WO2020059382A1 - Film de protection contre la lumière, procédé de fabrication d'un film de protection contre la lumière, élément optique, élément d'imagerie à semi-conducteurs et unité de phare - Google Patents

Film de protection contre la lumière, procédé de fabrication d'un film de protection contre la lumière, élément optique, élément d'imagerie à semi-conducteurs et unité de phare Download PDF

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Publication number
WO2020059382A1
WO2020059382A1 PCT/JP2019/032377 JP2019032377W WO2020059382A1 WO 2020059382 A1 WO2020059382 A1 WO 2020059382A1 JP 2019032377 W JP2019032377 W JP 2019032377W WO 2020059382 A1 WO2020059382 A1 WO 2020059382A1
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Prior art keywords
light
group
black
shielding film
layer
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PCT/JP2019/032377
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English (en)
Japanese (ja)
Inventor
貴洋 大谷
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富士フイルム株式会社
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Priority to CN201980050527.6A priority Critical patent/CN112513692A/zh
Priority to JP2020548151A priority patent/JP7245843B2/ja
Priority to KR1020217001039A priority patent/KR102660236B1/ko
Publication of WO2020059382A1 publication Critical patent/WO2020059382A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
    • F21S41/40—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by screens, non-reflecting members, light-shielding members or fixed shades
    • F21S41/43—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by screens, non-reflecting members, light-shielding members or fixed shades characterised by the shape thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S45/00—Arrangements within vehicle lighting devices specially adapted for vehicle exteriors, for purposes other than emission or distribution of light
    • F21S45/10—Protection of lighting devices
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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
    • 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
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H01L27/14623—Optical shielding

Definitions

  • the present invention relates to a light-shielding film, a method for manufacturing the light-shielding film, an optical element, a solid-state imaging device, and a headlight unit.
  • a color filter used in a liquid crystal display device is provided with a light-shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
  • a solid-state imaging device such as a charge coupled device (CCD) image sensor and a complementary metal-oxide semiconductor (CMOS) image sensor is provided with a light shielding film for the purpose of preventing noise generation and improving image quality.
  • CCD charge coupled device
  • CMOS complementary metal-oxide semiconductor
  • a technique of providing an oxygen blocking layer on a light shielding film and a colored pixel is known.
  • a black matrix, a color filter layer, an oxygen blocking layer that covers the black matrix and the color filter layer and contains at least an oxygen blocking compound, and a color filter layer and an oxygen blocking layer is disclosed.
  • a color filter including a mixed layer containing a dye and an oxygen-blocking compound therebetween.
  • the present inventors have examined the black matrix including the oxygen barrier layer described in Patent Document 1, and found that the black matrix (light-shielding film) may not be able to sufficiently satisfy the light resistance and the moisture resistance. did.
  • the black color material contains at least one metal oxynitride selected from the group consisting of titanium, vanadium, zirconium, and niobium.
  • the black color material contains carbon black, a benzofuranone compound or a perylene compound.
  • [4] The light-shielding film according to any one of [1] to [3], wherein the content of the black colorant is 20 to 80% by mass based on the total mass of the black layer.
  • [5] The light-shielding film according to any one of [1] to [4], wherein the oxygen barrier layer contains silicon oxide.
  • [6] The light-shielding film according to any one of [1] to [5], wherein a ratio of a thickness of the black layer to a thickness of the oxygen barrier layer is 2 to 100.
  • [7] The light-shielding film according to any one of [1] to [6], wherein the oxygen barrier layer has an oxygen permeability of 10 ml / (m 2 ⁇ day ⁇ atm) or less.
  • the method for producing a light-shielding film according to [9], wherein the step of forming the oxygen barrier layer includes a step of depositing an inorganic material.
  • Method for manufacturing a light-shielding film [12] The method for producing a light-shielding film according to any one of [9] to [11], wherein the light-shielding composition contains at least two kinds of polymerizable compounds.
  • a headlight unit for a vehicular lamp comprising: a light source; and a light shielding unit that shields at least a part of light emitted from the light source, wherein the light shielding unit is any one of [1] to [8].
  • a headlight unit comprising the light-shielding film according to item 1.
  • a light-shielding film having excellent light resistance and moisture resistance can be provided. Further, the present invention can provide a method for manufacturing a light-shielding film, an optical element, a solid-state imaging device, and a headlight unit.
  • FIG. 3 is a schematic sectional view illustrating a configuration example of a solid-state imaging device.
  • FIG. 2 is a schematic cross-sectional view showing, on an enlarged scale, an imaging unit provided in the solid-state imaging device shown in FIG. 1.
  • FIG. 3 is a schematic sectional view illustrating a configuration example of an infrared sensor. It is a schematic diagram which shows the example of a structure of a headlight unit.
  • FIG. 3 is a schematic perspective view illustrating a configuration example of a light shielding unit of the headlight unit. It is a schematic diagram which shows an example of the light distribution pattern by a headlight unit. It is a schematic diagram which shows the other example of the light distribution pattern by a headlight unit.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • the notation of not indicating substituted or unsubstituted includes a group having a substituent as well as a group having no substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • actinic rays or “radiation” means, for example, far ultraviolet rays, extreme ultraviolet (EUV), X-rays, electron beams, and the like.
  • light means actinic rays and radiation.
  • exposure in this specification includes not only exposure with far ultraviolet rays, X-rays, EUV light, and the like, but also drawing with particle beams such as electron beams and ion beams.
  • (meth) acrylate represents acrylate and methacrylate.
  • (meth) acryl represents acryl and methacryl.
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • (meth) acrylamide represents acrylamide and methacrylamide.
  • “monomer” and “monomer” have the same meaning.
  • ppm means “parts-per-million (10 ⁇ 6 )
  • ppb means “parts-per-billion (10 ⁇ 9 )
  • ppt is “ppt”. parts-per-trillion (10 -12 ) ".
  • the weight average molecular weight (Mw) is a value in terms of polystyrene measured by a GPC (Gel Permeation Chromatography) method.
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), and uses TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as a column and THF (tetrahydrofuran) as an eluent. ).
  • the light-shielding film of the present invention includes a black layer containing a black coloring material, and an oxygen blocking layer provided on the black layer.
  • the oxygen barrier layer is a single layer made of an inorganic material.
  • the thickness of the oxygen barrier layer is 10 to 500 nm.
  • the light-shielding film of the present invention on a support, a black colorant, a resin, a polymerizable compound, and a light-shielding composition containing a polymerization initiator is applied, and the obtained coating film is cured, It can be manufactured by a manufacturing method including a step of forming a black layer and a step of forming an oxygen barrier layer on the black layer.
  • the black layer contained in the light-shielding film of the present invention contains a black color material.
  • the black layer is not limited by the manufacturing method, and is, for example, a black layer (including a patterned black layer) obtained by curing a coating film formed using the light-shielding composition.
  • the light-shielding composition used for forming the black layer (hereinafter, simply referred to as “composition”) will be described.
  • the light-shielding composition contains at least a black coloring material, a resin, a polymerizable compound, and a polymerization initiator.
  • the light-shielding composition contains a black coloring material.
  • a black coloring material at least one selected from the group consisting of black pigments and black dyes can be used.
  • One type of black color material may be used alone, or two or more types may be used.
  • the content of the black color material in the black layer is not particularly limited, and may be, for example, 20 to 80% by mass based on the total mass of the black layer.
  • the content of the black colorant is preferably more than 20% by mass, more preferably 30% by mass or more, even more preferably 50% by mass or more based on the total mass of the black layer, from the viewpoint that the heat resistance of the light-shielding film is more excellent.
  • the content of the black colorant is preferably less than 80% by mass, more preferably 70% by mass or less, and more preferably 65% by mass or less based on the total mass of the black layer, from the viewpoint that the moisture resistance of the light-shielding film is more excellent. More preferred.
  • the content of the black colorant in the light-shielding composition may be, for example, 20 to 80% by mass based on the total solid content of the light-shielding composition, and from the viewpoint that the heat resistance of the light-shielding film is more excellent, It is preferably more than 20% by mass, more preferably 30% by mass or more, even more preferably 50% by mass or more based on the total solid content of the light-shielding composition. Further, the content of the black colorant in the light-shielding composition is preferably less than 80% by mass, and more preferably 70% by mass or less based on the total solid content of the light-shielding composition, from the viewpoint that the moisture resistance of the light-shielding film is more excellent.
  • the “total solid content” of the composition means a component that forms a layer or a film by curing or the like, and when the composition contains a solvent (organic solvent, water, or the like), the solvent is used. Means all components except. Liquid components are also considered as solids as long as they form a film. That is, by adjusting the content of the black coloring material with respect to the total solid content of the light-shielding composition, the content of the black coloring material in the black layer can be adjusted to a desired value.
  • a plurality of colorants that cannot be used alone as a black color material may be combined and adjusted so as to be black as a whole to be used as a black color material.
  • a single pigment may be used as a black pigment by combining a plurality of pigments having colors other than black.
  • a black dye may be used alone as a black dye by combining a plurality of dyes having colors other than black, and a pigment having a color other than black alone and a dye having a color other than black alone may be used. You may use as.
  • a black colorant means a colorant that absorbs over the entire wavelength range of 400 to 700 nm. More specifically, for example, a black color material that meets the evaluation criteria Z described below is preferable.
  • a composition containing a coloring material, a transparent resin matrix (such as an acrylic resin), and a solvent, and having a coloring material content of 60% by mass based on the total solid content is prepared.
  • the obtained composition is applied on a glass substrate so that the thickness of the coating film after drying becomes 1 ⁇ m to form a coating film.
  • the light-shielding properties of the dried coating film are evaluated using a spectrophotometer (UV-3600 manufactured by Hitachi, Ltd.). If the maximum value of the transmittance of the coating film after drying at a wavelength of 400 to 700 nm is less than 10%, it can be determined that the coloring material is a black coloring material that meets the evaluation criterion Z.
  • Black pigment Various known black pigments can be used as the black pigment.
  • the black pigment may be an inorganic pigment or an organic pigment.
  • a black pigment is preferable because the light resistance of the black layer is more excellent.
  • the black pigment a pigment that independently expresses black is preferable, and a pigment that independently expresses black and absorbs infrared light is more preferable.
  • the black pigment that absorbs infrared rays has, for example, absorption in a wavelength region of an infrared region (preferably, a wavelength of 650 to 1300 nm).
  • a black pigment having a maximum absorption wavelength in a wavelength range of 675 to 900 nm is also preferable.
  • the particle size of the black pigment is not particularly limited, but is preferably 5 to 100 nm, more preferably 5 to 50 nm, since the balance between the handleability and the stability over time of the composition (the black pigment does not settle out) is more excellent. 5 to 30 nm is more preferred.
  • particle diameter means the average primary particle diameter of the particle measured by the following method.
  • the average primary particle diameter can be measured using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
  • the maximum length of a particle image obtained using a transmission electron microscope (Dmax: the maximum length at two points on the contour of the particle image), and the maximum vertical length (DV-max: two straight lines parallel to the maximum length)
  • Dmax the maximum length at two points on the contour of the particle image
  • DV-max maximum vertical length
  • the geometric mean value (Dmax ⁇ DV-max) 1/2 was defined as the particle diameter.
  • the particle diameter of 100 particles was measured by this method, and the arithmetic average value was defined as the average primary particle diameter of the particles.
  • the inorganic pigment is not particularly limited as long as it has a light-shielding property and is a particle containing an inorganic compound, and a known inorganic pigment can be used.
  • a known inorganic pigment can be used.
  • an inorganic pigment is preferable because the black layer has more excellent low reflectivity and light blocking properties.
  • 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), and chromium (Cr). , Copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and one or more selected from the group consisting of silver (Ag) Metal oxides, metal nitrides, metal oxynitrides, and the like containing the above metal element.
  • the metal oxide, metal nitride, and metal oxynitride particles in which other atoms are mixed may be used.
  • metal nitride-containing particles further containing an atom (preferably an oxygen atom and / or a sulfur atom) selected from the elements of Groups 13 to 17 of the periodic table can be used.
  • the method for producing the above-described metal nitride, metal oxide or metal oxynitride is not particularly limited as long as a black pigment having desired physical properties can be obtained. You can use any method. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, and a thermal plasma method is preferable in that impurities are less mixed, particle diameters are easily formed, and productivity is high.
  • the above-mentioned metal nitride, metal oxide or metal oxynitride may be subjected to a surface modification treatment.
  • the surface modification treatment may be performed with a surface treatment agent having both a silicone group and an alkyl group. Examples of such inorganic particles include the “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a nitride or oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium and niobium is more preferable, since generation of an undercut when forming a black layer can be suppressed.
  • the black color material further contains at least one metal oxynitride selected from the group consisting of titanium, vanadium, zirconium and niobium, in that the light resistance and the moisture resistance of the light-shielding film are more excellent. It is particularly preferable to contain a titanium oxynitride (titanium black).
  • Titanium black is black particles containing titanium oxynitride.
  • the surface of titanium black can be modified as needed for the purpose of improving dispersibility, suppressing cohesion, and the like. Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and a water-repellent substance as disclosed in JP-A-2007-302636. Processing is also possible.
  • a method for producing titanium black a method in which a mixture of titanium dioxide and metallic titanium is reduced by heating in a reducing atmosphere (Japanese Patent Application Laid-Open No. 49-5432), an ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride.
  • a method of reducing titanium in a hydrogen-containing reducing atmosphere Japanese Patent Application Laid-Open No. 57-205322
  • a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia Japanese Patent Application Laid-Open No. 60-65069
  • the particle size of titanium black is not particularly limited, but is preferably from 10 to 45 nm, more preferably from 12 to 20 nm.
  • the specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is 5 to 5 because the water repellency after surface treatment with a water repellent has a predetermined performance. It is preferably 150 m 2 / g, more preferably 20 to 100 m 2 / g.
  • titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilac D (Trade name, manufactured by Ako Kasei Co., Ltd.) and MT-150A (trade name, manufactured by Teika Co., Ltd.).
  • the light-shielding composition also preferably contains titanium black as a dispersion containing titanium black and Si atoms.
  • titanium black is contained in the composition as a dispersion.
  • the content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion is preferably 0.05 to 0.5 in terms of mass, more preferably 0.07 to 0.4.
  • the above-mentioned dispersion target includes both those in which titanium black is in the state of primary particles and those in the form of aggregates (secondary particles).
  • the Si / Ti of the dispersion is too small, a residue tends to remain in the removed portion when the coating film using the dispersion is patterned by photolithography or the like, and the Si / Ti of the dispersion is large. If too much, the light-shielding ability tends to decrease.
  • the following means can be used.
  • a dispersion is obtained by dispersing titanium oxide particles and silicon oxide particles using a dispersing machine, and the mixture is subjected to a reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are reduced.
  • a dispersed object containing Si and Ti as a main component can be obtained.
  • Titanium black with adjusted Si / Ti can be produced, for example, by the method described in paragraphs 0005 and 0016 to 0021 of paragraph number publication of JP-A-2008-266045.
  • the content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion is determined, for example, by the method (2-1) or the method (2-3) described in paragraphs 0054 to 0056 of WO2011 / 049090. ) Can be measured.
  • the above-mentioned titanium black can be used.
  • a black pigment composed of iron oxide, carbon black, aniline black, or the like may be used alone or in combination of two or more as a dispersion. In this case, it is preferable that 50% by mass or more of the entirety of the dispersion is occupied by the dispersion composed of titanium black.
  • the light-shielding composition also preferably contains zirconium nitride or zirconium oxynitride.
  • Zirconium nitride or zirconium oxynitride is preferably coated with an inorganic compound.
  • the photocatalytic activity of the light-shielding pigment is suppressed without deteriorating the light-shielding properties of the pigment (light-shielding pigment), and the deterioration of the light-shielding composition is prevented. It will be easier.
  • Preferred specific examples of the inorganic compound include titanium dioxide, zirconia, silica, and alumina, and examples thereof include silica and alumina. It is also preferable to use a combination of titanium black and zirconium nitride, titanium black and zirconium oxynitride, titanium black and zirconium nitride coated with silica, and titanium black and zirconium nitride coated with alumina.
