WO2020054695A1 - 光学フィルターおよびその用途 - Google Patents

光学フィルターおよびその用途 Download PDF

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Publication number
WO2020054695A1
WO2020054695A1 PCT/JP2019/035476 JP2019035476W WO2020054695A1 WO 2020054695 A1 WO2020054695 A1 WO 2020054695A1 JP 2019035476 W JP2019035476 W JP 2019035476W WO 2020054695 A1 WO2020054695 A1 WO 2020054695A1
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WIPO (PCT)
Prior art keywords
optical filter
wavelength
group
transmittance
infrared
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PCT/JP2019/035476
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English (en)
French (fr)
Japanese (ja)
Inventor
寛之 岸田
勝也 長屋
達之 山本
敦記 長尾
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Jsr株式会社
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Application filed by Jsr株式会社 filed Critical Jsr株式会社
Priority to JP2020546021A priority Critical patent/JP7255600B2/ja
Priority to CN201980054202.5A priority patent/CN112585508B/zh
Priority to KR1020217007260A priority patent/KR20210055704A/ko
Publication of WO2020054695A1 publication Critical patent/WO2020054695A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • 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
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B11/00—Filters or other obturators specially adapted for photographic purposes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B17/00—Details of cameras or camera bodies; Accessories therefor
    • G03B17/02—Bodies
    • G03B17/12—Bodies with means for supporting objectives, supplementary lenses, filters, masks, or turrets
    • 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
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
    • H04N23/50—Constructional details
    • H04N23/55—Optical parts specially adapted for electronic image sensors; Mounting thereof

Definitions

  • the present invention relates to an optical filter and its use. More specifically, the present invention relates to an optical filter (for example, a near-infrared cut filter) having specific optical characteristics, and a solid-state imaging device and a camera module using the optical filter.
  • an optical filter for example, a near-infrared cut filter
  • a solid-state imaging device and a camera module using the optical filter.
  • Solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions use CCDs and CMOS image sensors, which are solid-state imaging devices for color images. These solid-state imaging devices use a sensor having sensitivity to near-infrared light in the light-receiving unit, and thus need to perform visibility correction, and often use an optical filter (for example, a near-infrared cut filter). .
  • a near-infrared cut filter having a near-infrared reflective film in which a dielectric multilayer film is laminated on a norbornene-based resin is known.
  • Patent Document 1 Japanese Patent Document 1
  • the incident angle dependence of the light transmission characteristics is large, and in a solid-state imaging device having a wide viewing angle, the color difference between the center and the periphery of the image occurs.
  • an optical filter such as a near infrared cut filter containing a near infrared absorber is widely known.
  • a near-infrared cut filter is known that uses a resin as a base material and contains a near-infrared absorber having a steep absorption characteristic in the resin, thereby improving the incident angle dependence in the near-infrared region.
  • Patent Document 2 Japanese Patent Document 1
  • Patent Document 3 In recent years, image sensing systems that detect near infrared rays as well as wavelengths at which human visibility is high, from 400 nm to 700 nm, and measure the degree of plant growth and the amount of oxygenated hemoglobin in humans have been studied (for example, Patent Document 3 and 4).
  • Patent Document 3 it is known that the reflectance of rice leaves at wavelengths of 500 nm to 800 nm changes in accordance with the nitrogen content, and the growth of plants is determined from the reflection intensity of visible light and the reflection intensity of near-infrared light.
  • a method for obtaining an index has been proposed.
  • the ratio (F690 / F740) of the fluorescence intensity (F690) at a wavelength of 690 nm to the fluorescence intensity (F740) at a wavelength of 740 nm is an index of the chlorophyll concentration in the living body of a plant. It is known that diagnosis can be made (for example, see Non-Patent Document 1).
  • a conventional optical filter such as a near infrared cut filter containing a near infrared absorber absorbs a wavelength of 700 to 700 nm used for detection.
  • the light transmittance at 750 nm was low, and it was difficult to maintain sufficient sensitivity.
  • a near-infrared cut filter having a near-infrared reflective film in which dielectric multilayer films are laminated it is known that the reflection band is shifted to a longer wavelength by increasing the thickness of the laminated dielectric multilayer film. For this reason, it is easy to provide a dielectric multilayer film having a high transmittance at a wavelength of 700 nm to 750 nm.
  • the incident angle dependence at a high angle of incidence is large, and the In addition, there is a problem that the intensity of light obtained by sensing differs between the center and the periphery of the image depending on the incident angle.
  • An object of the present invention is to provide an optical filter having both low incident angle dependence in the near infrared region and excellent transmittance characteristics of light having a wavelength of 700 to 750 nm required for sensing and having improved ghost, and an optical filter having the same. It is to provide an apparatus using a filter.
  • An optical filter according to one embodiment of the present invention satisfies the following requirements (A) to (D).
  • C In the wavelength range of 700 to 750 nm, the average value of the transmittance as measured from the direction perpendicular to the surface of the optical filter is more than 46%.
  • the absolute value of the difference from the shortest wavelength value (Yb) at which the transmittance is 50% when measured from an angle of 30 ° from the direction is less than 15 nm.
  • an optical filter having both low incident angle dependence in the near infrared region and excellent transmittance characteristics of light having a wavelength of 700 to 750 nm required for sensing and having improved ghost and the optical filter are provided.
  • An apparatus using a filter can be provided.
  • the optical filter of the present invention is suitable as a near-infrared cut filter.
  • FIG. 9 is a schematic diagram illustrating an example of a method of measuring the reflectance of light incident at an angle of 5 ° from a direction perpendicular to a surface of an optical filter. It is the schematic which shows an example of a camera module. It is the schematic which shows an example of a ghost generation
  • FIG. 9 is a schematic diagram illustrating an example of a method of measuring the reflectance of light incident at an angle of 5 ° from a direction perpendicular to a surface of an optical filter. It is the schematic which shows an example of a camera module. It is the schematic which shows an example of a ghost generation
  • FIG. 3 is a diagram showing optical characteristics of the optical filter obtained in Example 1.
  • FIG. 14 is a diagram illustrating optical characteristics of the optical filter obtained in Example 5.
  • FIG. 9 is a diagram illustrating optical characteristics of the optical filter obtained in Comparative Example 1.
  • FIG. 9 is a view illustrating optical characteristics of the optical filter obtained in Comparative Example 4.
  • FIG. 14 is a diagram illustrating optical characteristics of the optical filter obtained in Comparative Example 7.
  • the optical filter of the present invention satisfies the following requirements (A) to (D).
  • C In the wavelength range of 700 to 750 nm, the average value of the transmittance as measured from the direction perpendicular to the surface of the optical filter is more than 46%.
