
[4] The black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, or a nitride or oxynitride of niobium [1] ] The manufacturing method of the cured film in any one of-[3].
[5] The method for producing a cured film according to any one of [1] to [4], wherein the black pigment is a nitride or oxynitride of titanium, or a nitride or oxynitride of zirconium.
[6] The method for producing a cured film according to any one of [1] to [5], wherein the irradiance is from 20000 to 50000 W / m 2 in the exposure.
[7] The method for producing a cured film according to any one of [1] to [6], wherein the irradiance is 25000 to 40000 W / m 2 in the exposure.
[8] The cured film according to any one of [1] to [7], wherein the optical density A is 2.80 to 4.00, and the optical density B is 2.50 to 7.00. Production method.
[9] The method for producing a cured film according to any one of [1] to [8], wherein the ratio of the optical density B to the optical density A is 0.5 to 2.0.
[10] The curable composition further contains a resin, and the resin contains a resin containing an ethylenically unsaturated group, and the content of the ethylenically unsaturated group with respect to the total mass of the resin Of from 0.10 to 3.00 mmol / g. The method for producing a cured film according to any one of [1] to [9].
[11] The method for producing a cured film according to any one of [1] to [10], wherein the curable composition further contains a polymerization initiator.
[12] The method for producing a cured film according to any one of [1] to [11], wherein the curable composition further contains a polymerization inhibitor.
[13] Assuming that the above optical density A is X, the oxygen concentration at the above exposure is Y, and the above irradiance is Z, the value calculated by the equation (1) described later is 2.80 × 10 −5 to 5 The method for producing a cured film according to any one of [1] to [12], which results in 20 × 10 −5 .
[14] The method for producing a cured film according to any one of [1] to [13], wherein the cured film is a light shielding film.
[15] A manufacturing method of a solid-state imaging device, which manufactures a solid-state imaging device having a cured film through the manufacturing method according to any one of [1] to [14].
[16] A manufacturing method of an image display device, which manufactures an image display device having a cured film through the manufacturing method according to any one of [1] to [14].
また、本発明によれは、固体撮像素子の製造方法、及び、画像表示装置の製造方法も提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the cured film which is excellent in the rectangularity of cross-sectional shape can be manufactured, and the manufacturing method of the cured film which can maintain excellent rectangularity even when using the curable composition layer drawn can be provided.
The present invention can also provide a method of manufacturing a solid-state imaging device and a method of manufacturing an image display device.
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
なお、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及び上限値として含む範囲を意味する。 Hereinafter, the present invention will be described in detail.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
本明細書においてGPC法は、HLC-8020GPC(東ソー社製)を用い、カラムとしてTSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ2000(東ソー社製、4.6mmID×15cm)を、溶離液としてTHF(テトラヒドロフラン)を用いる方法に基づく。 In the present specification, the weight-average molecular weight (Mw) is a polystyrene conversion value by GPC (Gel Permeation Chromatography) method.
In this specification, GPC method uses HLC-8020GPC (made by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ 2000 (made by Tosoh Corp., 4.6 mm ID × 15 cm) as columns, and THF (tetrahydrofuran as the eluent Based on the method using
これに対して、本発明の製造方法を用いることで、断面形状の矩形性が優れる硬化膜(パターン状の硬化膜)を得られる理由は必ずしも定かではないが、本発明者らは次のように考えている。つまり、特定の波長に対して所定の光学濃度を示す硬化性組成物層に対して、高酸素濃度下で露光を行うことで、酸素が表層部における硬化反応を適度に阻害し、硬化性組成物層の表層部と下層部とでバランス良く硬化を進行できるためであると考えている。また、上述のようにバランス良く硬化を進行できることにより、形成してから期間(例えば1週間)が空いた硬化性組成物層を使用した場合にいても、得られる硬化膜の良好な矩形性を維持できていると考えている。
更に、本発明の製造方法で使用される硬化性組成物層は、光学濃度Aおよび光学濃度Bが所定の範囲であるのが、硬化膜の断面形状の矩形性改善に寄与していると考えている。 When exposing a curable composition layer formed using a curable composition containing a colorant (in particular, a black pigment) to obtain a cured film in the form of a pattern, the surface layer portion of the curable composition layer and There is a problem that the way of hitting light is different in the lower layer portion, and the shape of the obtained patterned cured film is deteriorated. More specifically, light is less likely to penetrate to the surface layer portion in the lower layer portion, and curing is less likely to progress in the lower layer portion, and as a result, there is a problem that the rectangularity of the cross-sectional shape of the patterned cured film is deteriorated. .
On the other hand, the reason why the cured film (patterned cured film) excellent in the rectangularity of the cross-sectional shape can be obtained by using the production method of the present invention is not necessarily clear, but the present inventors are as follows. I am thinking about it. That is, by exposing the curable composition layer exhibiting a predetermined optical density to a specific wavelength under high oxygen concentration, oxygen appropriately inhibits the curing reaction in the surface layer portion, and the curable composition It is believed that this is because curing can proceed in a well-balanced manner in the surface layer portion and the lower layer portion of the object layer. In addition, since curing can proceed in a well-balanced manner as described above, good rectangularity of the resulting cured film can be obtained even when using a curable composition layer having a period (for example, one week) after formation. I think that I can maintain it.
Furthermore, in the curable composition layer used in the production method of the present invention, it is considered that the optical density A and the optical density B being within the predetermined range contributes to the improvement of the rectangularity of the cross-sectional shape of the cured film. ing.
本明細書においては、まず、本発明の製造方法に用いられる硬化性組成物について説明する。次いで、この硬化性組成物を用いて硬化性組成物層を形成し、上記硬化性組成物層を露光して硬化膜を製造する方法について説明する。
その後、本発明の製造方法を用いて得られる硬化膜の用途について説明する。 In the production method of the present invention, as described above, the curable composition layer containing a specific component and exhibiting a predetermined optical density is exposed under a constant oxygen concentration to produce a cured film.
In the present specification, first, a curable composition used in the production method of the present invention will be described. Subsequently, a curable composition layer is formed using this curable composition, and the method of exposing the said curable composition layer and manufacturing a cured film is demonstrated.
Then, the use of the cured film obtained using the manufacturing method of this invention is demonstrated.
次に、本発明の製造方法で使用される硬化性組成物について説明する。
本発明の製造方法に使用される硬化性組成物が含有する成分について説明する。 [Curable composition]
Next, the curable composition used by the manufacturing method of this invention is demonstrated.
The component which the curable composition used for the manufacturing method of this invention contains is demonstrated.
硬化性組成物は、黒色顔料を含有する。黒色顔料は、各種公知の黒色顔料を使用できる。黒色顔料は、無機顔料であっても有機顔料であってもよい。
黒色の無機顔料としては、チタン(Ti)及びジルコニウム(Zr)等の第4族の金属元素、バナジウム(V)及びニオブ(Nb)等の第5族の金属元素、コバルト(Co)、クロム(Cr)、銅(Cu)、マンガン(Mn)、ルテニウム(Ru)、鉄(Fe)、ニッケル(Ni)、錫(Sn)、並びに、銀(Ag)からなる群より選ばれた1種又は2種以上の金属元素を含む、金属酸化物、金属窒化物、及び金属酸窒化物等が挙げられる。無機顔料には、表面修飾処理が施されていてもよい。例えば、シリコーン基とアルキル基を併せ持つ表面処理剤で表面修飾処理が施された無機粒子が挙げられ、「KTP-09」シリーズ(信越化学工業社製)などが挙げられる。また、金属酸化物、金属窒化物、及び金属酸窒化物は、更に他の原子が混在した粒子として使用してもよい。例えば、更に周期表13~17族元素から選択される原子(好ましくは酸素原子、及び/又は、硫黄原子)を含有する、金属窒化物含有粒子として使用されてもよい。
黒色顔料としては、カーボンブラックも挙げられる。カーボンブラックの具体例としては、市販品である、C.I.ピグメントブラック 1等の有機顔料、及び、C.I.ピグメントブラック 7等の無機顔料が挙げられる。 <Black pigment>
The curable composition contains a black pigment. As the black pigment, various known black pigments can be used. The black pigment may be an inorganic pigment or an organic pigment.
Examples of black inorganic pigments include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), cobalt (Co), chromium Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and one or two selected from the group consisting of silver (Ag) Examples thereof include metal oxides, metal nitrides, metal oxynitrides, and the like containing a metal element of a kind or more. The inorganic pigment may be subjected to surface modification treatment. Examples include inorganic particles that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, such as the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.). In addition, metal oxides, metal nitrides, and metal oxynitrides may be used as particles in which other atoms are mixed. For example, it may be used as a metal nitride-containing particle further containing an atom (preferably an oxygen atom and / or a sulfur atom) selected from periodic table elements 13-17.
The black pigment also includes carbon black. Specific examples of carbon black include C.I. I. Organic pigments such as C.I. pigment black 1; I. And inorganic pigments such as CI pigment black 7.
なお、チタンの窒化物とは窒化チタンであり、ジルコニウムの窒化物とは窒化ジルコニウムであり、バナジウムの窒化物とは窒化バナジウムであり、ニオブの窒化物とは窒化ニオブである。また、チタンの酸窒化物とは酸窒化チタンであり、ジルコニウムの酸窒化物とは酸窒化ジルコニウムであり、バナジウムの酸窒化物とは酸窒化バナジウムであり、ニオブの酸窒化物とは酸窒化ニオブである。
また、黒色顔料として、市販品である「NITRBLACK(ナイトブラック)UB-1」(三菱マテリアル社製、特開2017-222559号公報に記載の窒化ジルコニウム粉末、及び、特許第4931011号公報に記載の微粒子低次酸化ジルコニウム・窒化ジルコニウム複合体等の黒色顔料も挙げられる。 Among them, as the black pigment, nitrides or oxides of Group 4 metal elements, nitrides or oxynitrides of Group 5 metal elements, or carbon black are preferable, and titanium nitride or oxynitride , Zirconium nitride or oxynitride, vanadium nitride or oxynitride, niobium nitride or oxynitride, or carbon black is more preferable, titanium nitride or oxynitride, zirconium nitride or Oxynitrides, nitrides or oxynitrides of vanadium, or nitrides or oxynitrides of niobium are more preferable, and nitrides or oxynitrides of titanium, or nitrides or oxynitrides of zirconium are particularly preferable.
The nitride of titanium is titanium nitride, the nitride of zirconium is zirconium nitride, the nitride of vanadium is vanadium nitride, and the nitride of niobium is niobium nitride. The titanium oxynitride is titanium oxynitride, the zirconium oxynitride is zirconium oxynitride, the vanadium oxynitride is vanadium oxynitride, and the niobium oxynitride is oxynitride. It is niobium.
In addition, as a black pigment, a commercially available product "NITRBLACK (night black) UB-1" (manufactured by Mitsubishi Materials Co., Ltd., zirconium nitride powder described in JP-A-2017-222559, and JP-A-4931011) There may also be mentioned black pigments such as particulate low-order zirconium oxide-zirconium nitride composites.
透過型電子顕微鏡を用いて得た粒子像の最大長(Dmax:粒子画像の輪郭上の2点における最大長さ)、及び最大長垂直長(DV-max:最大長に平行な2本の直線で画像を挟んだ時、2直線間を垂直に結ぶ最短の長さ)を測長し、その相乗平均値(Dmax×DV-max)1/2を粒子径とする。この方法で100個の粒子の粒子径を測定し、その算術平均値を平均粒子径として、黒色顔料の平均一次粒子径とする。 The average primary particle size of the black pigment can be measured using a transmission electron microscope (TEM). As a transmission electron microscope, for example, a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
Maximum length of particle image obtained using transmission electron microscope (Dmax: maximum length at two points on the contour of particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length When the image is sandwiched, the shortest length connecting two straight lines vertically is measured, and the geometric mean value (Dmax × DV-max) 1/2 is defined as the particle diameter. The particle diameter of 100 particles is measured by this method, and the arithmetic mean value is taken as an average particle diameter to obtain an average primary particle diameter of the black pigment.
本明細書において、窒化チタンとは、CuKα線をX線源とした場合の(200)面に由来するピークの回折角2θが42.5°~42.8°である化合物を意図する。
また、本明細書において、酸窒化チタンとは、CuKα線をX線源とした場合の(200)面に由来するピークの回折角2θが42.8°超の化合物を意図する。酸窒化チタンの上記回折角2θの上限値としては特に制限されないが、43.5°以下が好ましい。
酸窒化チタンとしては、例えば、チタンブラック等が挙げられ、より具体的には、例えば、TiO2、TinO2n-1(1≦n≦20)で表せる低次酸化チタン、及び/又は、TiNxOy(0<x<2.0,0.1<y<2.0)で表せる酸窒化チタンを含有する形態が挙げられる。以下の説明では、窒化チタン(上記回折角2θが42.5°~42.8°)、及び、酸窒化チタン(上記回折角2θが42.8°超)を併せてチタン窒化物といい、その形態について説明する。
また、チタン窒化物は、更に他の原子が混在した粒子として使用してもよい。例えば、チタン窒化物は、更に周期表13~17族元素から選択される原子(好ましくは、硫黄原子)を含有する、チタン窒化物含有粒子として使用されてもよい。なお、その他の金属窒化物においても同様で、窒化金属と酸窒化金属を併せていう金属窒化物は、更に他の原子が混在した粒子として使用してもよい。例えば、金属窒化物は、更に周期表13~17族元素から選択される原子(好ましくは、硫黄原子)を含有する、金属窒化物含有粒子として使用されてもよい。 In the present specification, titanium nitride is intended to be TiN, and may contain unavoidable oxygen atoms in production (for example, unintentional oxidation of the surface of TiN particles, etc.).
In the present specification, titanium nitride means a compound having a diffraction angle 2θ of 42.5 ° to 42.8 ° of a peak derived from the (200) plane when a CuKα ray is used as an X-ray source.
Further, in the present specification, titanium oxynitride means a compound having a diffraction angle 2θ of a peak derived from the (200) plane in the case of using CuKα radiation as an X-ray source over 42.8 °. The upper limit value of the above-mentioned diffraction angle 2θ of titanium oxynitride is not particularly limited, but 43.5 ° or less is preferable.
The titanium nitride, for example, include titanium black or the like, more specifically, for example, low-order titanium oxide represented by TiO 2, Ti n O 2n- 1 (1 ≦ n ≦ 20), and / or, forms containing TiN x O y titanium oxynitride represented by (0 <x <2.0,0.1 <y <2.0) can be mentioned. In the following description, titanium nitride (the diffraction angle 2θ is 42.5 ° to 42.8 °) and titanium oxynitride (the diffraction angle 2θ is more than 42.8 °) are collectively referred to as titanium nitride, The form will be described.
In addition, titanium nitride may be used as particles in which other atoms are further mixed. For example, titanium nitride may be used as titanium nitride-containing particles further containing atoms (preferably, sulfur atoms) selected from Periodic Table Group 13-17 elements. The same applies to the other metal nitrides, and the metal nitride which is a combination of metal nitride and metal oxynitride may be used as particles in which other atoms are mixed. For example, the metal nitride may be used as a metal nitride-containing particle further containing an atom (preferably, a sulfur atom) selected from elements of periodic table 13-17.
熱プラズマ法において、熱プラズマを発生させる方法としては、特に制限されず、直流アーク放電、多層アーク放電、高周波(RF)プラズマ、及び、ハイブリッドプラズマ等が挙げられ、電極からの不純物の混入が少ない高周波プラズマがより好ましい。
熱プラズマ法による黒色顔料の具体的な製造方法としては、特に制限されないが、例えば、チタン窒化物の製造方法として、プラズマ炎中で四塩化チタンとアンモニアガスを反応させる方法(特開平2-22110号公報)、チタン粉末を高周波熱プラズマにより蒸発させ窒素をキャリアーガスとして導入し冷却過程にて窒化させ合成する方法(特開昭61-11140号公報)、及び、プラズマの周縁部にアンモニアガスを吹き込む方法(特開昭63-85007号)等が挙げられる。
ただし、黒色顔料の製造方法としては、上記に制限されるものではなく、所望とする物性を有する黒色顔料が得られれば、製造方法は制限されない。 It does not restrict | limit especially as a manufacturing method of a black pigment, A well-known manufacturing method can be used, for example, a gas phase reaction method is mentioned. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferable from the viewpoint that the mixing of impurities is small, the particle diameter is easy to be uniform, and the productivity is high.
In the thermal plasma method, the method of generating thermal plasma is not particularly limited, and direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, etc. may be mentioned, and contamination with impurities from the electrode is small. High frequency plasma is more preferred.
A specific method for producing a black pigment by a thermal plasma method is not particularly limited. For example, as a method for producing a titanium nitride, a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 2-22110) Gazette), a method of evaporating titanium powder by high-frequency thermal plasma, introducing nitrogen as a carrier gas, nitriding it in the cooling process (JP-A-61-11140), and ammonia gas at the periphery of plasma And the like (Japanese Patent Application Laid-Open No. 63-85007) and the like.
However, the method for producing a black pigment is not limited to the above, and the production method is not limited as long as a black pigment having desired physical properties is obtained.
金属原子の(酸)窒化物を被覆する方法としては、特に制限されず、公知の方法を使用でき、例えば、特開昭53-33228号公報の2頁右下~4頁右上に記載された方法(チタン酸化物に代えて、金属原子の(酸)窒化物を用いる)、特開2008-69193の段落0015~0043段落に記載された方法(微粒子二酸化チタンに代えて、金属原子の(酸)窒化物を用いる)、特開2016-74870号公報の0020段落、及び、0124~0138段落に記載された方法(金属酸化物微粒子に代えて、金属原子の(酸)窒化物を用いる)が挙げられ、上記の内容は本明細書に組み込まれる。 The black pigment may contain a layer of a silicon-containing compound (hereinafter referred to as "silicon-containing compound") on its surface. That is, the (acid) nitride of the metal atom may be coated with a silicon-containing compound to form a black pigment.
The method for coating the (acid) nitride of the metal atom is not particularly limited, and any known method can be used. For example, it is described in JP-A-53-33228, page 2, lower right to page 4, upper right Method (in place of titanium oxide, (acidic nitride of metal atom is used), the method described in paragraph 0015 to 0043 of JP-A 2008-69193 (in place of fine particle titanium dioxide, (acid of metal atom The method described in paragraphs 0020 and 0124 to 0138 of JP-A-2016-74870) (using (oxide) nitride of metal atom in place of metal oxide fine particles) The contents of which are incorporated herein by reference.
このような範囲の含有量とすることで、硬化性組成物から形成される硬化性組成物層の光学濃度を所望の範囲に設定しやすい。
黒色顔料は1種を単独で用いても、2種以上を併用してもよい。2種以上の黒色顔料を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 40 to 70 mass% is preferable with respect to the total solid of a curable composition, as for content of the black pigment in a curable composition, 45 to 70 mass% is more preferable, and 50 to 65 mass% is still more preferable. .
By setting the content in such a range, the optical density of the curable composition layer formed from the curable composition can be easily set in a desired range.
The black pigment may be used alone or in combination of two or more. When two or more types of black pigments are used in combination, the total content is preferably in the above range.
上記硬化性組成物は、黒色顔料以外の着色剤を含有してもよい。着色剤としては特に制限されず、公知の着色剤を使用できる。着色剤としては、各種公知の顔料(着色顔料)、及び、染料(着色染料)等を使用できる。
硬化性組成物中における着色剤の含有量としては特に制限されないが、硬化性組成物の全固形分に対して、20~99質量%が好ましく、20~80質量%がより好ましい。
着色剤は1種を単独で用いても、2種以上を併用してもよい。2種以上の着色剤を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 <Colorant>
The curable composition may contain a colorant other than the black pigment. The colorant is not particularly limited, and known colorants can be used. As the colorant, various known pigments (colored pigments), dyes (colored dyes) and the like can be used.
The content of the colorant in the curable composition is not particularly limited, but is preferably 20 to 99% by mass, and more preferably 20 to 80% by mass, with respect to the total solid content of the curable composition.
The colorant may be used alone or in combination of two or more. When two or more colorants are used in combination, the total content is preferably within the above range.
着色顔料としては、例えば、R(レッド)、G(グリーン)、及び、B(ブルー)等の有彩色系の顔料(有彩色顔料)も使用できる。 Examples of colored dyes include, in addition to colored dyes such as R (red), G (green) and B (blue) (chromatic dyes), those described in paragraphs 0027 to 0200 of JP-A 2014-42375. Colorants can also be used. Also, black dyes can be used.
As the color pigment, for example, chromatic color pigments (chromatic color pigments) such as R (red), G (green), and B (blue) can also be used.
着色剤として使用される顔料は、無機顔料であっても有機顔料であってもよい。 (Pigment)
The pigment used as a colorant may be an inorganic pigment or an organic pigment.
無機顔料としては、特に制限されず、公知の無機顔料を使用できる。
無機顔料としては、例えば、亜鉛華、鉛白、リトポン、酸化チタン、酸化クロム、酸化鉄、沈降性硫酸バリウム及びバライト粉、鉛丹、酸化鉄赤、黄鉛、亜鉛黄(亜鉛黄1種、亜鉛黄2種)、ウルトラマリン青、プロシア青(フェロシアン化鉄カリ)ジルコングレー、プラセオジムイエロー、クロムチタンイエロー、クロムグリーン、ピーコック、ビクトリアグリーン、紺青(プルシアンブルーとは無関係)、バナジウムジルコニウム青、クロム錫ピンク、陶試紅、並びに、サーモンピンク等が挙げられる。
無機顔料は表面修飾処理がなされていてもよい。例えば、シリコーン基とアルキル基を併せ持つ表面処理剤で表面修飾処理が施された無機顔料が挙げられ、「KTP-09」シリーズ(信越化学工業社製)などが挙げられる。 Inorganic pigment The inorganic pigment is not particularly limited, and known inorganic pigments can be used.