  • the inorganic pigment examples include carbon black.
  • the black coloring material preferably contains carbon black from the viewpoint of excellent light-shielding light resistance and more excellent suppression of fluctuations in optical characteristics after a light resistance test.
  • Examples of the carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black.
  • a carbon black produced by a known method such as an oil furnace method may be used, or a commercially available product may be used.
  • Specific examples of commercially available carbon black include C.I. I. An organic pigment such as CI Pigment Black 1; I. Pigment Black 7 and the like.
  • the carbon black surface-treated carbon black is preferable.
  • the surface treatment By the surface treatment, the particle surface state of the carbon black can be modified, and the dispersion stability in the composition can be improved.
  • the surface treatment include a coating treatment with a resin, a surface treatment for introducing an acidic group, and a surface treatment with a silane coupling agent.
  • the carbon black carbon black coated with a resin is preferable.
  • the coating resin include epoxy resin, polyamide, polyamideimide, novolak resin, phenol resin, urea resin, melamine resin, polyurethane, diallyl phthalate resin, alkylbenzene resin, polystyrene, polycarbonate, polybutylene terephthalate, and modified polyphenylene oxide.
  • the content of the coating resin is preferably from 0.1 to 40% by mass, more preferably from 0.5 to 30% by mass, based on the total of the carbon black and the coating resin, from the viewpoint that the black layer has more excellent light-shielding properties and insulating properties. More preferred.
  • Organic pigment is not particularly limited as long as it has a light-shielding property and contains an organic compound, and a known organic pigment can be used.
  • Specific examples of the organic pigment include a benzofuranone compound, an azomethine compound, a perylene compound, and an azo compound.
  • the black coloring material preferably contains a benzofuranone compound or a perylene compound from the viewpoint that the moisture resistance of the light-shielding film is more excellent.
  • the benzofuranone compound is a compound having a benzofuran-2 (3H) -one structure or a benzofuran-3 (2H) -one structure in a molecule and which is colored black by absorbing light having a visible light wavelength.
  • benzofuranone compound examples include compounds described in JP-T-2010-534726, JP-T-2012-515233, and JP-T-2012-515234. Further, as the benzofuranone compound, a compound represented by any of the general formulas (63) to (68) is preferable.
  • R 206 , R 207 , R 212 , R 213 , R 218 and R 219 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or Represents an alkyl group having 1 to 20 carbon atoms and having 1 to 20 fluorine atoms.
  • a plurality of R 208 , R 209 , R 214 , R 215 , R 220 or R 221 may form a ring by a direct bond or an oxygen atom bridge, a sulfur atom bridge, an NH bridge or an NR 251 bridge.
  • R 210 , R 211 , R 216 , R 217 , R 222 and R 223 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • a, b, c, d, e and f each independently represent an integer of 0 to 4.
  • R 206 , R 207 , R 212 , R 213 , R 218 and R 219 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or An alkyl group having 1 to 6 carbon atoms and having 1 to 12 fluorine atoms is preferable.
  • R 251 and R 252 each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkenyl having 4 to 7 carbon atoms.
  • R 210 , R 211 , R 216 , R 217 , R 222 and R 223 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • the above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group and aryl group may have a hetero atom, and may be unsubstituted or substituted.
  • R 253 , R 254 , R 259 , R 260 , R 265 and R 266 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or Represents an alkyl group having 1 to 20 carbon atoms and having 1 to 20 fluorine atoms.
  • a plurality of R 255 , R 256 , R 261 , R 262 , R 267 or R 268 may form a direct bond or a ring with an oxygen atom bridge, a sulfur atom bridge, an NH bridge or an NR 271 bridge.
  • R 257 , R 258 , R 263 , R 264 , R 269 and R 270 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • a, b, c, d, e and f each independently represent an integer of 0 to 4.
  • R 253 , R 254 , R 259 , R 260 , R 265 and R 266 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or An alkyl group having 1 to 6 carbon atoms and having 1 to 12 fluorine atoms is preferable.
  • R 271 and R 272 each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkenyl having 4 to 7 carbon atoms.
  • R 257 , R 258 , R 263 , R 264 , R 269 and R 270 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • the above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group and aryl group may have a hetero atom, and may be unsubstituted or substituted.
  • the benzofuranone compound is available, for example, as Irgaphor Black S0100CF (trade name, manufactured by BASF).
  • a perylene compound is a compound that has a perylene structure in the molecule and is colored black by absorbing light having a wavelength of visible light.
  • Examples of the perylene compound include compounds described in JP-A-62-1753 and JP-B-63-26784. Further, as the perylene compound, a perylene compound represented by any of the general formulas (69) to (71) is preferable.
  • X 92 , X 93 , X 94 and X 95 each independently represent an alkylene group having 1 to 10 carbon atoms.
  • R 224 and R 225 each independently represent hydrogen, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.
  • R 273 and R 274 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • a and b each independently represent an integer of 0 to 5.
  • X 92 , X 93 , X 94 and X 95 are each independently preferably an alkylene group having 1 to 6 carbon atoms.
  • R 224 and R 225 are each independently preferably a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, or an acyl group having 2 to 4 carbon atoms.
  • Each of R 273 and R 274 is preferably independently hydrogen or an alkyl group having 1 to 6 carbon atoms.
  • the above-mentioned alkylene group, alkoxy group, acyl group and alkyl group may have a hetero atom and may be either unsubstituted or substituted.
  • Perylene compounds are described, for example, in C.I. I. Pigment Black 21, 30, 31, 32, 33, and 34, and Paliogen Black S0084, K0084, L0086, K0086, EH0788, and FK4281 (all of which are brand names, all manufactured by BASF). .
  • Black dye a dye that expresses black alone can be used, for example, a pyrazole azo compound, a pyrromethene compound, an anilino azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxonol compound, a pyrazolotriazole azo compound, and a pyridone azo compound.
  • black dyes examples include JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-T-2592207, and US Pat. No. 4,808,501. Specification, US Pat. No. 5,679,920, US Pat. No. 505,950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828. Reference can be made to compounds described in gazettes and the like, the contents of which are incorporated herein.
  • these black dyes include dyes defined by the color index (CI) of Solvent Black 27 to 47, and C.I. of Solvent Black 27, 29 or 34. I. Are preferred.
  • commercially available products of these black dyes include Spiron Black MH, Black BH (all manufactured by Hodogaya Chemical Industry Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (all manufactured by Orient Chemical Industry Co., Ltd.), Dyes such as Savinyl Black RLSN (all manufactured by Clariant), KAYASET Black KR and K-BL (all manufactured by Nippon Kayaku Co., Ltd.).
  • a dye multimer may be used as the black dye.
  • the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097.
  • a polymerizable dye having polymerizability in the molecule may be used, and examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries.
  • a single dye having a color other than black may be used alone as a black dye. Examples of such coloring dyes include chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), as well as paragraphs 0027 to 264 of JP-A-2014-42375. No. 0200 can also be used.
  • the black coloring material contains a nitride or oxynitride of at least one metal selected from the group consisting of titanium, vanadium, zirconium and niobium from the viewpoint of suppressing the occurrence of undercut when forming the black layer. More preferably, from the viewpoint that the light resistance and moisture resistance of the light-shielding film are more excellent, it is further preferable that the light-shielding film contains at least one metal oxynitride selected from the group consisting of titanium, vanadium, zirconium and niobium. It is particularly preferable to contain titanium oxynitride (titanium black). Further, the black coloring material preferably contains carbon black, a benzofuranone compound or a perylene compound.
  • the light-shielding composition may contain a coloring agent other than the black coloring material.
  • the light-shielding characteristics of the black layer (light-shielding film) can be adjusted by using both the black colorant and one or more colorants. Further, for example, when a black layer is used as a light attenuating film, it is easy to uniformly attenuate each wavelength with respect to light containing a wide wavelength component.
  • the coloring agent include pigments and dyes other than the above-described black coloring material.
  • the total content of the black colorant and the colorant is preferably from 10 to 90% by mass, more preferably from 30 to 70% by mass, based on the total mass of the solid content of the composition.
  • the total content of the black coloring material and the coloring agent is preferably smaller than the above preferred range.
  • the mass ratio of the content of the coloring agent to the content of the black coloring material is preferably 0.1 to 9.0.
  • the composition may further contain an infrared absorber.
  • the infrared absorbing agent means a compound having absorption in a wavelength region of an infrared region (preferably, a wavelength of 650 to 1300 nm).
  • a compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm is preferable.
  • colorants having such spectral characteristics include, for example, pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylene Compounds, dithiol metal complex-based compounds, croconium compounds, and the like.
  • phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound and croconium compound the compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-11110 may be used. Will be incorporated into the book.
  • the cyanine compound can be referred to, for example, “Functional Dye, Shin Ogawara / Sen Matsuoka / Teijiro Kitao / Tsunaki Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
  • Examples of the colorant having the above-mentioned spectral characteristics include compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254.
  • Near-infrared absorbing particles comprising a crystallite of an oxide containing Cu and / or P disclosed in Paragraphs 0034 to 0067 of JP-A No. 003-0067 and having a number average agglomerated particle size of 5 to 200 nm can also be used.
  • the compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound is preferable.
  • the infrared absorbent is preferably a compound that dissolves in water at 25 ° C in an amount of 1% by mass or more, and more preferably a compound that dissolves in water at 25 ° C in an amount of 10% by mass or more. By using such a compound, the solvent resistance is improved.
  • paragraphs 0049 to 0062 of JP-A-2010-222557 can be referred to, and the contents thereof are incorporated herein.
  • the cyanine compound and the squarylium compound are described in paragraphs 0022 to 0063 of WO 2014/088063, paragraphs 0053 to 0118 of WO 2014/030628, paragraphs 0028 to 0074 of JP-A-2014-59550, and WO 2012/2012.
  • 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, and JP-A-2015-157893.
  • Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP-A-2014-095007, paragraphs 0013 to 0047 of JP-A-2014-80487, and paragraphs 0007 to 0028 of JP-A-2013-227403 can be referred to. This content is incorporated herein.
  • the light-shielding composition contains a resin.
  • the resin include a dispersion resin and an alkali-soluble resin.
  • the content of the resin in the composition is not particularly limited, but is preferably 3 to 60% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass based on the total solid content of the composition. .
  • One type of resin may be used alone, or two or more types may be used in combination.
  • a dispersion resin described below and an alkali-soluble resin described later may be used in combination as the resin.
  • the total content is preferably within the above range.
  • the resin is a component dissolved in the composition and means a component having a molecular weight of more than 2000. When the molecular weight of the resin is polydisperse, the weight average molecular weight of the resin is more than 2,000.
  • the light-shielding composition preferably contains a dispersion resin.
  • a dispersion resin means a compound different from an alkali-soluble resin described below.
  • the content of the dispersing resin in the composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 20% by mass based on the total solid content of the composition. .
  • the dispersion resin one type may be used alone, or two or more types may be used in combination. When two or more dispersing resins are used in combination, the total content is preferably within the above range.
  • the mass ratio of the content of the dispersing resin (preferably the graft polymer) to the content of the black coloring material (content of the dispersing resin / content of the black coloring material) is from 0.05 to 0.05. 1.00 is preferred, 0.05 to 0.35 is more preferred, and 0.20 to 0.35 is even more preferred.
  • the dispersing resin for example, a known dispersing agent can be appropriately selected and used. Among them, a polymer compound is preferable.
  • the dispersing resin include polymer dispersants (eg, polyamidoamine and its salts, polycarboxylic acids and its salts, high-molecular unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic-based resins). Copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and pigment derivatives.
  • the polymer compound can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer based on its structure.
  • ⁇ Polymer compound The high molecular compound is adsorbed on the surface of a dispersion target such as a black pigment and other pigments used in combination as required (hereinafter, the black pigment and the other pigments are collectively referred to simply as “pigment”) and the like, Acts to prevent re-aggregation of Therefore, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, or a block-type polymer containing an anchor site to the pigment surface is preferable.
  • the polymer compound may have a curable group.
  • the curable group include a group containing an ethylenically unsaturated bond (hereinafter, also referred to as an “ethylenically unsaturated group”) (eg, a (meth) acryloyl group, a vinyl group, and a styryl group), And a cyclic ether group (for example, an epoxy group, an oxetanyl group, and the like) and the like, but are not limited thereto.
  • the ethylenically unsaturated group is preferable as the curable group, and a (meth) acryloyl group is more preferable, since polymerization can be controlled by a radical reaction.
  • the light-shielding composition preferably contains a dispersion resin having a curable group (more preferably, an ethylenically unsaturated group) from the viewpoint that the light-shielding film has more excellent light resistance, moisture resistance, and heat resistance.
  • the dispersion resin containing a curable group include a polymer compound having a structural unit having a curable group (more preferably, an ethylenically unsaturated group such as a (meth) acryloyl group).
  • structural unit is synonymous with “repeating unit”.
  • a curable group may be introduced at a terminal of a graft chain of a structural unit containing the following graft chain.
  • a curable group (preferably, an ethylenically unsaturated group such as a (meth) acryloyl group) may be introduced.
  • the content of the structural unit having a curable group is preferably from 2 to 90% by mass, more preferably from 5 to 30% by mass, based on the total mass of the polymer compound in terms of mass.
  • 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.
  • the polymer may be used.
  • the chains may have a polyester structure and / or a polyether structure.
  • the polymer chain it is more preferable that the polymer chain has a polyester structure.
  • the polymer compound preferably contains a structural unit containing a graft chain.
  • structural unit is synonymous with “repeating unit”. Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent due to the graft chain, the dispersibility of a pigment or the like and the dispersion stability after aging (stability with time) Excellent.
  • the polymer compound containing the structural unit containing the graft chain has an affinity for a polymerizable compound or another resin that can be used in combination. As a result, residues are less likely to be generated in alkali development.
  • the number of atoms in the graft chain excluding hydrogen atoms is preferably from 40 to 10,000, more preferably from 50 to 2000 except for hydrogen atoms, and the number of atoms excluding hydrogen atoms is more preferably 50 to 2000. More preferably, it is 60 to 500.
  • the term “graft chain” refers to the range 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 terminal of the group branched from the main chain.
  • the graft chain preferably contains a polymer structure.
  • a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acryl structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide.
  • a polyether structure preferably 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 and thereby enhance the dispersibility of the pigment or the like. Further, it is preferable that the graft chain contains at least one kind, and it is more preferable that the graft chain contains 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 binding to the main chain of the copolymer to form a graft chain) is not particularly limited, but contains an ethylenically unsaturated group. Macromonomers can be suitably used.
  • the polymer compound preferably contains a curable group, and contains an ethylenically unsaturated group such as a (meth) acryloyl group, from the viewpoint of more excellent light resistance, moisture resistance, and heat resistance of the light-shielding film. Is more preferable.
  • AA-6, AA-10, AB-6, AS-6, AN-6, AW-6, AA-714, AY-707, AY-714, AK-5, AK-30, and AK-32 all trade names, manufactured by Toagosei Co., Ltd.
  • Blemmer PP- 100, Blemmer PP-500, Blemmer PP-800, Blemmer PP-1000, Blemmer 55-PET-800, Blemmer PME-4000, Blemmer PSE-400, Blemmer PSE-1300, and Blemmer 43PAPE-600B all trade names
  • AA-6, AA-10, AB-6, AS-6, AN-6 or Blemmer PME-4000 are preferred.
  • the dispersion resin preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and a cyclic or linear polyester, and includes polymethyl acrylate and polymethacrylic acid.
  • Methyl and more preferably contain at least one structure selected from the group consisting of linear polyesters, polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure, and polyvalerolactone structure More preferably, it contains at least one structure selected from the group consisting of
  • the dispersed resin may contain the above structure alone in one resin, or may contain a plurality of these structures in one resin.
  • 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.