  • the absolute value of the difference from the shortest wavelength value (Yb) at which the transmittance is 50% when measured from an angle of 30 ° from the direction is less than 15 nm.
  • the amount of light captured by the solid-state imaging device in the wavelength range of 430 nm to 580 nm can be increased.
  • the average value of the transmittance in the requirement (A) is preferably 80% or more. If it is 80% or more, imaging can be performed even in a darker environment.
  • the amount of light captured by the solid-state imaging device in the wavelength range of 800 nm to 1000 nm can be reduced.
  • the average value of the transmittance in the requirement (B) is preferably 7% or less, more preferably 6% or less, and further preferably 5% or less.
  • the amount of light captured by the solid-state imaging device in the wavelength range of 700 nm to 750 nm is secured, and the sensing sensitivity is improved.
  • the average value of the transmittance in the requirement (C) is preferably 55% or more, more preferably 65% or more, and further preferably 75% or more. The higher the transmittance, the better.
  • the upper limit is preferably 100%, more preferably 90%, and still more preferably 80%. Within the above range, the amount of light taken in by the solid-state imaging device is adjusted, and light necessary for sensing can be transmitted efficiently.
  • the incident angle dependence of the amount of light incident on the solid-state imaging device can be reduced in the wavelength range of 560 nm to 800 nm.
  • the incident angle dependence of the spectral sensitivity of the solid-state imaging device in this wavelength range can be reduced. Since the dependence on the incident angle is reduced, the difference between the colors at the center and the periphery of the image obtained by the solid-state imaging device and the difference in sensor sensitivity is small, and the sensitivity is higher.
  • the optical filter of the present invention preferably further satisfies the following requirement (E).
  • E The wavelength value (Ya) in the requirement (D) is 730 nm or more and 800 nm or less.
  • the transmittance of visible light at a wavelength of 400 to 700 nm and the transmittance of near-infrared light at a wavelength of 700 to 750 nm used for sensing are kept high, and the wavelength 800 unnecessary for sensing is used. It is easy to achieve both low transmittance (high shielding property) of up to 1200 nm.
  • the wavelength (Ya) is preferably 740 nm to 800 nm, more preferably 745 nm to 800 nm.
  • the optical filter of the present invention preferably further satisfies the following requirements (Z1) and (Z2).
  • Z1 At a wavelength of 700 nm, the reflectance measured at an angle of 5 ° from the direction perpendicular to the surface of the optical filter is 10% or less when incident from either surface of the optical filter.
  • Z2 In the range of wavelengths of 600 nm or more, which of the optical filters has the shortest wavelength value (Za) at which the reflectance is 50% when measured from an angle of 5 ° from the direction perpendicular to the surface of the optical filter. Is 730 nm or more even when the light is incident from the surface.
  • the near-infrared reflective film made of a dielectric multilayer film has a tendency that the reflection band shifts to a short wavelength as the light is obliquely incident at a higher angle from the surface of the optical filter. Therefore, the wavelength (Za) in the requirement (Z2) is more preferably 740 nm or more, further preferably 750 nm or more, and particularly preferably 780 nm or more. As a result, it is possible to sufficiently suppress the occurrence of a ghost even in light that is observed by the human eyes and that is incident at a high angle with respect to the surface of the optical filter.
  • the optical filter of the present invention preferably has a substrate containing a near-infrared absorbing agent and a near-infrared reflecting film.
  • An optical filter having a substrate containing a near-infrared absorbing agent can suppress near-infrared reflection of the optical filter and reduce ghost.
  • An optical filter having a near-infrared reflective film is excellent in near-infrared shielding performance, and excellent in visible light transmission performance in a wavelength range of 430 to 580 nm, and can make the obtained solid-state imaging device highly sensitive.
  • the near-infrared absorber has an absorption maximum wavelength in the wavelength range of 751 to 950 nm, and the near-infrared absorber is contained in such an amount that the transmittance of the substrate at the absorption maximum wavelength becomes 10%.
  • the transmittance of near-infrared light having a wavelength of 700 to 750 nm can be increased. It is easy to achieve both the maintenance and the low transmittance (high shielding property) at a wavelength of 800 to 1200 nm that is unnecessary for sensing.
  • the absolute value of the difference is preferably as small as possible, more preferably less than 100 nm, further preferably less than 70 nm.
  • the lower limit is 1 nm.
  • the near-infrared absorbing agent has a maximum absorption wavelength at a wavelength of 751 to 950 nm, and that the absolute value of the difference between (Aa) and (Ab) is less than 150 nm.
  • the properties of one kind of absorbent may be satisfied, or the properties of a plurality of kinds may be mixed. Further, the near-infrared absorbing agent obtained by mixing a plurality of types may include one that does not satisfy the characteristics by itself.
  • the substrate preferably has transparency.
  • the transparency in the present invention means that the average value of the transmittance in the wavelength range of 420 to 600 nm is 50% or more.
  • Examples of the material of such a substrate include glass, tempered glass, special glasses such as phosphate glass, fluorophosphate glass, alumina glass, yttrium aluminate, and yttrium oxide, and resins.
  • the base material may be composed of one layer or a plurality of layers, may be composed of one kind of material selected from the above materials, may be composed of a plurality of kinds, or may be a material appropriately mixed.
  • At least one of the layers constituting the substrate preferably contains a near-infrared absorbing agent, and may also contain a near-ultraviolet absorbing agent.
  • the layer containing the near infrared absorber and the layer containing the near ultraviolet absorber may be the same layer or different layers.
  • Glass examples include silicate glass, soda-lime glass, borosilicate glass, and quartz glass.
  • tempered glass examples include physically tempered glass, tempered laminated glass, and chemically tempered glass.
  • chemically strengthened glass is preferred, in which the thickness of the compression layer is small and the thickness of the base material can be reduced.
  • specific examples of the chemically strengthened glass include “Dragonrail” manufactured by Asahi Glass Co., Ltd. and “Gorilla Glass” manufactured by Corning.
  • phosphate glass or the fluorophosphate glass for example, International Publication No. WO2012 / 018826, such as BS3, BS4, BS6, BS7, BS8, BS10, BS11, BS12, BS13, BS16, BS17 manufactured by Matsunami Glass Industry Co., Ltd. And the like.
  • alumina glass for example, "HI-CERAM” manufactured by NGK Insulators, Ltd. is exemplified.
  • Examples of the yttrium aluminate and the yttrium oxide include "EXYRIA (registered trademark)" manufactured by Coorstech.
  • the resin examples include a polyester resin, a polyether resin, an acrylic resin, a polyolefin resin, a polycycloolefin resin, a norbornene resin, a polycarbonate resin, an enthiol resin, an epoxy resin, and a polyamide resin.