Examples of inorganic pigments include zinc flower, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow 1 type, Zinc yellow 2), ultramarine blue, Prussian blue (ferrous iron potassium) zircon gray, praseodymium yellow, chromium titanium yellow, chromium green, peacock, Victoria green, bitumen blue (independent of Prussian blue), vanadium zirconium blue Chrome tin pink, pottery test pink, and salmon pink etc. are mentioned.
The inorganic pigment may be surface-modified. Examples thereof include inorganic pigments that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, such as the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
赤外線吸収性を有する顔料としては、タングステン化合物、及び、金属ホウ化物等が好ましく、なかでも、赤外領域の波長における遮光性に優れる点から、タングステン化合物が好ましい。特に露光による硬化効率に関わるオキシム系重合開始剤の光吸収波長領域と、可視光領域の透光性に優れる観点からタングステン化合物が好ましい。 Pigments having infrared absorptivity can also be used.
As the pigment having infrared absorptivity, tungsten compounds, metal borides and the like are preferable. Among them, tungsten compounds are preferable from the viewpoint of being excellent in the light shielding property at the wavelength in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of the excellent light absorption wavelength region of the oxime polymerization initiator related to the curing efficiency by exposure and the light transmittance of the visible light region.
更に、後述する赤外線吸収剤を加えてもよい。 These pigments may be used in combination of two or more, and may be used in combination with the dyes described later. In order to adjust the color tone and to enhance the light shielding property of a desired wavelength range, for example, pigments having black color or infrared ray shielding property such as red, green, yellow, orange, purple, and blue The form which mixes a pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a violet pigment or dye, with the pigment having infrared light shielding properties, and more preferable to mix a red pigment with the pigment having infrared light shielding properties.
Furthermore, an infrared absorber described later may be added.
有機顔料としては、例えば、カラーインデックス(C.I.)ピグメントイエロー1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214等、
C.I.ピグメントオレンジ 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等、
C.I.ピグメントレッド 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279等;
C.I.ピグメントグリーン 7,10,36,37,58,59等;
C.I.ピグメントバイオレット 1,19,23,27,32,37,42等;
C.I.ピグメントブルー 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80等;
が挙げられる。なお、顔料は1種を単独で用いても、2種以上を併用してもよい。 -Organic pigment As an organic pigment, color index (CI) pigment yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,18, for example. 20, 24, 31, 32, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37, 1, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7, 168, 169, 170, 171, 172, 173, 174, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc.
C. I. Pigment orange 2, 5, 13, 16, 17: 1, 13, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 25: 2, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 208, 209, 210, 216, 220, 224, 226, 246, 254, 255, 264, 270, 272, 279, etc .;
C. I. Pigment green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment violet 1,19,23,27,32,37,42 etc;
C. I. Pigment blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc .;
Can be mentioned. The pigments may be used alone or in combination of two or more.
染料としては、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、特開平5-333207号公報、特開平6-35183号公報、特開平6-51115号公報、及び、特開平6-194828号公報等に開示されている色素を使用できる。化学構造として区分すると、ピラゾールアゾ化合物、ピロメテン化合物、アニリノアゾ化合物、トリフェニルメタン化合物、アントラキノン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、又は、ピロロピラゾールアゾメチン化合物等を使用できる。また、染料としては色素多量体を用いてもよい。色素多量体としては、特開2011-213925号公報、及び、特開2013-041097号公報に記載されている化合物が挙げられる。また、分子内に重合性を有する重合性染料を用いてもよく、市販品としては、例えば、和光純薬工業社製RDWシリーズが挙げられる。 (dye)
Examples of the dyes include, for example, JP-A 64-90403, JP-A 64-91102, JP-A 1-94301, JP-A 6-11614, JP-B 2592 207, and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,505,950, Japanese Patent Application Laid-Open Nos. 5-333207, 6-35183, 6-51115, and 6-194828. The disclosed dyes can be used. When classified as a chemical structure, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, or pyrrolopyrazole azomethines Compounds etc. can be used. In addition, as the dye, a dye multimer may be used. Examples of the dye multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097. Moreover, you may use the polymeric dye which has a polymerizability in a molecule | numerator, As a commercial item, Wako Pure Chemical Industries Ltd. RDW series by which it is mentioned are mentioned, for example.
上記着色剤は、更に赤外線吸収剤を含有してもよい。
赤外線吸収剤は、赤外領域(好ましくは、波長650~1300nm)の波長領域に吸収を有する化合物を意味する。赤外線吸収剤としては、波長675~900nmの波長領域に極大吸収波長を有する化合物が好ましい。
このような分光特性を有する着色剤としては、例えば、ピロロピロール化合物、銅化合物、シアニン化合物、フタロシアニン化合物、イミニウム化合物、チオール錯体系化合物、遷移金属酸化物系化合物、スクアリリウム化合物、ナフタロシアニン化合物、クアテリレン化合物、ジチオール金属錯体系化合物、及び、クロコニウム化合物等が挙げられる。
フタロシアニン化合物、ナフタロシアニン化合物、イミニウム化合物、シアニン化合物、スクアリリウム化合物、及び、クロコニウム化合物は、特開2010-111750号公報の段落0010~0081に開示の化合物を使用してもよく、この内容は本明細書に組み込まれる。シアニン化合物は、例えば、「機能性色素、大河原信/松岡賢/北尾悌次郎/平嶋恒亮・著、講談社サイエンティフィック」を参酌でき、この内容は本願明細書に組み込まれる。 (Infrared absorber)
The colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in a wavelength range of infrared range (preferably, wavelength of 650 to 1300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm.
Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squalilium compounds, naphthalocyanine compounds, quaterrylene A compound, a dithiol metal complex type compound, and a croconium compound etc. are mentioned.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, the compounds disclosed in paragraphs [0010] to [0081] of JP-A-2010-111750 may be used, and the contents of this specification are as described herein. Incorporated into the book. The cyanine compound can be referred to, for example, "Functional pigment, Shin Ookawara / Ken Matsuoka / Keijiro Kitao / Tsunehiro Hiraiso, Kodansha Scientific", the contents of which are incorporated herein.
また、赤外線吸収剤は、25℃の水に1質量%以上溶解する化合物であるのが好ましく、25℃の水に10質量%以上溶解する化合物がより好ましい。このような化合物を用いることで、耐溶剤性が良化する。
ピロロピロール化合物は、特開2010-222557号公報の0049~0062段落を参酌でき、この内容は本明細書に組み込まれる。シアニン化合物及びスクアリリウム化合物は、国際公開2014/088063号公報の0022~0063段落、国際公開2014/030628号公報の0053~0118段落、特開2014-59550号公報の0028~0074段落、国際公開2012/169447号公報の0013~0091段落、特開2015-176046号公報の0019~0033段落、特開2014-63144号公報の0053~0099段落、特開2014-52431号公報の0085~0150段落、特開2014-44301号公報の0076~0124段落、特開2012-8532号公報の0045~0078段落、特開2015-172102号公報の0027~0067段落、特開2015-172004号公報の0029~0067段落、特開2015-40895号公報の0029~0085段落、特開2014-126642号公報の0022~0036段落、特開2014-148567号公報の0011~0017段落、特開2015-157893号公報の0010~0025段落、特開2014-095007号公報の0013~0026段落、特開2014-80487号公報の0013~0047段落、及び、特開2013-227403号公報の0007~0028段落等を参酌でき、この内容は本明細書に組み込まれる。 The compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.
The infrared absorber is preferably a compound soluble in water at 25 ° C. in 1% by mass or more, and more preferably a compound soluble in water at 25 ° C. in 10% by mass or more. The solvent resistance is improved by using such a compound.
The pyrrolopyrrole compounds can be referred to paragraphs 0049 to 0062 of JP-A-2010-222557, the contents of which are incorporated herein. Cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 in WO 2014/088063, 0053 to 0118 in WO 2014/030628, 0028 to 0074 in JP 2014-59550, WO 2012 / JP-A-2015-147, JP-A-2015-176046, JP-A-2014-63144, JP-A-2014-63144, JP-A-2014-52431, JP-A-2014-523, paragraph Paragraphs 0076 to 0124 of 2014-44301, paragraphs 0045 to 0078 of JP 2012-8532, 0027 to 0067 of JP 2015-172102, 0029 ... JP 2015-172004 Paragraph 067, Paragraphs 0029 to 0085 of JP-A-2015-40895, Paragraphs 0022 to 0036 of JP-A-2014-126642, Paragraphs 0011 to 0017 of JP-A-2014-148567, JP-A-2015-157893 Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007, paragraphs 0013 to 0047 of JP 2014-80487, and paragraphs 0007 to 0028 of JP 2013-227403 can be referred to. This content is incorporated herein.
硬化性組成物は重合性化合物を含有する。本明細書において重合性化合物とは、後述する重合開始剤の作用を受けて重合する化合物を意図し、後述する、分散剤及びアルカリ可溶性樹脂とは異なる成分を意図する。 <Polymerizable compound>
The curable composition contains a polymerizable compound. In the present specification, the term "polymerizable compound" is intended to mean a compound which is polymerized under the action of a polymerization initiator described later, and intends a component different from the dispersant and the alkali-soluble resin described later.
重合性化合物の分子量は2000以下であるのが好ましい。 The content of the polymerizable compound in the curable composition is not particularly limited, but it is preferably 5 to 30% by mass with respect to the total solid content of the curable composition. The polymerizable compounds may be used alone or in combination of two or more. When two or more types of polymerizable compounds are used in combination, the total content is preferably in the above range.
The molecular weight of the polymerizable compound is preferably 2000 or less.
重合性化合物は、3~15官能の(メタ)アクリレート化合物であるのが好ましく、3~6官能の(メタ)アクリレート化合物であるのがより好ましい。 The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof, and multimers thereof.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
以下に好ましい重合性化合物の態様を示す。 The polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), Pentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E; Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol residue or propylene glycol residue (for example, SR454, SR499 commercially available from Sartmar) are preferable. . These oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), and KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) can also be used.
The aspect of a preferable polymeric compound is shown below.
カプロラクトン構造を含有する化合物としては、分子内にカプロラクトン構造を含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、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、又は、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)アクリレートが挙げられる。なかでも下記式(Z-1)で表されるカプロラクトン構造を含有する化合物が好ましい。 As the polymerizable compound, a compound having a caprolactone structure is also a preferred embodiment.
The compound having a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentacene. Ε-caprolactone modified polyfunctional (meth) obtained by esterifying a polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol or trimethylolmelamine with (meth) acrylic acid and ε-caprolactone ) Acrylates. Among them, compounds having a caprolactone structure represented by the following formula (Z-1) are preferable.
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はそれぞれ独立に0~10の整数を表し、各mの合計は0~40の整数である。
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はそれぞれ独立に0~10の整数を表し、各nの合計は0~60の整数である。 Wherein (Z-4) and (Z-5), E are each independently, - ((CH 2) y CH 2 O) -, or ((CH 2) y CH ( CH 3) O) - a And y each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
In formula (Z-4), the total of (meth) acryloyl groups is three or four, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In formula (Z-5), the total of (meth) acryloyl groups is five or six, n independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60.
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の整数が更に好ましい。
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の整数が更に好ましい。
また、式(Z-4)又は式(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 the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 8.
In the 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 still more preferably an integer of 6 to 12.
Further, the formula (Z-4) or formula (Z-5) in the - ((CH 2) y CH 2 O) - , or ((CH 2) y CH ( CH 3) O) - , the oxygen atom side A form in which the end is bonded to X is preferred.
式(Z-4)又は式(Z-5)で表される化合物のなかでも、ペンタエリスリトール誘導体及び/又はジペンタエリスリトール誘導体がより好ましい。 The total content of the compound represented by Formula (Z-4) or Formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
Among the compounds represented by Formula (Z-4) or Formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
カルド骨格を含有する重合性化合物としては、9,9-ビスアリールフルオレン骨格を含有する重合性化合物が好ましい。
カルド骨格を含有する重合性化合物としては、限定されないが、例えば、オンコートEXシリーズ(長瀬産業社製)及びオグソール(大阪ガスケミカル社製)等が挙げられる。
重合性化合物は、イソシアヌル酸骨格を中心核として含有する化合物も好ましい。このような重合性化合物の例としては、例えば、NKエステルA-9300(新中村化学社製)が挙げられる。
重合性化合物のエチレン性不飽和基の含有量(重合性化合物中のエチレン性不飽和基の数を、重合性化合物の分子量(g/mol)で除した値を意図する)は5.0mmol/g以上であるのが好ましい。上限は特に制限されないが、一般に、20.0mmol/g以下である。
なお、硬化性組成物中が、複数種類の重合性化合物を含有し、それぞれの二重結合当量が同一ではない場合は、全重合性化合物中における各重合性化合物の質量比と、各重合性化合物の二重結合当量との積を、それぞれ合計した値が、上記範囲内にあるのが好ましい。 In addition, the polymerizable compound may contain a cardo skeleton.
The polymerizable compound containing a cardo skeleton is preferably a polymerizable compound containing a 9,9-bisarylfluorene skeleton.
Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, On Coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. As an example of such a polymerizable compound, for example, NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.
The content of the ethylenically unsaturated group in the polymerizable compound (the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is 5.0 mmol / It is preferably g or more. Although the upper limit is not particularly limited, it is generally 20.0 mmol / g or less.
In the case where the curable composition contains a plurality of types of polymerizable compounds and the respective double bond equivalents are not the same, the mass ratio of each polymerizable compound in all the polymerizable compounds and the respective polymerizability It is preferable that the sum of the products of the compounds and the double bond equivalents be in the above range.
硬化性組成物は樹脂を含有するのが好ましい。樹脂としては例えば、分散剤及びアルカリ可溶性樹脂等が挙げられる。
硬化性組成物中における樹脂の含有量としては特に制限されないが、硬化性組成物の全固形分に対して、3~60質量%が好ましく、5~40質量%がより好ましい。樹脂は、1種を単独で用いても、2種以上を併用してもよい。2種以上の樹脂を併用する場合には、合計含有量が上記範囲内であるのが好ましい。
樹脂の分子量は2000超である。なお、樹脂の分子量が多分散である場合、重量平均分子量が2000超である。 <Resin>
The curable composition preferably contains a resin. Examples of the resin include dispersants and alkali-soluble resins.
The content of the resin in the curable composition is not particularly limited, but is preferably 3 to 60% by mass, and more preferably 5 to 40% by mass, with respect to the total solid content of the curable composition. The resins may be used alone or in combination of two or more. When two or more resins are used in combination, the total content is preferably in the above range.
The molecular weight of the resin is greater than 2000. When the molecular weight of the resin is polydispersed, the weight average molecular weight is more than 2000.
硬化性組成物は分散剤を含有するのが好ましい。なお、本明細書において、分散剤とは、後述するアルカリ可溶性樹脂とは異なる化合物を意図する。
硬化性組成物中における分散剤の含有量としては特に制限されないが、硬化性組成物の全固形分に対して2~40質量%が好ましく、5~30質量%がより好ましい。
分散剤は、1種を単独で用いても、2種以上を併用してもよい。2種以上の分散剤を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 (Dispersant)
The curable composition preferably contains a dispersant. In the present specification, the dispersant is intended to be a compound different from the alkali-soluble resin described later.
The content of the dispersant in the curable composition is not particularly limited, but is preferably 2 to 40% by mass, and more preferably 5 to 30% by mass, relative to the total solid content of the curable composition.
The dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably in the above range.
分散剤としては、高分子分散剤〔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〕、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、及び、顔料誘導体等を挙げられる。
高分子化合物は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、及び、ブロック型高分子に分類できる。 As a dispersing agent, a well-known dispersing agent can be used selecting it suitably, for example. Among these, high molecular compounds are preferable.
As the dispersant, polymer dispersants [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.
高分子化合物は、黒色顔料及び所望により併用するその他の顔料(以下、黒色顔料及びその他の顔料を総称して、単に「顔料」ともいう)等の被分散体の表面に吸着し、被分散体の再凝集を防止するように作用する。そのため、顔料表面へのアンカー部位を含有する、末端変性型高分子、グラフト型(高分子鎖を含有する)高分子、又は、ブロック型高分子が好ましい。 Polymer compound The polymer compound is adsorbed on the surface of a material to be dispersed, such as a black pigment and other pigments optionally used in combination (hereinafter, the black pigment and other pigments are collectively referred to simply as “pigments”) , Acts to prevent reaggregation of the material to be dispersed. Therefore, terminal modified polymers, grafted polymers (containing polymer chains), or block polymers containing anchor sites on the pigment surface are preferred.
硬化性基としては、例えば、エチレン性不飽和基(例えば、(メタ)アクリロイル基、ビニル基、及び、スチリル基等)、及び、環状エーテル基(例えば、エポキシ基、オキセタニル基等)等が挙げられるが、これらに制限されない。
なかでも、ラジカル反応で重合制御が可能な点で、硬化性基としては、エチレン性不飽和基が好ましい。エチレン性不飽和基は(メタ)アクリロイル基がより好ましい。 The polymer compound may contain a curable group.
Examples of the curable group include ethylenically unsaturated groups (eg, (meth) acryloyl group, vinyl group, and styryl group), and cyclic ether groups (eg, epoxy group, oxetanyl group etc.), etc. But not limited to.
Among them, an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by a radical reaction. The ethylenically unsaturated group is more preferably a (meth) acryloyl group.
上記樹脂としては、上記高分子鎖がポリエステル構造を含有するのがより好ましい。 The resin containing a curable group preferably contains at least one selected from the group consisting of a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and / or a polyether structure, and as described later, when the resin contains a structural unit containing a graft chain, the above polymer The chain may contain a polyester structure and / or a polyether structure.
As said resin, it is more preferable that the said polymeric chain contains a polyester structure.
このようなグラフト鎖を含有する構造単位を含有する高分子化合物は、グラフト鎖によって溶剤との親和性を有するために、顔料等の分散性、及び、経時後の分散安定性(経時安定性)に優れるものである。また、グラフト鎖の存在により、グラフト鎖を含有する構造単位を含有する高分子化合物は重合性化合物又はその他の併用可能な樹脂等との親和性を有する。結果として、アルカリ現像で残渣を生じにくくなる。
グラフト鎖が長くなると立体反発効果が高くなり顔料等の分散性は向上する。一方、グラフト鎖が長すぎると顔料等への吸着力が低下して、顔料等の分散性は低下する傾向となる。このため、グラフト鎖は、水素原子を除いた原子数が40~10000であるのが好ましく、水素原子を除いた原子数が50~2000であるのがより好ましく、水素原子を除いた原子数が60~500であるのが更に好ましい。
ここで、グラフト鎖とは、共重合体の主鎖の根元(主鎖から枝分かれしている基において主鎖に結合する原子)から、主鎖から枝分かれしている基の末端までを示す。 The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
The polymer compound containing a structural unit containing such a graft chain has an affinity to a solvent by the graft chain, and thus the dispersibility of the pigment etc. and the dispersion stability after aging (stability over time) Excellent. Further, due to the presence of the graft chain, the polymer compound containing a structural unit containing a graft chain has an affinity to a polymerizable compound or other usable resin and the like. As a result, alkaline development is less likely to produce a residue.
The longer the graft chain, the higher the steric repulsion effect and the better the dispersibility of the pigment and the like. On the other hand, when the graft chain is too long, the adsorptive power to the pigment and the like decreases, and the dispersibility of the pigment and the like tends to decrease. For this reason, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and more than 40 atoms excluding hydrogen atoms. More preferably, it is 60 to 500.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.
グラフト鎖と溶剤との相互作用性を向上させ、それにより顔料等の分散性を高めるために、グラフト鎖は、ポリエステル構造、ポリエーテル構造、及び、ポリ(メタ)アクリレート構造からなる群から選ばれた少なくとも1種を含有するグラフト鎖であるのが好ましく、ポリエステル構造及びポリエーテル構造の少なくともいずれかを含有するグラフト鎖であるのがより好ましい。 The graft chain preferably contains a polymer structure, and as such a polymer structure, for example, poly (meth) acrylate structure (eg, poly (meth) acrylic structure), polyester structure, polyurethane structure, polyurea structure, polyamide And polyether structures and the like.
The graft chain is selected from the group consisting of a polyester structure, a polyether structure, and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent, thereby enhancing the dispersibility of the pigment etc. It is preferable that it is a graft chain containing at least one, more preferably a graft chain containing at least one of a polyester structure and a polyether structure.
ここで、ポリカプロラクトン構造とは、ε-カプロラクトンを開環した構造を繰り返し単位として含有する構造をいう。ポリバレロラクトン構造とは、δ-バレロラクトンを開環した構造を繰り返し単位として含有する構造をいう。
ポリカプロラクトン構造を含有する分散剤の具体例としては、下記式(1)及び下記式(2)におけるj及びkが5である分散剤が挙げられる。また、ポリバレロラクトン構造を含有する分散剤の具体例としては、下記式(1)及び下記式(2)におけるj及びkが4である分散剤が挙げられる。
ポリアクリル酸メチル構造を含有する分散剤の具体例としては、下記式(4)におけるX5が水素原子であり、R4がメチル基である分散剤が挙げられる。また、ポリメタクリル酸メチル構造を含有する分散剤の具体例としては、下記式(4)におけるX5がメチル基であり、R4がメチル基である分散剤が挙げられる。 The dispersant preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate and cyclic or chain polyester, and is preferably polymethyl acrylate or polymethacrylic acid. It is more preferable to contain at least one structure selected from the group consisting of methyl and linear polyesters, and a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure More preferably, it contains at least one structure selected from the group consisting of The dispersing agent may be a dispersing agent containing the above structure alone in one dispersing agent, or may be a dispersing agent containing a plurality of these structures in one dispersing agent.