  • Specific examples of the dispersed resin having a polycaprolactone structure include resins in which j and k in the following formulas (1) and (2) are 5: Further, specific examples of the dispersion resin having a polyvalerolactone structure include resins in which j and k in the following formulas (1) and (2) are 4.
  • dispersed resin having a polymethyl acrylate structure examples include a resin in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group.
  • dispersion resin having a polymethyl methacrylate structure examples include a resin in which X 5 in the following formula (4) is a methyl group, and R 4 is a methyl group.
  • the polymer compound preferably contains a structural unit represented by any one of the following formulas (1) to (4) as a structural unit containing a graft chain, and includes the following formulas (1A) and (2A) ), The following formula (3A), the following formula (3B), and more preferably a structural unit represented by any of the 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.
  • X 1 , X 2 , X 3 , X 4 and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms) from the viewpoint of synthesis restrictions. Independently, a hydrogen atom or a methyl group is more preferred, and a methyl group is even more preferred.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited 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).
  • a and B mean the binding sites to the left terminal group and right terminal group in formulas (1) to (4), respectively.
  • (Y-2) or (Y-13) is more preferable from the viewpoint of convenience 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 And the like.
  • a group having a steric repulsion effect is particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms.
  • alkyl group or an alkoxy group having up to 24 carbon atoms 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 group having 5 to 24 carbon atoms is particularly preferable. 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 are preferably integers of 4 to 6, and more preferably 5 from the viewpoint of the stability over time and the developability of the composition.
  • n and m are preferably integers of 10 or more, and more preferably integers of 20 or more.
  • the number of repetitions of the polycaprolactone structure and the sum of the number of repetitions of the polyvalerolactone are preferably integers of 10 or more, and 20 or more. Integers are more preferred.
  • R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the structure of the monovalent organic group is not particularly limited. 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.
  • R 4 is an alkyl group
  • examples of the alkyl group include a linear alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms.
  • a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is further preferable.
  • q is 2 to 500
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different.
  • the polymer compound may contain a graft chain-containing structural unit having two or more different structures. That is, in the molecule of the polymer compound, structural units represented by formulas (1) to (4) having different structures may be included, and in the formulas (1) to (4), n, m, p , And q each represent an integer of 2 or more, in formulas (1) and (2), j and k may include different structures in the side chain, and formulas (3) and (4) )), A plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of stability over time and developability of the composition.
  • the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of stability over time and developability of the composition.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoint of stability over time and developability of the composition. .
  • the polymer compound contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
  • the content of the structural unit containing the graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is calculated in terms of mass with respect to the total mass of the polymer compound. It is preferably from 2 to 90% by mass, more preferably from 5 to 30% by mass.
  • the structural unit containing a graft chain is contained within this range, the dispersibility of the pigment is high and the developability when forming a black layer is good.
  • the polymer compound preferably contains a hydrophobic structural unit different from the structural unit containing the graft chain (that is, does not correspond to the structural unit containing the 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, and the like).
  • the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and is a structural unit derived from a compound having a ClogP value of 1.2 to 8. Is more preferable. Thereby, the effect of the present invention can be more reliably achieved.
  • ClogP values are measured using Daylight Chemical Information System, Inc. This is a value calculated by the program “CLOGP” available from. This program provides the value of "calculated log P" calculated by the Hansch, Leo fragment approach (see literature below). The fragment approach is based on the chemical structure of a compound, dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments to estimate the logP value of the compound. The details are described in the following documents. In this specification, a ClogP value calculated by the program CLOGP v4.82 is used. A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P .; G. FIG. Sammmens, J .; B. Taylor and C.I.
  • logP means a common logarithm of a partition coefficient P (Partition Coefficient), and quantitatively describes how an organic compound is distributed in an equilibrium of a two-phase system of an oil (generally, 1-octanol) and water. It is a physical property value expressed as a simple 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, at least one structural unit 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 (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or Represents an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, and a propyl group).
  • 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 a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (eg, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group) and a divalent aromatic group (eg, an arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Represents an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and a combination thereof.
  • a divalent aliphatic group eg, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene
  • 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 from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • the aromatic group may have a substituent.
  • substituents 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.
  • Another heterocycle, aliphatic ring, or aromatic ring may be condensed to the heterocycle.
  • 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 include a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • As the polyoxyalkylene structure a polyoxyethylene structure or a polyoxypropylene structure is preferable.
  • the polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z represents an aliphatic group (eg, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (eg, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group) , A heterocyclic group, and a combination thereof.
  • These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, where R 31 is an aliphatic group or an aromatic group. Group or heterocyclic group) or a carbonyl group (—CO—).
  • 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-assembled hydrocarbon group and a cross-linked cyclic hydrocarbon group. Examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like.
  • bridged cyclic hydrocarbon ring examples include, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring and the like) and the like.
  • Tricyclic hydrocarbon rings such as a cyclic hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane ring , And tetracyclo [4.4.0.1 2,5 .
  • the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenalene ring is also included.
  • perhydronaphthalene decalin
  • perhydroanthracene perhydrophenanthrene
  • perhydroacenaphthene perhydrofluorene
  • perhydroindene perhydroindene
  • a condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenalene ring is also included.
  • the aliphatic group a saturated aliphatic group is more preferable than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the number of carbon atoms in the aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 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. However, the aromatic 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 a C 1-6 carbon atom.
  • a halogen atom eg, a fluorine atom, a chlorine atom, a bromine atom, etc.
  • C 1-6 carbon atom Represents an alkyl group (eg, a methyl group, an ethyl group, and a propyl group), Z, or LZ.
  • L and Z have the same meaning as the above groups.
  • 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, and L contains a single bond or an alkylene group or an oxyalkylene structure.
  • Compounds that are divalent linking groups, wherein X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group are preferred.
  • R 1 is a hydrogen atom or a methyl group
  • L is an alkylene group
  • Z is an aliphatic group, a heterocyclic group, or an aromatic group.
  • Compounds that are groups are preferred.
  • R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds that are groups are preferred.
  • Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylates, methacrylates, styrenes, and the like.
  • Examples of typical compounds represented by formulas (i) to (iii) compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417 can be referred to, and the contents thereof are described in the present specification. Incorporated in
  • the content of the hydrophobic structural unit in terms of mass is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, based on the total mass of the polymer compound. When the content is in the above range, a sufficient pattern formation can be obtained.
  • the polymer compound can introduce a functional group capable of forming an interaction with a pigment or the like (for example, a black pigment).
  • the polymer compound preferably further contains a structural unit having 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 or the like include an acid group, a basic group, a coordinating group, and a reactive functional group.
  • the polymer compound contains an acid group, a basic group, a coordinating group, or a reactive functional group
  • the structural unit containing an acid group the structural unit containing a basic group
  • the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, developability for pattern formation by alkali development can be imparted to the polymer compound. That is, if an alkali-soluble group is introduced into the polymer compound, the above-mentioned composition contains a polymer compound as a dispersing resin that contributes to dispersion of pigments and the like, which is alkali-soluble.
  • the composition containing such a polymer compound is excellent in the light-shielding property of a black layer formed by exposure, and the alkali developability of an unexposed portion is improved. Further, when the polymer compound contains a structural unit containing an acid group, the polymer compound is easily compatible with a solvent, and the coating property tends to be improved. This is because the acid group in the structural unit containing an 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 that disperses the pigment and the like becomes low. This is presumed to be because the polymer compound itself is easily dispersed stably.
  • the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit containing a graft chain, or may be a different structural unit.
  • the structural unit containing a soluble group is a structural unit different from the above-mentioned hydrophobic structural unit (that is, does not correspond to the above-mentioned hydrophobic structural unit).
  • the acid group which is a functional group capable of forming an interaction with a pigment
  • examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. And at least one phosphoric acid group is preferable, and a carboxylic acid group is more preferable.
  • Carboxylic acid groups have good adsorptivity to pigments and the like and have 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 if it does, the content of the structural unit containing an acid group is 5% based on the total mass of the polymer compound.
  • the amount is preferably from 80 to 80% by mass, and more preferably from 10 to 60% by mass, from the viewpoint of suppressing damage to image strength due to alkali development.
  • Examples of the basic group which is a functional group capable of forming an interaction with a pigment or the like include a primary amino group, a secondary amino group, a tertiary amino group, a hetero ring containing an N atom, and an amide.
  • Preferred basic groups are tertiary amino groups because they have good adsorptivity to pigments and the like and have 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 calculated based on the total amount of the polymer compound in terms of mass. The amount is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass, from the viewpoint of suppressing the inhibition of developing property.
  • Examples of the coordinating group which is a functional group capable of forming an interaction with a pigment
  • the reactive functional group include, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acid chloride Objects and the like.
  • a preferred functional group is an acetylacetoxy group in that it has good adsorptivity to pigments and the like and high dispersibility of the 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 reactive functional group, but if it contains, the content of these structural units Is preferably from 10 to 80% by mass, and more preferably from 20 to 60% by mass, in terms of suppression of development property inhibition, based on the total mass of the polymer compound.
  • the polymer compound other than the graft chain, contains a functional group capable of forming an interaction with a pigment or the like, it is sufficient that the polymer compound contains a functional group capable of forming an interaction with the various pigments described above,
  • the manner in which these functional groups are introduced is not particularly limited, and the polymer compound may be one selected from structural units derived from monomers represented by the following formulas (iv) to (vi). It is preferable to contain the above 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, or the like) or a carbon atom.
  • a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, or the like
  • R 11 , R 12 , and R 13 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 12 and R 13 are more preferably hydrogen atoms.
  • X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the formula (v) represents a methine group or a nitrogen atom.
  • L 1 in the 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 the formula (i).
  • 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 include a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • a polyoxyethylene structure or a polyoxypropylene structure is preferable.
  • the polyoxyethylene structure is represented by-(OCH 2 CH 2 ) n-, where n is preferably an integer of 2 or more, and 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 other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, and is preferably a carboxylic acid group. More preferred.
  • R 14 , R 15 , and R 16 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms. group (e.g., methyl group, ethyl group, and propyl group), - Z 1, or an L 1 -Z 1.
  • L 1 and Z 1 have the same meanings as L 1 and Z 1 described above, and preferred examples are also the same.
  • R 14 , R 15 , and R 16 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 are each independently a hydrogen atom or a methyl group, and L 1 is a divalent group containing an alkylene group or an oxyalkylene structure. Preferred are compounds in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group. Further, as the 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. Are preferred.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group
  • L 1 is a single bond or an alkylene group
  • Z Compounds in which 1 is a carboxylic acid group are preferred.
  • Examples of the monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction of a compound containing an addition-polymerizable double bond and a hydroxyl group in a molecule (eg, 2-hydroxyethyl methacrylate) with succinic anhydride.
  • the content of the structural unit containing a functional group capable of forming an interaction with a pigment or the like is, in terms of the interaction with the pigment or the like, the stability over time, and the permeability into a developer, the amount of the polymer compound in terms of mass. Is preferably from 0.05 to 90% by mass, more preferably from 1.0 to 80% by mass, and still more preferably from 10 to 70% by mass, based on the total mass.
  • the polymer compound interacts with a graft chain-containing structural unit, a hydrophobic structural unit, and a pigment, for the purpose of improving various performances such as image strength, as long as the effects of the present invention are not impaired.
  • It further has another structural unit having various functions different from the structural unit containing a functional group that can be formed (for example, a structural unit containing a functional group having an affinity for a solvent described below). Is also good.
  • Such other structural units include, for example, structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the polymer compound may use one or more of these other structural units, and its content is preferably from 0 to 80% by mass, and preferably from 10 to 80% by mass, based on the total mass of the polymer compound. 60 mass% is more preferable. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably from 0 to 250 mgKOH / g, more preferably from 10 to 200 mgKOH / g, still more preferably from 30 to 180 mgKOH / g, particularly preferably from 70 to 120 mgKOH / g.
  • the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development in forming a black layer can be more effectively suppressed.
  • the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better.
  • the acid value of the polymer compound is 20 mgKOH / g or more, sedimentation of pigments and the like can be further suppressed, the number of coarse particles can be reduced, and the stability over time of the composition can be further improved.
  • the acid value can be calculated, for example, from the average content of acid groups in the compound.
  • a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group, which is a constituent component of the resin.
  • the weight average molecular weight of the polymer compound is preferably from 4,000 to 300,000, more preferably from 5,000 to 200,000, still more preferably from 6,000 to 100,000, particularly preferably from 10,000 to 50,000. preferable.
  • the polymer compound can be synthesized based on a known method.
  • polymer compound examples include “DA-7301” manufactured by Kusumoto Kasei, “Disperbyk-101 (polyamideamine phosphate)” manufactured by BYK Chemie, 107 (carboxylate), and 110 (copolymer containing an acid group).
  • MYS-IEX polyoxyethylene monostearate
  • Hinoact T-8000E manufactured by Kawaken Fine Chemical, Shin-Etsu Chemical Co., Ltd.
  • organosiloxane polymer KP-341 Yu "W001: cationic surfactant"
  • polyoxyethylene lauryl ether polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate
  • Nonionic surfactants such as stearates and sorbitan fatty acid esters
  • anionic surfactants such as "W004, W005, W017”;"EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA” manufactured by Morishita Sangyo Polymer 400, EFKA polymer 401, EFKA polymer
  • amphoteric resin containing an acid group and a basic group.
  • the amphoteric resin is preferably a resin having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more.
  • Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, and DISPERBY manufactured by BYK Chemie.
  • One of these polymer compounds may be used alone, or two or more thereof may be used in combination.
  • polymer compound As specific examples of the polymer compound, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP-A-2013-249417, the contents of which are incorporated herein.
  • the dispersing resin besides the above-mentioned polymer compounds, graft copolymers described in paragraphs 0037 to 0115 of JP-A-2010-106268 (corresponding to columns 0075 to 0133 of US2011 / 0124824) can be used. Is incorporated herein by reference. Further, in addition to the above, it contains a side chain structure in which an acidic group described in paragraphs 0028 to 0084 of JP-A-2011-153283 (corresponding to columns 2011 to 0133 of US2011 / 0279759) is bonded via a linking group. High molecular compounds containing the following constituents can be used, the contents of which are incorporated herein by reference.
  • dispersing resin resins described in paragraphs 0033 to 0049 of JP-A-2016-109763 can also be used, and the contents thereof are incorporated herein.
  • the composition preferably contains an alkali-soluble resin.
  • the alkali-soluble resin means a resin containing a group that promotes alkali solubility (an alkali-soluble group, for example, an acid group such as a carboxylic acid group), and a resin different from the dispersion resin described above. I do.
  • the content of the alkali-soluble resin in the composition is not particularly limited, but is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and more preferably 5 to 15% by mass based on the total solid content of the composition. More preferred.
  • One alkali-soluble resin may be used alone, or two or more alkali-soluble resins may be used in combination. When two or more alkali-soluble resins are used in combination, the total content is preferably within the above range.
  • alkali-soluble resin examples include resins containing at least one alkali-soluble group in a molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, and (meth) acrylic resin.
  • An acryl / (meth) acrylamide copolymer resin, an epoxy resin, a polyimide resin, and the like can be given.
  • the alkali-soluble resin include a copolymer resin of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
  • the unsaturated carboxylic acid is not particularly limited, but monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and vinyl acetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or acid anhydrides thereof
  • polyvalent carboxylic acid monoesters such as mono (2- (meth) acryloyloxyethyl) phthalate; and the like.
  • Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate. Further, the compounds described in paragraph 0027 of JP-A-2010-97210 and paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, and the above description is incorporated in the present specification.
  • a copolymerizable ethylenically unsaturated compound having a side chain containing an ethylenically unsaturated group may be used in combination.
  • 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. Obtained.
  • an alkali-soluble resin containing a curable group is also preferable.
  • the curable group include curable groups that may be contained in the above-mentioned polymer compound, and the preferable range is also the same.
  • the alkali-soluble resin containing a curable group an alkali-soluble resin having a curable group in a side chain is preferable.