  • Resin polyimide-based resin, polyurethane-based resin, polystyrene-based resin, and the like.
  • norbornene-based resins, polyimide-based resins, and polyether-based resins are preferred.
  • the refractive index of the resin can be adjusted by adjusting the molecular structure of the raw material components. Specifically, there is a method of giving a specific structure to the main chain or side chain of the polymer as a raw material component.
  • the structure provided in the polymer is not particularly limited, and examples thereof include a norbornene skeleton and a fluorene skeleton.
  • a commercial product may be used as the resin.
  • Commercially available products include “OGSOL (registered trademark) EA-F5003” (acrylic resin, refractive index: 1.60) manufactured by Osaka Gas Chemical Co., Ltd., and “Polymethyl methacrylate” (refractive index) manufactured by Tokyo Chemical Industry Co., Ltd. 1.1.49), “Polyisobutyl methacrylate” (refractive index: 1.48) manufactured by Tokyo Chemical Industry Co., Ltd., and "BR50” (refractive index: 1.56) manufactured by Mitsubishi Rayon Co., Ltd.
  • polyester-based resins examples include “OKP4HT” (refractive index: 1.64), “OKP4” (refractive index: 1.61), and “B-OKP2” (manufactured by Osaka Gas Chemical Co., Ltd.). Refractive index: 1.64), “OKP-850” (refractive index: 1.65), “Byron (registered trademark) 103” (refractive index: 1.55) manufactured by Toyobo Co., Ltd., and the like.
  • resins include, for example, “LeXan (registered trademark) ML9103” (refractive index: 1.59) and “xylex (registered trademark) 7507” manufactured by sabic, and “EP5000” (refracted) manufactured by Mitsubishi Gas Chemical Company, Ltd. Rate: 1.63), Teijin Chemicals Ltd.'s “SP3810” (refractive index: 1.63), “SP1516” (refractive index: 1.60) ⁇ , “TS2020” (refractive index: 1.59), and the like.
  • the polyether-based resin is a polymer obtained by a reaction for forming an ether bond in a main chain, and comprises at least one structural unit selected from the group consisting of structural units represented by the following formulas (1) and (2).
  • the polymer has Further, it may have a structural unit represented by the following formula (3).
  • R 1 to R 4 each independently represent a monovalent organic group having 1 to 12 carbon atoms.
  • a to d each independently represent an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
  • Examples of the monovalent organic group having 1 to 12 carbon atoms include a monovalent hydrocarbon group having 1 to 12 carbon atoms, and a monovalent organic group having at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And 12 monovalent organic groups.
  • the monovalent hydrocarbon group having 1 to 12 carbon atoms includes a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a C6 to C12 monovalent hydrocarbon group. And an aromatic hydrocarbon group.
  • the straight-chain or branched-chain hydrocarbon group having 1 to 12 carbon atoms is preferably a straight-chain or branched-chain hydrocarbon group having 1 to 8 carbon atoms, and is preferably a straight-chain or branched-chain hydrocarbon group having 1 to 5 carbon atoms. Hydrogen groups are more preferred.
  • linear or branched hydrocarbon group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and n-pentyl.
  • the alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, and more preferably an alicyclic hydrocarbon group having 3 or 4 carbon atoms.
  • Preferred specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group; a cyclobutenyl group, a cyclopentenyl group and a cyclohexenyl group. And the like.
  • the binding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.
  • aromatic hydrocarbon group having 6 to 12 carbon atoms examples include a phenyl group, a biphenyl group and a naphthyl group.
  • the binding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.
  • Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom include an organic group including a hydrogen atom, a carbon atom and an oxygen atom, and among them, a total carbon atom including an ether bond, a carbonyl group or an ester bond and a hydrocarbon group.
  • Preferred examples include organic groups of the formulas 1 to 12.
  • Examples of the organic group having 1 to 12 carbon atoms having an ether bond include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 2 to 12 carbon atoms, and a 6 to 12 carbon atoms. And specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, and a cyclohexyloxy group. And a methoxymethyl group.
  • Examples of the organic group having 1 to 12 carbon atoms having a carbonyl group include an acyl group having 2 to 12 carbon atoms, and specific examples include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group. .
  • Examples of the organic group having 1 to 12 carbon atoms having an ester bond include an acyloxy group having 2 to 12 carbon atoms, and specifically, an acetyloxy group, a propionyloxy group, an isopropionyloxy group and a benzoyloxy group And the like.
  • Examples of the organic group having 1 to 12 carbon atoms including a nitrogen atom include an organic group including a hydrogen atom, a carbon atom and a nitrogen atom, and specific examples thereof include a cyano group, an imidazole group, a triazole group, a benzimidazole group, and a benzimidazole group. And a triazole group.
  • Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom include an organic group composed of a hydrogen atom, a carbon atom, an oxygen atom, and a nitrogen atom.
  • an oxazole group, an oxadiazole Groups, benzoxazole groups and benzoxadiazole groups are examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom.
  • a monovalent hydrocarbon group having 1 to 12 carbon atoms is preferable from the viewpoint of water absorbing (wet) properties of the resin (1), and an aromatic group having 6 to 12 carbon atoms. Hydrocarbon groups are more preferred, and phenyl groups are even more preferred.
  • R 1 to R 4 and ad are each independently the same as R 1 to R 4 and ad in the formula (1), and Y is a single bond, -SO Represents 2 -or -CO-;
  • R 7 and R 8 each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and m represents 0 or 1; However, when m is 0, R 7 is not a cyano group.
  • g and h each independently represent an integer of 0 to 4, and is preferably 0.
  • the mechanical characteristics refer to properties such as tensile strength, elongation at break, and tensile modulus of the resin.
  • the resin (1) further includes at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4) (hereinafter referred to as “structural unit (3) -4) "). It is preferable that the resin (1) has such a structural unit (3-4) because the mechanical properties of a substrate containing the resin (1) are improved.
  • R 5 and R 6 each independently represent a monovalent organic group having 1 to 12 carbon atoms
  • Z represents a single bond, —O—, —S—, —SO 2 —, —CO—, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms
  • n represents 0 or 1.
  • e and f each independently represent an integer of 0 to 4, preferably 0.
  • Examples of the monovalent organic group having 1 to 12 carbon atoms include the same as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).
  • the divalent organic group having 1 to 12 carbon atoms includes a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom and a nitrogen atom.
  • divalent hydrocarbon group having 1 to 12 carbon atoms examples include linear or branched divalent hydrocarbon groups having 1 to 12 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 12 carbon atoms, and Examples thereof include a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • Examples of the linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.