Here, the polycaprolactone structure refers to a structure containing a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opened structure of δ-valerolactone as a repeating unit.
As a specific example of the dispersing agent containing a polycaprolactone structure, the dispersing agent whose j and k in a following formula (1) and a following formula (2) are 5 is mentioned. Moreover, as a specific example of the dispersing agent containing a polyvalerolactone structure, the dispersing agent whose j and k in following formula (1) and following formula (2) are 4 is mentioned.
Examples of dispersants containing polymethyl acrylate structure, X 5 in formula (4) is a hydrogen atom, R 4 can be cited dispersants are methyl groups. Specific examples of dispersants containing polymethyl methacrylate structure, X 5 in formula (4) is a methyl group, R 4 can be cited dispersants are methyl groups.
高分子化合物は、グラフト鎖を含有する構造単位として、下記式(1)~式(4)のいずれかで表される構造単位を含有するのが好ましく、下記式(1A)、下記式(2A)、下記式(3A)、下記式(3B)、及び、下記(4)のいずれかで表される構造単位を含有するのがより好ましい。 -Structural unit containing a graft chain The polymer compound preferably contains, as a structural unit containing a graft chain, a structural unit represented by any one of the following formulas (1) to (4), and the following formula It is more preferable to contain the structural unit represented by either of (1A), following formula (2A), following formula (3A), following formula (3B), and following (4).
式(1)~(4)において、X1、X2、X3、X4、及び、X5は、それぞれ独立に、水素原子又は1価の有機基を表す。X1、X2、X3、X4、及び、X5としては、合成上の制約の観点からは、それぞれ独立に、水素原子又は炭素数(炭素原子数)1~12のアルキル基であるのが好ましく、それぞれ独立に、水素原子又はメチル基であるのがより好ましく、メチル基が更に好ましい。 In formulas (1) to (4), W 1 , W 2 , W 3 and W 4 each independently represent an oxygen atom or NH. W 1 , W 2 , W 3 and W 4 are preferably oxygen atoms.
In formulas (1) to (4), X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group. Each of X 1 , X 2 , X 3 , X 4 and X 5 independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms), from the viewpoint of the restriction on synthesis And each independently preferably represents a hydrogen atom or a methyl group, more preferably a methyl group.
また、式(1)及び(2)において、j及びkは、それぞれ独立に、2~8の整数を表す。式(1)及び(2)におけるj及びkは、組成物の経時安定性及び現像性の観点から、4~6の整数が好ましく、5がより好ましい。
また、式(1)及び(2)において、n、及び、mは、10以上の整数が好ましく、20以上の整数がより好ましい。また、分散剤が、ポリカプロラクトン構造、及び、ポリバレロラクトン構造を含有する場合、ポリカプロラクトン構造の繰り返し数と、ポリバレロラクトンの繰返し数の和としては、10以上の整数が好ましく、20以上の整数がより好ましい。 In the formulas (1) to (4), n, m, p and q are each independently an integer of 1 to 500.
In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5 from the viewpoint of the temporal stability and developability of the composition.
In the formulas (1) and (2), n and m are preferably integers of 10 or more, and more preferably 20 or more. When the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the repeating number of the polycaprolactone structure and the repeating number of the polyvalerolactone is preferably an integer of 10 or more, 20 or more An integer is more preferred.
式(4)中、R4は水素原子又は1価の有機基を表し、この1価の有機基としては特に構造上限定はされない。R4としては、水素原子、アルキル基、アリール基、又は、ヘテロアリール基が好ましく、水素原子又はアルキル基がより好ましい。R4がアルキル基である場合、アルキル基としては、炭素数1~20の直鎖状アルキル基、炭素数3~20の分岐鎖状アルキル基、又は、炭素数5~20の環状アルキル基が好ましく、炭素数1~20の直鎖状アルキル基がより好ましく、炭素数1~6の直鎖状アルキル基が更に好ましい。式(4)において、qが2~500のとき、グラフト共重合体中に複数存在するX5及びR4は互いに同じであっても異なっていてもよい。 In formula (3), R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, plural R 3 s may be the same as or different from each other.
In Formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. As R 4 , a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group is preferable, and a hydrogen atom or an alkyl group is more preferable. When R 4 is an alkyl group, the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. The linear alkyl group having 1 to 20 carbon atoms is more preferable, and the linear alkyl group having 1 to 6 carbon atoms is further preferable. In the formula (4), when q is 2 to 500, a plurality of X 5 and R 4 in the graft copolymer may be the same or different.
また、式(2)で表される構造単位としては、組成物の経時安定性及び現像性の観点から、下記式(2A)で表される構造単位であるのがより好ましい。 The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of the temporal stability of the composition and the developability.
Moreover, as a structural unit represented by Formula (2), it is more preferable that it is a structural unit represented by following formula (2A) from a time-lapse stability of a composition, and a developability.
また、高分子化合物は、グラフト鎖を含有する構造単位とは異なる(すなわち、グラフト鎖を含有する構造単位には相当しない)疎水性構造単位を含有するのが好ましい。ただし、本明細書において、疎水性構造単位は、酸基(例えば、カルボン酸基、スルホン酸基、リン酸基、フェノール性水酸基等)を有さない構造単位である。 Hydrophobic Structural Unit Further, the polymer compound preferably contains a hydrophobic structural unit which is different from the structural unit containing a graft chain (that is, not corresponding to a structural unit containing a graft chain). However, in the present specification, the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).
A. J. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A.J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993. ClogP values are from Daylight Chemical Information System, Inc. Is a value calculated by the program "CLOGP" available from This program provides the value of "computed logP" calculated by the fragment approach of Hansch, Leo (see the following document). The fragment approach is based on the chemical structure of the compound, dividing the chemical structure into substructures (fragments) and estimating the logP value of the compound by summing the logP contributions assigned to the fragment. The details are described in the following documents. The ClogP value calculated by the program CLOGP v4.82 is used herein.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P .; G. Sammnens, J.J. B. Taylor and C. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev. , 93, 1281-1306, 1993.
logP=log(Coil/Cwater)
式中、Coilは油相中の化合物のモル濃度を、Cwaterは水相中の化合物のモル濃度を表す。
logPの値が0をはさんでプラスに大きくなると油溶性が増し、マイナスで絶対値が大きくなると水溶性が増すことを意味し、有機化合物の水溶性と負の相関があり、有機化合物の親疎水性を見積るパラメータとして広く利用されている。 log P means the common logarithm of partition coefficient P (Partition Coefficient), and it quantitatively determines how an organic compound is distributed in the equilibrium of oil (generally 1-octanol) and water. Is a physical property value represented as a numerical value, and is represented by the following equation.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value becomes larger than 0, the oil solubility increases, and when it is negative and the absolute value increases, the water solubility increases, which has a negative correlation with the water solubility of the organic compound, and the affinity of the organic compound is negative. It is widely used as a parameter to estimate water quality.
R1、R2、及び、R3は、水素原子又は炭素数が1~3のアルキル基であるのが好ましく、水素原子又はメチル基であるのがより好ましい。R2及びR3は、水素原子であるのが更に好ましい。
Xは、酸素原子(-O-)又はイミノ基(-NH-)を表し、酸素原子であるのが好ましい。 In the above formulas (i) to (iii), R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom etc.), or a carbon number Represents an alkyl group of 1 to 6 (eg, a methyl group, an ethyl group, a propyl group, etc.).
R 1 , R 2 and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R 2 and R 3 are more preferably hydrogen atoms.
X represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.
脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基及び複素環基が挙げられる。ただし、脂肪族基は、置換基として酸基を有さない。 The aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The aliphatic group further includes a ring-aggregated hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the ring-aggregated hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and And-include cyclohexylphenyl and the like. As the bridged cyclic hydrocarbon ring, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) 2 Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredane, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane rings And tetracyclo [4.4.0.1 2,5 . [1 7,10 ] dodecane and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring and the like can be mentioned. In addition, as the crosslinked cyclic hydrocarbon ring, a fused cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and Also included are fused rings in which a plurality of 5- to 8-membered cycloalkane rings such as perhydrophenalene rings are fused.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, the aliphatic group does not have an acid group as a substituent.
また、上記式(ii)で表される単量体として、R1が水素原子又はメチル基であって、Lがアルキレン基であって、Zが脂肪族基、複素環基、又は、芳香族基である化合物が好ましい。また、上記式(iii)で表される単量体として、R4、R5、及び、R6が水素原子又はメチル基であって、Zが脂肪族基、複素環基、又は、芳香族基である化合物が好ましい。 As a monomer represented by the said Formula (i), R < 1 >, R < 2 > and R < 3 > are a hydrogen atom or a methyl group, Comprising: L contains a single bond or an alkylene group or an oxyalkylene structure. Compounds in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group are preferable.
Further, as the monomer represented by the above formula (ii), an R 1 is hydrogen atom or a methyl group, L is an alkylene group, Z is an aliphatic group, a heterocyclic group, or an aromatic Compounds which are groups are preferred. Further, as the monomer represented by the above formula (iii), R 4, R 5, and, R 6 is a hydrogen atom or a methyl group, Z is an aliphatic group, a heterocyclic group, or an aromatic Compounds which are groups are preferred.
なお、式(i)~(iii)で表される代表的な化合物の例としては、特開2013-249417号公報の段落0089~0093に記載の化合物を参照でき、これらの内容は本明細書に組み込まれる。 Examples of representative compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes and the like.
In addition, as an example of a typical compound represented by Formula (i)-(iii), the compound as described in stage 0089-0093 of Unexamined-Japanese-Patent No. 2013-249417 can be referred, and these contents are described in this specification. Incorporated into
高分子化合物は、顔料等と相互作用を形成しうる官能基を導入できる。ここで、高分子化合物は、顔料等と相互作用を形成しうる官能基を含有する構造単位を更に含有するのが好ましい。
この顔料等と相互作用を形成しうる官能基としては、例えば、酸基、塩基性基、配位性基、及び、反応性を有する官能基等が挙げられる。
高分子化合物が、酸基、塩基性基、配位性基、又は、反応性を有する官能基を含有する場合、それぞれ、酸基を含有する構造単位、塩基性基を含有する構造単位、配位性基を含有する構造単位、又は、反応性を有する構造単位を含有するのが好ましい。
特に、高分子化合物が、更に、酸基として、カルボン酸基等のアルカリ可溶性基を含有することで、高分子化合物に、アルカリ現像によるパターン形成のための現像性を付与できる。
すなわち、高分子化合物にアルカリ可溶性基を導入することで、上記組成物は、顔料等の分散に寄与する分散剤としての高分子化合物がアルカリ可溶性を含有することになる。このような高分子化合物を含有する組成物は、露光部の遮光性に優れたものとなり、かつ、未露光部のアルカリ現像性が向上される。
また、高分子化合物が酸基を含有する構造単位を含有することにより、高分子化合物が溶剤となじみやすくなり、塗布性も向上する傾向となる。
これは、酸基を含有する構造単位における酸基が顔料等と相互作用しやすく、高分子化合物が顔料等を安定的に分散すると共に、顔料等を分散する高分子化合物の粘度が低くなっており、高分子化合物自体も安定的に分散されやすいためであると推測される。 Functional group capable of forming an interaction with a pigment etc. The polymer compound can introduce a functional group capable of forming an interaction with the pigment etc. Here, the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with a pigment or the like.
Examples of the functional group capable of forming an interaction with the pigment and the like include an acid group, a basic group, a coordinating group, and a functional group having reactivity.
When the polymer compound contains an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit containing an acid group, a structural unit containing a basic group, It is preferable to contain a structural unit containing a reactive group or a structural unit having reactivity.
In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be provided with developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as the dispersant contributing to the dispersion of the pigment etc. contains alkali solubility by the composition described above. A composition containing such a polymer compound is excellent in the light shielding property of the exposed area, and the alkali developability of the unexposed area is improved.
In addition, when the polymer compound contains a structural unit containing an acid group, the polymer compound tends to be compatible with the solvent, and the coatability tends to be improved.
This is because the acid group in the structural unit containing the acid group easily interacts with the pigment and the like, and the polymer compound stably disperses the pigment and the like, and the viscosity of the polymer compound in which the pigment and the like are dispersed decreases. It is presumed that the polymer compound itself is also easily dispersed stably.
すなわち、高分子化合物は、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも1種を含有する構造単位を更に含有するのが好ましい。 Examples of the acid group that is a functional group capable of forming an interaction with a pigment and the like include, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. And at least one of phosphoric acid groups is preferable, and a carboxylic acid group is more preferable. The carboxylic acid group has good adsorptivity to pigments and the like, and has high dispersibility.
That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
高分子化合物は、酸基を含有する構造単位を含有してもしなくてもよいが、含有する場合、酸基を含有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、5~80質量%であるのが好ましく、アルカリ現像による画像強度のダメージ抑制という観点から、10~60質量%がより好ましい。 The polymer compound may have one or more structural units containing an acid group.
The polymer compound may or may not contain a structural unit containing an acid group, but when it is contained, the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, the content is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass from the viewpoint of suppressing damage to the image strength due to alkaline development.
高分子化合物は、塩基性基を含有する構造単位を含有してもしなくてもよいが、含有する場合、塩基性基を含有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、0.01~50質量%が好ましく、現像性阻害抑制という観点から、0.01~30質量%がより好ましい。 As a basic group which is a functional group capable of forming an interaction with a pigment etc., for example, a primary amino group, a secondary amino group, a tertiary amino group, a heterocycle containing N atom, and an amide The preferred basic group is a tertiary amino group in that it has a group etc. and is preferable in that it has good adsorptivity to pigments etc and high dispersibility. The polymer compound can contain one or more of these basic groups.
The polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total of the polymer compound in terms of mass. The content is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass from the viewpoint of development inhibition inhibition.
高分子化合物は、配位性基を含有する構造単位、又は、反応性を有する官能基を含有する構造単位を含有してもしなくてもよいが、含有する場合、これらの構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、10~80質量%が好ましく、現像性阻害抑制という観点から、20~60質量%がより好ましい。 As a coordinating group which is a functional group capable of forming an interaction with a pigment or the like, and as a functional group having reactivity, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acidification Things etc. The preferred functional group is an acetylacetoxy group in that it has good adsorptivity to pigments and the like and high dispersibility of pigments and the like. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit containing a coordinating group, or a structural unit containing a functional group having reactivity, but when it is contained, the content of these structural units In terms of mass, 10 to 80% by mass is preferable based on the total mass of the polymer compound, and 20 to 60% by mass is more preferable from the viewpoint of development inhibition inhibition.
式(iv)~(vi)中、R11、R12、及びR13は、それぞれ独立に水素原子、又は炭素数が1~3のアルキル基であるのが好ましく、それぞれ独立に水素原子又はメチル基であるのがより好ましい。一般式(iv)中、R12及びR13は、それぞれ水素原子であるのが更に好ましい。 In formulas (iv) to (vi), R 11 , R 12 and R 13 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a carbon number of 1 to 6 represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
In formulas (iv) to (vi), R 11 , R 12 and R 13 each independently represent preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently represents a hydrogen atom or methyl More preferred is a group. In General Formula (iv), each of R 12 and R 13 is more preferably a hydrogen atom.
また、式(v)中のYは、メチン基又は窒素原子を表す。 X 1 in the formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.
Moreover, Y in Formula (v) represents a methine group or a nitrogen atom.
4、R15、及び、R16としては、それぞれ独立に水素原子、又は炭素数が1~3のアルキル基が好ましく、水素原子がより好ましい。 In formula (vi), R 14 , R 15 and R 16 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like), or an alkyl group having 1 to 6 carbon atoms for example, a methyl group, an ethyl group, a propyl group, etc.), - Z 1, or an L 1 -Z 1. Wherein L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples. R 1
As 4 , R 15 and R 16 , each independently, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.
また、式(v)で表される単量体として、R11が水素原子又はメチル基であって、L1がアルキレン基であって、Z1がカルボン酸基であって、Yがメチン基である化合物が好ましい。
更に、式(vi)で表される単量体として、R14、R15、及びR16がそれぞれ独立に水素原子又はメチル基であって、L1が単結合又はアルキレン基であって、Z1がカルボン酸基である化合物が好ましい。 As a monomer represented by Formula (iv), R 11 , R 12 and R 13 each independently represent a hydrogen atom or a methyl group, and L 1 is a divalent having an alkylene group or an oxyalkylene structure. Compounds in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group are preferable.
Further, as a monomer represented by the formula (v), R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is a methine group Compounds which are are preferred.
Furthermore, as the monomer represented by the formula (vi), R 14 , R 15 and R 16 each independently represent a hydrogen atom or a methyl group, and L 1 represents a single bond or an alkylene group, and Z Compounds in which 1 is a carboxylic acid group are preferred.
単量体の例としては、メタクリル酸、クロトン酸、イソクロトン酸、分子内に付加重合性二重結合及び水酸基を含有する化合物(例えば、メタクリル酸2-ヒドロキシエチル)とコハク酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物とフタル酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物とテトラヒドロキシフタル酸無水物との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物と無水トリメリット酸との反応物、分子内に付加重合性二重結合及び水酸基を含有する化合物とピロメリット酸無水物との反応物、アクリル酸、アクリル酸ダイマー、アクリル酸オリゴマー、マレイン酸、イタコン酸、フマル酸、4-ビニル安息香酸、ビニルフェノール、及び、4-ヒドロキシフェニルメタクリルアミド等が挙げられる。 Hereinafter, representative examples of the monomers (compounds) represented by the formulas (iv) to (vi) are shown.
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, and the reaction of succinic anhydride with a compound having an addition-polymerizable double bond and hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate). , A reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with a phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule, and tetrahydroxyphthalic anhydride , A reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule, and pyromellitic anhydride Of acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and Hydroxyphenyl methacrylamide.
更に、高分子化合物は、画像強度等の諸性能を向上する目的で、本発明の効果を損なわない限りにおいて、グラフト鎖を含有する構造単位、疎水性構造単位、及び、顔料等と相互作用を形成しうる官能基を含有する構造単位とは異なる、種々の機能を有する他の構造単位(例えば、後述する溶剤との親和性を有する官能基等を含有する構造単位)を更に有していてもよい。
このような、他の構造単位としては、例えば、アクリロニトリル類、及び、メタクリロニトリル類等から選ばれるラジカル重合性化合物に由来の構造単位が挙げられる。
高分子化合物は、これらの他の構造単位を1種又は2種以上使用でき、その含有量は、質量換算で、高分子化合物の総質量に対して、0~80質量%が好ましく、10~60質量%以下がより好ましい。含有量が上記範囲において、十分なパターン形成性が維持される。 -Other Structural Units Furthermore, the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a pigment as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength. And other structural units having various functions (eg, structural units containing a functional group having an affinity for a solvent described later, etc.) different from the structural unit containing a functional group capable of forming an interaction with etc. Furthermore, you may have.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles and the like.
As the polymer compound, one or more of these other structural units can be used, and the content thereof is preferably 0 to 80% by mass with respect to the total mass of the polymer compound in terms of mass, 60 mass% or less is more preferable. Sufficient pattern formability is maintained in the above range of content.
高分子化合物の酸価は、0mg~250mgKOH/gの範囲であるのが好ましく、10~200mgKOH/gの範囲がより好ましく、20~120mgKOH/gの範囲が更に好ましい。
高分子化合物の酸価が160mgKOH/g以下であれば、硬化膜を形成する際の現像時におけるパターン剥離がより効果的に抑えられる。また、高分子化合物の酸価が10mgKOH/g以上であればアルカリ現像性がより良好となる。また、高分子化合物の酸価が20mgKOH/g以上であれば、顔料等の沈降をより抑制でき、粗大粒子数をより少なくでき、組成物の経時安定性をより向上できる。 Physical Properties of Polymer Compound The acid value of the polymer compound is preferably in the range of 0 mg to 250 mg KOH / g, more preferably in the range of 10 to 200 mg KOH / g, and still more preferably in the range of 20 to 120 mg KOH / g.
When the acid value of the polymer compound is 160 mg KOH / g or less, pattern peeling during development when forming a cured film can be more effectively suppressed. When the acid value of the polymer compound is 10 mg KOH / g or more, the alkali developability becomes better. In addition, when the acid value of the polymer compound is 20 mg KOH / g or more, sedimentation of the pigment and the like can be further suppressed, the number of coarse particles can be further reduced, and the temporal stability of the composition can be further improved.
高分子化合物は、公知の方法に基づいて合成できる。 The weight average molecular weight of the polymer compound is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, and still more preferably 6,000 to 100,000. Particular preference is given to 10,000 to 50,000.
The polymer compound can be synthesized based on a known method.
両性樹脂の市販品としては、例えば、ビックケミー社製のDISPERBYK-130、DISPERBYK-140、DISPERBYK-142、DISPERBYK-145、DISPERBYK-180、DISPERBYK-187、DISPERBYK-191、DISPERBYK-2001、DISPERBYK-2010、DISPERBYK-2012、DISPERBYK-2025、BYK-9076、味の素ファインテクノ社製のアジスパーPB821、アジスパーPB822、及び、アジスパーPB881等が挙げられる。
これらの高分子化合物は、1種を単独で用いても、2種以上を併用してもよい。 It is also preferred to use an amphoteric resin containing an acid group and a basic group. The amphoteric resin is preferably a resin having an acid value of 5 mg KOH / g or more and an amine value of 5 mg KOH / g or more.
As a commercial item of the amphoteric resin, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2001, DISPERBYK-2010, manufactured by BIC Chemie Examples include DISPERBYK-2012, DISPERBYK-2025, BYK-9076, and Ajisame Fine Techno Co., Ltd. Ajisper PB 821, Ajisper PB 822, and Ajisper PB 881 and the like.
One of these polymer compounds may be used alone, or two or more thereof may be used in combination.