  • the alkali-soluble resin containing a curable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polythane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, and KS resist 106 (KS).
  • alkali-soluble resin examples include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, and JP-A-54-92723.
  • polyvinyl alcohol-based binder resin containing an alkali-soluble group described in JP-A-2001-318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon and 2,2-bis- (4 -Hydroxyphenyl) -propane and epichlorohydrin
  • polyimide resin described in WO 2008/123097 pamphlet; and the like can be used polyethers such as that.
  • 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 description is incorporated herein.
  • a polyimide precursor can also be used as the alkali-soluble resin.
  • the polyimide precursor means a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C.
  • the polyimide precursor include a resin containing a repeating unit represented by the formula (1).
  • the structure of the polyimide precursor include, for example, an amic acid structure represented by the following formula (2), the following formula (3) in which the amic acid structure is partially imide-closed, and the following formula (4) in which all imides are closed.
  • the polyimide precursor containing an imide structure represented by the formula (1) In this specification, 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 examples include, for example, the compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, the compounds described in paragraphs 0022 to 0039 of JP-A-2016-122101, and Compounds described in paragraphs 0061 to 0092 of 2016-68401 can be mentioned, and the above description is incorporated herein.
  • the alkali-soluble resin is also preferable to contain at least one selected from the group consisting of a polyimide resin and a polyimide precursor, in that the pattern shape of the patterned black layer obtained using the composition is more excellent. .
  • 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. Examples include the resins described in paragraphs 0012 to 0013, and the contents described above are incorporated herein.
  • a polybenzoxazole precursor can also be used as the alkali-soluble resin.
  • the polybenzoxazole precursor is a resin synthesized from a hydroxyl group-containing diamine and a dicarboxylic acid derivative.
  • the hydroxyl group-containing diamine include aromatic diamines having a phenolic hydroxyl group, such as bisaminophenol compounds.
  • Specific examples of the hydroxyl group-containing diamine include 3,3-dihydroxybenzidine and 3,3′-dihydroxy-4,4′-diaminodiphenyl ether.
  • dicarboxylic acid derivatives examples include dicarboxylic acid derivatives such as dicarboxylic acid chloride and dicarboxylic acid ester, and aromatic dicarboxylic acid derivatives are preferable.
  • dicarboxylic acid derivative examples include isophthalic acid dichloride and terephthalic acid dichloride.
  • polybenzoxazole precursor examples include polyhydroxyamide, polyaminoamide, polyamide, and polyamideimide.
  • polybenzoxazole precursor examples include, for example, the compounds described in paragraphs 0049 to 0062 of JP-A-2003-121997, the compounds described in paragraphs 0050 to 0057 of WO2017 / 057281 and international publications
  • the compounds described in paragraphs 0015 to 0043 of JP-A-2016 / 043203 are exemplified, and the above description is incorporated herein.
  • the copolymer of the polyimide precursor and the polybenzoxazole precursor is a copolymer having a polyamic acid ester structural unit and a hydroxypolyamide structural unit, for example, an alternating copolymer structure of a polyamic acid ester structural unit and a hydroxypolyamide structural unit And a copolymer having the formula:
  • the alkali-soluble resin at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a copolymer thereof is preferable because the light resistance and the heat resistance of the light-shielding film are more excellent. Is more preferred.
  • alkali-soluble resin examples include [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid]. / If necessary, other addition-polymerizable vinyl monomers] copolymers are suitable because they have an excellent balance of film strength, sensitivity, and developability. The above-mentioned other addition-polymerizable vinyl monomers may be used alone or in combination of two or more.
  • the above-mentioned copolymer preferably has a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth) acryloyl group, in that the moisture resistance of the black layer is more excellent.
  • a curable group may be introduced into the copolymer using a monomer having a curable group as the above-mentioned other addition-polymerizable vinyl monomer.
  • a curable group (preferably ((A) or (B)) may be added to a part or all of one or more of units derived from (meth) acrylic acid and / or units derived from the other addition-polymerizable vinyl monomers in the copolymer.
  • a (meth) acryloyl group or other ethylenically unsaturated group examples include methyl (meth) acrylate, styrene-based monomers (such as hydroxystyrene), and ether dimers.
  • the ether dimer examples include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP-A-2010-168538 can be referred to.
  • ether dimer for example, paragraph 0317 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated herein.
  • the ether dimer may be only one kind or two or more kinds.
  • the acid value of the alkali-soluble resin is not particularly limited, but is generally preferably from 30 to 500 mgKOH / g, and more preferably from 50 to 200 mgKOH / g.
  • the light-shielding composition contains a polymerizable compound.
  • the polymerizable compound means a compound which is polymerized by the action of a polymerization initiator described later, and means a component different from the above-described dispersion resin and alkali-soluble resin.
  • the content of the polymerizable compound in the composition is not particularly limited, but is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and preferably 15 to 25% by mass based on the total solid content of the composition. More preferred.
  • the polymerizable compound one type may be used alone, or two or more types may be used in combination. When two or more polymerizable compounds are used in combination, the total content is preferably within the above range.
  • the molecular weight (or weight average molecular weight) of the polymerizable compound is not particularly limited, but is preferably 2000 or less.
  • the light-shielding composition preferably contains a low-molecular compound containing an ethylenically unsaturated group as a polymerizable compound.
  • a compound containing one or more ethylenically unsaturated bonds is preferable, a compound containing two or more ethylenically unsaturated bonds is more preferable, a compound containing three or more ethylenically unsaturated bonds is more preferable, and a compound containing five or more ethylenically unsaturated bonds is particularly preferable.
  • the upper limit is, for example, 15 or less.
  • Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound for example, the compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-68893 can be used, and the contents described above are incorporated herein. It is.
  • the polymerizable compound may be in any of chemical forms such as, for example, monomers, prepolymers, oligomers, and mixtures thereof, and multimers thereof.
  • the polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, more preferably a 3-6 functional (meth) acrylate compound.
  • a compound containing at least one ethylenically unsaturated group and having a boiling point of 100 ° C. or more under normal pressure is also preferable.
  • the compounds described in paragraphs 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, and the contents thereof are incorporated herein.
  • Polymerizable compounds include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available product KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, commercially available from Sartomer, SR454 , SR499)
  • oligomer types can also be used.
  • NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 (all products) Name, manufactured by Nippon Kayaku Co., Ltd.
  • Preferred embodiments of the polymerizable compound are shown below.
  • the light-shielding composition preferably contains at least two kinds of polymerizable compounds. Among them, from the viewpoint of more excellent heat resistance and moisture resistance of the light-shielding film, it has a similar structure, contains two or more polymerizable compounds having different numbers of ethylenically unsaturated groups, and has an ethylenically unsaturated group. Is preferably a compound containing at least one or more hydroxyl groups. By using such two or more polymerizable compounds, the reason why the heat resistance and moisture resistance of the light-shielding film are improved is not clear, but by using a polymerizable compound having a hydroxyl group, an alkali-soluble resin can be obtained.
  • Examples of such a mixture of two or more compounds having similar structures and different numbers of ethylenically unsaturated groups include, for example, formulas (Z-1), (Z-4), and ( Z-5), a mixture of compounds having different numbers of terminal ethylenically unsaturated groups (preferably (meth) acryloyl groups), wherein the compound having a smaller number of ethylenically unsaturated groups is at least Mixtures that are compounds containing one or more hydroxyl groups are included.
  • 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 an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to form an acid.
  • a polymerizable compound having a group is more preferable, and in this ester, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is further preferable.
  • Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
  • the acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g, more preferably from 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing dissolution property is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
  • the polymerizable compound is a compound having a caprolactone structure.
  • the compound having a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule.
  • a compound having a caprolactone structure represented by the following formula (Z-1) is preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents the number of 1 or 2
  • “*” represents a bond.
  • R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
  • Commercially available polymerizable compounds having a caprolactone structure include M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd.
  • a compound represented by the following formula (Z-4) or (Z-5) can also be used.
  • E represents — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) —, and y is , 0 to 10, and X represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
  • the total number of the (meth) acryloyl groups is 3 or 4
  • m represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • the total number of the (meth) acryloyl groups is 5 or 6, and n represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, more preferably 0 to 4. Further, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and further preferably an integer of 6 to 12.
  • -((CH 2 ) y CH 2 O)-or ((CH 2 ) y CH (CH 3 ) O)- A form in which the terminal is bonded to X is preferred.
  • the compound represented by the formula (Z-4) or (Z-5) may be used alone or in combination of two or more.
  • a form in which all six Xs are acryloyl groups in Formula (Z-5), a compound in which all six Xs are acryloyl groups,
  • a preferred embodiment is a mixture with a compound in which at least one is a hydrogen atom.
  • the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
  • the polymerizable compound may contain a cardo skeleton.
  • a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable.
  • examples of the polymerizable compound having a cardo skeleton include, but are not limited to, Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogusol (manufactured by Osaka Gas Chemical Company).
  • a compound containing an isocyanuric acid skeleton as a central nucleus is also preferable.
  • Examples of such a polymerizable compound include, for example, NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the content of the ethylenically unsaturated group in the polymerizable compound (meaning 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 / g or more is preferable.
  • the upper limit is not particularly limited, but is generally 20.0 mmol / g or less.
  • the light-shielding composition preferably contains a polymerization initiator.
  • the polymerization initiator is not particularly limited, and a known polymerization initiator can be used. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and a photopolymerization initiator is preferable. In addition, what is called a radical polymerization initiator is preferable as a polymerization initiator.
  • the content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and more preferably 1.5 to 10% by mass based on the total solid content of the composition. -8% by mass is more preferred.
  • One type of polymerization initiator may be used alone, or two or more types may be used in combination. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.
  • thermal polymerization initiator examples include 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalenonitrile, and dimethyl- (2,2 ′)-azobis (2 -Methylpropionate) [V-601], and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • AIBN 2,2′-azobisisobutyronitrile
  • 3-carboxypropionitrile 3-carboxypropionitrile
  • azobismalenonitrile examples
  • organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • the composition preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as the polymerization of the polymerizable compound can be started, and a known photopolymerization initiator can be used.
  • a photopolymerization initiator for example, a photopolymerization initiator having photosensitivity from an ultraviolet region to a visible light region is preferable.
  • an activator that generates an active radical by causing some action with the photoexcited sensitizer may be used, or an initiator that starts cationic polymerization depending on the type of the polymerizable compound may be used.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction 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 composition is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, based on the total solid content of the composition. More preferably, it is from 0.5 to 8% by mass.
  • One photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination. When two or more photopolymerization initiators are used in combination, the total content is preferably within the above range.
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds such as 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 herein.
  • the photopolymerization initiator for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.
  • the hydroxyacetophenone compound for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can be used.
  • the aminoacetophenone compound for example, commercially available products IRGACURE-907, IRGACURE-369 and IRGACURE-379EG (trade names, all manufactured by BASF) can be used.
  • aminoacetophenone compound a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source having a wavelength of 365 nm or 405 nm can also be used.
  • acylphosphine compound commercially available products IRGACURE-819 and IRGACURE-TPO (trade names, both manufactured by BASF) can be used.
  • an oxime ester-based polymerization initiator (oxime compound) is more preferable.
  • oxime compounds are preferable because they have high sensitivity and high polymerization efficiency, and the content of the coloring material in the composition is easy to design.
  • compounds described in JP-A-2001-233842 compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166 can be used.
  • Examples of the oxime compound include 3-benzoyloximinobtan-2-one, 3-acetoxyimiminobtan-2-one, 3-propionyloxyimiminobtan-2-one, 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 Carbonyloxyimino-1-phenylpropan-1-one and the like.
  • J.I. C. S. Perkin II (1979) pp. 1653-1660 C. S. Perkin II (1979) pp.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • IRGACURE-OXE03 manufactured by BASF
  • IRGACURE-OXE04 manufactured by BASF
  • TR-PBG-304 manufactured by Changzhou Strong Electronics New Materials Co., Ltd.
  • Adeka Aquel's NCI-831 Adeka Aquel's NCI-930
  • N-1919 a carbazole / oxime ester skeleton-containing light Initiators
  • oxime compounds other than those described above include compounds described in JP-T-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; Compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye site; ketoxime compounds described in WO 2009-131189; and a triazine skeleton A compound described in US Pat. No.
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above-mentioned substituent may be further substituted with another 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, and an aryl group.
  • 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. Examples of the substituent include the substituents described above.
  • the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
  • Oxime compounds containing a fluorine atom can also be used as the photopolymerization initiator.
  • fluorine-containing oxime compounds include compounds described in JP-A-2010-262028; compounds 24, 36 to 40 described in JP-A-2014-500852; and JP-A-2013-164471.
  • photopolymerization initiator compounds represented by the following general formulas (1) to (4) can also be used.
  • 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 When R 1 and R 2 are a phenyl group, the phenyl groups may combine with each other to form a fluorene group, and R 3 and R 4 each independently represent a fluorene group.
  • X 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; Represents 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 , —CN represents a halogen atom or a hydroxyl group
  • 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 C 4 to C 4 20 represents a heterocyclic group
  • 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 group 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, Represents a heterocyclic group represented by Formulas 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 , -COR 6 , -CN, halogen atom, Or a hydroxyl group
  • 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 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 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 the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein.
  • oxime compound preferably used in the above composition
  • the oxime compound represented by the formula (C-13) is more preferable.
  • the oxime compound the compound described in Table 1 of International Publication No. 2015-036910 Pamphlet can also be used, and the above description is incorporated herein.
  • the oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in a wavelength region of 360 to 480 nm, and further preferably has high absorbance at wavelengths of 365 nm and 405 nm. .
  • the molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and still more preferably from 5,000 to 200,000, from the viewpoint of sensitivity.
  • the molar extinction coefficient of the compound can be measured by a known method.
  • the molar extinction coefficient is measured at a concentration of 0.01 g / L using ethyl acetate with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian). Is preferred. Photopolymerization initiators may be used in combination of two or more as necessary.
  • photopolymerization initiator examples include compounds described in paragraph 0052 of JP-A-2008-260927, paragraphs 0033 to 0037 of JP-A-2010-97210, and paragraph 0044 of JP-A-2015-68893. Can also be used, and the above is incorporated herein.
  • the composition may contain a polymerization inhibitor.
  • the polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used.
  • the polymerization inhibitor include phenol-based polymerization inhibitors (eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-ditert-butyl-4-methylphenol, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4-methoxynaphthol and the like; hydroquinone-based polymerization inhibitors (for example, Quinone-based polymerization inhibitors (eg, benzoquinone); free-radical polymerization inhibitors (eg, 2,2,6,6-tetramethylpiperidine 1-).
  • phenol-based polymerization inhibitors eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-diter
  • Nitrobenzene-based polymerization inhibitor e.g., nitrobenzene, 4-nitrotoluene, etc.
  • phenothiazine-based polymerization inhibitor e.g., phenothiazine, 2-methoxy phenothiazine, etc.
  • a phenol-based polymerization inhibitor or a free radical-based polymerization inhibitor is preferable in that the composition has a more excellent effect.
  • the effect of the polymerization inhibitor is remarkable when it is used together with a resin containing a curable group.
  • the content of the polymerization inhibitor in the composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, more preferably 0.001 to 0.2% by mass, based on the total solid content of the composition. It is more preferably 0.008 to 0.05% by mass.
  • the polymerization inhibitor one type may be used alone, or two or more types may be used in combination. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
  • the ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the composition is preferably more than 0.0005, 0.0006 to 0.02 is more preferable, and 0.0006 to 0.005 is still more preferable.
  • the composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of the black layer can be made more excellent (fine).
  • an ultraviolet absorber salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
  • compounds described in paragraphs 0137 to 0142 of JP-A-2012-068418 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292 can be used, and the contents thereof can be referred to and incorporated herein. .
  • a diethylamino-phenylsulfonyl-based ultraviolet absorber (trade name, UV-503, manufactured by Daito Chemical Co., Ltd.) and the like are also preferably used.
  • the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP-A-2012-32556.