  • Examples of the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include a cycloalkylene group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group and a cyclohexylene group; a cyclobutenylene group, a cyclopentenylene group; And cycloalkenylene groups such as cyclohexenylene groups.
  • Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group, a naphthylene group, and a biphenylene group.
  • Examples of the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include linear or branched divalent halogenated hydrocarbon groups having 1 to 12 carbon atoms and divalent halogenated aliphatic groups having 3 to 12 carbon atoms. Examples include a cyclic hydrocarbon group and a divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms examples include difluoromethylene, dichloromethylene, tetrafluoroethylene, tetrachloroethylene, hexafluorotrimethylene, and hexachlorotrimethylene.
  • the divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms at least a part of the hydrogen atoms of the groups exemplified in the above divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is a fluorine atom , A group substituted by a chlorine atom, a bromine atom or an iodine atom.
  • the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms at least a part of the hydrogen atoms of the groups exemplified as the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms is a fluorine atom or a chlorine atom. And a group substituted with an atom, a bromine atom or an iodine atom.
  • Examples of the organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom and a carbon atom and an oxygen atom and / or a nitrogen atom. And a divalent organic group having a total of 1 to 12 carbon atoms having an ether bond, a carbonyl group, an ester bond or an amide bond and a hydrocarbon group.
  • the divalent halogenated organic group having 1 to 12 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom is specifically selected from the group consisting of an oxygen atom and a nitrogen atom.
  • Examples of the divalent organic group having 1 to 12 carbon atoms containing at least one atom include a group in which at least a part of the hydrogen atoms of the groups exemplified above is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. .
  • Z in the formula (3) is preferably a single bond, —O—, —SO 2 —, —CO— or a divalent organic group having 1 to 12 carbon atoms, and the resin (1) has a water absorbing (wet) property.
  • a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is more preferable.
  • the substrate has a resin layer containing a near-infrared absorbing agent, and the resin layer contains at least one selected from the group consisting of a norbornene-based resin, a polyimide-based resin, and a polyether resin.
  • the solid-state imaging device including the optical filter having the resin layer has high image quality and can be easily manufactured.
  • the average value of the transmittance of the resin layer at a wavelength of 430 to 580 nm is preferably 70% or more at a thickness of 1 ⁇ m, since the solid-state imaging device has high sensitivity.
  • the glass transition temperature of the resin layer is preferably 140 ° C. or higher because a solid-state imaging device can be manufactured by a low-temperature reflow process.
  • the Young's modulus of the resin layer is preferably 2 GPa or more from the viewpoint of obtaining an optical filter that is hardly warped.
  • the in-plane retardation R 0 of the resin layer is preferably 50 nm or less, more preferably 20 nm or less, further preferably 10 nm or less, and particularly preferably 5 nm or less.
  • an optical filter having a small in-plane phase difference R 0 when an imaging element having different sensitivity according to polarization is provided, the polarization characteristics can be accurately detected, and errors are reduced.
  • the resin layer may be a single layer or a plurality of layers in the substrate, and the substrate may be composed of only the resin layer.
  • the thickness of the base material can be appropriately selected depending on the desired use, and is not particularly limited, but the upper limit is preferably 250 ⁇ m or less, more preferably 200 ⁇ m or less, further more preferably 150 ⁇ m or less, and the lower limit is Preferably it is 30 ⁇ m or more, more preferably 40 ⁇ m or more. When the thickness is in the above range, the warp of the optical filter is small, and a sufficiently thin solid-state imaging device can be obtained.
  • the resin layer can be formed by, for example, melt molding or cast molding, and if necessary, after molding, is manufactured by a method of coating a coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent. Can be.
  • a coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent.
  • the resin layer is a method of melt-molding a pellet obtained by melt-kneading a resin and a near-infrared absorber; melt-molding a resin composition containing a resin and a near-infrared absorber. Method; or a method of melt-molding a pellet obtained by removing a solvent from a resin composition containing a near-infrared absorbing agent, a resin and a solvent, or the like.
  • the melt molding method include injection molding, melt extrusion molding, and blow molding.
  • the resin layer is formed by casting a resin composition containing a near-infrared absorbing agent, a resin and a solvent on a suitable support to remove the solvent; an antireflection agent, a hard coating agent and / or A method of casting a resin composition containing a coating agent such as an antistatic agent, a near-infrared absorbing agent, and a resin on a suitable support; or an antireflection agent, a hard coating agent, and / or an antistatic agent
  • the curable composition containing the coating agent, the coloring compound, and the resin may be cast on a suitable support, cured and dried, or the like.
  • the support is not particularly limited, and a glass support, a tempered glass, a support made of special glass or a resin as an example of the material of the base material, and a support other than the material of the base material can be used.
  • a glass support a tempered glass, a support made of special glass or a resin as an example of the material of the base material, and a support other than the material of the base material can be used.
  • a steel belt, a steel drum, or the like may be used.
  • the substrate When the substrate is a substrate composed of a resin substrate, the substrate can be obtained by peeling a coating film from a support after cast molding, and the substrate is a support. In the case of a substrate having a resin layer laminated thereon, the substrate can be obtained by not peeling off the coating film after casting.
  • the amount of residual solvent in the resin layer obtained by the above method is preferably as small as possible, and is usually 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass, based on the weight of the resin layer. % Or less.
  • amount of the residual solvent is in the above range, a resin layer which is less likely to deform the optical filter or change optical characteristics and which can easily exhibit desired functions can be obtained.
  • the near-infrared absorber preferably has an absorption maximum wavelength in the range of 751 to 950 nm, more preferably 760 to 940 nm, still more preferably 770 to 930 nm, and particularly preferably 775 to 925 nm.
  • the absorption maximum wavelength is in the above range, the amount of light taken in by the solid-state imaging device in the wavelength range of 700 nm to 750 nm is adjusted, and light in the wavelength range of 751 nm or more, which has low human visibility, is transmitted to the solid-state imaging device.
  • the amount of light entering can be reduced, and the solid-state imaging device can be made closer to human visibility.
  • the near-infrared absorbing agent examples include a cyanine dye, a phthalocyanine dye, a dithiol dye, a diimonium dye, a squarylium dye, a croconium dye, and a copper phosphate salt.
  • the structures of these dyes are not particularly limited, and generally known or commercially available dyes can be used as long as they do not impair the effects of the present invention. Further, as long as the effects of the present invention are not impaired, one or more near-infrared absorbers may be added to the optical filter.
  • the near-infrared absorbing agent is preferably contained in the range of 0.01 to 60.0% by mass with respect to the resin layer.
  • the content of the near-infrared absorber is in the above range, appropriate optical characteristics are easily obtained.