また、上記以外にも、特開2011-153283号公報の段落0028~0084(対応するUS2011/0279759の段落0075~0133欄)の酸性基が連結基を介して結合してなる側鎖構造を含有する構成成分を含有する高分子化合物が使用でき、これらの内容は援用でき、本明細書に組み込まれる。 Further, as the dispersant, in addition to the above-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 of JP 2010-106268 A (columns 0075 to 0133 of corresponding US 2011/0124824) can be used. The contents of are incorporated herein by reference.
Moreover, it contains the side chain structure which the acidic group of Unexamined-Japanese-Patent No.2011-153283, Paragraph 0028-0084 (Correspondence US2011 / 02729759 corresponding column 0075-0133 column) joins via a coupling group besides the above. Polymer compounds containing the following components can be used, the contents of which can be incorporated and incorporated herein.
硬化性組成物は、アルカリ可溶性樹脂を含有するのが好ましい。本明細書において、アルカリ可溶性樹脂とは、アルカリ可溶性を促進する基(アルカリ可溶性基)を含有する樹脂を意図し、既に説明した分散剤とは異なる樹脂を意図する。
硬化性組成物中におけるアルカリ可溶性樹脂の含有量としては特に制限されないが、硬化性組成物の全固形分に対して、1~30質量%が好ましく、1~15質量%がより好ましい。
アルカリ可溶性樹脂は1種を単独で用いても、2種以上を併用してもよい。2種以上のアルカリ可溶性樹脂を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 (Alkali-soluble resin)
The curable composition preferably contains an alkali soluble resin. In the present specification, an alkali-soluble resin is intended to be a resin containing a group that promotes alkali solubility (alkali-soluble group), and is intended to be a resin different from the dispersant described above.
The content of the alkali-soluble resin in the curable composition is not particularly limited, but is preferably 1 to 30% by mass, and more preferably 1 to 15% by mass with respect to the total solid content of the curable composition.
The alkali-soluble resin may be used alone or in combination of two or more. When using 2 or more types of alkali-soluble resin together, it is preferable that total content is in the said range.
不飽和カルボン酸としては特に制限されないが、(メタ)アクリル酸、クロトン酸、及び、ビニル酢酸等のモノカルボン酸類;イタコン酸、マレイン酸、及び、フマル酸などのジカルボン酸、又は、その酸無水物;並びに、フタル酸モノ(2-(メタ)アクリロイロキシエチル)等の多価カルボン酸モノエステル類;等が挙げられる。 Specific examples of the alkali-soluble resin include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.
The unsaturated carboxylic acid is not particularly limited, but monocarboxylic acids such as (meth) acrylic acid, crotonic acid and vinyl acetic acid; itaconic acid, maleic acid and dicarboxylic acids such as fumaric acid or acid anhydride thereof And monohydric carboxylic acid monoesters such as phthalic acid mono (2- (meth) acryloyloxyethyl); and the like.
上記硬化性基としては、上述の高分子化合物が含有してもよい硬化性基が同様に挙げられ、好ましい範囲も同様である。
硬化性基を含有するアルカリ可溶性樹脂としては、硬化性基を側鎖に有するアルカリ可溶性樹脂等が好ましい。硬化性基を含有するアルカリ可溶性樹脂としては、ダイヤナールNRシリーズ(三菱レイヨン社製)、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社製)、サイクロマーPシリーズ(例えば、ACA230AA)、プラクセル CF200シリーズ(いずれもダイセル社製)、Ebecryl3800(ダイセル・オルネクス社製)、及び、アクリキュアRD-F8(日本触媒社製)等が挙げられる。 As the alkali-soluble resin, an alkali-soluble resin containing a curable group is also preferable.
As the said curable group, the curable group which the above-mentioned high molecular compound may contain is mentioned similarly, A preferable range is also the same.
As an alkali-soluble resin containing a curable group, an alkali-soluble resin having a curable group in a side chain is preferable. As an alkali-soluble resin containing a curable group, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (containing COOH containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), Biscoat R-264, KS resist 106 All of them are Osaka Organic Chemical Industry Co., Ltd., Cyclomer P series (for example, ACA 230 AA), Plaxcel CF 200 series (all of which are manufactured by Daicel), Ebecryl 3800 (manufactured by Daicel Ornex), And the like.
ポリイミド前駆体としては、例えば、式(1)で表される繰り返し単位を含有する樹脂が挙げられる。ポリイミド前駆体の構造としては、例えば、下記式(2)で示されるアミック酸構造と、アミック酸構造が一部イミド閉環してなる下記式(3)、及び、全てイミド閉環した下記式(4)で示されるイミド構造を含有するポリイミド前駆体が挙げられる。
なお、本明細書において、アミック酸構造を有するポリイミド前駆体をポリアミック酸ということがある。 A polyimide precursor can also be used as an alkali soluble resin. The polyimide precursor intends a resin obtained by the addition polymerization reaction of a compound containing an acid anhydride group and a diamine compound at 40 to 100 ° C.
As a polyimide precursor, resin containing the repeating unit represented by Formula (1) is mentioned, for example. Examples of the structure of the polyimide precursor include an amic acid structure represented by the following formula (2), a following formula (3) in which the amic acid structure is partially imide ring-closed, and a following formula (4) in which all imide ring closure The polyimide precursor containing the imide structure shown by these) is mentioned.
In the present specification, a polyimide precursor having an amic acid structure may be referred to as a polyamic acid.
アルカリ可溶性基を含有するポリイミド樹脂としては、特に制限されず、公知のアルカリ可溶性基を含有するポリイミド樹脂を使用できる。上記ポリイミド樹脂としては、例えば、特開2014-137523号公報の0050段落に記載された樹脂、特開2015-187676号公報の0058段落に記載された樹脂、及び、特開2014-106326号公報の0012~0013段落に記載された樹脂等が挙げられ、上記の内容は本明細書に組み込まれる。 The alkali-soluble resin contains at least one selected from the group consisting of a polyimide resin and a polyimide precursor in that the pattern shape of the cured film in a pattern obtained by using the curable composition is more excellent. Is also preferred.
The polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include a resin described in paragraph 0050 of JP-A-2014-137523, a resin described in paragraph 0058 of JP-A-2015-187676, and a resin described in JP-A-2014-106326. The resins described in the paragraphs [0012] to [0013] and the like are mentioned, and the above contents are incorporated in the present specification.
得られる硬化膜の断面形状の矩形性がより優れる点から、本発明の製造方法に用いられる硬化性組成物は、エチレン性不飽和基を含有する樹脂を含有するのが好ましい。エチレン性不飽和基を含有する樹脂は、分散剤であってもよくアルカリ可溶性樹脂であってもよい。また、分散剤又はアルカリ可溶性樹脂以外の樹脂であってもよい。
硬化性組成物中のエチレン性不飽和基を含有する樹脂の含有量の下限は、硬化性組成物が含有する樹脂全体の質量に対して、40質量%以上が好ましく、45質量%以上がより好ましく、50質量%以上が更に好ましい。
硬化性組成物中のエチレン性不飽和基を含有する樹脂の含有量の上限は、硬化性組成物が含有する樹脂全体の質量に対して、100質量%以下が好ましい。
なお、エチレン性不飽和基を含有する樹脂とは、1分子の中にエチレン性不飽和基を1個以上含有する樹脂をいう。 (Resin containing an ethylenically unsaturated group)
It is preferable that the curable composition used for the manufacturing method of this invention contains resin containing an ethylenically unsaturated group from the point which the rectangularity of the cross-sectional shape of the cured film obtained is more excellent. The resin containing an ethylenically unsaturated group may be a dispersant or an alkali soluble resin. Moreover, resin other than a dispersing agent or alkali-soluble resin may be sufficient.
The lower limit of the content of the resin having an ethylenically unsaturated group in the curable composition is preferably 40% by mass or more, more preferably 45% by mass or more based on the mass of the entire resin contained in the curable composition. Preferably, 50% by mass or more is more preferable.
The upper limit of the content of the resin containing an ethylenically unsaturated group in the curable composition is preferably 100% by mass or less based on the total mass of the resin contained in the curable composition.
In addition, resin containing an ethylenically unsaturated group means resin which contains one or more ethylenically unsaturated groups in 1 molecule.
なお、上記樹脂全質量とは、硬化性組成物に含まれる樹脂の合計質量を意図し、例えば、エチレン性不飽和基を含有する樹脂とエチレン性不飽和基を含有しない樹脂とを硬化性組成物が含有する場合、両者の合計質量が上記樹脂の合計質量に該当する。
したがって、上記エチレン性不飽和基の含有量は、樹脂全質量に対する、エチレン性不飽和基を含有する樹脂中のエチレン性不飽和基の含有量を表す。
また、樹脂とは、硬化性組成物中に溶解している成分であって、重量平均分子量が2000超である成分を意図する。 In addition, the content of the ethylenically unsaturated group is not particularly limited, but is preferably 0.001 to 5.00 mmol / g, more preferably 0.10 to 3.00 mmol / g, and the like. More preferred is 26 to 2.50 mmol / g. When the content of the ethylenically unsaturated group is in the range of 0.10 to 3.00 mmol / g, the rectangularity of the cross-sectional shape of a cured film obtained using the curable composition is more excellent.
In addition, the said resin total mass intends the total mass of resin contained in a curable composition, for example, curable composition of resin containing an ethylenically unsaturated group, and resin which does not contain an ethylenically unsaturated group When the substance contains, the total mass of both corresponds to the total mass of the above-mentioned resin.
Therefore, the content of the above-mentioned ethylenically unsaturated group represents the content of the ethylenically unsaturated group in the resin containing the ethylenically unsaturated group with respect to the total mass of the resin.
Moreover, resin is a component which is melt | dissolving in a curable composition, Comprising: The component whose weight average molecular weight is more than 2000 is intended.
本明細書において、エチレン性不飽和基含有量(C=C価)は、以下の方法により測定される値を意図する。なお、エチレン性不飽和基を含有する樹脂を合成する場合、原料の仕込み量から計算することにより、測定に代えることができる。
また、硬化性組成物が複数種類の樹脂を含有しており、かつ、各樹脂のC=C価が明らかである場合、各樹脂の配合比から、硬化性組成物が含有する樹脂全質量としてのC=C価を計算して求めてもよい。 In the present specification, the content of the ethylenically unsaturated group may be referred to as “C = C value”.
In the present specification, the ethylenically unsaturated group content (C = C number) is intended to be a value measured by the following method. In addition, when synthesize | combining resin containing an ethylenically unsaturated group, it can replace with measurement by calculating from the preparation amount of a raw material.
In addition, when the curable composition contains a plurality of resins, and the C = C value of each resin is clear, the total weight of the resin contained in the curable composition is determined from the compounding ratio of each resin. You may calculate and obtain | require C = C number of.
まず、遠心分離法によって硬化性組成物中の固体成分(黒色顔料等)を沈殿させて残った液体成分を分取する。更に、得られた液体成分から、GPC法で重量平均分子量が2000超である成分を分取し、これを測定対象の樹脂とする。
次に、測定対象となる樹脂0.25mgをTHF(tetrahydrofuran)50mLに溶解させ、更にメタノール15mLを添加し、溶液を作製する。
作製した溶液に、4N 水酸化ナトリウム水溶液を10mL加え、混合液を得る。次に、上記混合液を液温40℃で2時間撹拌する。更に、混合液に4N メタンスルホン酸水溶液を10.2mL添加し、撹拌する。更に、混合液に脱塩水を5mL添加し、続けてメタノール2mLを添加し、測定溶液を調製する。
測定溶液中の(メタ)アクリル酸の含有量を、HPLC(high performance liquid chromatography)法(絶対検量線法)により測定し、エチレン性不飽和基含有量を計算する。
HPLC測定条件カラム:Phenomenex製Synergi 4μ Polar-RP 80A(4.6mm×250mm)
カラム温度:40℃
流速:1.0mL/min
検出器波長:210nm
溶離液:THF(テトラヒドロフラン、HPLC用)55/バッファー水 45*バッファー水…0.2%-リン酸、0.2%-トリエチルアミン水溶液注入量:5μL As a method of measuring the ethylenically unsaturated group content of the resin, when the ethylenically unsaturated group is a (meth) acryloyl group, it is measured by the following method.
First, solid components (black pigment and the like) in the curable composition are precipitated by centrifugation, and the remaining liquid component is separated. Further, from the obtained liquid component, a component having a weight average molecular weight of more than 2000 is separated by a GPC method, and this is used as a resin to be measured.
Next, 0.25 mg of a resin to be measured is dissolved in 50 mL of THF (tetrahydrofuran), and 15 mL of methanol is further added to prepare a solution.
To the prepared solution, 10 mL of 4N aqueous sodium hydroxide solution is added to obtain a mixture. Next, the mixture is stirred at a liquid temperature of 40 ° C. for 2 hours. Further, 10.2 mL of 4 N aqueous methanesulfonic acid solution is added to the mixture and stirred. Furthermore, 5 mL of demineralized water is added to the mixture, followed by 2 mL of methanol to prepare a measurement solution.
The content of (meth) acrylic acid in the measurement solution is measured by a high performance liquid chromatography (HPLC) method (absolute calibration method) to calculate the ethylenically unsaturated group content.
HPLC measurement conditions Column: Phenomenex Synergi 4μ Polar-RP 80A (4.6 mm × 250 mm)
Column temperature: 40 ° C
Flow rate: 1.0 mL / min
Detector wavelength: 210 nm
Eluent: THF (tetrahydrofuran, for HPLC) 55 / buffer water 45 * buffer water ... 0.2%-phosphoric acid, 0.2%-triethylamine aqueous solution injection amount: 5 μL
なお、ここで、エチレン性不飽和基含有量は、上記臭素価で得られた測定する樹脂100gに対して付加した臭素(Br2)のグラム数(gBr2/100g)から、樹脂1g当たりの付加した臭素(Br2)のモル数に変換した値である。 As a method of measuring the ethylenically unsaturated group content of the resin, the ethylenically unsaturated group is a combination of a (meth) acryloyl group other than (meth) acryloyl group and a group other than a (meth) acryloyl group and a (meth) acryloyl group In some cases, a method of measuring the bromination of the resin to be measured that has been separated by the above-mentioned method may be mentioned. The bromine number is measured in accordance with JIS K2605: 1996.
Here, ethylenically unsaturated group content, bromine was added to the resin 100g of measurements obtained in bromine number (Br 2) grams of (gBr 2 / 100g), the resin per 1g It is a value converted to the number of moles of added bromine (Br 2 ).
硬化性組成物は、重合開始剤を含有するのが好ましい。
重合開始剤としては、特に制限されず、公知の重合開始剤を使用できる。重合開始剤としては、例えば、光重合開始剤、及び、熱重合開始剤等が挙げられ、光重合開始剤が好ましい。なお、重合開始剤としては、いわゆるラジカル重合開始剤が好ましい。
硬化性組成物中における重合開始剤の含有量としては特に制限されないが、硬化性組成物の全固形分に対して0.5~20質量%が好ましい。重合開始剤は、1種を単独で用いても、2種以上を併用してもよい。2種以上の重合開始剤を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 <Polymerization initiator>
The curable composition preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited, and known polymerization initiators can be used. As a polymerization initiator, a photoinitiator, a thermal-polymerization initiator etc. are mentioned, for example, A photoinitiator is preferable. In addition, as a polymerization initiator, what is called a radical polymerization initiator is preferable.
The content of the polymerization initiator in the curable composition is not particularly limited, but it is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition. The polymerization initiator may be used alone or in combination of two or more. When two or more polymerization initiators are used in combination, the total content is preferably in the above range.
熱重合開始剤としては、例えば、2,2’-アゾビスイソブチロニトリル(AIBN)、3-カルボキシプロピオニトリル、アゾビスマレノニトリル、及び、ジメチル-(2,2’)-アゾビス(2-メチルプロピオネート)[V-601]等のアゾ化合物、並びに、過酸化ベンゾイル、過酸化ラウロイル、及び、過硫酸カリウム等の有機過酸化物が挙げられる。
重合開始剤の具体例としては、例えば、加藤清視著「紫外線硬化システム」(株式会社総合技術センター発行:平成元年)の第65~148頁に記載されている重合開始剤などを挙げられる。 (Thermal polymerization initiator)
As a thermal polymerization initiator, for example, 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, and dimethyl- (2,2 ′)-azobis (2) Azo compounds such as -methyl propionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
Specific examples of the polymerization initiator include, for example, the polymerization initiators described on pages 65 to 148 of "UV Curing System" (Senior Technology Center Co., Ltd., published by General Technology Center, Inc.) published by Seiji Kato .
上記硬化性組成物は光重合開始剤を含有するのが好ましい。
光重合開始剤としては、重合性化合物の重合を開始できれば特に制限されず、公知の光重合開始剤を使用できる。光重合開始剤としては、例えば、紫外線領域から可視光領域に対して感光性を有する光重合開始剤が好ましい。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、重合性化合物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、300~800nm(330~500nmがより好ましい。)の範囲内に少なくとも50のモル吸光係数を有する化合物を、少なくとも1種含有しているのが好ましい。 (Photopolymerization initiator)
The curable composition preferably contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as polymerization of the polymerizable compound can be initiated, and known photopolymerization initiators can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity to an ultraviolet light region to a visible light region is preferable. In addition, it may be an activator that produces an action with photoexcited sensitizers to generate active radicals, and may be an initiator that initiates cationic polymerization depending on the type of the polymerizable compound.
The photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least 50 in the range of 300 to 800 nm (more preferably 330 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を参酌でき、この内容は本明細書に組み込まれる。 As the photopolymerization initiator, for example, a halogenated hydrocarbon derivative (for example, one containing a triazine skeleton, one containing an oxadiazole skeleton, etc.), an acylphosphine compound such as an acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP-A-2013-29760 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化合物としては、例えば、IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959、及び、IRGACURE-127(商品名:いずれもBASF社製)を使用できる。
アミノアセトフェノン化合物としては、例えば、市販品であるIRGACURE-907、IRGACURE-369、又は、IRGACURE-379EG(商品名:いずれもBASF社製)を使用できる。アミノアセトフェノン化合物としては、波長365nm又は波長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使用できる。
アシルホスフィン化合物としては、市販品であるIRGACURE-819、又は、IRGACURE-TPO(商品名:いずれもBASF社製)を使用できる。 More specifically, as the photopolymerization initiator, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone compound, for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Corporation) can be used.
As the aminoacetophenone compound, for example, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade name: all manufactured by BASF Corp.) can be used. As the aminoacetophenone compound, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long wave light source having a wavelength of 365 nm or a wavelength of 405 nm can also be used.
As an acyl phosphine compound, IRGACURE-819 which is a commercial item, or IRGACURE-TPO (trade name: all manufactured by BASF Corporation) can be used.
光重合開始剤として、オキシムエステル系重合開始剤(オキシム化合物)がより好ましい。特にオキシム化合物は高感度で重合効率が高く、硬化性組成物中における黒色顔料の含有量を高く設計しやすいため好ましい。
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、又は、特開2006-342166号公報記載の化合物を使用できる。
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-オン等が挙げられる。
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、及び、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)、IRGACURE-OXE03(BASF社製)、又は、IRGACURE-OXE04(BASF社製)も好ましい。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、アデカアークルズNCI-930(ADEKA社製)、又は、N-1919(カルバゾール・オキシムエステル骨格含有光開始剤(ADEKA社製)も使用できる。 -Oxime compound As a photoinitiator, an oxime ester-type polymerization initiator (oxime compound) is more preferable. In particular, oxime compounds are preferable because they have high sensitivity and high polymerization efficiency, and the black pigment content in the curable composition is easily designed to be high.
As specific examples of the oxime compound, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, or compounds described in JP-A-2006-342166 can be used.
Examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentan-3-one. 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy Examples include carbonyloxyimino-1-phenylpropan-1-one and the like.
Also, J.J. C. S. Perkin II (1979) pp. 1653-1660), J.F. C. S. Perkin II (1979) pp. 156-162, Journal
of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A-2000-66385, and compounds described in JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166, etc. are also listed. Be
Among commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) is also preferable. In addition, TR-PBG-304 (made by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Akuls NCI-831, Adeka Ark's NCI-930 (made by ADEKA), or N-1919 (carbazole oxime ester skeleton containing light) An initiator (made by ADEKA) can also be used.
例えば、特開2013-29760号公報の段落0274~0275を参酌でき、この内容は本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、オキシム化合物の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. Compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced at a dye site; a ketoxime compound described in WO 2009-131189; and a triazine skeleton and an oxime skeleton The compound described in US Pat. No. 7,556,910 contained in the same molecule; the compound described in JP-A 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source; etc. Good.
For example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, the contents of which are incorporated herein.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. Whether the N-O bond of the oxime compound is an oxime compound of (E) form, an oxime compound of (Z) form, or a mixture of (E) form and (Z) form Good.
式(OX-1)中、Rで表される1価の置換基としては、1価の非金属原子団であるのが好ましい。
1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、及び、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、更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又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、及び、アリール基等が挙げられる。
式(OX-1)中、Bで表される1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く、アリール基、又は、複素環基が好ましい。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。
式(OX-1)中、Aで表される2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、又は、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 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 Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetal atomic group.
Examples of the monovalent nonmetal atom 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. Also, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by the other 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, an aryl group and the like.
In the formula (OX-1), as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group is preferable, and an aryl group or a heterocyclic group is preferable. preferable. These groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified.
In the 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. As the substituent, the above-mentioned substituents can be exemplified.