  • the content of the ultraviolet absorbent is preferably from 0.001 to 15% by mass, more preferably from 0.01 to 10% by mass, even more preferably from 0.1 to 5% by mass, based on the total solid content of the composition.
  • the composition may contain a silane coupling agent.
  • the silane coupling agent functions as an adhesive for improving the adhesion between the substrate and the black layer when forming the black layer on the substrate.
  • the silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by a hydrolysis reaction and / or a condensation reaction.
  • hydrolyzable group examples include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
  • the hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, more preferably 4 or less. Particularly, 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 black layer, so that a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded) are used. It is preferable not to contain a fluorine atom, a silicon atom (however, a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted by a silicon atom, a linear alkyl group having 8 or more carbon atoms, and It is desirable not to include a branched alkyl group having 3 or more carbon atoms.
  • the silane coupling agent may contain an ethylenically unsaturated group such as a (meth) acryloyl group.
  • an ethylenically unsaturated group When an ethylenically unsaturated group is contained, the number is preferably 1 to 10, more preferably 4 to 8.
  • a silane coupling agent containing an ethylenically unsaturated group (for example, a compound containing a hydrolyzable group and an ethylenically unsaturated group and having a molecular weight of 2000 or less) does not correspond to the above-described polymerizable compound.
  • the content of the silane coupling agent in the composition is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 8% by mass, and more preferably from 1.0 to 10% by mass, based on the total solids in the composition. 6% by mass is more preferred.
  • the composition may contain one kind of the silane coupling agent alone, or may contain two or more kinds. When the composition contains two or more silane coupling agents, the total may be within the above range.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Vinyl trimethoxy silane, vinyl triethoxy silane and the like can be mentioned.
  • the composition may contain a surfactant.
  • the surfactant contributes to improving the coatability of the composition.
  • the content of the surfactant is preferably from 0.001 to 2.0% by mass, and more preferably from 0.005 to 0. 5 mass% is more preferable, and 0.01 to 0.1 mass% is further preferable.
  • One type of surfactant may be used alone, or two or more types may be used in combination. When two or more surfactants are used in combination, the total amount is preferably within the above range.
  • surfactant examples include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.
  • the liquid properties (particularly, fluidity) of the composition are further improved. That is, when a film is formed using a composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating solution is reduced, the wettability to the surface to be coated is improved, and The applicability to the surface is improved. For this reason, even when a thin film having a thickness of about several ⁇ m is formed with a small amount of liquid, it is effective in that a uniform thickness film having small thickness unevenness can be more suitably formed.
  • the fluorine content in the fluorinated surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, even more preferably from 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of the thickness of the coating film and / or liquid saving properties, and has good solubility in the composition.
  • fluorine-based surfactant examples include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479.
  • F482, F554, and F780 all made by DIC Corporation
  • Florado FC430, FC431, and FC171 all made by Sumitomo 3M Limited
  • Surflon S-382, SC-101, same SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 all manufactured by Asahi Glass Co., Ltd.
  • PF636, PF656, PF6320, PF6520, and PF7002 manufactured by OMNOVA
  • a block polymer can also be used as the fluorinated surfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
  • the composition preferably contains a solvent.
  • the solvent is not particularly limited, and a known solvent can be used.
  • the content of the solvent in the composition is not particularly limited, but is preferably an amount such that the solid content of the composition is 10 to 90% by mass, more preferably 10 to 40% by mass, and more preferably 15 to 35% by mass. Is more preferred.
  • One type of solvent may be used alone, or two or more types may be used in combination. When two or more solvents are used in combination, the composition is preferably adjusted so that the total solid content of the composition falls within the above range.
  • Examples of the solvent include water and an organic solvent.
  • organic solvent examples 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, and 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 Butyl 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, ⁇ -butyrolactone, ethyl acetate, Examples include, but are not limited to, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.
  • water When the composition contains water, its content is preferably from 0.001 to 5.0% by mass, more preferably from 0.01 to 3.0% by mass, based on the total mass of the composition. More preferably, the amount is from 1 to 1.0% by mass. Above all, if the content of water is 3.0% by mass or less (more preferably 1.0% by mass or less) with respect to the total mass of the composition, the viscosity over time due to hydrolysis of the components in the composition and the like. It is easy to suppress the deterioration of stability, and if it is 0.01% by mass or more (preferably 0.1% by mass or more), the sedimentation stability over time is easily improved.
  • the composition may further contain other optional components other than the components described above.
  • a sensitizer, a co-sensitizer, a cross-linking agent, a curing accelerator, a thermosetting accelerator, a filler, a plasticizer, a diluent, and a sensitizer may be used.
  • Agents and other auxiliaries eg, conductive particles, fillers, defoamers, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc. May be added as necessary.
  • paragraphs 0183 to 0228 of JP-A-2012-003225 paragraphs 0237 to 0309 of US Patent Application Publication No. 2013/0034812
  • paragraph 0101 of JP-A-2008-250074 paragraphs 0103 to 0104, paragraphs 0107 to 0109, and paragraphs 0159 to 0184 of JP-A-2013-195480 can be referred to, and the contents thereof are incorporated in the specification of the present application.
  • the composition is preferably prepared by first producing a coloring material composition containing a black coloring material, and further mixing the obtained coloring material composition with other components.
  • the coloring material composition is preferably prepared by mixing a black coloring material, a resin (preferably, a dispersing resin), and a solvent. It is also preferable to include a polymerization inhibitor in the coloring material composition.
  • the coloring material 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 emulsifier, a wet pulverizer, or a wet disperser). .
  • a known mixing method for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser.
  • the components may be blended together, or the components may be dissolved or dispersed in a solvent and then blended sequentially.
  • the order of charging and the working conditions for mixing are not particularly limited.
  • the light-shielding composition is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects.
  • the filter can be used without any particular limitation as long as it is a filter conventionally used for filtration or the like.
  • 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 ultra high molecular weight) such as polyethylene and polypropylene (PP) can be used.
  • 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 ultra high molecular weight) such as polyethylene and polypropylene (PP) can be used. .
  • polypropylene (including high-density polypropylene) and nylon are preferable.
  • the pore size of the filter is preferably from 0.1 to 7.0 ⁇ m, more preferably from 0.2 to 2.5 ⁇ m, even more preferably from 0.2 to 1.5 ⁇ m, and particularly preferably from 0.3 to 0.7 ⁇ m. Within this range, fine foreign substances such as impurities and agglomerates contained in the pigment can be reliably removed while suppressing clogging of the pigment (including the black pigment) by filtration.
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed two or more times. When filtering is performed two or more times by combining different filters, it is preferable that the diameters of the holes after the second filtering are the same as or larger than the diameters of the holes after the first filtering.
  • first filters having different hole diameters within the above-described range may be combined.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • Commercially available filters can be selected from various filters provided by, for example, Nippon Pall Co., Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), and Kitz Micro Filter Co., Ltd.
  • As the second filter a filter formed of the same material as the first filter described above can be used.
  • the pore size of the second filter is preferably from 0.2 to 10.0 ⁇ m, more preferably from 0.2 to 7.0 ⁇ m, even more preferably from 0.3 to 6.0 ⁇ m.
  • the composition preferably does not contain impurities such as metals, metal salts containing halogens, acids, and alkalis.
  • the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and it is substantially free of ( Below the detection limit of the measuring device).
  • the impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
  • the method for forming the black layer is not particularly limited, and the light-shielding composition of the present invention is applied on a support, and the obtained coating film is cured to form a black layer (including a patterned black layer). Is done.
  • the method for forming a black layer preferably includes the following steps. ⁇ Film formation process ⁇ Curing process ⁇ Development process Hereinafter, each step will be described.
  • a light-shielding composition is applied on a support to form a coating film (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 CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (eg, a silicon substrate). It can. If necessary, an undercoat layer may be provided on the support for improving adhesion to an upper layer, preventing diffusion of a substance, and flattening the surface of the substrate.
  • an imaging device light-receiving device
  • CCD Charge Coupled Device
  • CMOS Complementary Metal-Oxide Semiconductor
  • the composition on the support As a method of applying the composition on the support, various application methods such as a slit coating method, an ink jet method, a spin coating method, a casting coating method, a roll coating method, and a screen printing method can be applied.
  • the thickness of the coating film is preferably from 0.1 to 10 ⁇ m, more preferably from 0.2 to 5 ⁇ m, even more preferably from 0.2 to 3 ⁇ m. Drying (prebaking) of the coating film applied on the support can be performed, for example, on a hot plate or an oven at a temperature of 50 to 140 ° C. for 10 to 300 seconds.
  • the coating film formed in the coating film forming step is exposed to actinic rays or radiation and exposed to cure the light-irradiated coating film.
  • the method of light irradiation is not particularly limited, but light irradiation is preferably performed through a photomask having a pattern-shaped opening. Exposure is preferably performed by irradiation with radiation.
  • radiation that can be used for exposure ultraviolet rays such as g-rays, h-rays and i-rays are particularly preferred, and a high-pressure mercury lamp is preferred as a light source.
  • the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2.
  • a composition contains a thermal-polymerization initiator
  • the heating temperature is not particularly limited, but is preferably from 80 to 250 ° C.
  • the heating time is not particularly limited, but is preferably 30 to 300 seconds.
  • the developing step is a step of developing the exposed coating film.
  • the type of the developing solution used in the developing step is not particularly limited, but an alkali developing solution that does not cause damage to the underlying image pickup device, circuits, and the like is preferable.
  • the development temperature is, for example, 20 to 30 ° C.
  • the development time is, for example, 20 to 90 seconds. In order to remove the residue better, in recent years, it may be performed for 120 to 180 seconds. Further, in order to further improve the residue removal property, the step of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • an alkaline aqueous solution prepared by dissolving an alkaline compound in water so as to have a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass) is preferable.
  • the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropyl.
  • Ammonium hydroxide tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like. preferable.).
  • a washing treatment with water is generally performed after development.
  • Post-bake is a heat treatment after development to complete curing.
  • the heating temperature is preferably 240 ° C. or lower, more preferably 220 ° C. or lower. There is no particular lower limit, but in consideration of efficient and effective treatment, the temperature is preferably 50 ° C or higher, more preferably 100 ° C or higher.
  • Post-baking can be performed in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater.
  • the post-baking is preferably performed in an atmosphere having a 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, and most preferably 3% by volume or less. There is no particular lower limit, but 10 ppm by volume or more is practical.
  • the curing may be completed by UV (ultraviolet) irradiation instead of the post-baking by heating.
  • the above-mentioned composition 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 using ordinary i-ray exposure.
  • the UV curing agent for example, Chibile Gacure 2959 (trade name) can be mentioned.
  • the coating film is a material that cures at a wavelength of 340 nm or less.
  • the exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and further preferably 800 to 3500 mJ.
  • This UV curing step is preferably performed after the curing step in order to more effectively perform low-temperature curing.
  • the exposure light source preferably uses an ozone-less mercury lamp.
  • the optical density (OD: Optical Density) per 1.0 ⁇ m in the wavelength region of 400 to 1200 nm is preferably 1.7 or more, more preferably 2.0 or more. Preferably, 2.1 or more is more preferable.
  • the upper limit is not particularly limited, but is generally preferably 10 or less.
  • the expression that the optical density per 1.0 ⁇ m thickness in the wavelength region of 400 to 1200 nm is 2.0 or more means that the optical density per 1.0 ⁇ m thickness in the entire wavelength range of 400 to 1200 nm. Is 2.0 or more.
  • the optical density of the black layer is determined by first forming a black layer (light-shielding film) on a glass substrate and using a spectrophotometer U-4100 (trade name, manufactured by Hitachi High-Technologies Corp.) It can be measured by measuring using a unit, measuring the thickness of the measurement location, and calculating the optical density per predetermined thickness.
  • the thickness of the black layer is, for example, preferably from 0.1 to 4.0 ⁇ m, more preferably from 1.0 to 2.5 ⁇ m.
  • the black layer may be thinner or thicker than this range depending on the application.
  • the light-shielding property may be adjusted by making the black layer thinner (for example, 0.1 to 0.5 ⁇ m) than the above range.
  • the optical density per 1.0 ⁇ m thickness in the wavelength region of 400 to 1200 nm is preferably 0.1 to 1.5, and more preferably 0.2 to 1.0.
  • the oxygen blocking layer is a layer formed on the black layer, and has a function of blocking oxygen passing from the surface opposite to the surface in contact with the black layer to the black layer.
  • the oxygen barrier layer include a layer having an oxygen permeability in the thickness direction (hereinafter, also simply referred to as “oxygen permeability”) of 50 ml / (m 2 ⁇ day ⁇ atm) or less, and an oxygen permeability of 10 ml. / (m 2 ⁇ day ⁇ atm ) layers preferably not more than, 1.5 ml / more preferably the layer is (m 2 ⁇ day ⁇ atm) or less, 1.0ml / (m 2 ⁇ day ⁇ atm) or less Certain layers are more preferred.
  • the lower limit of the oxygen permeability is preferably 0.001 ml / (m 2 ⁇ day ⁇ atm).
  • the oxygen transmission rate can be measured using, for example, an oxygen transmission measurement apparatus (Model 8001, manufactured by Illinois Co., Ltd.).
  • the oxygen barrier layer is a single layer made of an inorganic material.
  • single layer means a layer in which the composition of the material constituting the layer is uniform along the thickness direction and the in-plane direction.
  • a laminate of the layer A made of the inorganic material a and the layer B made of the inorganic material b having a different composition from the inorganic material a has a function of blocking oxygen in both the layer A and the layer B. If it does, it is not included in the oxygen barrier layer as defined herein.
  • “comprising an inorganic material” means that the content of carbon atoms in the material constituting the oxygen barrier layer is 5% by mass or less based on the total mass of the oxygen barrier layer.
  • the content of the carbon atoms is preferably 2.5% by mass or less based on the total mass of the oxygen barrier layer.
  • the lower limit of the content of the carbon atom is not particularly limited, and may be lower than the detection limit.
  • the content of carbon atoms in the material constituting the oxygen-blocking layer is determined by forming a smooth surface on the oxygen-blocking layer by polishing or cutting, and then forming the formed smooth surface on an electron beam microanalyzer (EPMA). (Eg, “JXA-8530F” (trade name) manufactured by JEOL Ltd.) and analyzed.
  • the thickness of the oxygen barrier layer is 10 to 500 nm.
  • a light-shielding film having a more excellent balance between light resistance and moisture resistance can be manufactured. More specifically, when the thickness of the oxygen barrier layer is 10 nm or more, the effect of suppressing the variation in the thickness of the light-shielding film and the variation in optical characteristics (transmittance and reflectance) after the light resistance test is improved.
  • the thickness of the layer is 500 nm or less, the effect of suppressing peeling of the black layer from the substrate after the moisture resistance test is improved.
  • the reason why the moisture resistance is improved when the thickness of the oxygen barrier layer is 500 nm or less is not clear, when the thickness of the oxygen barrier layer is more than 500 nm, the black layer with the oxygen barrier layer and the substrate after the moisture resistance test are performed. This is presumed to be due to the fact that the stress generated due to the difference in the shrinkage ratio between the substrate and the substrate increases, causing the black layer to peel off from the substrate.
  • the thickness of the oxygen blocking layer is 500 nm or less, the light reflected on the surface of the black layer and the light reflected on the surface of the oxygen blocking layer when a light-shielding film composed of the black layer and the oxygen blocking layer are provided on the device. Can be reduced, and a decrease in device performance can be prevented.
  • the thickness of the oxygen barrier layer is preferably more than 50 nm and less than 250 nm, more preferably 70 to 200 nm, from the viewpoint that the moisture resistance and heat resistance of the light shielding film are more excellent.
  • the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer may be 2 to 100, and the moisture resistance and the heat resistance of the light-shielding film are more improved. From the viewpoint of superiority, 7 to 30 is preferable, and 10 to 25 is more preferable.
  • the inorganic material constituting the oxygen barrier layer is not particularly limited, and includes a metal oxide, a metal nitride, and a metal oxynitride.