  • the content is more than 60.0% by mass, the above-described properties such as high transparency, high heat resistance, low warpage, and low breakage are lost, and the image quality of the solid-state imaging device is reduced, and the factors that increase the difficulty in manufacturing are as follows. Become.
  • the near-infrared absorbing agent preferably satisfies the following conditions (a) and (b).
  • (A) (absorbance ⁇ 700 ) / (absorbance ⁇ max ) ⁇ 0.1
  • the absorbance at a wavelength of 700 nm of the near-infrared absorber is “absorbance ⁇ 700 ”
  • the absorbance at a wavelength of 751 nm is “absorbance ⁇ 751 ”
  • the absorbance at the maximum absorption wavelength is “absorbance ⁇ max ”
  • the absorbance ⁇ at the wavelength ⁇ is Is calculated from the transmittance ⁇ at the wavelength ⁇ according to the following generally used equation.
  • Absorbance ⁇ -Log (internal transmittance ⁇ ) For example, when the internal transmittance ⁇ is 0.1 (10%), the absorbance is 1.0.
  • the internal transmittance is a value obtained by removing the surface reflectance from the obtained transmittance, and is obtained by dividing the obtained transmittance by the transmittance of the medium excluding the near-infrared absorbing agent.
  • the absorbance ⁇ 700 of the optical filter is preferably 0.25 or less, more preferably 0.2 or less, and still more preferably. Is 0.18 or less, particularly preferably 0.16 or less.
  • the lower limit of the absorbance ⁇ 700 of the optical filter is 0.
  • the absorbance ⁇ 751 of the optical filter is preferably 0.2 or more, and more preferably 0.2 or more. Is 0.21 or more, more preferably 0.23 or more, particularly preferably 0.25 or more. Further, the absorbance ⁇ 751 of the optical filter is preferably 0.8 or less, more preferably 0.6 or less, and further preferably 0.5 or less. By using a near-infrared absorber that satisfies the condition (b), the absorbance ⁇ 751 of the optical filter can be set in the above range.
  • the near-infrared absorbent that satisfies the condition (b) tends to have a smaller (absorbance ⁇ 751 ) / (absorbance ⁇ max ) as the absorption maximum wavelength ⁇ max becomes longer from 751 nm to 950 nm. . Therefore, as the absorption maximum wavelength ( ⁇ max ) becomes longer from 751 nm to 950 nm, it is necessary to increase the concentration of the near infrared absorber contained in the base material. On the other hand, if the near-infrared absorbing agent satisfying the condition (a) is excessively contained in the base material, it may be difficult for the optical filter to maintain the requirement (C).
  • the near-infrared absorbing agent contained in the base material preferably satisfies the following condition (c).
  • dye (n) in “ ⁇ dye (n) ” means each near-infrared absorbing agent contained in the base material.
  • the “shortest absorption maximum wavelength” means the shortest wavelength (nm) among the absorption maximum wavelengths at wavelengths of 751 to 950 nm, and the “dye concentration” is the concentration of the near-infrared absorber contained in the base material. (Mass%) and “dye medium thickness” means the thickness (mm) of the substrate containing the near-infrared absorbing agent.
  • the absorbance ⁇ 700 and the absorbance ⁇ 751 of the optical filter can be set in the above-described preferable ranges. , Requirements (C) and (D).
  • the cyanine dye is not particularly limited as long as it does not impair the effects of the present invention. Examples thereof include those described in JP-A-2009-108267, JP-A-2010-72575, and JP-A-2016-060774. Of cyanine-based dyes.
  • Some cyanine dyes do not have an absorption maximum wavelength at a wavelength of 751 to 950 nm, but a cyanine dye having an absorption maximum wavelength at a wavelength of 751 to 950 nm is selected, or an absorption maximum at a wavelength of 751 to 950 nm is selected.
  • a combination of a cyanine dye having no wavelength and a cyanine dye having an absorption maximum at a wavelength of 751 to 950 nm, or a cyanine dye having no absorption maximum at a wavelength of 751 to 950 nm and an absorption maximum at a wavelength of 751 to 950 nm By using a dye other than a cyanine-based dye having the following in combination, the dye can be used as a near-infrared absorbing agent for obtaining the effects of the present invention.
  • the phthalocyanine dye is not particularly limited as long as it does not impair the effects of the present invention. Examples thereof include JP-A-60-224589, JP-A-1005-533319, JP-A-4-23868, JP-A-4-39361, JP-A-5-78364, JP-A-5-220247, JP-A-5-222301, JP-A-5-222302, JP-A-5-345861, and JP-A-5-34561.
  • Some phthalocyanine dyes do not have an absorption maximum wavelength at a wavelength of 751 to 950 nm, but a phthalocyanine dye having an absorption maximum wavelength at a wavelength of 751 to 950 nm is selected, or an absorption maximum at a wavelength of 751 to 950 nm is selected.
  • a phthalocyanine dye having no wavelength and a phthalocyanine dye having an absorption maximum wavelength of 751 to 950 nm are used together, or a phthalocyanine dye having no absorption maximum wavelength of 751 to 950 nm and an absorption maximum wavelength of 751 to 950 nm are used.
  • a dye other than a phthalocyanine dye having the following formula (1) it can be used as a near-infrared absorbing agent for obtaining the effects of the present invention.
  • Phthalocyanine dyes often have a steep absorption characteristic near the absorption maximum wavelength, and when a phthalocyanine dye is used in the optical filter of the present invention, it may be used in combination with at least one other near-infrared absorber. preferable.
  • the dithiol dye is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include dithiol dyes described in JP-A-2006-215395 and WO2008 / 086931.
  • dithiol dyes include those that do not have a maximum absorption wavelength at a wavelength of 751 to 950 nm. However, a dithiol dye having a maximum absorption wavelength at a wavelength of 751 to 950 nm is selected, or a maximum absorption at a wavelength of 751 to 950 nm is selected.
  • a combination of a dithiol dye having no wavelength and a dithiol dye having a maximum absorption wavelength of 751 to 950 nm, or a dithiol dye having no maximum absorption wavelength of 751 to 950 nm and a maximum absorption wavelength of 751 to 950 nm By using a dye other than a dithiol-based dye having the following in combination, the dye can be used as a near-infrared absorbing agent for obtaining the effects of the present invention. Further, for example, as described in WO1998 / 034988, a counter ion conjugate of a dithiol dye may be used.
  • the squarylium-based dye is not particularly limited as long as it does not impair the effects of the present invention.
  • squarylium-based dyes represented by the following formulas (4) to (6) are disclosed in JP-A-2014-074002.
  • X is independently an oxygen atom, a sulfur atom, a selenium atom or -NH-, said each independently as R 1 and R 1 ', a hydrogen atom, a chlorine atom, Fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group and nitro group
  • Preferred are a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a hydroxyl group.