また、上記式(3)及び(4)において、R1は、それぞれ独立に、メチル基、エチル基、n-プロピル基、i-プロピル基、シクロヘキシル基、又は、フェニル基が好ましい。R3はメチル基、エチル基、フェニル基、トリル基、又は、キシリル基が好ましい。R4は炭素数1~6のアルキル基、又は、フェニル基が好ましい。R5はメチル基、エチル基、フェニル基、トリル基、又は、ナフチル基が好ましい。Xは直接結合が好ましい。
式(1)及び式(2)で表される化合物の具体例としては、例えば、特開2014-137466号公報の0076~0079段落に記載された化合物が挙げられる。この内容は本明細書に組み込まれることとする。 In the above formulas (1) and (2), R 1 and R 2 are each independently preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
In the above formulas (3) and (4), R 1 is preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compounds represented by the formulas (1) and (2) include, for example, compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein by reference.
オキシム化合物の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であるのが好ましく、2,000~300,000であるのがより好ましく、5,000~200,000であるのが更に好ましい。
化合物のモル吸光係数は、公知の方法を使用できるが、例えば、紫外可視分光光度計(Varian社製Cary-5 spctrophotometer)にて、酢酸エチル溶媒を用い、0.01g/Lの濃度で測定するのが好ましい。
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よい。 The oxime compound preferably has a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a maximum absorption wavelength in a wavelength range of 360 to 480 nm, and still more preferably a high absorbance at 365 nm and 405 nm. .
From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, 5,000 to 200, More preferably, it is 000.
The molar absorptivity of the compound can be measured by a known method, for example, using an ethyl acetate solvent at a concentration of 0.01 g / L with an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian). Is preferred.
You may use a photoinitiator in combination of 2 or more types as needed.
硬化性組成物は、重合禁止剤を含有するのが好ましい。
重合禁止剤としては特に制限されず、公知の重合禁止剤を使用できる。重合禁止剤としては、例えば、フェノール系重合禁止剤(例えば、p-メトキシフェノール、2,5-ジ-tert-ブチル-4-メチルフェノール、2,6-ジtert-ブチル-4-メチルフェノール、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)、4-メトキシナフトール等);ハイドロキノン系重合禁止剤(例えば、ハイドロキノン、2,6-ジ-tert-ブチルハイドロキノン等);キノン系重合禁止剤(例えば、ベンゾキノン等);フリーラジカル系重合禁止剤(例えば、2,2,6,6-テトラメチルピペリジン1-オキシルフリーラジカル、4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン1-オキシルフリーラジカル等);ニトロベンゼン系重合禁止剤(例えば、ニトロベンゼン、4-ニトロトルエン等);及び、フェノチアジン系重合禁止剤(例えば、フェノチアジン、2-メトキシフェノチアジン等);等が挙げられる。
なかでも、硬化性組成物がより優れた効果を有する点で、フェノール系重合禁止剤、又は、フリーラジカル系重合禁止剤が好ましい。 <Polymerization inhibitor>
The curable composition preferably contains a polymerization inhibitor.
The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used. Examples of the polymerization inhibitor include phenolic polymerization inhibitors (eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4-methoxynaphthol etc .; hydroquinone polymerization inhibitors (eg Hydroquinone, 2,6-di-tert-butyl hydroquinone, etc .; quinone type polymerization inhibitors (eg, benzoquinone etc.); free radical polymerization inhibitors (eg, 2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical etc ; Nitrobenzene-based polymerization inhibitor (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitor (e.g., phenothiazine, 2-methoxy phenothiazine, etc.), and the like.
Among them, a phenol type polymerization inhibitor or a free radical type polymerization inhibitor is preferable in that the curable composition has more excellent effects.
硬化性組成物中における重合禁止剤の含有量としては特に制限されないが、硬化性組成物の全固形分に対して、0.0001~0.5質量%が好ましく、0.001~0.2質量%がより好ましい。重合禁止剤は、1種を単独で用いても、2種以上を併用してもよい。2種以上の重合禁止剤を併用する場合には、合計含有量が上記範囲内であるのが好ましい。 The effect of the polymerization inhibitor is remarkable when used together with a resin containing a curable group.
The content of the polymerization inhibitor in the curable composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, and more preferably 0.001 to 0.2%, based on the total solid content of the curable composition. % By mass is more preferred. The polymerization inhibitor may be used alone or in combination of two or more. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
硬化性組成物は、界面活性剤を含有してもよい。界面活性剤は、硬化性組成物の塗布性向上に寄与する。
上記硬化性組成物が、界面活性剤を含有する場合、界面活性剤の含有量としては、硬化性組成物の全固形分に対して、0.001~2.0質量%が好ましい。
界面活性剤は、1種を単独で用いても、2種以上を併用してもよい。界面活性剤を2種以上併用する場合は、合計量が上記範囲内であるのが好ましい。 <Surfactant>
The curable composition may contain a surfactant. The surfactant contributes to the improvement of the coatability of the curable composition.
When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
The surfactant may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total amount is preferably in the above range.
フッ素系界面活性剤としてブロックポリマーも使用でき、具体例としては、例えば特開第2011-89090号公報に記載されたが化合物が挙げられる。 Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like. The same F482, the same F554, and the same F780 (above, DIC Corporation); Florard FC430, the same FC431, and the same FC171 (above, Sumitomo 3M Co., Ltd.); Surfron S-382, the same SC-101 , SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by Asahi Glass Co., Ltd.) And PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA Corporation).
A block polymer can also be used as the fluorine-based surfactant, and as a specific example, for example, compounds described in JP-A No. 2011-89090 can be mentioned.
硬化性組成物は、紫外線吸収剤を含有してもよい。これにより、硬化膜のパターンの形状をより優れた(精細な)形状にできる。
紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、及び、トリアジン系の紫外線吸収剤を使用できる。これらの具体例としては、特開2012-068418号公報の段落0137~0142(対応するUS2012/0068292の段落0251~0254)の化合物が使用でき、これらの内容が援用でき、本明細書に組み込まれる。
他にジエチルアミノ-フェニルスルホニル系紫外線吸収剤(大東化学社製、商品名:UV-503)なども好適に用いられる。
紫外線吸収剤としては、特開2012-32556号公報の段落0134~0148に例示される化合物が挙げられる。
紫外線吸収剤の含有量は、硬化性組成物の全固形分に対して、0.001~15質量%が好ましく、0.01~10質量%がより好ましく、0.1~5質量%が更に好ましい。 <UV absorber>
The curable composition may contain a UV absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine) shape.
As a UV absorber, UV absorbers of salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type and triazine type can be used. As specific examples thereof, the compounds of paragraphs 0137 to 0142 of JP 2012-068418 A (corresponding to paragraphs 0251 to 0254 of corresponding US 2012/0068292) can be used, and the contents thereof can be incorporated and incorporated herein. .
In addition, diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Industries, trade name: UV-503) is preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs [0134] to [0148] of JP-A-2012-32556.
The content of the UV absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.1 to 5% by mass, based on the total solid content of the curable composition. preferable.
硬化性組成物はシランカップリング剤を含有してもよい。
シランカップリング剤とは、分子中に加水分解性基とそれ以外の官能基とを含有する化合物である。なお、アルコキシ基等の加水分解性基は、珪素原子に結合している。
加水分解性基とは、珪素原子に直結し、加水分解反応及び/又は縮合反応によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基、及び、アルケニルオキシ基が挙げられる。加水分解性基が炭素原子を含有する場合、その炭素数は6以下であるのが好ましく、4以下であるのがより好ましい。特に、炭素数4以下のアルコキシ基又は炭素数4以下のアルケニルオキシ基が好ましい。
また、基板上に硬化膜を形成する場合、シランカップリング剤は基板と硬化膜間の密着性を向上させるため、フッ素原子及び珪素原子(ただし、加水分解性基が結合した珪素原子は除く)を含まないのが好ましく、フッ素原子、珪素原子(ただし、加水分解性基が結合した珪素原子は除く)、珪素原子で置換されたアルキレン基、炭素数8以上の直鎖状アルキル基、及び、炭素数3以上の分岐鎖状アルキル基は含まないのが望ましい。 <Silane coupling agent>
The curable composition may contain a silane coupling agent.
The silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. In addition, hydrolysable groups, such as an alkoxy group, are couple | bonded with the silicon atom.
The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis reaction and / or condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned, for example. When the hydrolyzable group contains a carbon atom, the carbon number thereof is preferably 6 or less, more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
When a cured film is formed on a substrate, the silane coupling agent improves the adhesion between the substrate and the cured film, so fluorine atoms and silicon atoms (but excluding silicon atoms to which a hydrolyzable group is bonded) It is preferable not to contain, and a fluorine atom, a silicon atom (but excluding a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, It is desirable not to include a branched alkyl group having 3 or more carbon atoms.
上記硬化性組成物は、シランカップリング剤を1種単独で含んでいてもよく、2種以上を含んでいてもよい。硬化性組成物がシランカップリング剤を2種以上含有する場合は、その合計が上記範囲内であればよい。 The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, and more preferably 0.5 to 8% by mass, relative to the total solid content in the curable composition. 1.0 to 6% by mass is more preferable.
The said curable composition may contain the silane coupling agent individually by 1 type, and may contain 2 or more types. When a curable composition contains 2 or more types of silane coupling agents, the sum total should just be in the said range.
硬化性組成物は、溶剤を含有するのが好ましい。
溶剤としては特に制限されず公知の溶剤を使用できる。
硬化性組成物中における溶剤の含有量としては特に制限されないが、硬化性組成物の固形分が10~90質量%となるように調整されるのが好ましく、15~90質量%となるように調整されるのがより好ましい。
溶剤は1種を単独で用いても、2種以上を併用してもよい。2種以上の溶剤を併用する場合には、硬化性組成物の全固形分が上記範囲内となるように調整されるのが好ましい。 <Solvent>
The curable composition preferably contains a solvent.
The solvent is not particularly limited and known solvents can be used.
Although the content of the solvent in the curable composition is not particularly limited, it is preferably adjusted so that the solid content of the curable composition is 10 to 90% by mass, and is 15 to 90% by mass. It is more preferable to be adjusted.
The solvents may be used alone or in combination of two or more. When using 2 or more types of solvents together, it is preferable to adjust so that the total solid of a curable composition may become in the said range.
有機溶剤としては、例えば、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、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、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、シクロペンタノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、3-メトキシプロパノール、メトキシメトキシエタノール、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ジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、3-メトキシプロピルアセテート、N,N-ジメチルホルムアミド、ジメチルスルホキシド、γ-ブチロラクトン、酢酸ブチル、乳酸メチル、N-メチル-2-ピロリドン、及び、乳酸エチル等が挙げられるが、これらに限定されない。 As a solvent, water and an organic solvent are mentioned, for example.
Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone , Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Ethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, butyl acetate, Examples thereof include, but are not limited to, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.
硬化性組成物は、まず、黒色顔料及び着色剤を分散させた分散組成物を製造し、得られた分散組成物を更にその他の成分と混合して硬化性組成物とするのが好ましい。
分散組成物は、黒色顔料、着色剤、樹脂(好ましくは分散剤)、及び、溶剤を混合して調製するのが好ましい。また、分散組成物に重合禁止剤を含有させるのも好ましい。 [Method of producing curable composition]
In the curable composition, it is preferable to first prepare a dispersion composition in which a black pigment and a colorant are dispersed, and further mix the obtained dispersion composition with other components to obtain a curable composition.
The dispersion composition is preferably prepared by mixing a black pigment, a colorant, a resin (preferably a dispersant), and a solvent. It is also preferable to incorporate a polymerization inhibitor in the dispersion composition.
フィルタの孔径は、0.1~7.0μmが好ましく、0.2~2.5μmがより好ましく、0.2~1.5μmが更に好ましく、0.3~0.7μmが特に好ましい。この範囲とすることにより、顔料(黒色顔料を含む)のろ過詰まりを抑えつつ、顔料に含まれる不純物及び凝集物など、微細な異物を確実に除去できるようになる。
フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第1のフィルタでのフィルタリングは、1回のみでもよいし、2回以上行ってもよい。異なるフィルタを組み合わせて2回以上フィルタリングを行う場合は1回目のフィルタリングの孔径より2回目以降の孔径が同じ、又は、大きい方が好ましい。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)、及び、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フィルタを使用できる。第2のフィルタの孔径は、0.2~10.0μmが好ましく、0.2~7.0μmがより好ましく、0.3~6.0μmが更に好ましい。
硬化性組成物は、金属、ハロゲンを含む金属塩、酸、アルカリ等の不純物を含まないのが好ましい。これら材料に含まれる不純物の含有量としては、1ppm以下が好ましく、1ppb以下がより好ましく、100ppt以下が更に好ましく、10ppt以下が特に好ましく、実質的に含まないこと(測定装置の検出限界以下であること)が最も好ましい。
なお、上記不純物は、誘導結合プラズマ質量分析装置(横河アナリティカルシステムズ製、Agilent 7500cs型)により測定できる。 The curable composition is preferably filtered through a filter for the purpose of removing foreign matter and reducing defects. As a filter, if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular. For example, a filter made of a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP) can be mentioned. . Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, still more preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filter clogging of the pigment (including the black pigment).
When using filters, different filters may be combined. At this time, the filtering with the first filter may be performed only once or may be performed twice or more. When different filters are combined to perform filtering twice or more, it is preferable that the second and subsequent pore sizes be the same or larger than the pore size of the first filtering. Moreover, you may combine the 1st filter of the hole diameter which is different within the range mentioned above. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it is possible to select from, for example, various filters provided by Nippon Pall Co., Advantec Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like.
The second filter can use a filter formed of the same material as the first filter described above. The pore size of the second filter is preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and still more preferably 0.3 to 6.0 μm.
The curable composition is preferably free of impurities such as metals, metal salts containing halogen, acids, alkalis and the like. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially not including (less than detection limit of measuring device Is most preferred.
The above impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
上記光硬化性組成物を用いて形成された硬化性組成物層(組成物層)を硬化してパターン状の硬化膜を得ることができる。
より具体的には、本発明の製造方法は、上述の硬化性組成物を用いて、膜厚1.5μmあたりの波長365nmにおける光学濃度Aが2.60~10.00となり、かつ、膜厚1.5μmあたりの波長550nmにおける光学濃度Bが2.00~10.00となる硬化性組成物層を形成する工程(硬化性組成物層形成工程)と、
上記硬化性組成物層を酸素濃度が30~50体積%の条件下で露光する工程(露光工程)と、
上記露光後の上記硬化性組成物層を現像して硬化膜を形成する工程(現像工程)と、
を含有する。
また、所望により現像工程の後にポストベークを行ってもよい。
以下、上記の各工程について説明する。 [Method of producing a cured film]
The curable composition layer (composition layer) formed using the above-mentioned photocurable composition can be cured to obtain a cured film in a pattern.
More specifically, the production method of the present invention makes it possible to obtain an optical density A of 2.60 to 10.00 at a wavelength of 365 nm per 1.5 μm of film thickness using the above-described curable composition, and Forming a curable composition layer having an optical density B at a wavelength of 550 nm per 1.5 μm of 2.00 to 10.00 (curable composition layer forming step),
Exposing the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume (exposure step);
Developing the curable composition layer after the exposure to form a cured film (developing step);
Contains
Also, if desired, post-baking may be performed after the developing step.
Hereinafter, each of the above steps will be described.
硬化性組成物層形成工程においては、露光に先立ち、支持体等の上に、硬化性組成物を付与して硬化性組成物の層(硬化性組成物層)を形成する。支持体としては、例えば、基板(例えば、シリコン基板)上にCCD(Charge Coupled Device)又はCMOS(Complementary Metal-Oxide Semiconductor)等の撮像素子(受光素子)が設けられた固体撮像素子用基板を使用できる。また、支持体上には、必要により、上部の層との密着改良、物質の拡散防止及び基板表面の平坦化等のために下塗り層を設けてもよい。 [Curable Composition Layer Forming Step]
In the curable composition layer forming step, prior to exposure, the curable composition is applied on a support or the like to form a layer of the curable composition (curable composition layer). As a support, for example, a substrate for a solid-state imaging device in which an imaging device (light receiving device) such as a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS) is provided on a substrate (for example, a silicon substrate) it can. In addition, if necessary, a subbing layer may be provided on the support for the purpose of improving adhesion with the upper layer, preventing diffusion of substances, flattening of the substrate surface, and the like.
本発明の製造方法において、硬化性組成物層(好ましくは乾燥(プリベーク)された硬化性組成物層、又は、自然乾燥された硬化性組成物層)は、光学濃度Aが2.60~10.00であり、得られる硬化膜の断面形状の矩形性がより優れる点から、2.80~4.00であるのが好ましく、2.90~3.50であるのがより好ましい。
同様に、光学濃度Bは、2.00~10.00であり、得られる硬化膜の断面形状の矩形性がより優れる点から、2.50~7.00が好ましく、2.80~6.50がより好ましい。
また、光学濃度Aに対する光学濃度Bの比(光学濃度B/光学濃度A)は0.3~3.5が好ましく、0.5~2.0がより好ましく、0.8~1.2が更に好ましい。 <Curable composition layer>
In the production method of the present invention, the curable composition layer (preferably a dried (prebaked) curable composition layer or a naturally dried curable composition layer) has an optical density A of 2.60 to 10 It is preferably 2.00 to 4.00, and more preferably 2.90 to 3.50 from the viewpoint that the rectangularity of the cross-sectional shape of the resulting cured film is further improved.
Similarly, the optical density B is from 2.00 to 10.00, and it is preferably 2.50 to 7.00, and 2.80 to 6 from the viewpoint that the rectangularity of the cross-sectional shape of the obtained cured film is more excellent. 50 is more preferred.
The ratio of optical density B to optical density A (optical density B / optical density A) is preferably 0.3 to 3.5, more preferably 0.5 to 2.0, and 0.8 to 1.2. More preferable.
なお、硬化性組成物層の膜厚が1.5μmである場合、透過濃度計で測定した値をそのまま使用できる。 In the present specification, as a method of measuring the optical density A and the optical density B, first, a curable composition layer dried on a glass substrate is formed, and a transmission densitometer (X-rite 361 T (visual) is provided. The film thickness is also measured using a densitometer, and the optical density per 1.5 μm of film thickness is calculated.
In addition, when the film thickness of a curable composition layer is 1.5 micrometers, the value measured with the transmission densitometer can be used as it is.
露光工程では、硬化性組成物層を酸素濃度が30~50体積%の条件下で露光できればよく、例えば、ステッパー等の露光装置を用い、所定のマスクパターンを有するマスクを介して硬化性組成物層をパターン露光する態様が挙げられる。
露光の際の光としては、g線、h線、i線、KrF線(エキシマレーザー線)、及びArF線(エキシマレーザー線)から選ばれる光が挙げられる。
放射照度は、20000~50000W/m2が好ましく、25000~40000W/m2がより好ましい。 [Exposure process]
In the exposure step, the curable composition layer may be exposed under conditions of an oxygen concentration of 30 to 50% by volume. For example, using an exposure apparatus such as a stepper, the curable composition may be through a mask having a predetermined mask pattern. The aspect which pattern-exposes a layer is mentioned.
Examples of light at the time of exposure include light selected from g-rays, h-rays, i-rays, KrF rays (excimer laser rays), and ArF rays (excimer laser rays).
Irradiance is preferably 20000 ~ 50000W / m 2, more preferably 25000 ~ 40000W / m 2.
このような条件下で露光を行うことで、得られる硬化膜の断面形状の矩形性が良好となる。
この酸素濃度の制御は、通常の手法によって行うことができる。例えば、露光装置を内包した装置室内を密閉構造として、所望の割合の酸素ガスと窒素ガスとを供給して、室内の酸素濃度を調節できる。または、露光装置の室内に所定流量の酸素ガスと窒素ガスとを流通させ、露光雰囲気が所定の酸素濃度とするようにしてもよい。 The exposure step is performed under the conditions of an oxygen concentration of 30 to 50% by volume.
By performing exposure under such conditions, the rectangularity of the cross-sectional shape of the obtained cured film is improved.
Control of this oxygen concentration can be performed by a usual method. For example, the apparatus chamber containing the exposure apparatus has a sealed structure, and oxygen gas and nitrogen gas in a desired ratio can be supplied to adjust the oxygen concentration in the room. Alternatively, oxygen gas and nitrogen gas of predetermined flow rates may be circulated in the chamber of the exposure apparatus so that the exposure atmosphere has a predetermined oxygen concentration.
式(1) X×Y÷Z Here, in the manufacturing method of the present invention, when the optical density A is X, the oxygen concentration (volume fraction) at the time of exposure is Y, and the irradiance (W / m 2 ) is Z, calculation is performed by the following formula (1) The value to be set is preferably 1.60 × 10 −5 to 10.00 × 10 −5, and more preferably 2.80 × 10 −5 to 5.20 × 10 −5 .
Formula (1) X × Y ÷ Z
露光時の酸素濃度であるYが大きい場合、硬化性組成物層の表層部での硬化反応が酸素によって抑制されやすくなる。
放射照度(W/m2)であるZが大きい場合、硬化性組成物層の表層部と下層部の両方において硬化反応を促進する。
これらの硬化性組成物層の硬化の進行に密接に関連した、X、Y、及び、Zが組み合わされた式(1)で計算される値が、上述のような範囲内に収まる場合、硬化膜の矩形性が良好になる。
また、調製してから長期間(例えば1か月)経過した硬化性組成物を用いた場合でも、式(1)で計算される値が、上述のような範囲内に収まる場合、作製される硬化膜の断面形状の矩形性が劣化しにくい。 When X, which is the optical density A in the formula (1), is large, the light irradiated in the exposure step is likely to be blocked at the surface layer portion of the curable composition layer, and the curing reaction in the lower layer portion hardly progresses.
When Y which is an oxygen concentration at the time of exposure is large, the curing reaction in the surface layer portion of the curable composition layer is easily suppressed by oxygen.
When Z, which is the irradiance (W / m 2 ), is large, the curing reaction is promoted in both the surface layer portion and the lower layer portion of the curable composition layer.