  • the metal contained in the inorganic material include silicon, titanium, aluminum, indium, tin, niobium, zirconium, cerium, tantalum, and zinc, with silicon, titanium or aluminum being preferred, and silicon being more preferred.
  • the inorganic material constituting the oxygen barrier layer silicon oxide, silicon nitride, indium oxide, tin oxide, niobium oxide, titanium oxide, zirconium oxide, cerium oxide, tantalum oxide, aluminum oxide and zinc oxide, Silicon oxide and silicon nitride are preferred, and silicon oxide is more preferred because the light-shielding film has better light resistance and moisture resistance.
  • the oxygen barrier layer of the present invention is a single layer made of an inorganic material, and does not substantially contain an organic component.
  • the oxygen barrier layer contains an organic component
  • the organic component contained therein is decomposed by light irradiation on the oxygen barrier layer, and the oxygen barrier ability is reduced.
  • the oxygen barrier layer of the present invention which is a single layer made of an inorganic material, can prevent such a decrease in oxygen barrier ability.
  • the oxygen-barrier layer "contains substantially no organic component” means that the content of carbon atoms in the material constituting the oxygen-barrier layer is 5 mass% with respect to the total mass of the oxygen-barrier layer. % Or less.
  • the content of carbon atoms in the material constituting the oxygen barrier layer is measured by the above-described method using an electron beam microanalyzer.
  • the oxygen barrier layer does not substantially contain particles from the viewpoint of more excellent heat resistance.
  • the composition of the material constituting the layer is not uniform, and a region having different heat shrinkage is generated, so that the oxygen barrier layer is greatly distorted in a high temperature environment, and the heat resistance is reduced. This is because there are times.
  • the oxygen barrier layer contains substantially no particles from the viewpoint that the surface becomes smoother and the in-plane uniformity of the reflectance is more excellent.
  • the “particles” described above are particles of a substance having a different composition from the inorganic material forming the oxygen barrier layer, and mean particles having a particle size of 10 nm or more.
  • the content of the particles in the oxygen barrier layer can be measured by the following method using an electron beam microanalyzer (EPMA) (for example, “JXA-8530F” (trade name) manufactured by JEOL Ltd.).
  • EPMA electron beam microanalyzer
  • the oxygen barrier layer is polished or cut to form a smooth surface.
  • the distribution of the element composition on the formed smooth surface is measured using an electron beam microanalyzer to obtain a mapping image of the element composition.
  • a region where the particles exist is specified based on a difference in element composition from the continuous phase.
  • the area ratio of the particles on the observation surface is obtained by dividing the total area of the particle regions by the observation area.
  • the area ratio is converted into a volume ratio (3/2 power of the area ratio), and further converted into a mass ratio based on the elemental composition, thereby obtaining the content of the particles with respect to the total amount of the oxygen barrier layer.
  • silicon oxide particles are present in an oxygen barrier layer made of silicon oxide (SiO 2 )
  • the outline of the silicon oxide particles is displayed on a mapping image due to silanol groups (SiOH) present on the surface of the silicon oxide particles. Therefore, the presence of particles can be confirmed.
  • the content of the particles can be measured based on the difference in the composition between the continuous phase and the particles in the oxygen barrier layer.
  • the oxygen barrier layer "substantially contains no particles" means that the content of the particles in the oxygen barrier layer measured by the above method is based on the total mass of the oxygen barrier layer. 5% by mass or less, or below the detection limit.
  • the method for forming the oxygen barrier layer is not particularly limited, and a known method for forming a film of an inorganic material can be used.
  • a film forming method a sputtering method, a vacuum deposition method, an ion beam assisted deposition method, an ion plate method, a deposition method such as a plasma CVD (chemical vapor deposition) method, a spin coating method, a dip coating method, and a casting method Method, a slit coating method, and a wet method such as a spray method.
  • an oxygen barrier layer by vapor deposition because it is easier to form a thin film, it is easier to control the thickness, and the adhesion to the black layer that is the object is more excellent. It is more preferable to form an oxygen barrier layer by a sputtering method.
  • the sputtering method is not particularly limited, and may be a known method such as a pulse sputtering method, an AC sputtering method, and a digital sputtering method.
  • an oxygen barrier layer is formed by a sputtering method
  • a substrate having a black layer formed on a surface thereof is disposed in a chamber in a mixed gas atmosphere of an inert gas and a reactive gas (eg, oxygen or nitrogen),
  • a target is selected so as to have a desired composition, and an oxygen barrier layer is formed.
  • the type of the inert gas is not particularly limited, and an inert gas such as argon or helium can be used.
  • the reactive gas may be selected according to the composition of the oxygen barrier layer to be formed.
  • the pressure in the chamber by the mixed gas of the inert gas and the reactive gas is not particularly limited, and may be 1.0 Pa or less, preferably 0.5 Pa or less.
  • the lower limit of the pressure in the chamber due to the mixed gas of the inert gas and the reactive gas is not particularly limited, but is preferably, for example, 0.1 Pa or more.
  • the thickness of the oxygen barrier layer can be adjusted by adjusting the discharge power or the deposition time.
  • the method for producing the light-shielding film of the present invention is not particularly limited.
  • the light-shielding film of the present invention on a support, a black colorant, a resin, a polymerizable compound, and a light-shielding composition containing a polymerization initiator is applied, and the obtained coating film is cured to form a black layer.
  • a step of forming an oxygen barrier layer on the black layer As the "step of forming a black layer”, the method described in the above “formation of a black layer” may be applied, and as the “step of forming an oxygen barrier layer”, the "step of forming an oxygen barrier layer” May be applied.
  • the thickness of the light-shielding film is, for example, preferably from 0.1 to 6.0 ⁇ m, more preferably from 1.0 to 3.5 ⁇ m.
  • the light-shielding film may be thinner or thicker than this range depending on the application.
  • the reflectance of the light-shielding film is preferably less than 5%, more preferably less than 3%, even more preferably less than 2%.
  • the light-shielding film may be a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, and a digital camera; an OA (Office Automation) device such as a multifunction printer and a scanner; a monitoring camera, a barcode reader, and cash Industrial equipment such as an automated teller machine (ATM), a high-speed camera, and a device having a personal authentication function using face image authentication or biometric authentication; a vehicle-mounted camera device; an endoscope, in a capsule Medical camera equipment such as endoscopes and catheters; and biometric sensors, biosensors, military reconnaissance cameras, stereo map cameras, weather and ocean observation cameras, land resources exploration cameras, and astronomical and deep space astronomy Space equipment such as exploration cameras for targets Light blocking member and the light-shielding film of the optical filter and module used etc., and further is suitable for anti-reflection member and the antireflection film.
  • OA Office Automation
  • ATM automated teller machine
  • the light-shielding film can also be used for applications such as a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode).
  • the light-shielding film is suitable for a member having a light-shielding function or an anti-reflection function, in addition to an optical filter and an optical film used for a micro LED and a micro OLED.
  • Examples of the micro LED and the micro OLED include the examples described in JP-T-2015-500562 and JP-T-2014-533890.
  • the light-shielding 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. Further, it is suitable as a member for providing a light blocking function and an anti-reflection function. Examples of the quantum dot sensor and the quantum dot solid-state imaging device include those described in U.S. Patent Application Publication No. 2012/37789 and WO 2008/131313.
  • the light-shielding film of the present invention is also preferably used for a solid-state imaging device. As described above, the light-shielding film of the present invention is excellent in light resistance and moisture resistance. Further, the light-shielding film of the present invention has excellent heat resistance.
  • the present invention also includes the invention of an optical element.
  • the optical element of the present invention is an optical element having the above-mentioned light shielding film.
  • Examples of the optical element include an optical element used for an optical device such as a camera, binoculars, a microscope, and a semiconductor exposure apparatus. Above all, as the optical element, for example, a solid-state imaging element mounted on a camera or the like is preferable.
  • a solid-state imaging device is a solid-state imaging device having the light-shielding film.
  • the form in which the solid-state imaging device includes the light-shielding film is not particularly limited. For example, a plurality of photodiodes, polysilicon, and the like, which form a light receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, and the like) on the substrate And a light-shielding film on the side of the support on which the light-receiving element is formed (for example, a portion other than the light-receiving portion and / or the pixel for color adjustment) or on the side opposite to the formation surface.
  • the dynamic range of the solid-state imaging device can be improved.
  • the solid-state imaging device includes the solid-state imaging device.
  • FIG. 1 is a schematic sectional view showing a configuration example of a solid-state imaging device including the solid-state imaging device of the present invention.
  • the solid-state imaging device 100 includes a rectangular solid-state imaging device 101, and a transparent cover glass 103 that is held above the solid-state imaging device 101 and seals the solid-state imaging device 101. I have. Further, a lens layer 111 is provided on the cover glass 103 with a spacer 104 interposed therebetween.
  • the lens layer 111 includes 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.
  • the peripheral area of the lens layer 111 is shielded from light by providing the light shielding film 114.
  • the light shielding film of the present invention can 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, which is a light receiving surface, and outputs an image signal.
  • the solid-state imaging device 101 includes a laminated substrate 105 in which two substrates are laminated.
  • the laminated substrate 105 includes a rectangular chip substrate 106 and a circuit substrate 107 having 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 a known material can be used.
  • the imaging unit 102 is provided at the center of the surface of the chip substrate 106. Further, a light-shielding film 115 is provided in a peripheral area of the imaging unit 102. Since the light shielding film 115 shields the stray light incident on the peripheral region, generation of dark current (noise) from circuits in the peripheral region can be prevented. It is preferable to use the light-shielding film of the present invention as the light-shielding film 115.
  • a plurality of electrode pads 108 are provided on 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) (not shown) provided on the surface of the chip substrate 106.
  • External connection terminals 109 are provided on the rear surface of the circuit board 107 at positions substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to an electrode pad 108 via a through electrode 110 vertically penetrating the laminated substrate 105. In addition, each external connection terminal 109 is connected to a control circuit that controls 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, and the like via wiring (not shown). Have been.
  • FIG. 2 is a schematic cross-sectional view of the imaging unit 102.
  • the imaging unit 102 includes various units provided on a substrate 204 such as a light receiving element 201, a color filter 202, and a micro lens 203.
  • the color filter 202 has a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm.
  • the light shielding film of the present invention may be used as the black matrix 205bm.
  • a p-well layer 206 is formed on the surface of the substrate 204.
  • light receiving elements 201 which are made of an n-type layer and generate and accumulate signal charges by photoelectric conversion are arranged in a square lattice.
  • a vertical transfer path 208 made of an n-type layer is formed via a readout gate 207 on the surface of the p-well layer 206.
  • a vertical transfer path 208 belonging to an adjacent pixel is formed via an element isolation region 209 made of a p-type layer.
  • the read gate unit 207 is a channel region for reading signal charges accumulated 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 so as to cover the vertical transfer path 208, the read gate unit 207, and almost immediately above the element isolation region 209.
  • the vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to transfer charges and a read electrode that drives the read gate unit 207 to read signal charges.
  • the signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output unit (floating diffusion amplifier), and then output as a voltage signal.
  • a light shielding film 212 is formed 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 other areas from light.
  • the light shielding film of the present invention may be used as the light shielding film 212.
  • an insulating film 213 made of borophosphosilicate glass (BPSG), an insulating film (passivation film) 214 made of P-SiN, and a transparent intermediate layer made of a flattening film 215 made of a transparent resin or the like are provided. ing.
  • the color filter 202 is formed on the intermediate layer.
  • the image display device of the present invention includes the light-shielding film of the present invention.
  • Examples of the mode in which the image display device has a light-shielding film include a mode in which a color filter containing a light-shielding film as a black matrix is used in the image display device.
  • a black matrix and a color filter containing a black matrix will be described, and a liquid crystal display device containing such a color filter will be described as a specific example of an image display device.
  • the light-shielding film of the present invention is also preferably used as a black matrix.
  • the black matrix may be included 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 on the periphery of an image display device such as a liquid crystal display device; grids between red, blue, and green pixels, and / or stripes A black portion; and a dot and / or linear black pattern for light blocking of a thin film transistor (TFT).
  • TFT thin film transistor
  • the black matrix has a high light-shielding property (at an optical density OD) in order to improve display contrast and, in the case of an active matrix drive type liquid crystal display device using a thin film transistor (TFT), to prevent deterioration in image quality due to light current leakage. 3 or more).
  • TFT thin film transistor
  • the method for producing the black matrix is not particularly limited, it can be produced by the same method as the above-mentioned method for producing the light shielding film. Specifically, by applying the composition to the substrate, forming a coating film, exposure, and, after forming a patterned black layer by developing, by forming an oxygen barrier layer on the black layer, A black matrix can be manufactured.
  • the thickness of the light shielding film used as the black matrix is preferably from 0.1 to 4.0 ⁇ m.
  • the material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more with respect to visible light (wavelength: 400 to 800 nm).
  • a material include glasses such as soda lime glass, non-alkali glass, quartz glass, and borosilicate glass; and plastics such as polyester resin and polyolefin resin. In view of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferred.
  • the light-shielding film of the present invention is preferably contained in a color filter.
  • the form in which the color filter contains a light-shielding film is not particularly limited, and examples thereof include a color filter including a substrate and the above-described black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.
  • a color filter containing a black matrix can be manufactured, for example, by the following method.
  • the composition for each color is not particularly limited, and a known composition can be used.However, in the composition described in this specification, a composition in which a black coloring material is replaced with a coloring agent corresponding to each pixel is used. It is preferred to use.
  • the coating film is exposed through a photomask having a pattern corresponding to the opening of the black matrix.
  • baking is performed to form colored pixels in the openings of the black matrix.
  • the light-shielding film of the present invention is preferably contained in a liquid crystal display device.
  • the mode in which the liquid crystal display device includes the light-shielding film is not particularly limited, and examples include a mode in which the color filter including the black matrix described above is included.
  • the liquid crystal display device includes, for example, a mode including a pair of substrates arranged to face each other and a liquid crystal compound sealed between the substrates.
  • the substrate is as described above for the substrate for the black matrix.
  • liquid crystal display device for example, from a user side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) A laminated body containing an element / substrate / polarizing plate / backlight unit in this order is exemplified.
  • the liquid crystal display device is not limited to the above.
  • display device by Junsho Ibuki, Sangyo Tosho Co., Ltd., Heisei Gen) Liquid crystal display device described in “A.
  • a liquid crystal display device described in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by the Industrial Research Institute, Inc., 1994)” may be mentioned.
  • the light-shielding film of the present invention is preferably contained in an infrared sensor.
  • the infrared sensor according to the above embodiment will be described with reference to FIG.
  • FIG. 3 is a schematic sectional view showing a configuration example of an infrared sensor having the light-shielding film of the present invention.
  • the infrared sensor 300 shown in FIG. The imaging region provided on the solid-state imaging device 310 is configured by combining an infrared absorption filter 311 and a color filter 312 according to the embodiment of the present invention.
  • the infrared absorption filter 311 transmits light in the visible light range (for example, light having a wavelength of 400 to 700 nm), and transmits light in the infrared range (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1200 nm).
  • it is a film that blocks light having a wavelength of 900 to 1000 nm), and a cured film containing an infrared absorbing agent as a coloring agent (the form of the infrared absorbing agent is as described above) 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.
  • red (R), green (G), and blue (B) pixels are formed.
  • a 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 having a wavelength transmitted through the infrared transmission filter 313 is arranged.
  • the infrared transmission filter 313 is a filter that has a visible light shielding property and transmits infrared light of a specific wavelength, and is a colorant that absorbs light in a visible light region (for example, a perylene compound and / or a benzofuranone compound).
  • an infrared absorber for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound
  • the infrared transmission filter 313 preferably blocks light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm.
  • a micro lens 315 is arranged on the side of the incident light h ⁇ of the color filter 312 and the infrared transmission filter 313.
  • a flattening film 316 is formed so as to cover the microlens 315. In the embodiment shown in FIG.