  • Each R 2 ⁇ R 8 is independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L 1 or -NR g R h groups.
  • R g and R h are each independently a hydrogen atom, -L a , -L b , -L c , -L d , -L e , -L f , -L g , -L h or -C (O)
  • R i represents a group represented by R i (R i represents -L a , -L b , -L c , -L d or -L e ), and R 9 independently represents a hydrogen atom, -L a , -L b represents -L c, -L d, -L e , -L f, -L g or -L h.
  • L 1 is L a , L b , L c , L d , L e , L f , L g or L h .
  • L a to L h represent the following groups.
  • the compound (5) can adjust the maximum absorption wavelength by the substituent, but the X is preferably a sulfur atom from the viewpoint that the compound easily becomes a compound having a maximum absorption wavelength of 751 to 950 nm.
  • squarylium-based dyes do not have an absorption maximum wavelength at a wavelength of 751 to 950 nm, but a squarylium-based dye having an absorption maximum at a wavelength of 751 to 950 nm is selected, or an absorption maximum at a wavelength of 751 to 950 nm is selected.
  • a squarylium dye having no wavelength and a squarylium dye having an absorption maximum wavelength of 751 to 950 nm are used in combination, or a squarylium dye having no absorption maximum wavelength of 751 to 950 nm and an absorption maximum wavelength of 751 to 950 nm are used.
  • a dye other than a squarylium-based dye having the above-described formula (1) it can be used as a near-infrared absorbing agent to obtain the effects of the present invention.
  • the diimonium-based dye is not particularly limited as long as it does not impair the effects of the present invention.
  • a diimonium-based dye represented by the following formula (7-1) or (7-2) Patent No. 4168031 And diimmonium dyes described in JP-A No. 425,296, JP-A-63-165392, WO 2004/048480 and the like, and may be synthesized by a generally known method.
  • the Rdi1 ⁇ Rdi12 each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -SR i group , -SO 2 R i group, or an -OSO 2 R i group or a group represented by L a ⁇ L h
  • R g and R h are each independently a hydrogen atom, -C (O) R i groups or the following L i represents any of L a to L e , R i represents one of the following L a to L e , (L a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L c ) an alicyclic hydrocarbon group having 3 to 14
  • the substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms. At least one selected from the group consisting of a hydrogen group and a heterocyclic group having 3 to 14 carbon atoms, Adjacent Rdi1 and Rdi2, Rdi3 and Rdi4, Rdi5 and Rdi6, and Rdi7 and Rdi8 may form a ring that may have a substituent L, X represents an anion necessary for neutralizing the charge,
  • Rdi1 to Rdi8 are preferably selected from a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group and a benzyl group. And more preferably a group selected from an isopropyl group, a sec-butyl group, a tert-butyl group and a benzyl group.
  • Rdi9 to Rdi12 are preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group.
  • X - is an anion necessary for neutralizing the electric charge.
  • the anion is divalent as in the formula (7-2), it is one ion, and as in the formula (7-1), the anion is one.
  • the two anions X - may be the same or different, but are preferably the same from the viewpoint of synthesis.
  • X - or X 2- is not particularly limited as long as it is such an anion.
  • compounds represented by the formulas (4), (5), (7-1) and (7-2) have a high visible light transmittance and a wavelength of 700 to 750 nm. It is preferable from the viewpoint of absorption characteristics in the range and shielding performance in the wavelength range of 800 to 1100 nm.
  • the near-infrared reflective film that can be used in the present invention is a film having the ability to reflect near-infrared light.
  • a near-infrared reflective film includes an aluminum vapor-deposited film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as a main component and a small amount of tin oxide are dispersed, or a high refractive index material layer and a low refractive index layer.
  • a dielectric multi-layer film in which a dielectric material layer is alternately laminated. With such a near-infrared reflecting film, near-infrared rays can be cut more effectively.
  • the near-infrared reflective film may be provided on one side of the substrate or on both sides.
  • the manufacturing cost and ease of manufacture are excellent, and when provided on both sides, it is possible to obtain an optical filter having high strength and hardly causing warpage.
  • the near-infrared reflective films low scattering, good adhesion, high transmission characteristics of visible light in the wavelength range of 430 to 580 nm, and high shielding performance of light in the wavelength range of 800 to 1100 nm are provided. For this reason, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated is preferable.
  • the near-infrared reflecting film is a dielectric multilayer film, the image quality of the obtained solid-state imaging device can be improved.
  • a material constituting the high refractive index material layer a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of usually 1.7 to 2.5 is selected.
  • Such materials include, for example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as a main component, and titanium oxide, tin oxide, or the like. And / or cerium oxide containing a small amount (for example, 0 to 10% based on the main component).
  • a material having a refractive index of less than 1.7 can be used, and a material having a refractive index range of usually 1.2 or more and less than 1.7 is selected.
  • a material having a refractive index range of usually 1.2 or more and less than 1.7 examples include resin, silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride, and a mixture thereof, and the above material is depleted so as to have a refractive index of less than 1.7. And the like.
  • the method of laminating the high-refractive-index material layer and the low-refractive-index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed.
  • a high-refractive-index material layer and a low-refractive-index layer are directly formed on the substrate by a CVD method, a vacuum evaporation method, a sputtering method, an ion-assisted evaporation method, an ion plating method, a radical-assisted sputtering method, or an ion beam sputtering method.
  • a dielectric multilayer film in which the dielectric material layers are alternately stacked can be formed.
  • the ion-assisted vapor deposition method, the ion plating method, and the radical-assisted sputtering method are preferable because a high-quality film in which the optical film thickness of the obtained multilayer film hardly changes according to the environment can be obtained.
  • the ion-assisted vapor deposition method is more preferable because the obtained optical filter has less warpage.
  • the thickness of each layer of the high refractive index material layer and the low refractive index material layer is 0.1 ⁇ except for the two layers adjacent to the base material and the outermost layer.
  • An optical thickness of 0.50.5 ⁇ is preferred.
  • the product (n ⁇ d) of the refractive index (n) and the film thickness (d) is calculated by ⁇ / 4, the optical film thickness, the high refractive index material layer, and the low refractive index.
  • each layer of the material layer becomes almost the same value, and there is a tendency that the shielding / transmission of a specific wavelength can be easily controlled from the relation of the optical characteristics of reflection and refraction.
  • the two layers adjacent to the substrate preferably have a physical thickness of 5 nm to 45 nm or less.
  • the outermost layer preferably has an optical thickness of 0.05 to 0.2 ⁇ . If the two layers and the outermost layer adjacent to the base material have a thickness in the above range, the reflectance of visible light can be reduced, and ghost can be reduced by matching the requirement (Z).