Curing if the value calculated by the equation (1) in which X, Y and Z are combined, which is closely related to the progress of curing of these curable composition layers, falls within the above-mentioned range The rectangularity of the film is good.
In addition, even when using a curable composition which has been prepared for a long time (for example, one month), it is produced when the value calculated by the formula (1) falls within the above range. The rectangularity of the cross-sectional shape of the cured film does not easily deteriorate.
光学濃度Aが3.00である硬化性組成物層に対して、酸素濃度が30質量%、放射照度が30000W/m2の条件で露光を行う場合、X=3.00、Y=0.30、Z=30000となり、式(1)の計算値は3.00×10-5である。 The specific calculation based on Formula (1) is as follows, for example.
In the case of performing exposure under the conditions of an oxygen concentration of 30% by mass and an irradiance of 30,000 W / m 2 to the curable composition layer having an optical density A of 3.00, X = 3.00, Y = 0. 30, Z = 30000, and the calculated value of equation (1) is 3.00 × 10 −5 .
現像工程は、露光後の上記硬化性組成物層を現像して硬化膜を形成する工程である。本工程により、露光工程における光未照射部分の硬化性組成物層が溶出し、光硬化した部分だけが残り、パターン状の硬化膜が得られる。
現像工程で使用される現像液の種類は特に制限されないが、下地の撮像素子及び回路などにダメージを起さない、アルカリ現像液が望ましい。
現像温度としては、例えば、20~30℃である。
現像時間は、例えば、20~90秒である。より残渣を除去するため、近年では120~180秒実施する場合もある。更には、より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、更に新たに現像液を供給する工程を数回繰り返す場合もある。 [Development process]
The developing step is a step of developing the curable composition layer after exposure to form a cured film. In this step, the curable composition layer in the non-light-irradiated portion in the exposure step is eluted, and only the light-cured portion remains, and a patterned cured film is obtained.
The type of developing solution used in the developing step is not particularly limited, but an alkaline developing solution which does not cause damage to the underlying imaging device and circuit is desirable.
The development temperature is, for example, 20 to 30.degree.
The developing time is, for example, 20 to 90 seconds. In order to remove more residue, it may be carried out for 120 to 180 seconds in recent years. Furthermore, in order to further improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
アルカリ性化合物は、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,硅酸ナトリウム、メタ硅酸ナトリウム、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシ、ベンジルトリメチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、及び、1,8-ジアザビシクロ[5.4.0]-7-ウンデセン等が挙げられる(このうち、有機アルカリが好ましい。)。
なお、アルカリ現像液として用いた場合は、一般に現像後に水で洗浄処理が施される。 The alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water so that the concentration is 0.001 to 10% by mass (preferably 0.01 to 5% by mass).
The alkaline compound is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium borate, sodium metaborate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl Ammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo [5.4.0] -7-undecene etc. (of which the organic alkali is preferable.).
In addition, when using as an alkali developing solution, washing processing is generally performed by water after image development.
露光工程の後、加熱処理(ポストベーク)を行うことが好ましい。ポストベークは、硬化を完全にするための現像後の加熱処理である。その加熱温度は、240℃以下が好ましく、220℃以下がより好ましい。下限は特にないが、効率的かつ効果的な処理を考慮すると、50℃以上が好ましく、100℃以上がより好ましい。
ポストベークは、ホットプレート、コンベクションオーブン(熱風循環式乾燥機)、又は、高周波加熱機等の加熱手段を用いて、連続式又はバッチ式で行うことができる。 Post-bake
After the exposure step, heat treatment (post-baking) is preferably performed. Post-baking is a heat treatment after development to complete curing. 240 degrees C or less is preferable and, as for the heating temperature, 220 degrees C or less is more preferable. There is no particular lower limit, but in consideration of efficient and effective treatment, 50 ° C. or higher is preferable, and 100 ° C. or higher is more preferable.
Post-baking can be performed by a continuous system or a batch system using heating means, such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater.
この場合、上述した硬化性組成物は、更にUV硬化剤を含有するのが好ましい。UV硬化剤は、通常のi線露光によるリソグラフィー工程のために添加する重合開始剤の露光波長である365nmより短波の波長で硬化できるUV硬化剤が好ましい。UV硬化剤としては、例えば、チバ イルガキュア 2959(商品名)が挙げられる。UV照射を行う場合においては、硬化性組成物層が波長340nm以下で硬化する材料であるのが好ましい。波長の下限値は特にないが、220nm以上であるのが一般的である。またUV照射の露光量は100~5000mJが好ましく、300~4000mJがより好ましく、800~3500mJが更に好ましい。このUV硬化工程は、リソグラフィー工程の後に行うことが、低温硬化をより効果的に行うために、好ましい。露光光源はオゾンレス水銀ランプを使用するのが好ましい。 Also, instead of the post-baking by heating described above, UV (ultraviolet) irradiation may complete the curing.
In this case, the curable composition described above preferably further contains a UV curing agent. The UV curing agent is preferably a UV curing agent that can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for the lithography process by ordinary i-ray exposure. Examples of UV curing agents include Ciba Irgacure 2959 (trade name). When UV irradiation is performed, the curable composition layer is preferably a material that cures at a wavelength of 340 nm or less. Although the lower limit of the wavelength is not particularly limited, it is generally 220 nm or more. The exposure dose of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and still more preferably 800 to 3500 mJ. This UV curing step is preferably performed after the lithography step in order to perform low temperature curing more effectively. The exposure light source is preferably an ozoneless mercury lamp.
〔硬化膜の物性〕
本発明の製造方法で得られる硬化膜は、膜厚1.5μmあたりの波長365nmにおける光学濃度は、2.60~10.00が好ましく、2.80~4.00がより好ましく、2.90~3.50が更に好ましい。
本発明の製造方法で得られる硬化膜の、膜厚1.5μmあたりの波長550nmにおける光学濃度は、2.00~10.00が好ましく、2.50~7.00がより好ましく、2.80~6.50が更に好ましい。
また、硬化膜は、後述する遮光膜とした場合の性能がより優れる点で、硬化膜の、400~1200nmの波長領域における膜厚1.5μmあたりの光学濃度は、2.00超が好ましく、3.00超がより好ましい。なお、上限値は特に制限されないが、10以下が好ましい。このような硬化膜は、遮光膜として好ましく使用できる。
なお、本明細書において、硬化膜の光学濃度の測定方法としては、まず、ガラス基板上硬化膜を形成して、透過濃度計(X-rite 361T(visual)densitometer)を用いて測定し、測定箇所の膜厚も測定し、所定の膜厚あたりの光学濃度を算出する。
また、本明細書において、400~1200nmの波長領域における膜厚1.5μmあたりの光学濃度が、2.00超とは、波長400~1200nmの全域において、膜厚1.5μmあたりの光学濃度が2.00超であることを意図する。 [Physical properties of cured film, and application of cured film]
[Physical properties of cured film]
The cured film obtained by the production method of the present invention preferably has an optical density at a wavelength of 365 nm per 1.5 μm of film thickness of 2.60 to 10.00, more preferably 2.80 to 4.00, 2.90 -3.50 is more preferable.
The optical density at a wavelength of 550 nm per 1.5 μm of film thickness of the cured film obtained by the production method of the present invention is preferably 2.00 to 10.00, more preferably 2.50 to 7.00, 2.80 To 6.50 is more preferable.
The cured film preferably has an optical density of more than 2.00 per 1.5 μm in the wavelength region of 400 to 1200 nm, since the cured film has better performance when used as a light shielding film described later. More than 3.00 is more preferable. Although the upper limit value is not particularly limited, it is preferably 10 or less. Such a cured film can be preferably used as a light shielding film.
In the present specification, as a method of measuring the optical density of a cured film, first, a cured film on a glass substrate is formed, and measurement is performed using a transmission densitometer (X-rite 361 T (visual) densitometer). The film thickness of the portion is also measured, and the optical density per predetermined film thickness is calculated.
In the present specification, an optical density of 1.5 μm or more in the wavelength range of 400 to 1200 nm means an optical density of 1.5 μm or more in the entire wavelength range of 400 to 1200 nm. Intended to be over 2.00.
硬化膜の反射率は、5%以下が好ましく、3%以下がより好ましく、2%以下が更に好ましい。
表面凹凸構造を作製する方法は特に限定されないが、硬化膜若しくはそれ以外の層に、有機フィラー及び/又は無機フィラーを含む方法、露光現像を利用したリソグラフィー法、又は、エッチング法、スパッタ法及びナノインプリント法などで硬化膜若しくはそれ以外の層の表面を粗面化する方法であってもよい。
また、上記硬化膜の反射率をさげる方法としては、上記以外に、硬化膜上に低屈折率層を設ける方法、更に屈折率の異なる層(例えば、高屈折率層)を複数設ける方法、及び、特開2015-1654号公報に記載の、低光学濃度層と高光学濃度層とを形成する方法等が挙げられる。 Moreover, it is also preferable that the said cured film has a surface asperity structure. By doing so, the reflectance of the cured film can be reduced when the cured film is a light shielding film. Even if it has a concavo-convex structure on the surface of a cured film itself, another layer may be provided on a cured film and a concavo-convex structure may be given. The shape of the surface asperity structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 μm to 1.5 μm.
5% or less is preferable, as for the reflectance of a cured film, 3% or less is more preferable, and 2% or less is still more preferable.
Although the method for producing the surface concavo-convex structure is not particularly limited, a method including an organic filler and / or an inorganic filler in a cured film or other layers, a lithography method using exposure and development, or an etching method, a sputtering method and nanoimprinting The surface of the cured film or other layers may be roughened by a method or the like.
In addition to the above methods, a method of providing a low refractive index layer on the cured film, a method of providing a plurality of layers having different refractive indexes (for example, high refractive index layers), and a method of reducing the reflectance of the cured film And a method of forming a low optical density layer and a high optical density layer, as described in JP-A-2015-1654.
マイクロLED及びマイクロOLEDの例としては、特表2015-500562号及び特表2014-533890に記載されたものが挙げられる。 The said cured film can be used also for uses, such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The said cured film is suitable for the member which provides a light shielding function or an antireflection function other than the optical filter and optical film which are used for micro LED and micro OLED.
Examples of micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.
本発明の製造方法で得られた硬化膜は、いわゆる遮光膜として使用するのも好ましい。このような遮光膜は、固体撮像素子に使用するのも好ましい。
なお、遮光膜は、本発明の製造方法で得られる硬化膜における好ましい用途の1つであって、本発明の遮光膜の製造方法は、上述の硬化膜の製造方法として説明した方法で同様に行える。具体的には、基板に硬化性組成物を塗布して、硬化性組成物層を形成し、露光、及び、現像して遮光膜を製造できる。
また、本発明の固体撮像素子の製造方法は、上述した本発明の製造方法を介して硬化膜(遮光膜)を製造する工程を含有する、上記硬化膜(遮光膜)を有する固体撮像素子を製造する方法である。
上述の通り、本発明の製造方法に係る、固体撮像素子は、上記硬化膜(遮光膜)を含有する。固体撮像素子が硬化膜(遮光膜)を含有する形態としては特に制限されず、例えば、基板上に、固体撮像素子(CCDイメージセンサ、CMOSイメージセンサ等)の受光エリアを構成する複数のフォトダイオード及びポリシリコン等からなる受光素子を有し、支持体の受光素子形成面側(例えば、受光部以外の部分及び/又は色調整用画素等)又は形成面の反対側に硬化膜を有するものが挙げられる。
固体撮像装置は、上記固体撮像素子を含有する。 [Light-shielding film, solid-state imaging device and solid-state imaging device]
It is also preferable to use the cured film obtained by the manufacturing method of the present invention as a so-called light shielding film. It is also preferable to use such a light shielding film for a solid-state imaging device.
In addition, a light shielding film is one of the preferable uses in the cured film obtained by the manufacturing method of this invention, Comprising: The manufacturing method of the light shielding film of this invention is similarly the method demonstrated as the manufacturing method of the above-mentioned cured film. It can do. Specifically, the curable composition is applied to a substrate to form a curable composition layer, and the light shielding film can be produced by exposure and development.
Further, a method of manufacturing a solid-state imaging device according to the present invention includes a step of manufacturing a cured film (light shielding film) through the above-described manufacturing method of the present invention, the solid-state imaging device having the cured film (light shielding film) It is a method of manufacturing.
As described above, the solid-state imaging device according to the manufacturing method of the present invention contains the cured film (light shielding film). The form in which the solid-state imaging device contains a cured film (light-shielding film) is not particularly limited. For example, a plurality of photodiodes constituting the light receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate And a light receiving element made of polysilicon or the like, and having a cured film on the light receiving element forming surface side of the support (for example, a portion other than the light receiving portion and / or a pixel for color adjustment) It can be mentioned.
The solid-state imaging device contains the above-described solid-state imaging device.
図1に示すように、固体撮像装置100は、矩形状の固体撮像素子101と、固体撮像素子101の上方に保持され、この固体撮像素子101を封止する透明なカバーガラス103とを備えている。更に、このカバーガラス103上には、スペーサー104を介してレンズ層111が重ねて設けられている。レンズ層111は、支持体113とレンズ材112とで構成されている。レンズ層111は、支持体113とレンズ材112とが一体成形された構成でもよい。レンズ層111の周縁領域に迷光が入射すると光の拡散によりレンズ材112での集光の効果が弱くなり、撮像部102に届く光が低減する。また、迷光によるノイズの発生も生じる。そのため、このレンズ層111の周縁領域は、遮光膜114が設けられて遮光されている。本発明の製造方法で得られる硬化膜は上記遮光膜114としても使用できる。 A configuration example of a solid-state imaging device and a solid-state imaging device will be described with reference to FIGS. In addition, in FIGS. 1 and 2, in order to clarify each part, the mutual thickness and / or the ratio of the width is neglected and is partially displayed in an exaggerated manner.
As shown in FIG. 1, the solid-
遮光膜212上には、BPSG(borophospho silicate glass)からなる絶縁膜213、P-SiNからなる絶縁膜(パシベーション膜)214、透明樹脂等からなる平坦化膜215からなる透明な中間層が設けられている。カラーフィルタ202は、中間層上に形成されている。 A
On the
本発明の製造方法で製造される画像表示装置は、本発明の製造方法で得られる硬化膜を含有する。
また、本発明の画像表示装置の製造方法は、上述した本発明の製造方法を介して硬化膜を製造する工程を含有する、上記硬化膜を有する画像表示装置を製造する方法である。
画像表示装置が硬化膜を有する形態としては、例えば、硬化膜がブラックマトリクスに含有され、このようなブラックマトリクスを含有するカラーフィルタが、画像表示装置に使用される形態が挙げられる。
次に、ブラックマトリクス及びブラックマトリクスを含有するカラーフィルタについて説明し、更に、画像表示装置の具体例として、このようなカラーフィルタを含有する液晶表示装置について説明する。 [Image display device]
The image display manufactured by the manufacturing method of this invention contains the cured film obtained by the manufacturing method of this invention.
Further, a method of producing an image display device of the present invention is a method of producing an image display device having the above-mentioned cured film, including the step of producing a cured film through the above-mentioned production method of the present invention.
As a form in which an image display apparatus has a cured film, a form in which a cured film is contained in a black matrix, and the color filter containing such a black matrix is used for an image display apparatus is mentioned, for example.
Next, a black matrix and a color filter containing the black matrix will be described, and a liquid crystal display device containing such a color filter will be described as a specific example of the image display device.
本発明の製造方法で得られる硬化膜は、ブラックマトリクスに含有されるのも好ましい。ブラックマトリクスは、カラーフィルタ、固体撮像素子、及び、液晶表示装置などの画像表示装置に含有される場合がある。
ブラックマトリクスとしては、上記で既に説明したもの;液晶表示装置等の画像表示装置の周縁部に設けられた黒色の縁;赤、青、及び、緑の画素間の格子状、及び/又は、ストライプ状の黒色の部分;TFT(thin film transistor)遮光のためのドット状、及び/又は、線状の黒色パターン;等が挙げられる。このブラックマトリクスの定義については、例えば、菅野泰平著、「液晶ディスプレイ製造装置用語辞典」、第2版、日刊工業新聞社、1996年、p.64に記載がある。
ブラックマトリクスは表示コントラストを向上させるため、また薄膜トランジスタ(TFT)を用いたアクティブマトリックス駆動方式の液晶表示装置の場合には光の電流リークによる画質低下を防止するため、高い遮光性(光学濃度ODで3以上)を有するのが好ましい。 <Black matrix>
It is also preferable that the cured film obtained by the production method of the present invention is contained in a black matrix. The black matrix may be contained in an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.
As the black matrix, those already described above; black edges provided at the periphery of an image display device such as a liquid crystal display device; grids between red, blue and green pixels, and / or stripes Black portions; dot-like and / or linear black patterns for light shielding of TFT (thin film transistor); and the like. For the definition of the black matrix, see, for example, Taiho Ogino, "Glossary of Liquid Crystal Display Manufacturing Device Dictionary", Second Edition, Nikkan Kogyo Shimbun, 1996, p. 64.
The black matrix has a high light-shielding property (optical density OD) in order to improve the display contrast, and in the case of an active matrix drive liquid crystal display device using thin film transistors (TFTs), to prevent image quality deterioration due to light current leakage. It is preferable to have three or more.
本発明の製造方法で得られる硬化膜は、カラーフィルタに含有されるのも好ましい。
カラーフィルタが硬化膜を含有する形態としては、特に制限されないが、基板と、上記ブラックマトリクスと、を備えるカラーフィルタが挙げられる。すなわち、基板上に形成された上記ブラックマトリクスの開口部に形成された赤色、緑色、及び、青色の着色画素と、を備えるカラーフィルタが例示できる。 <Color filter>
It is also preferable that the cured film obtained by the production method of the present invention is contained in a color filter.
Although it does not restrict | limit especially as a form in which a color filter contains a cured film, A color filter provided with a board | substrate and said black matrix is mentioned. That is, a color filter provided with red, green and blue colored pixels formed in the opening of the black matrix formed on the substrate can be exemplified.
まず、基板上に形成されたパターン状のブラックマトリクスの開口部に、カラーフィルタの各着色画素に対応する顔料を含有した樹脂組成物の塗膜(樹脂組成物層)を形成する。なお、各色用樹脂組成物としては特に制限されず、公知の樹脂組成物を使用できるが、本明細書で説明した硬化性組成物において、黒色顔料を、各画素に対応した着色剤に置き換えたものを使用するのが好ましい。
次に、樹脂組成物層に対して、ブラックマトリクスの開口部に対応したパターンを有するフォトマスクを介して露光する。次いで、現像処理により未露光部を除去した後、ベークすることでブラックマトリクスの開口部に着色画素を形成できる。一連の操作を、例えば、赤色、緑色、及び、青色顔料を含有した各色用樹脂組成物を用いて行うことにより、赤色、緑色、及び、青色画素を有するカラーフィルタを製造できる。 The color filter containing the black matrix (cured film) can be produced, for example, by the following method.
First, a coating (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in the opening of a pattern-like black matrix formed on a substrate. In addition, it does not restrict | limit especially as a resin composition for each color, Although a well-known resin composition can be used, In the curable composition demonstrated in this specification, the black pigment was substituted to the coloring agent corresponding to each pixel It is preferred to use one.
Next, the resin composition layer is exposed to light through a photomask having a pattern corresponding to the opening of the black matrix. Next, after removing the unexposed area by development processing, baking is performed to form colored pixels in the opening of the black matrix. A color filter having red, green and blue pixels can be produced by performing a series of operations using, for example, resin compositions for each color containing red, green and blue pigments.
本発明の製造方法で得られる硬化膜は、液晶表示装置に含有されるのも好ましい。液晶表示装置が硬化膜を含有する形態としては特に制限されないが、すでに説明したブラックマトリクス(硬化膜)を含有するカラーフィルタを含有する形態が挙げられる。 <Liquid crystal display device>
It is also preferable that the cured film obtained by the production method of the present invention is contained in a liquid crystal display device. The form in which the liquid crystal display device contains the cured film is not particularly limited, but the form containing the color filter containing the black matrix (cured film) described above can be mentioned.