  • the resin film 314 is provided, but an infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared transmission filter 313 may be formed on the solid-state imaging device 310.
  • the thickness of the color filter 312 and the thickness of the infrared transmission filter 313 are the same, but the thicknesses of the two may be different.
  • the color filter 312 is provided on the incident light h ⁇ side of the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 is changed, and 311 may be provided closer to the incident light h ⁇ than the color filter 312. Further, in the embodiment shown in FIG.
  • 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.
  • the light-shielding film of the present invention can be used as a light-shielding film at the end and / or the side surface of the surface of the infrared absorption filter 311, and when it is used on the inner wall of the device of the infrared sensor, light that does not imply internal reflection and / or light to the light-receiving unit. Can be prevented and sensitivity can be improved.
  • this infrared sensor since image information can be taken in at the same time, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Further, according to this infrared sensor, since distance information can be obtained, it is possible to capture an image including 3D information. Further, this infrared sensor can be used as a biometric authentication sensor.
  • 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 of JP-A-2011-233983 can be referred to, and the contents thereof are incorporated in the specification of the present application.
  • the light-shielding film of the present invention is also preferably contained in a headlight unit of a vehicle lamp such as an automobile.
  • the light-shielding film of the present invention contained in the headlight unit is preferably formed in a pattern so as to shield at least a part of light emitted from the light source.
  • FIGS. FIG. 4 is a schematic diagram illustrating a configuration example of a headlight unit
  • FIG. 5 is a schematic perspective view illustrating a configuration example of a light blocking unit of the headlight unit. As shown in FIG.
  • the headlight unit 10 includes a light source 12, a light shielding unit 14, and a lens 16, and the light source 12, the light shielding unit 14, and the lens 16 are arranged in this order.
  • the light shielding part 14 has a base 20 and a light shielding film 22 as shown in FIG.
  • the light-shielding film 22 has a pattern-shaped opening 23 for irradiating light emitted from the light source 12 in a specific shape.
  • the light distribution pattern emitted from the lens 16 is determined by the shape of the opening 23 of the light shielding film 22.
  • the lens 16 projects the light L from the light source 12 that has passed through the light shielding unit 14. If a specific light distribution pattern can be emitted from the light source 12, the lens 16 is not always necessary.
  • the lens 16 is appropriately determined according to the irradiation distance of the light L and the irradiation range.
  • the configuration of the base 20 is not particularly limited as long as the base 20 can hold the light-shielding film 22, but it is preferable that the base 20 is not deformed by heat of the light source 12, and is made of, for example, glass. You.
  • FIG. 5 shows an example of the light distribution pattern, but the present invention is not limited to this.
  • the number of the light sources 12 is not limited to one.
  • the light sources 12 may be arranged in a row or in a matrix.
  • a configuration in which one light shielding unit 14 is provided for one light source 12 may be employed. In this case, all the light shielding films 22 of the plurality of light shielding portions 14 may have the same pattern or different patterns.
  • FIG. 6 is a schematic diagram illustrating an example of a light distribution pattern by a headlight unit
  • FIG. 7 is a schematic diagram illustrating another example of a light distribution pattern by a headlight unit.
  • Each of the light distribution pattern 30 shown in FIG. 6 and the light distribution pattern 32 shown in FIG. 7 shows an area to be irradiated with light.
  • the region 31 shown in FIG. 6 and the region 31 shown in FIG. 7 indicate irradiation regions irradiated with the light source 12 (see FIG. 4) when the light shielding film 22 is not provided.
  • the light distribution pattern 30 shown in FIG. 6 is, for example, a pattern that does not illuminate oncoming vehicles when traveling on the left. Further, like the light distribution pattern 32 shown in FIG. 7, a part of the light distribution pattern 30 shown in FIG. 6 may be cut out. Also in this case, similarly to the light distribution pattern 30 shown in FIG. 6, the intensity of the light is sharply reduced at the edge 32a. For example, the pattern does not illuminate the oncoming vehicle when traveling on the left. Further, the intensity of the light is also sharply reduced in the notch 33. For this reason, in the area corresponding to the notch 33, for example, a mark indicating a state such as a curved road, an upward slope, a downward slope, or the like can be displayed. As a result, safety during night driving can be improved.
  • the light shielding unit 14 is not limited to being fixedly arranged between the light source 12 and the lens 16, and may be disposed between the light source 12 and the lens 16 by a driving mechanism (not shown) as necessary. , And a specific light distribution pattern can be obtained. Further, a shade member capable of blocking the light from the light source 12 may be configured by the light shielding unit 14. In this case, it is also possible to adopt a configuration in which a specific light distribution pattern is obtained by entering the light source 12 and the lens 16 as needed by a driving mechanism (not shown).
  • a coloring material composition containing the following black coloring material was prepared and used for preparing a light-shielding composition.
  • the obtained mixture was treated at a revolution speed of 1360 rpm and a revolution speed of 1047 rpm for 20 minutes using MAZERSTAR KK-400W manufactured by KURABO to obtain a uniform dispersion.
  • This dispersion was filled in a quartz container and heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Corporation). Thereafter, the atmosphere was replaced with nitrogen, and a nitriding reduction treatment was performed by flowing ammonia gas at the same temperature at 100 mL / min for 5 hours. After completion of the nitridation reduction treatment, the recovered powder was pulverized in a mortar to obtain a powdery titanium black (coloring material a-1) having a specific surface area of 73 m 2 / g.
  • the dispersion resin X-1 (5.5 parts by mass) having a structure represented by the following formula (X-1) was added to the coloring material a-1 (20 parts by mass) obtained above, Propylene glycol monomethyl ether acetate (hereinafter, referred to as “PGMEA”) was further added so that the concentration of the components became 35% by mass.
  • PGMEA Propylene glycol monomethyl ether acetate
  • the number given to each repeating unit means the molar ratio of each repeating unit.
  • the weight average molecular weight of the above-mentioned dispersed resin X-1 was 32,000.
  • the obtained dispersion was sufficiently stirred by a stirrer to perform premixing.
  • the obtained dispersion is subjected to a dispersion treatment using a dispersing machine NPM Pilot (trade name, manufactured by Shinmaru Enterprises Co., Ltd.) under the following conditions to obtain a color which is a dispersion containing the coloring material a-1.
  • a material composition A-1 was obtained.
  • Organic pigment containing a benzofuranone compound (trade name “Irgaphor Black S0100CF”, manufactured by BASF) (150 parts by mass), dispersing resin X-1 (75 parts by mass), Solsperse 20000 (pigment derivative, Lubri (Zol Co.) (25 parts by mass) and 3-methoxybutyl acetate (MBA) (750 parts by mass).
  • the dispersion resin X-1 is the same as that used for preparing the dispersion of the coloring material composition A-2.
  • the obtained mixture was stirred with a homomixer (manufactured by Primix) for 20 minutes to obtain a preliminary dispersion.
  • the obtained preliminary dispersion liquid was subjected to a dispersion treatment under the following dispersion conditions for 3 hours using an Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator to obtain a dispersion composition. .
  • the beads and the dispersion were separated by a filter to obtain a colorant composition A-2 as a dispersion containing the colorant a-2.
  • the solid content concentration of the obtained dispersion was 25% by mass, and the ratio of the coloring material a-2 / the resin component (the total of the dispersion resin X-1 and the pigment derivative) was 60/40 (mass ratio).
  • Solsperse 20000 is a compound having an amine value of 29 mgKOH / g, no acid value, and having a tertiary amine as a pigment adsorbing group.
  • Coloring Material Composition A-3 ⁇ Preparation of Organic Pigment Dispersion (Coloring Material Composition A-3)> The above-described coloring material composition A- was used except that an organic pigment containing a perylene compound (trade name “PALIOGEN Black S0084”, manufactured by BASF) was used as the coloring material a-3 instead of the coloring material a-2. According to the production method 2, a coloring material composition A-3 which is a dispersion containing the coloring material a-3 was obtained.
  • an organic pigment containing a perylene compound trade name “PALIOGEN Black S0084”, manufactured by BASF
  • Carbon black was produced by the usual oil furnace method. However, as a raw material oil, ethylene bottom oil having a small Na content, a small Ca content, and a small S content was used, and combustion was performed using gas fuel. Further, pure water treated with an ion exchange resin was used as reaction stop water. Using a homomixer, the obtained carbon black (540 g) was stirred with pure water (14500 g) at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry.
  • This slurry was transferred to a container equipped with a screw-type stirrer, and while mixing at about 1,000 rpm, toluene (600 g) in which epoxy resin “Epicoat 828” (manufactured by Japan Epoxy Resin) (60 g) was dissolved in the container. Was added in small portions. In about 15 minutes, all of the carbon black dispersed in the water migrated to the toluene side, and became particles having a particle size of about 1 mm. Next, after draining with a 60-mesh wire net, the separated granules are put into a vacuum drier and dried at 70 ° C.
  • the resin coating amount of the obtained resin-coated carbon black was 10% by mass based on the total amount of the carbon black and the resin.
  • the coloring material a-4 (20 parts by mass) obtained above, the dispersing resin X-1 (4.5 parts by mass), and Solsperse 12000 (manufactured by Nippon Lubrizol) (1 part by mass) were mixed to obtain a mixture.
  • PGMEA was added to the obtained mixture so that the solid content concentration became 35% by mass.
  • the dispersion resin X-1 is the same as that used in the preparation of the coloring material composition A-1.
  • the obtained dispersion was sufficiently stirred by a stirrer to perform premixing.
  • the obtained dispersion was subjected to a dispersion treatment using Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd. under the following conditions to obtain a dispersion composition. After the dispersion was completed, the beads and the dispersion were separated by a filter to obtain a colorant composition A-4, which is a dispersion containing the colorant a-4.
  • the number given to each repeating unit means the molar ratio of each repeating unit.
  • the weight average molecular weight of the above-mentioned dispersed resin X-2 was 33,000.
  • alkali-soluble resin B-2 a resin having a structure represented by the following formula (B-2) was used.
  • a polymerization initiator C-1 a compound represented by the following formula (C-1) -Polymerization initiator C-2: IRGACURE OXE-02 (trade name, manufactured by BASF) -Polymerization initiator C-3: IRGACURE 369 (trade name, manufactured by BASF)
  • C-1 and C-2 are oxime ester-based polymerization initiators.
  • a polymerizable compound D-1 represented by the following formula (D-1) and a polymerizable compound D-2 represented by the following formula (D-2) were used for preparing a composition.
  • the value of the above “functionality” indicates the number of ethylenically unsaturated groups in one molecule of the polymerizable compound.
  • the surfactant represented by the following formula (S-1) was used for preparing a composition.
  • the weight average molecular weight of the surfactant represented by the formula (S-1) is 15,000.
  • Polymerization inhibitor As a polymerization inhibitor, p-methoxyphenol was used for preparing a light-shielding composition.
  • Example 1 ⁇ Preparation of light-shielding composition 1>
  • the light-shielding composition 1 of Example 1 was prepared by mixing the following components with a stirrer. -63 parts by mass of the coloring material composition A-1 prepared above ⁇ 3.5 parts by mass of alkali-soluble resin B-1 ⁇ 1.8 parts by mass of polymerization initiator C-1 -Polymerizable compound D-1 6.1 parts by mass ⁇ Surfactant 0.02 parts by mass ⁇ Polymerization inhibitor 0.003 parts by mass ⁇ Solvent 25.5 parts by mass
  • the light-shielding composition 1 obtained above was applied on a glass substrate by a spin coating method to form a coating film having a thickness of 1.7 ⁇ m.
  • the coated substrate was prebaked at 100 ° C. for 120 seconds.
  • a UX-1000SM-EH04 trade name, manufactured by Ushio Inc.
  • L / S line and space
  • a high-pressure mercury lamp lamp power 50 mW / cm.
  • exposure by the proximity method was performed on the substrate with the coating film.
  • a developing solution “CD-2060” (trade name, manufactured by Fuji Film Electronics Materials Co., Ltd.) was developed with a paddle using AD-1200 (manufactured by Mikasa Corporation) for 15 seconds.
  • AD-1200 manufactured by Mikasa Corporation
  • the substrate was washed with pure water for 30 seconds using a shower nozzle to remove uncured portions, thereby forming a black layer on the substrate.
  • ⁇ Formation of oxygen barrier layer E-1> A mixed gas of argon and oxygen (oxygen: 40% by volume) is introduced into a vacuum chamber of a sputtering apparatus (trade name “SRV-4300” manufactured by Shinko Seiki Co., Ltd.) and sputtering is performed using a silicon target. As a result, an oxygen barrier layer E-1 (thickness: 100 nm) made of silicon oxide (SiO 2 ) was formed on the surface of the black layer prepared above. Thus, the light-shielding film of Example 1 in which the black layer and the oxygen blocking layer E-1 were formed on the substrate in this order, was obtained.
  • Examples 2 to 6, 8, 9, 14 to 17 Except that the components used were changed or the addition amount of the coloring material composition A-1 was adjusted so that the composition of the light-shielding composition became the composition described in Tables 1 and 2, According to the method described in Example 1, the light-shielding compositions of each Example were prepared. Examples 2 to 6, 8 in which a black layer and an oxygen blocking layer are formed in this order on a substrate according to the method described in Example 1 except that each light-shielding composition obtained above is used. , 9 and 14 to 17 were produced, respectively.
  • Example 7 In the sputtering process, by introducing a mixed gas of argon and nitrogen (nitrogen: 50% by volume) into the vacuum chamber and performing sputtering, the surface of the black layer is blocked from oxygen made of silicon nitride (Si 3 N 4 ).
  • a black layer and an oxygen barrier layer E-2 are formed in this order on a substrate according to the method described in Example 1 except that a layer E-2 (thickness: 100 nm) is formed. 7 light-shielding films were produced.
  • Example 10 to 13 In the sputtering step, the procedure was performed except that the discharge power and the film formation time were adjusted, and the oxygen barrier layers E-3 to E-6 made of silicon oxide (SiO 2 ) having the thicknesses shown in Table 2 were formed. According to the method described in Example 1, the light-shielding films of Examples 10 to 13 each having a black layer and an oxygen blocking layer formed in this order on a substrate were produced.
  • Comparative Example 1 ⁇ Preparation of composition for forming oxygen barrier layer> The following components were mixed to prepare Comparative Composition 1.
  • -Polyvinyl alcohol (PVA): 32.2 parts by mass (trade name: PVA205, manufactured by Kuraray Co., Ltd., saponification degree 88%, polymerization degree 550)
  • PVA205 32.2 parts by mass
  • PVA205 32.2 parts by mass
  • PVP205 Polyvinyl pyrrolidone
  • Distilled water 524 parts by mass
  • Methanol 429 parts by mass
  • a black layer was formed on a substrate.
  • Composition 1 was applied to the surface of the produced black layer using a spin coater. The coating amount of the composition 1 was adjusted so that the thickness of the layer after drying was 1000 nm. Thereafter, the coating film of the resin composition 1 was dried at 100 ° C. for 120 seconds using a hot plate to form a comparative oxygen barrier layer CE-1 (thickness: 1000 nm).
  • the light-shielding film of Comparative Example 1 in which the black layer and the oxygen blocking layer CE-1 were formed on the substrate in this order was obtained.
  • Comparative Example 2 In the step of forming the oxygen blocking layer, a black layer and a black layer were formed on the substrate according to the method described in Comparative Example 1 except that the amount of the composition 1 was adjusted so that the thickness of the layer after drying was 500 nm. A light-shielding film of Comparative Example 2 in which the oxygen blocking layer CE-2 was formed in this order was produced.
  • Comparative Example 3 In the step of preparing the light-shielding composition, a black layer and an oxygen-blocking layer were formed on a substrate according to the method described in Comparative Example 1, except that the alkali-soluble resin B-2 was used instead of the alkali-soluble resin B-1. A light-shielding film of Comparative Example 3 in which CE-1 was formed in this order was produced.