  • the total number of high refractive index material layers and low refractive index material layers in the dielectric multilayer film is desirably 5 to 60, and preferably 10 to 50.
  • a dielectric multilayer film may be formed on both surfaces of the base material, or the dielectric multilayer film of the base material may be removed.
  • a method of irradiating an electromagnetic wave such as an ultraviolet ray on the surface on which is formed can be adopted. When irradiating an electromagnetic wave, it may be applied during the formation of the dielectric multilayer film or may be separately applied after the formation.
  • the dielectric multilayer film is preferably designed to satisfy the following condition (e).
  • the layers other than the two layers and the outermost layer adjacent to the substrate do not include a layer having an optical film thickness of 205 nm or less (hereinafter also referred to as “layer (e1)”).
  • the optical thickness represents a physical quantity of physical thickness ⁇ refractive index
  • the refractive index is a refractive index at a wavelength of 550 nm.
  • a dielectric multilayer film in which layers having different refractive indices are stacked is designed so as to block a wavelength near the optical thickness ⁇ 4. Since the layers other than the two layers adjacent to the base material and the outermost layer adjacent to the emission medium are layers that contribute to the formation of the shielding layer that reduces the transmittance, the layer ( Preferably, e1) is not included.
  • the dielectric multilayer films formed on both surfaces of the base material satisfy the condition (e).
  • the optical thickness of the layer (e1) under the condition (e) is preferably 210 nm or less, more preferably 215 nm or less.
  • the dielectric multilayer film is preferably designed to satisfy the following condition (f).
  • the standard deviation of the optical film thickness of the layers other than the two layers and the outermost layer adjacent to the substrate is 6 to 20 nm.
  • the average value of the transmittance when measured from the direction perpendicular to the surface of the optical filter in the wavelength range of 800 to 1000 nm in the requirement (B) Is 10% or less "and the characteristic of the requirement (Z1) can be easily achieved.
  • the optical filter has a dielectric multilayer film on both surfaces of the substrate, it is more preferable that both of the dielectric multilayer films on both surfaces satisfy the condition (f).
  • the standard deviation of the optical film thickness under the condition (f) is preferably from 6 to 18 nm, more preferably from 6 to 16 nm.
  • Near-ultraviolet absorbers that can be used in the present invention include azomethine compounds, indole compounds, benzotriazole compounds, triazine compounds, melophthalocyanine compounds, oxazole compounds, naphthylimide compounds, oxadiazole compounds, It is preferably at least one selected from the group consisting of oxazine-based compounds, oxazolidine-based compounds, and anthracene-based compounds, and preferably has at least one absorption maximum at a wavelength of 300 to 420 nm.
  • a near-ultraviolet absorber in addition to the near-infrared absorber, it is possible to obtain an optical filter having a small incident angle dependence even in the near ultraviolet wavelength region.
  • (A) Azomethine-based compound is not particularly limited, but can be represented by, for example, the following formula (8).
  • R a1 to R a5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms. Represents an alkoxycarbonyl group.
  • Indole Compound is not particularly limited, but can be represented by, for example, the following formula (9).
  • R b1 to R b5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a cyano group, a phenyl group, an aralkyl group, an alkyl group having 1 to 9 carbon atoms, Or an alkoxycarbonyl group having 1 to 9 carbon atoms.
  • (C) Benzotriazole-based compound The benzotriazole-based compound is not particularly limited, but can be represented by, for example, the following formula (10).
  • R c1 to R c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an aralkyl group, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or a carbon atom as a substituent. Represents an alkyl group having 1 to 9 carbon atoms having an alkoxycarbonyl group having 1 to 9 carbon atoms.
  • Triazine-based compound is not particularly limited, but can be represented by, for example, the following formula (11), (12) or (13).
  • R d1 independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, Represents an aryl group having 6 to 18 carbon atoms, an alkylaryl group or an arylalkyl group having 7 to 18 carbon atoms.
  • alkyl group, cycloalkyl group, alkenyl group, aryl group, alkylaryl group and arylalkyl group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, It may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. Also, the replacement and interruption may be combined.
  • R d2 to R d9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, Represents an aryl group having 6 to 18 atoms, an alkylaryl group or an arylalkyl group having 7 to 18 carbon atoms.
  • UV 381A "UV 381B”, “UV 382A”, “UV 386A” manufactured by BASF
  • TINUVIN 326 "TINUVIN 460”
  • TINUVIN 479 "BONASORB UA3911” manufactured by Orient Chemical Co., Ltd. Or the like may be used.
  • the resin layer further contains additives such as an antioxidant, a dispersant, a flame retardant, a plasticizer, a heat stabilizer, a light stabilizer, and a metal complex compound as long as the effects of the present invention are not impaired. You may.
  • additives such as an antioxidant, a dispersant, a flame retardant, a plasticizer, a heat stabilizer, a light stabilizer, and a metal complex compound as long as the effects of the present invention are not impaired. You may.
  • a resin substrate is manufactured by the above-described cast molding, the production of the resin substrate can be facilitated by adding a leveling agent or an antifoaming agent.
  • These other components may be used alone or in combination of two or more.
  • antioxidants examples include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, and Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)- 1,3,5-triazyl-2,4,6 (1H, 3H, 5H) -trione and the like.
  • these additives may be mixed with a resin or the like when manufacturing a resin base material, or may be added when manufacturing a resin.
  • the addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass, per 100 parts by mass of the resin. Department.
  • a functional film in the optical filter of the present invention, can be appropriately provided as long as the effects of the present invention are not impaired.
  • the optical filter of the present invention may include one layer of a functional film, or may include two or more layers.
  • the optical filter of the present invention may include two or more similar layers or two or more different layers.
  • the method of laminating the functional film is not particularly limited, but a method of melt-molding or cast-molding a coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent on a substrate or a near-infrared reflective film. And the like.
  • the coating agent can also be produced by applying the curable composition onto a substrate or a near-infrared reflective film using a bar coater or the like, and then curing the composition by ultraviolet irradiation and / or heating. It is preferable to have a functional film of the curable composition from the viewpoint of improving the breaking strength of the obtained base material, making it hard to be scratched, and reducing warpage.
  • the curable composition examples include an ultraviolet (UV) / electron beam (EB) curable resin and a thermosetting resin, and specific examples thereof include vinyl compounds, urethane-based, urethane acrylate-based, and acrylate-based resins. , Epoxy and epoxy acrylate resins.
  • the curable composition containing these coating agents include vinyl, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate curable compositions.