本発明の製造方法で得られる硬化膜は、赤外線センサに含有されるのも好ましい。
上記実施態様に係る赤外線センサについて、図3を用いて説明する。図3に示す赤外線センサ300において、図番310は、固体撮像素子である。
固体撮像素子310上に設けられている撮像領域は、赤外線吸収フィルタ311とカラーフィルタ312とを組み合せて構成されている。
赤外線吸収フィルタ311は、可視光領域の光(例えば、波長400~700nmの光)を透過し、赤外領域の光(例えば、波長800~1300nmの光、好ましくは波長900~1200nmの光、より好ましくは波長900~1000nmの光)を遮蔽する膜であり、着色剤として赤外線吸収剤(赤外線吸収剤の形態としては既に説明したとおりである。)を含有する硬化膜を使用できる。
カラーフィルタ312は、可視光領域における特定波長の光を透過及び吸収する画素が形成されたカラーフィルタであって、例えば、赤色(R)、緑色(G)、青色(B)の画素が形成されたカラーフィルタ等が用いられ、その形態は既に説明したとおりである。
赤外線透過フィルタ313と固体撮像素子310との間には、赤外線透過フィルタ313を透過した波長の光を透過させることができる樹脂膜314(例えば、透明樹脂膜など)が配置されている。
赤外線透過フィルタ313は、可視光遮蔽性を有し、かつ、特定波長の赤外線を透過させるフィルタであって、可視光領域の光を吸収する着色剤(例えば、ペリレン化合物、及び/又は、ビスベンゾフラノン化合物等)と、赤外線吸収剤(例えば、ピロロピロール化合物、フタロシアニン化合物、ナフタロシアニン化合物、及び、ポリメチン化合物等)と、を含有する、本発明の製造方法で得られる硬化膜を使用できる。赤外線透過フィルタ313は、例えば、波長400~830nmの光を遮光し、波長900~1300nmの光を透過させるのが好ましい。
カラーフィルタ312及び赤外線透過フィルタ313の入射光hν側には、マイクロレンズ315が配置されている。マイクロレンズ315を覆うように平坦化膜316が形成されている。
図3に示す形態では、樹脂膜314が配置されているが、樹脂膜314に代えて赤外線透過フィルタ313を形成してもよい。すなわち、固体撮像素子310上に、赤外線透過フィルタ313を形成してもよい。
また、図3に示す形態では、カラーフィルタ312の膜厚と、赤外線透過フィルタ313の膜厚が同一であるが、両者の膜厚は異なっていてもよい。
また、図3に示す形態では、カラーフィルタ312が、赤外線吸収フィルタ311よりも入射光hν側に設けられているが、赤外線吸収フィルタ311と、カラーフィルタ312との順序を入れ替えて、赤外線吸収フィルタ311を、カラーフィルタ312よりも入射光hν側に設けてもよい。
また、図3に示す形態では、赤外線吸収フィルタ311とカラーフィルタ312は隣接して積層しているが、両フィルタは必ずしも隣接している必要はなく、間に他の層が設けられていてもよい。本発明の製造方法で得られる硬化膜は、赤外線吸収フィルタ311の表面の端部及び/又は側面などの遮光膜として使用できるほか、赤外線センサの装置内壁に用いることで、内部反射及び/又は受光部への意図しない光の入射を防ぎ、感度を向上させられる。
この赤外線センサによれば、画像情報を同時に取り込むことができるため、動きを検知する対象を認識したモーションセンシングなどが可能である。更には、距離情報を取得できるため、3D情報を含んだ画像の撮影等も可能である。 [Infrared sensor]
It is also preferable that the cured film obtained by the production method of the present invention is contained in an infrared sensor.
The infrared sensor according to the above embodiment will be described with reference to FIG. In the
The imaging region provided on the solid-
The
The
A resin film 314 (for example, a transparent resin film or the like) capable of transmitting light of the wavelength transmitted through the
The
A
Although the
Moreover, in the form shown in FIG. 3, although the film thickness of the
Further, in the embodiment shown in FIG. 3, the
In the embodiment shown in FIG. 3, the
According to this infrared sensor, it is possible to simultaneously capture image information, so that it is possible to perform motion sensing in which an object whose motion is to be detected is recognized. Furthermore, since distance information can be acquired, it is also possible to capture an image including 3D information.
上記固体撮像装置は、レンズ光学系と、固体撮像素子と、赤外発光ダイオード等を含有する。なお、固体撮像装置の各構成については、特開2011-233983号公報の段落0032~0036を参酌でき、この内容は本願明細書に組み込まれる。 Next, a solid-state imaging device to which the infrared sensor is applied will be described.
The solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like. Note that, regarding each configuration of the solid-state imaging device, paragraphs 0032 to 0036 in JP-A-2011-233983 can be referred to, and the contents thereof are incorporated in the present specification.
硬化性組成物の調製に用いられる分散組成物を調製した。
以下の表1に各分散組成物における各成分の組成比(質量部比)を示す。なお、分散組成物1、13、及び、14は同一の配合である。 [Preparation of Dispersion Composition]
A dispersion composition was prepared which was used to prepare a curable composition.
Table 1 below shows the composition ratio (parts by mass) of each component in each dispersion composition. The dispersion compositions 1, 13 and 14 have the same composition.
以下に示す顔料を使用した。
なお、Ti、Zr、V、Nb、及び、CB、無機黒色顔料(A)、無機黒色顔料(B)、無機黒色顔料(C)が黒色顔料で、PG58及びPY185は黒色顔料以外の顔料である。 <Pigment>
The pigment shown below was used.
In addition, Ti, Zr, V, Nb, and CB, inorganic black pigment (A), inorganic black pigment (B), inorganic black pigment (C) are black pigments, and PG58 and PY185 are pigments other than black pigments. .
中空構造の放電電極は、原材料供給装置と接続されており、放電電極の中空部分から原料ガスを真空チャンバ内へと供給できるようにした。 As a discharge electrode of the nano-particle production apparatus, a tungsten rod having a length of 500 mm, a diameter of 12 mm, and a rod shape of a hollow structure having a hollow diameter of 6 mm was used. The arrangement of the discharge electrodes was the same as that of FIG. 1 of JP-A-2005-343784. Specifically, 12 discharge electrodes were arranged in two stages of six each. The distance between the upper and lower portions was about 160 mm.
The hollow discharge electrode was connected to the raw material supply device so that the raw material gas could be supplied into the vacuum chamber from the hollow portion of the discharge electrode.
各金属窒化物含有粒子を、プレス機を用いてペレット状に成形して試料とした。上記試料について、X線光電子分光分析装置、及び、蛍光X線分析装置を用いて、以下測定条件で、金属窒化物含有粒子のTE/TXを測定した。 In addition, T E / T X of each metal nitride containing particle (a titanium nitride containing particle, a zirconium nitride containing particle, a vanadium nitride containing particle, and a niobium nitride containing particle) mentioned above was measured by the following method.
Each metal nitride-containing particle was formed into a pellet by using a press to obtain a sample. About the said sample, T E / T X of metal nitride containing particle | grains was measured on the following measurement conditions using a X-ray-photoelectron-spectroscopic-analysis apparatus and a fluorescent-X-ray-analysis apparatus.
装置:PHI社製Quantera-SXM(商品名)装置
X線源:単色化Al Kα線(1486.6ev、25W、15kV、ビーム径200μmφ)
測定領域:200μmφ
測定条件:Pass Energy=140eV、step=0.1eV、積算回数4~8回
測定方法:試料を装置にセットし、光電子取り出し角を10度として測定した。 X-ray photoelectron spectrometer (Measurement of T E)
Device: Quantera-SXM (trade name) device manufactured by PHI X-ray source: monochromatized Al K α ray (1486.6 ev, 25 W, 15 kV, beam diameter 200 μmφ)
Measurement area: 200 μmφ
Measurement conditions: Pass Energy = 140 eV, step = 0.1 eV, integration number 4 to 8 times Measurement method: The sample was set in the apparatus, and the photoelectron extraction angle was measured at 10 degrees.
装置 Rigaku製ZSM PrimusII型XRF
X線 Rh 30-50 kV, 48-80 mA
測定領域 10μmφ
測定時間 10-240 deg/min X-ray fluorescence analyzer (measurement of T X )
Equipment Rigaku ZSM Primus II XRF
X-ray Rh 30-50 kV, 48-80 mA
Measurement area 10 μmφ
Measurement time 10-240 deg / min
なお、得られた各金属窒化物含有粒子中の各原子の含有量は、蛍光X線分析装置を用いて測定した。具体的には、試料として各金属窒化物含有粒子を、プレス機を用いてペレット状に成形したものを準備し、上記試料について、蛍光X線分析装置を用いて、以下の条件で測定した。
装置 Rigaku製ZSM PrimusII型XRF
X線 Rh 30-50 kV, 48-80 mA
測定領域 10μmφ
測定時間 10-240 deg/min Also, transition metal atoms (titanium, zirconium, vanadium, or nitride) contained in each metal nitride-containing particle (titanium nitride-containing particle, zirconium nitride-containing particle, vanadium nitride-containing particle, and niobium nitride-containing particle) Containing atom number ratio X of content of nitrogen atom to content of niobium), contained atom number ratio Y of content of oxygen atom to content of transition metal atom contained in nitride, and transition contained in nitride The atomic number ratio Z of the sulfur atom to the content of the metal atom was such that X = 0.8, Y = 0.1, and Z = 0.1.
The content of each atom in each of the obtained metal nitride-containing particles was measured using a fluorescent X-ray analyzer. Specifically, each metal nitride-containing particle as a sample was formed into a pellet by using a press, and the sample was measured using the fluorescent X-ray analyzer under the following conditions.
Equipment Rigaku ZSM Primus II XRF
X-ray Rh 30-50 kV, 48-80 mA
Measurement area 10 μmφ
Measurement time 10-240 deg / min
・PG58:ピグメントグリーン58
・PY185:ピグメントイエロー185
・無機黒色顔料(A):商品名「NITRBLACK(ナイトブラック)UB-1」、三菱マテリアル社製
・無機黒色顔料(B):特開2017-222559号公報の実施例1に記載の窒化ジルコニウム粉末
・無機黒色顔料(C):特許第4931011号公報の実施例1に記載の微粒子低次酸化ジルコニウム・窒化ジルコニウム複合体。 -CB: carbon black (trade name "color black S170", manufactured by Degussa, average primary particle diameter 17 nm, BET specific surface area 200 m 2 / g)
・ PG 58: pigment green 58
・ PY 185: pigment yellow 185
Inorganic black pigment (A): trade name “NITRBLACK (night black) UB-1”, manufactured by Mitsubishi Materials Corporation Inorganic black pigment (B): zirconium nitride powder described in Example 1 of JP-A-2017-222559 Inorganic black pigment (C): The particulate low-order zirconium oxide-zirconium nitride composite described in Example 1 of Japanese Patent No. 4931011.
・分散剤A(エチレン性不飽和基を有さない樹脂):以下に示す方法で合成した。 <Dispersing agent>
Dispersant A (resin having no ethylenically unsaturated group): Synthesized by the method shown below.
容量3000mLの三口フラスコに、ε-カプロラクトン(1044.2g)、δ-バレロラクトン(184.3g)、及び、2-エチル-1-ヘキサノール(71.6g)を導入し、混合物を得た。次に、窒素を吹き込みながら、上記混合物を撹拌した。次に、混合物にDisperbyk111(12.5g、ビックケミー社製、リン酸樹脂)を加え、得られた混合物を90℃に加熱した。6時間後、1H-NMR(nuclear magnetic resonance)を用いて、混合物中における2-エチル-1-ヘキサノールに由来するシグナルが消失したのを確認後、混合物を110℃に加熱した。窒素下にて110℃で12時間重合反応を続けた後、1H-NMRでε-カプロラクトン及びδ-バレロラクトンに由来するシグナルの消失を確認し、得られた化合物について、GPC法により分子量測定を行った。化合物の分子量が所望の値に到達したことを確認した後、上記化合物を含有する混合物に2,6-ジt-ブチル-4-メチルフェノール(0.35g)を添加した後、更に、得られた混合物に対して、2-メタクリロイロキシエチルイソシアネート(87.0g)を30分かけて滴下した。滴下終了から6時間後、1H-NMRにて2-メタクリロイロキシエチルイソシアネート(MOI)に由来するシグナルが消失したのを確認後、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)(1387.0g)を混合物に添加し、濃度が50質量%のマクロモノマーA-1溶液(2770g)を得た。得られたマクロモノマーA-1の重量平均分子量は6,000であった。 Synthesis Example A1: Synthesis of Macromonomer A-1
In a three-necked flask with a volume of 3000 mL, ε-caprolactone (1044.2 g), δ-valerolactone (184.3 g), and 2-ethyl-1-hexanol (71.6 g) were introduced to obtain a mixture. The mixture was then stirred while blowing with nitrogen. Next, Disperbyk 111 (12.5 g, manufactured by Bick Chemie, phosphoric acid resin) was added to the mixture, and the resulting mixture was heated to 90 ° C. After 6 hours, the mixture was heated to 110 ° C. after confirming that the signal derived from 2-ethyl-1-hexanol in the mixture had disappeared using 1 H-NMR (nuclear magnetic resonance). After continuing the polymerization reaction at 110 ° C. under nitrogen for 12 hours, the disappearance of the signal derived from ε-caprolactone and δ-valerolactone is confirmed by 1 H-NMR, and the molecular weight of the obtained compound is measured by GPC. Did. After confirming that the molecular weight of the compound has reached the desired value, 2,6-di-t-butyl-4-methylphenol (0.35 g) is added to the mixture containing the above-mentioned compound, and further obtained To the resulting mixture, 2-methacryloyloxyethyl isocyanate (87.Og) was added dropwise over 30 minutes. After confirming that the signal derived from 2-methacryloyloxyethyl isocyanate (MOI) disappeared by 1 H-NMR six hours after the completion of the dropwise addition, a mixture of propylene glycol monomethyl ether acetate (PGMEA) (1387.0 g) was used. To give a 50% by weight solution of macromonomer A-1 (2770 g). The weight average molecular weight of the obtained macromonomer A-1 was 6,000.
容量1000mLの三口フラスコに、上記マクロモノマーA-1溶液(200.0g)、メタクリル酸(以下「MAA」ともいう、60.0g)、ベンジルメタクリレート(以下「BzMA」ともいう、40.0g)、PGMEA(プロピレングリコール1-モノメチルエーテル2-アセタート、366.7g)を導入し、混合物を得た。窒素を吹き込みながら、上記混合物を撹拌した。次に、窒素をフラスコ内に流しながら、混合物を75℃まで昇温した。次に、混合物に、ドデシルメルカプタン(5.85g)、次いで、2,2’-アゾビス(2-メチルプロピオン酸メチル)(1.48g、以下「V-601」ともいう。)を添加し、重合反応を開始した。混合物を75℃で2時間加熱した後、更にV-601(1.48g)を混合物に追加した。2時間後、更にV-601(1.48g)を混合物に追加した。更に2時間反応後、混合物を90℃に昇温し、3時間撹拌した。上記操作により、重合反応は終了し、その後、固形分を精製して分散剤Aを得た。
その後、分散剤Aを30質量%溶液(溶媒:PGMEA)として分散組成物の調製に使用した。 (Synthesis of Dispersant A)
The above macromonomer A-1 solution (200.0 g), methacrylic acid (hereinafter also referred to as “MAA”, 60.0 g), benzyl methacrylate (hereinafter also referred to as “BzMA”, 40.0 g) in a 1000 mL three-necked flask PGMEA (propylene glycol 1-monomethyl ether 2-acetate, 366.7 g) was introduced to give a mixture. The mixture was stirred while blowing with nitrogen. The mixture was then warmed to 75 ° C. while flowing nitrogen into the flask. Next, to the mixture, dodecyl mercaptan (5.85 g) and then 2,2'-azobis (methyl 2-methylpropionate) (1.48 g, hereinafter also referred to as "V-601") are added, and polymerization is performed. The reaction has started. After heating the mixture at 75 ° C. for 2 hours, more V-601 (1.48 g) was added to the mixture. After 2 hours, more V-601 (1.48 g) was added to the mixture. After further reacting for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. By the above operation, the polymerization reaction was completed, and then the solid content was purified to obtain dispersant A.
Thereafter, Dispersant A was used as a 30% by mass solution (solvent: PGMEA) for the preparation of the dispersion composition.
容量1000mLの三口フラスコに、上記マクロモノマーA-1溶液(200.0g)、MAA(60.0g)、BzMA(40.0g)、PGMEA(366.7g)を導入し、混合物を得た。窒素を吹き込みながら、上記混合物を撹拌した。次に、窒素をフラスコ内に流しながら、混合物を75℃まで昇温した。次に、混合物に、ドデシルメルカプタン(5.85g)、次いで、V-601(1.48g)を添加し、重合反応を開始した。混合物を75℃で2時間加熱した後、更にV-601(1.48g)を混合物に追加した。2時間後、更にV-601(1.48g)を混合物に追加した。更に2時間反応後、混合物を90℃に昇温し、3時間撹拌した。上記操作により、重合反応は終了した。
反応終了後、空気下でテトラブチルアンモニウムブロミド(TBAB、7.5g)とp-メトキシフェノール(MEHQ,0.13g)を加えた後、メタクリル酸グリシジル(以下、「GMA」ともいう、66.1g)を滴下した。滴下終了後、空気下で、7時間反応を続けた後、酸価測定により反応終了を確認した。得られた混合物にPGMEA(643.6g)を追加することで分散剤Bの20質量%溶液を得た。得られた分散剤Bの重量平均分子量は35000、酸価は50mgKOH/mgであった。 (Synthesis of Dispersant B)
The above macromonomer A-1 solution (200.0 g), MAA (60.0 g), BzMA (40.0 g), and PGMEA (366.7 g) were introduced into a 1000 mL three-necked flask to obtain a mixture. The mixture was stirred while blowing with nitrogen. The mixture was then warmed to 75 ° C. while flowing nitrogen into the flask. Next, to the mixture, dodecyl mercaptan (5.85 g) and then V-601 (1.48 g) were added to initiate the polymerization reaction. After heating the mixture at 75 ° C. for 2 hours, more V-601 (1.48 g) was added to the mixture. After 2 hours, more V-601 (1.48 g) was added to the mixture. After further reacting for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation.
After completion of the reaction, tetrabutylammonium bromide (TBAB, 7.5 g) and p-methoxyphenol (MEHQ, 0.13 g) were added under air, and then glycidyl methacrylate (hereinafter also referred to as "GMA", 66.1 g) ) Was added dropwise. After completion of the dropwise addition, the reaction was continued under air for 7 hours, and the completion of the reaction was confirmed by acid value measurement. A 20% by mass solution of Dispersant B was obtained by adding PGMEA (643.6 g) to the obtained mixture. The weight average molecular weight of the resulting dispersant B was 35,000, and the acid value was 50 mg KOH / mg.
容量1000mLの三口フラスコに、上記マクロモノマーA-1溶液(100.0g)、MAA(200.0g)、PGMEA(366.7g)を導入し、混合物を得た。これ以降は、分散剤Bの合成と同様の方法で、分散剤Cの20質量%溶液を作製した。得られた分散剤Cの重量平均分子量は28000、酸価は55mgKOH/mgであった。 (Synthesis of Dispersant C)
The above macromonomer A-1 solution (100.0 g), MAA (200.0 g), and PGMEA (366.7 g) were introduced into a 1000 mL three-necked flask to obtain a mixture. Thereafter, in the same manner as in the synthesis of Dispersant B, a 20 mass% solution of Dispersant C was prepared. The weight average molecular weight of the obtained dispersant C was 28,000, and the acid value was 55 mg KOH / mg.
・PGMEA:プロピレングリコールモノメチルエーテルアセテート <Solvent>
PGMEA: Propylene glycol monomethyl ether acetate
各成分を表1に示す組成比(質量部比)になるように混合して、得られた混合物を、(株)シンマルエンタープライゼス製のNPM-Pilotを使用して下記条件にて分散させ、分散組成物を得た。 <Method of Preparing Dispersion Composition>
Each component is mixed to have a composition ratio (part by mass ratio) shown in Table 1, and the obtained mixture is dispersed under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. , A dispersion composition was obtained.
・ビーズ径:φ0.05mm、(ニッカトー製ジルコニアビーズ、YTZ)
・ビーズ充填率:65体積%
・ミル周速:10又は12m/sec
・セパレータ周速:13m/s
・分散処理する混合液量:15kg
・循環流量(ポンプ供給量):90kg/hour
・処理液温度:19~21℃
・冷却水:水
・処理時間:22時間 (Distribution condition)
· Bead diameter: φ 0.05 mm, (Nikkato zirconia beads, YTZ)
・ Bead packing rate: 65% by volume
· Mill circumferential speed: 10 or 12 m / sec
・ Separator circumferential speed: 13 m / s
・ The amount of mixed liquid to be dispersed: 15 kg
Circulating flow rate (pump supply rate): 90 kg / hour
· Processing solution temperature: 19 to 21 ° C
Cooling water: Water Treatment time: 22 hours
上述した分散組成物と、以下に示す他の成分を混合して、実施例及び比較例で用いる各硬化性組成物を得た。
以下の表2に各硬化性組成物における各成分の組成比(質量部比)を示す。
なお、「含有する顔料の種類」の欄の「緑色」の記載は、PG58とPY185とが併用されており、全体として緑色の硬化膜を形成するため硬化性組成物となっていることを意味する。
「顔料(A)」、「顔料(B)」、「顔料(C)」の記載は、それぞれ「無機黒色顔料(A)」、「無機黒色顔料(B)」、「無機黒色顔料(C)」を意味する。
「樹脂のC=C価」の欄は、各硬化性組成物中に含有される樹脂全質量に対する、エチレン性不飽和基含有量(C=C価)(mmol/g)を意味する。
なお、C=C価は、以下の方法で求めた。まず、各樹脂の樹脂溶液(分散剤Bの20質量%溶液等)を用いて、HPLC法(絶対検量線法)で各樹脂のC=C価を求め、その上で、各硬化性組成物に配合した各樹脂の配合比から、各硬化性組成物中に含有される樹脂全体のC=C価を計算して求めた。 [Preparation of Curable Composition]
The dispersion composition described above and other components shown below were mixed to obtain each curable composition used in Examples and Comparative Examples.
Table 2 below shows the composition ratio (parts by mass) of each component in each curable composition.
In addition, description of "green" of the column of "the kind of pigment to contain" means that PG58 and PY185 are used together and it becomes a curable composition in order to form a green cured film as a whole. Do.
The descriptions for "pigment (A)", "pigment (B)" and "pigment (C)" are "inorganic black pigment (A)", "inorganic black pigment (B)" and "inorganic black pigment (C), respectively. Means ".
The column "C = C value of resin" means an ethylenically unsaturated group content (C = C value) (mmol / g) based on the total mass of the resin contained in each curable composition.
In addition, C = C number was calculated | required by the following method. First, using a resin solution of each resin (20 mass% solution of Dispersant B, etc.), the C = C value of each resin is determined by HPLC method (absolute calibration method), and then each curable composition is determined. The C = C value of the entire resin contained in each curable composition was calculated from the compounding ratio of each resin compounded in the above.
上述の方法で調製した分散組成物を使用した。
それぞれの番号の硬化性組成物で、対応する番号の分散組成物を使用した。 <Dispersion composition>
The dispersion composition prepared by the method described above was used.