  • composition for forming oxygen barrier layer A hydrolyzate of tetramethoxysilane (TMOS) and trifluoropropyltrimethoxysilane (TFPTMS) according to the method described in paragraphs 0032 to 0034 and 0042 (Example 1-1) of JP-A-2013-253145, and A silica sol in which beaded colloidal silica particles were dispersed was mixed to prepare Comparative Composition 2.
  • TMOS tetramethoxysilane
  • TFPTMS trifluoropropyltrimethoxysilane
  • Comparative Oxygen Blocking Layer CE-6 ⁇ Formation of Comparative Oxygen Blocking Layer CE-6>
  • the comparative composition 2 prepared above was used in place of the composition 1, and the comparative composition 2 was dried so that the thickness of the layer after drying was 190 nm.
  • a light-shielding film of Comparative Example 7 was formed by forming a black layer and an oxygen-blocking layer CE-6 on a substrate in this order according to the method described in Comparative Example 1 except that the amount of coating was adjusted.
  • the surface of the oxygen blocking layer CE-6 was polished to form a smooth surface, and then the formed smooth surface was analyzed with an electron beam microanalyzer (“JXA-8530F” (trade name) manufactured by JEOL Ltd.). And analyzed.
  • JXA-8530F electron beam microanalyzer
  • the thickness of the light-shielding film before and after the irradiation test was measured using a contact-type film thickness meter.
  • the rate of change in the thickness of the light-shielding film before and after the irradiation test was calculated using the following equation, and evaluated from the following viewpoints.
  • the “film thickness of the light-shielding film” means the sum of the thickness of the black layer and the thickness of the oxygen blocking layer, and does not include the thickness of the substrate.
  • Change rate of film thickness ((film thickness of light-shielding film before irradiation test ⁇ film thickness of light-shielding film after irradiation test) / (film thickness of light-shielding film before irradiation test) ⁇ 100)
  • D Change rate of film thickness is 10% or more
  • Change rate (%) of transmittance ((transmittance before irradiation test-transmittance after irradiation test) / transmittance before irradiation test x 100)
  • Change rate of reflectance (%) ((reflectance before irradiation test ⁇ reflectance after irradiation test) / reflectance before irradiation test ⁇ 100)
  • Both the rate of change of transmittance and the rate of change of reflectance are 2% or more.
  • the light-shielding film obtained above was placed in an oven and subjected to a heat resistance test at 150 ° C. for 500 hours.
  • the thickness of the light-shielding film before and after the heat test was measured using a contact-type film thickness meter.
  • the rate of change in the thickness of the light-shielding film before and after the heat resistance test was calculated using the following equation, and evaluated from the following viewpoints.
  • Rate of change of film thickness ((film thickness before heat resistance test ⁇ film thickness after heat resistance test) / (film thickness of light-shielding film before heat resistance test ⁇ substrate thickness) ⁇ 100)
  • Tables 1 to 3 show the compositions of the light-shielding compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 10, and the results of each test for the light-shielding films produced using those light-shielding compositions. Is shown.
  • the column of "colorant content” means the ratio (% by mass) of the content of the black colorant to the total solid content of each light-shielding composition.
  • the column of “Composition” of “Oxygen barrier layer” means that the oxygen barrier layer is a layer composed of the following materials.
  • the column of “thickness” of “oxygen blocking layer” means the thickness (nm) of each oxygen blocking layer measured using a contact type film thickness meter.
  • the column of “thickness of black layer / thickness of oxygen blocking layer” indicates the thickness of the black layer with respect to the thickness of the oxygen blocking layer measured using a contact-type film thickness meter. Means the ratio of
  • the content of the black coloring material is preferably 70% by mass or less, and more preferably 65% by mass or less, from the viewpoint that the moisture resistance of the light-shielding film is more excellent (comparison of Example 1, Examples 15 and 17). ). It was confirmed that the content of the black coloring material is preferably 30% by mass or more, and more preferably 50% by mass or more from the viewpoint that the heat resistance of the light-shielding film is more excellent (comparison of Example 1, Examples 14 and 16). ).
  • the black coloring material preferably contains a titanium oxynitride, a benzofuranone compound, or a perylene compound from the viewpoint that the moisture resistance of the light-shielding film is more excellent (Examples 1, 3, 4, and 5). Comparison). In addition, it was confirmed that the black coloring material preferably contains titanium oxynitride or carbon black from the viewpoint that the light resistance of the light-shielding film is more excellent (comparison of Examples 1, 3, 4 and 5). ).
  • the black color material containing vanadium nitride, niobium nitride or zirconium nitride is more suitable for black color containing titanium oxynitride because the light-shielding film is more excellent in moisture resistance and light resistance. It was confirmed that it was preferable as well as the material.
  • the dispersing resin preferably contains an ethylenically unsaturated group from the viewpoint of more excellent light resistance, heat resistance, and moisture resistance of the light-shielding film (comparison between Example 1 and Example 9).
  • the alkali-soluble resin is preferably a polyimide resin because the light resistance and the heat resistance of the light-shielding film are more excellent (comparison between Example 1 and Example 6).
  • a resin composed of a polybenzoxazole precursor was preferable, similarly to the polyimide resin, from the viewpoint that the light resistance and the moisture resistance of the light-shielding film were more excellent. .
  • the polymerization initiator it was confirmed that the polymerization initiator C-1 was preferable because the light resistance and the heat resistance of the light-shielding film were more excellent (comparison between Example 1 and Example 8).
  • the polymerizable compound it was confirmed that the polymerizable compound D-1 was preferable because the heat resistance and the moisture resistance of the light-shielding film were more excellent (comparison between Example 1 and Example 2).
  • the oxygen blocking layer preferably contains silicon oxide in terms of the light resistance and the moisture resistance of the light-shielding film being more excellent (comparison between Example 1 and Example 7). It was confirmed that the thickness of the oxygen blocking layer is preferably more than 50 nm and less than 250 nm from the viewpoint that the moisture resistance and the heat resistance of the light-shielding film are more excellent (comparison between Examples 1, 24 and 25 and Examples 10 and 11). ). It has been confirmed that the ratio of the thickness of the black layer to the thickness of the oxygen blocking layer is preferably 7 to 30 from the viewpoint that the light-shielding film has more excellent moisture resistance and heat resistance (Example 1 and Examples 10 and 11). And comparison).
  • Example 18 to 20 Except for using the following coloring materials a-5 to a-7 instead of titanium black (coloring material a-1), the coloring material composition A was prepared in accordance with the above-described method for preparing the coloring material composition A-1. -6 to A-8 were prepared respectively.
  • Coloring material a-5 Vanadium nitride (trade name “VN-O”, manufactured by Nippon Shinkin Co., Ltd.)
  • -Coloring material a-6 niobium nitride (trade name "NbN-O", manufactured by Nippon Shinmetal Co., Ltd.)
  • Coloring material a-7 zirconium nitride (prepared by the method of Example 1 in JP-A-2017-222559) Except that each of the coloring material compositions A-6 to A-8 prepared above was used in place of the coloring material composition A-1, the procedure was performed in accordance with the method for preparing the light-shielding composition 1 of Example 1. Light-shielding compositions of Examples 18 to 20 were respectively prepared.
  • a black layer and an oxygen blocking layer are formed in this order on a substrate according to the method described in Example 1, except that each of the obtained light-shielding compositions is used in place of the light-shielding composition 1.
  • the light-shielding films of Examples 18 to 20 were produced.
  • the evaluation results of the light-shielding films of Examples 18 to 20 were all the same as Example 1.
  • a coloring material composition was prepared according to the above-described method for preparing the coloring material composition A-1, except that the coloring material a-8 was used instead of titanium black (coloring material a-1). The same evaluation was performed.
  • Coloring material a-8 silica-coated zirconium nitride (Japanese Patent Laid-Open No.
  • Example 1 The evaluation results were the same as in Example 1.
  • a colorant composition was prepared according to the method for preparing the colorant composition A-1 described above, and the same evaluation as in Example 1 was performed.
  • the evaluation results were the same as in Example 1.
  • the evaluation results were the same as in Example 1.
  • Example 21 A light-shielding composition of Example 21 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that alkali-soluble resin B-3 was used instead of alkali-soluble resin B-1. Except that the obtained light-shielding composition is used instead of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate according to the method described in Example 1. A light-shielding film of Example 21 was produced. The evaluation results of the light-shielding film of Example 21 were all the same as those of Example 1.
  • Example 22 A light-shielding composition of Example 22 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that polymerization initiator C-3 was used instead of polymerization initiator C-2. Except that the obtained light-shielding composition is used instead of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate according to the method described in Example 1. A light-shielding film of Example 22 was produced. The evaluation result of the light-shielding film of Example 22 was the same as that of Example 8 except that the heat resistance was C.
  • Example 23 In the preparation of the light-shielding composition 1, a mixture of the polymerizable compound D-1 and the polymerizable compound D-2 having a mass ratio of 1: 1 was replaced with 6.1 parts by mass of the polymerizable compound D-1. Except for using 0.1 part by mass, the light-shielding composition of Example 23 was prepared according to the method of Example 1. Except that the obtained light-shielding composition is used instead of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate according to the method described in Example 1. A light-shielding film of Example 23 was produced. The evaluation result of the light-shielding film of Example 23 was the same as that of Example 1 except that the moisture resistance was B.
  • Examples 24 and 25 Except that in the sputtering process, the discharge power and the film formation time were adjusted, and oxygen barrier layers E-7 and E-8 made of silicon oxide (SiO 2 ) having a thickness of 70 nm and 200 nm were formed, respectively. According to the method described in No. 1, the light-shielding films of Examples 24 and 25 each having a black layer and an oxygen blocking layer formed in this order on a substrate were produced. The evaluation results of the light-shielding films of Examples 24 and 25 were the same as those of Example 1.
  • Example 26 A light-shielding composition of Example 26 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that the polymerization inhibitor was not used. Further, a light-shielding composition of Example 27 was prepared in accordance with the preparation method of light-shielding composition 1 of Example 1, except that no surfactant was used. According to the method described in Example 1, except that each obtained light-shielding composition is used in place of light-shielding composition 1, a black layer and an oxygen-shielding layer are formed in this order on a substrate. The light-shielding films of Examples 26 and 27 were produced, respectively. The evaluation results of the light-shielding films of Examples 26 and 27 were the same as those of Example 1.
  • Example 28 ⁇ Production of color filter with black matrix>
  • the light-shielding composition 1 of Example 1 was applied to a glass wafer by spin coating to form a composition layer.
  • the glass wafer was placed on a hot plate and prebaked at 120 ° C. for 2 minutes.
  • the composition layer was exposed at an exposure amount of 500 mJ / cm 2 through a photomask having a 0.1 mm Island pattern using an i-line stepper.
  • the exposed composition layer was paddle-developed with a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds to obtain a cured film.
  • the obtained cured film was rinsed using a spin shower, and further washed with pure water to form a patterned black layer.
  • an oxygen barrier layer made of silicon oxide was formed on the surface of the black layer produced above in accordance with the method for forming the oxygen barrier layer E-1 of Example 1, whereby a black layer was formed on the glass wafer.
  • a light-shielding film (black matrix) in which an oxygen barrier layer was formed in this order.
  • Example 29 ⁇ Preparation of solid-state imaging device including light-shielding film> 1% by mass of an arylsulfonium salt derivative (trade name “SP-172” manufactured by ADEKA Corporation) was added to a curable composition for lenses (alicyclic epoxy resin (trade name “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.)). Composition) (2 mL) was applied on a 5 ⁇ 5 cm glass substrate (1 mm thick, manufactured by Schott, trade name “BK7”), and the coating was cured by heating at 200 ° C. for 1 minute. A lens film was formed from which the residue could be evaluated.
  • an arylsulfonium salt derivative trade name “SP-172” manufactured by ADEKA Corporation
  • the light-shielding composition 1 of Example 1 was applied on a glass wafer on which the lens film was formed to form a composition layer.
  • the glass wafer was placed on a hot plate and prebaked at 120 ° C. for 120 seconds.
  • the thickness of the composition layer after heating was 2.0 ⁇ m.
  • the composition layer was exposed using a high-pressure mercury lamp at an exposure amount of 500 mJ / cm 2 through a photomask having a hole pattern of 10 mm.
  • the exposed composition layer was paddle-developed with a 0.3% aqueous solution of tetramethylammonium hydroxide at a temperature of 23 ° C. for 60 seconds to obtain a cured film.
  • the obtained cured film was rinsed using a spin shower, and further washed with pure water to form a patterned black layer.
  • an oxygen barrier layer made of silicon oxide was formed on the surface of the black layer produced above in accordance with the method for forming the oxygen barrier layer E-1 of Example 1, whereby a black layer was formed on the glass wafer. And a light-shielding film in which an oxygen blocking layer was formed in this order.
  • a curable composition for lenses (alicyclic epoxy resin (manufactured by Daicel Chemical Industries, trade name “EHPE-3150”) and an arylsulfonium salt derivative (manufactured by ADEKA Co.) And a composition (trade name “SP-172”) added at 1% by mass) to form a curable resin layer.
  • a wafer-level lens having a plurality of wafer-level lenses is obtained by transferring the shape with a quartz mold having a lens shape, exposing it with a high-pressure mercury lamp at an exposure amount of 400 mJ / cm 2 , and curing the curable resin layer. An array was made.
  • Example 30 ⁇ Production of headlight unit with light-shielding film>
  • the light-shielding composition 1 of Example 1 obtained above was applied on a 10 cm square glass substrate by a spin coating method to form a composition layer.
  • the glass substrate was placed on a hot plate and prebaked at 120 ° C. for 2 minutes.
  • the obtained composition layer was exposed through a mask (exposure amount: 1000 mJ / cm 2 ) using an i-line stepper so that a cured film having a light distribution pattern shown in FIG. 6 was obtained.
  • development processing was performed using a developing device (Act-8 manufactured by Tokyo Electron).

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Abstract

Ce film de protection contre la lumière comprend: une couche noire contenant un matériau colorant noir; et une couche barrière contre l'oxygène formée sur la couche noire. La couche barrière contre l'oxygène est une couche unique constituée d'un matériau inorganique, et l'épaisseur de la couche barrière contre l'oxygène est de 10 à 500 nm. Ce procédé de fabrication d'un film de protection contre la lumière comprend: une étape dans laquelle un support est revêtu d'une composition de protection contre la lumière contenant un matériau colorant noir, une résine, un composé polymérisable et un initiateur de polymérisation, et le film de revêtement obtenu est durci pour former une couche noire; et une étape dans laquelle une couche barrière contre l'oxygène est formée sur la couche noire.
PCT/JP2019/032377 2018-09-21 2019-08-20 Film de protection contre la lumière, procédé de fabrication d'un film de protection contre la lumière, élément optique, élément d'imagerie à semi-conducteurs et unité de phare WO2020059382A1 (fr)

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CN201980050527.6A CN112513692A (zh) 2018-09-21 2019-08-20 遮光膜、遮光膜的制造方法、光学元件、固体摄像元件、前照灯单元
JP2020548151A JP7245843B2 (ja) 2018-09-21 2019-08-20 遮光膜、遮光膜の製造方法、光学素子、固体撮像素子、ヘッドライトユニット
KR1020217001039A KR102660236B1 (ko) 2018-09-21 2019-08-20 차광막, 차광막의 제조 방법, 광학 소자, 고체 촬상 소자, 헤드라이트 유닛

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WO2022202486A1 (fr) * 2021-03-23 2022-09-29 東レ株式会社 Composition de résine photosensible négative, film de composition de résine photosensible négative, produit durci, procédé de préparation de produit durci, structure creuse et composant électronique
WO2024004793A1 (fr) * 2022-06-30 2024-01-04 富士フイルム株式会社 Composé, composition, film, procédé de production de composition colorée, et procédé de production de stratifié pour élément d'affichage

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CN113867101B (zh) * 2021-10-09 2023-10-24 杭州福斯特电子材料有限公司 用于led的白色感光覆盖膜组合物、覆盖膜及其制备方法

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KR20210021527A (ko) 2021-02-26
KR102660236B1 (ko) 2024-04-25

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