For each numbered curable composition, the corresponding numbered dispersion composition was used.
・I-1:下記の、式(I-1)で表される化合物 <Polymerization initiator>
I-1: a compound represented by the following formula (I-1)
・M1:KAYARAD DPHA、日本化薬社製、6官能重合性化合物(エチレン性不飽和基の量:10.4mmol/g)、及び、5官能重合性化合物(エチレン性不飽和基の量:9.5mmol/g)の混合物)
・M2:A-DPH-12E、新中村化学社製、6官能重合性化合物(エチレン性不飽和基の量:5.41mmol/g)
・M3:A-9300、新中村化学社製、3官能重合性化合物(エチレン性不飽和基の量:7.09mmol/g) <Polymerizable compound>
M1: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., hexafunctional polymerizable compound (amount of ethylenically unsaturated group: 10.4 mmol / g), and pentafunctional polymerizable compound (amount of ethylenically unsaturated group: 9 .5 mmol / g))
M2: A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., 6-functional polymerizable compound (amount of ethylenically unsaturated group: 5.41 mmol / g)
M3: A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional polymerizable compound (amount of ethylenically unsaturated group: 7.09 mmol / g)
・PI-1:p-メトキシフェノール <Polymerization inhibitor>
PI-1: p-methoxyphenol
・1:下記式により表される界面活性剤(重量平均分子量(Mw)=15311)
ただし、下記式において、式中(A)及び(B)で表される構造単位はそれぞれ62モル%、38モル%である。式(B)で表される構造単位中、aは、b、cは、それぞれ、a+c=14、b=17の関係を満たす。 <Surfactant>
· 1: Surfactant represented by the following formula (weight-average molecular weight (Mw) = 15311)
However, in the following formulas, structural units represented by (A) and (B) in the formula are 62 mol% and 38 mol%, respectively. In the structural unit represented by Formula (B), a and b and c satisfy the relationship of a + c = 14 and b = 17, respectively.
〔各硬化性組成物層の光学濃度〕
厚み0.7mm、大きさ10cm角のガラス基板(EagleXG、Corning社製)上に、各硬化性組成物をスピンコート法で塗布して、硬化性組成物層を得た。なお、このとき、90℃のホットプレートを用いて150秒間加熱処理(プリベーク)を行なって、乾燥させた後の硬化性組成物層の膜厚が1.5μmとなるように、スピンコーターの回転数を調整した。
得られた乾燥後の硬化性組成物層について、透過濃度計(X-rite 361T(visual)densitometer)を用いて、波長365nm及び波長550nmにおける光学濃度を測定した。
結果を表3に示す。 [Evaluation]
[Optical density of each curable composition layer]
Each curable composition was applied by spin coating on a glass substrate (EagleXG, manufactured by Corning) having a thickness of 0.7 mm and a size of 10 cm square to obtain a curable composition layer. At this time, heat treatment (pre-baking) is performed for 150 seconds using a hot plate at 90 ° C., and rotation of the spin coater is performed so that the film thickness of the curable composition layer after drying becomes 1.5 μm. Adjusted the number.
The optical density at a wavelength of 365 nm and a wavelength of 550 nm was measured for the resulting curable composition layer after drying using a transmission densitometer (X-rite 361 T (visual) densitometer).
The results are shown in Table 3.
あらかじめヘキサメチルジシラザンを噴霧した200mm(8インチ)シリコンウエハ(基板)に、調製直後の各硬化膜形成用組成物をスピンコート法で塗布し、硬化性組成物層を形成した。なお、このとき、90℃のホットプレートを用いて150秒間加熱処理(プリベーク)を行なって、乾燥させた後の硬化性組成物層の膜厚が1.5μmとなるように、スピンコーターの回転数を調整した。
乾燥させた膜厚1.5μmの硬化性組成物層に対して、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3.0μm四方のIslandパターンマスクを通して露光した。
各実施例及び比較例において、露光時の酸素濃度は25~55体積%の範囲、放射照度は15000~55000W/m2の範囲とし、最適露光量で露光した。
なお、露光は、プリベークをしてから10分以内に行った。 [Rectangularity evaluation (initial)]
The composition for cured film formation immediately after preparation was applied by spin coating to a 200 mm (8 inch) silicon wafer (substrate) previously sprayed with hexamethyldisilazane, to form a curable composition layer. At this time, heat treatment (pre-baking) is performed for 150 seconds using a hot plate at 90 ° C., and rotation of the spin coater is performed so that the film thickness of the curable composition layer after drying becomes 1.5 μm. Adjusted the number.
An i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.) is used for the dried curable composition layer with a film thickness of 1.5 μm to form a 3.0 μm-square pattern at a wavelength of 365 nm. It exposed through an Island pattern mask.
In each of the examples and the comparative examples, the exposure was performed at the optimum exposure dose with the oxygen concentration at the time of exposure set in the range of 25 to 55% by volume and the irradiance set in the range of 15,000 to 55,000 W / m 2 .
The exposure was performed within 10 minutes after prebaking.
このようにして、下塗り層付シリコンウエハに、パターン(3.0μm角の正方形ピクセルパターン状の硬化膜)を形成した。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、このシリコンウエハを回転装置によって回転数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した。その後、このシリコンウエハを乾燥した。得られたシリコンウエハを、更に、200℃で300秒間過熱(ポストベーク)して、パターン状硬化膜付シリコンウエハを得た。 After that, the silicon wafer on which the curable composition layer that has been exposed is formed is placed on the horizontal rotation table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (organic alkali) Paddle development was carried out at 23 ° C. for 60 seconds using a developer, manufactured by Fujifilm Electronics Materials.
In this way, a pattern (a cured film in the form of a square pixel pattern of 3.0 μm square) was formed on the undercoating silicon wafer. A silicon wafer on which a pattern is formed is fixed to a horizontal rotation table by a vacuum chuck method, and while rotating this silicon wafer at a rotation speed of 50 rpm by a rotation device, pure water is showered from above the rotation center from a spray nozzle It was supplied and rinsed. Thereafter, the silicon wafer was dried. The obtained silicon wafer was further heated (post-baked) at 200 ° C. for 300 seconds to obtain a silicon wafer with a patterned cured film.
結果を表3に示す。 The cross section of the obtained silicon wafer is observed with a scanning electron microscope, and the angle of the 3.0 μm square pixel pixel side wall (side wall of the square cured film) with respect to the silicon wafer surface is measured. Of the rectangularity of
The results are shown in Table 3.
「A」:側壁の角度が75°以上80°未満、又は、100°以上105°未満
「B」:側壁の角度が70°以上75°未満、又は、105°以上110°未満
「C」:側壁の角度が60°以上70°未満、又は、110°以上120°未満
「D」:側壁の角度が50°以上60°未満、又は、120°以上130°未満
「E」:側壁の角度が50°未満、又は、130°以上 “AA”: angle of side wall 80 ° to 100 ° “A”: angle of side wall 75 ° to less than 80 °, or 100 ° to less than 105 ° “B”: angle of side wall 70 ° to 75 ° Less than 105 ° or more and less than 110 ° “C”: angle of sidewall 60 ° or more and less than 70 °, or 110 ° or more but less than 120 ° “D”: angle of sidewall 50 ° or more and less than 60 ° or 120 ° or more and less than 130 ° "E": Sidewall angle is less than 50 ° or 130 ° or more
露光を、プリベークをしたあと1週間引き置きしてから行った以外は、上述したのと同様に矩形性評価を実施し、同様の基準で評価した。
結果を表3に示す。 [Evaluation of pattern rectangularity (one week after prebaking)]
The rectangularity evaluation was carried out in the same manner as described above except that exposure was carried out for 1 week after prebaking and then carried out, and evaluation was made based on the same criteria.
The results are shown in Table 3.
調製してから室温(23℃、相対湿度50%)で1ヶ月保管した後の硬化性組成物を使用して硬化性組成物層を形成した以外は、上述したのと同様に〔矩形性評価(初期)〕を実施し、同様の基準で評価した。
結果を表3に示す。 [Rectangularity evaluation of pattern (after one month of liquid aging)]
[Square property evaluation is the same as that described above except that a curable composition layer is formed using the curable composition after being prepared and stored for 1 month at room temperature (23.degree. C., relative humidity 50%). (Early)] was carried out and evaluated on the same basis.
The results are shown in Table 3.
以下の表3に、試験結果を示す。
なお、表3中、「顔料」の欄は、使用した硬化性組成物が含有する黒色顔料の種類を示す。この欄に記載の略号は、〔分散組成物の調製〕で説明したのと同様である。なお、「緑色」の記載は、PG58とPY185とを併用して、全体として緑色の硬化膜としたことを意味する。「顔料(A)」、「顔料(B)」、「顔料(C)」の記載は、それぞれ「無機黒色顔料(A)」、「無機黒色顔料(B)」、「無機黒色顔料(C)」を意味する。
「樹脂のC=C価」の欄は、使用した硬化性組成物中に含有される樹脂全体のエチレン性不飽和基含有量(mmol/g)を意味する。
「分散機ミル周速」の欄は、硬化性組成物の作製に使用した分散組成物を調製する際のミル周速を意味する。
「式(1)値」の欄は、各試験条件を上述の式(1)(X×Y÷Z)に当てはめて計算して得られた値である。計算方法は上述の通りである。
「矩形性」の欄における、「初期」「1週間」「1ヶ月」の欄には、それぞれ、〔矩形性評価(初期)〕〔パターンの矩形性評価(プリベークをしてから1週間後)〕〔パターンの矩形性評価(液経時1ヶ月後)〕の試験の評価結果を記載する。 [result]
The test results are shown in Table 3 below.
In Table 3, the column "pigment" indicates the type of black pigment contained in the curable composition used. The abbreviations described in this column are the same as those described in [Preparation of Dispersion Composition]. In addition, description of "green" means that PG58 and PY185 are used together and it was set as the green cured film as a whole. The descriptions for "pigment (A)", "pigment (B)" and "pigment (C)" are "inorganic black pigment (A)", "inorganic black pigment (B)" and "inorganic black pigment (C), respectively. Means ".
The column "C = C value of resin" means the ethylenic unsaturated group content (mmol / g) of the entire resin contained in the curable composition used.
The column "Disperser Mill Peripheral Speed" means the mill peripheral speed when preparing the dispersion composition used to make the curable composition.
The column of “Expression (1) value” is a value obtained by applying each test condition to the above-mentioned Expression (1) (X × Y ÷ Z). The calculation method is as described above.
[Rectangularity evaluation (initial)] [rectangularity evaluation of pattern (one week after prebaking) in the columns of “initial”, “one week” and “one month” in the “rectangularity” column Evaluation results of the test of [squareness evaluation of pattern (after 1 month liquid aging)] are described.
黒色顔料として、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、又は、ニオブの窒化物若しくは酸窒化物を使用する場合、引置き期間をおいても、得られるパターンの矩形性が劣化しにくい傾向が確認された(実施例10とその他の実施例との比較)。
黒色顔料として、チタンの窒化物若しくは酸窒化物、又は、ジルコニウムの窒化物若しくは酸窒化物を使用する場合、より矩形性が優れる硬化膜を得られる傾向が確認された(実施例1、3、及び、7の結果)。
硬化性組成物に含有される樹脂全体に対するエチレン性不飽和基の含有量が0.10~3.00mmol/gである場合、より矩形性が優れる硬化膜を得られる傾向が確認された(実施例1、13、及び、14の比較)。
硬化性組成物を用いて形成された硬化性組成物層の光学濃度Aが2.80~4.00となり、かつ、光学濃度Bが2.50~7.00である場合、より矩形性が優れる硬化膜を得られる傾向が確認された(実施例1、2、及び、6の結果)。
露光時の放射照度が20000~50000W/m2である場合、より矩形性が優れる硬化膜を得られ、露光時の放射照度が25000~40000W/m2である場合、更に矩形性が優れる硬化膜を得られる傾向が確認された(実施例1、4、5、11、12の結果)。
黒色顔料として、無機黒色顔料(A)、(B)、(C)を使用する場合、実施例1と同様に、より矩形性が優れる硬化膜を得られる傾向が確認された(実施例1、18、19、及び、20の結果)。
また、式(1)で算出した値が、2.80×10-5~5.20×10-5の範囲内である場合、室温(23℃、相対湿度50%)1ヶ月保管処理をした後の硬化性組成物を用いた場合においても、保管処理を経ていない硬化性組成物を用いて評価した場合とくらべて、作製される硬化膜の断面形状の矩形性の劣化が抑制されていた(実施例1~4、7~9、及び、13~17の結果)。 As shown in Table 3, according to the production method of the present invention, a cured film (patterned cured film) excellent in rectangularity of the cross-sectional shape can be produced, and even in the case where the drawn curable composition layer is used. The tendency to maintain excellent rectangularity (the evaluation of rectangularity is C or higher) was confirmed.
When using a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, or a nitride or oxynitride of niobium as the black pigment, the drawing period should be Also in this case, it was confirmed that the rectangularity of the obtained pattern did not easily deteriorate (comparison of Example 10 with other Examples).
When a nitride or oxynitride of titanium, or a nitride or oxynitride of zirconium is used as the black pigment, a tendency to obtain a cured film with more rectangularity was confirmed (Examples 1, 3, And 7).
When the content of the ethylenically unsaturated group with respect to the entire resin contained in the curable composition is 0.10 to 3.00 mmol / g, a tendency to obtain a cured film having more excellent rectangularity was confirmed (implementation Comparison of Examples 1, 13 and 14).
When the optical density A of the curable composition layer formed using the curable composition is 2.80 to 4.00 and the optical density B is 2.50 to 7.00, more rectangularity is obtained. The tendency which can acquire the outstanding cured film was confirmed (result of Example 1, 2 and 6).
When the irradiance at the time of exposure is from 20000 to 50000 W / m 2 , a cured film having more rectangularity is obtained, and when the irradiance at the exposure is from 25000 to 40000 W / m 2 , the cured film is more excellent in rectangularity. Tend to be obtained (Results of Examples 1, 4, 5, 11 and 12).
When inorganic black pigments (A), (B) and (C) were used as the black pigment, it was confirmed that a cured film having more excellent rectangularity could be obtained as in Example 1 (Example 1, 18, 19 and 20 results).
Moreover, when the value calculated by Formula (1) is in the range of 2.80 × 10 −5 to 5.20 × 10 −5 , storage treatment was performed for 1 month at room temperature (23 ° C., relative humidity 50%) Even in the case of using the later curable composition, deterioration of the rectangularity of the cross-sectional shape of the cured film to be produced was suppressed as compared with the case of evaluation using the curable composition which did not go through storage processing (Results of Examples 1 to 4, 7 to 9, and 13 to 17).
101・・・固体撮像素子
102・・・撮像部
103・・・カバーガラス
104・・・スペーサー
105・・・積層基板
106・・・チップ基板
107・・・回路基板
108・・・電極パッド
109・・・外部接続端子
110・・・貫通電極
111・・・レンズ層
112・・・レンズ材
113・・・支持体
114、115・・・硬化膜
201・・・受光素子
202・・・カラーフィルタ
201・・・受光素子
202・・・カラーフィルタ
203・・・マイクロレンズ
204・・・基板
205b・・・青色画素
205r・・・赤色画素
205g・・・緑色画素
205bm・・・ブラックマトリクス
206・・・pウェル層
207・・・読み出しゲート部
208・・・垂直転送路
209・・・素子分離領域
210・・・ゲート絶縁膜
211・・・垂直転送電極
212・・・硬化膜
213、214・・・絶縁膜
215・・・平坦化膜
300・・・赤外線センサ
310・・・固体撮像素子
311・・・赤外線吸収フィルタ
312・・・カラーフィルタ
313・・・赤外線透過フィルタ
314・・・樹脂膜
315・・・マイクロレンズ
316・・・平坦化膜
100: solid-state imaging device 101: solid-state imaging device 102: imaging unit 103: cover glass 104: spacer 105: laminated substrate 106: chip substrate 107:
Claims (16)
- 黒色顔料及び重合性化合物を含有する硬化性組成物を用いて、膜厚1.5μmあたりの波長365nmにおける光学濃度Aが2.60~10.00であり、かつ、膜厚1.5μmあたりの波長550nmにおける光学濃度Bが2.00~10.00である硬化性組成物層を形成する工程と、
前記硬化性組成物層を、酸素濃度が30~50体積%の条件下で露光する工程と、
前記露光後の前記硬化性組成物層を現像して硬化膜を形成する工程と、を含有する、
硬化膜の製造方法。 When using a curable composition containing a black pigment and a polymerizable compound, the optical density A at a wavelength of 365 nm per 1.5 μm of film thickness is 2.60 to 10.00, and per 1.5 μm of film thickness Forming a curable composition layer having an optical density B at a wavelength of 550 nm of 2.00 to 10.00,
Exposing the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume;
Developing the curable composition layer after the exposure to form a cured film,
Method of producing a cured film. - 前記黒色顔料が、第4族の金属元素の窒化物若しくは酸窒化物、第5族の金属元素の窒化物若しくは酸窒化物、又は、カーボンブラックである、請求項1に記載の硬化膜の製造方法。 The production of a cured film according to claim 1, wherein the black pigment is a nitride or oxynitride of a group 4 metal element, a nitride or oxynitride of a group 5 metal element, or carbon black. Method.
- 前記黒色顔料が、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、ニオブの窒化物若しくは酸窒化物、又は、カーボンブラックである、請求項1又は2に記載の硬化膜の製造方法。 The black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, a nitride or oxynitride of niobium, or carbon black. The manufacturing method of the cured film as described in 1 or 2.
- 前記黒色顔料が、チタンの窒化物若しくは酸窒化物、ジルコニウムの窒化物若しくは酸窒化物、バナジウムの窒化物若しくは酸窒化物、又は、ニオブの窒化物又は酸窒化物である、請求項1~3のいずれか1項に記載の硬化膜の製造方法。 4. The black pigment according to claim 1, wherein the black pigment is a nitride or oxynitride of titanium, a nitride or oxynitride of zirconium, a nitride or oxynitride of vanadium, or a nitride or oxynitride of niobium. The manufacturing method of the cured film of any one of these.
- 前記黒色顔料が、チタンの窒化物若しくは酸窒化物、又は、ジルコニウムの窒化物若しくは酸窒化物である、請求項1~4のいずれか1項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 4, wherein the black pigment is a nitride or oxynitride of titanium, or a nitride or oxynitride of zirconium.
- 前記露光における、放射照度が20000~50000W/m2である、請求項1~5のいずれか1項に記載の硬化膜の製造方法。 In the exposure, irradiance is 20000 ~ 50000W / m 2, process for preparing a cured film according to any one of claims 1 to 5.
- 前記露光における、放射照度が25000~40000W/m2である、請求項1~6のいずれか1項に記載の硬化膜の製造方法。 In the exposure, irradiance is 25000 ~ 40000W / m 2, process for preparing a cured film according to any one of claims 1-6.
- 前記光学濃度Aが2.80~4.00であり、かつ、前記光学濃度Bが2.50~7.00である、請求項1~7のいずれか1項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 7, wherein the optical density A is 2.80 to 4.00, and the optical density B is 2.50 to 7.00. .
- 前記光学濃度Aに対する前記光学濃度Bの比が0.5~2.0である、請求項1~8のいずれか1項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 8, wherein a ratio of the optical density B to the optical density A is 0.5 to 2.0.
- 前記硬化性組成物が、更に、樹脂を含有し、
前記樹脂が、エチレン性不飽和基を含有する樹脂を含有し、
前記樹脂の合計質量に対する、前記エチレン性不飽和基の含有量が、0.10~3.00mmol/gである、請求項1~9のいずれか1項に記載の硬化膜の製造方法。 The curable composition further contains a resin,
The resin contains a resin containing an ethylenically unsaturated group,
The method for producing a cured film according to any one of claims 1 to 9, wherein the content of the ethylenically unsaturated group is 0.10 to 3.00 mmol / g based on the total mass of the resin. - 前記硬化性組成物が、更に、重合開始剤を含有する、請求項1~10のいずれか1項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 10, wherein the curable composition further contains a polymerization initiator.
- 前記硬化性組成物が、更に、重合禁止剤を含有する、請求項1~11のいずれか1項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 11, wherein the curable composition further contains a polymerization inhibitor.
- 前記光学濃度AをX、前記露光時の酸素濃度をY、前記放射照度をZとした場合に、下記式(1)で計算される値が2.80×10-5~5.20×10-5となる、請求項1~12のいずれか1項に記載の硬化膜の製造方法。
式(1) X×Y÷Z Assuming that the optical density A is X, the oxygen concentration at the exposure is Y, and the irradiance is Z, the value calculated by the following equation (1) is 2.80 × 10 −5 to 5.20 × 10 The method for producing a cured film according to any one of claims 1 to 12, which is -5 .
Formula (1) X × Y ÷ Z - 前記硬化膜が遮光膜である、請求項1~13のいずれか1項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 1 to 13, wherein the cured film is a light shielding film.
- 請求項1~14のいずれか1項に記載の製造方法を介して、硬化膜を有する固体撮像素子の製造を行う、固体撮像素子の製造方法。 A method of manufacturing a solid-state imaging device, wherein a solid-state imaging device having a cured film is manufactured through the manufacturing method according to any one of claims 1 to 14.
- 請求項1~13のいずれか1項に記載の製造方法を介して、硬化膜を有する画像表示装置の製造を行う、画像表示装置の製造方法。
A method of manufacturing an image display device, wherein the image display device having a cured film is manufactured through the method of manufacturing according to any one of claims 1 to 13.
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WO2016158114A1 (en) * | 2015-03-30 | 2016-10-06 | 富士フイルム株式会社 | Coloring photosensitive composition, cured film, pattern forming method, infrared blocking filter with light shielding film, solid-state imaging element, image display device and infrared sensor |
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