  • Examples of the components contained in the urethane-based or urethane acrylate-based curable composition include tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, Oligourethane (meth) acrylates having two or more (meth) acryloyl groups in the molecule can be mentioned. These components may be used alone or in combination of two or more. Further, an oligomer or polymer such as polyurethane (meth) acrylate or an oligomer or polymer such as polyester (meth) acrylate may be blended.
  • vinyl compounds examples include vinyl acetate, vinyl propionate, divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and the like, but are not limited to these examples. Absent. These components may be used alone or in combination of two or more.
  • the components contained in the epoxy or epoxy acrylate curable composition are not particularly limited, but include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and oligo having two or more (meth) acryloyl groups in the molecule.
  • Epoxy (meth) acrylates and the like can be mentioned. These components may be used alone or in combination of two or more. Further, an oligomer or polymer such as polyepoxy (meth) acrylate may be blended.
  • curable composition Commercial products of the curable composition include “LCH” and "LAS” manufactured by Toyo Ink Mfg. Co., Ltd .; “Beamset” manufactured by Arakawa Chemical Industry Co., Ltd .; “EBECRYL” manufactured by Daicel Scitech Co., Ltd .; UVACURE “;” Opstar “and” Desolite Z “manufactured by JSR Corporation.
  • the curable composition may contain a polymerization initiator.
  • a polymerization initiator a known photopolymerization initiator or thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination.
  • One type of the polymerization initiator may be used alone, or two or more types may be used in combination.
  • the mixing ratio of the polymerization initiator in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, when the total amount of the curable composition is 100% by mass. More preferably, it is 1 to 5% by mass.
  • the curable composition has excellent curing properties and handleability, and an antireflection film having a desired hardness, a functional film such as a hard coat film or an antistatic film can be obtained. it can.
  • an organic solvent may be added as a solvent to the curable composition, and a known organic solvent can be used.
  • the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, ⁇ -butyrolactone, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, N- Amides such as methylpyrrolidone can be mentioned. These solvents may be used alone or in combination
  • the thickness of the functional film is preferably 0.1 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 10 ⁇ m, and particularly preferably 0.7 ⁇ m to 5 ⁇ m.
  • the surface of the substrate or the functional film is subjected to corona treatment, plasma treatment, or the like. Surface treatment.
  • the above material is used as a material for a low-pass filter or a wave plate for reducing moire and false colors in an imaging device such as a digital still camera, a digital video camera, a surveillance camera, a vehicle camera, a web camera, and an unmanned aerial vehicle. In some cases.
  • the optical filter of the present invention has a wide viewing angle, high red sensitivity, and improved ghost characteristics. Therefore, it is useful for correcting the visibility of a solid-state imaging device such as a CCD or a CMOS of a camera module.
  • a solid-state imaging device such as a CCD or a CMOS of a camera module.
  • digital still cameras mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, car cameras, televisions, car navigation systems, personal digital assistants, personal computers, video game machines, portable game machines, fingerprint authentication systems, distance measurement sensors , Iris authentication system, face authentication system, distance measurement camera, digital music player, etc.
  • the solid-state imaging device of the present invention includes the optical filter of the present invention.
  • the solid-state imaging device is an image sensor including a solid-state imaging device such as a CCD or a CMOS.
  • a photoelectric conversion device such as a silicon photodiode or an organic semiconductor that converts light of a specific wavelength into electric charges is used.
  • the pixels constituting the solid-state imaging device include pixels that are sensitive to at least near-infrared light having a wavelength of 700 to 750 nm.
  • a polarizer such as a retardation film or a wire grid may be provided on the entire surface of the solid-state imaging device.
  • a polarizing element When a polarizing element is provided, phase information of an image is obtained, and three-dimensional measurement of an image excluding reflected light of an object and a shape of the object is more preferable.
  • ⁇ Wire grid> As a wire grid provided in the solid-state imaging device of the present invention, aluminum, nickel, silver, platinum, tungsten, an alloy containing any of these metals, or the like can be used, and JP-A-2017-003878 and JP-A-2017-005111 can be used. It is preferable to provide a polarizer described in Japanese Patent Application Laid-Open No. H10-26095.
  • the camera module of the present invention includes the optical filter of the present invention.
  • the camera module is a device that includes an image sensor, a focus adjustment mechanism, a phase detection mechanism, a distance measurement mechanism, and the like, and outputs images and distance information as electric signals.
  • FIG. 9 shows a schematic sectional view 9 of the camera module 400.
  • the optical filter 1 of the present invention there is no large difference between the transmission wavelength of the light incident from the vertical direction and the light incident from 30 ° with respect to the vertical direction of the filter 1 (the dependence of the absorption (transmission) wavelength on the incident angle. Therefore, even if the filter 1 is provided between the lens 301 and the sensor 302, the color change of the entire sensor is small. For this reason, when the optical filter 1 of the present invention is used for a camera module, it is possible to use a lens corresponding to a higher angle of incidence, and the height of the camera module can be reduced.
  • the ghost that causes image quality deterioration is that light reflected on the front or back surface of the optical component between the subject and the imaging device is reflected on other components and the like, and is incident on the imaging device at a position different from the original imaging position. This is an image defect caused by light.
  • the conventional optical filter has a large reflection particularly in the vicinity of a wavelength of 680 to 720 nm, which causes ghosting.
  • the optical filter 1 of the present invention has a reflectance of 10% or less on both sides at a wavelength of 700 nm and a value of (Za) on both sides of 730 nm or more, the reflection at a wavelength of 700 to (Za) nm is obtained.
  • the rate will be lower than 50%. Therefore, the reflection on the surface of the filter near the wavelength of 680 to 720 nm is small on both surfaces. Therefore, the occurrence of ghosts 304 and ghosts 305 that are erroneously incident on the sensor is small, and good image quality can be obtained.
  • FIG. 11 is an example of a ghost.
  • Parts and % mean “parts by mass” and “% by mass” unless otherwise specified.
  • the methods for measuring and evaluating various physical properties in the examples are as follows.
  • the transmittance was measured using a spectrophotometer “U-4100” manufactured by Hitachi High-Technologies Corporation.
  • U-4100 spectrophotometer
  • an unpolarized light beam transmitted perpendicular to the optical filter as shown in FIG. 6 was measured.
  • the transmittance when measured from an angle of 30 ° with respect to the direction perpendicular to the plane of the optical filter is P-polarized light transmitted at an angle of 30 ° with respect to the direction perpendicular to the filter, as shown in FIG. S-polarized light was measured and calculated from their average.
  • the average value of the transmittance at wavelengths A to Bnm is obtained by measuring the transmittance at each wavelength of 1 nm or more from Anm to Bnm and dividing the total transmittance by the number of measured transmittances (wavelength range, B -A + 1).
  • spectral reflectance was measured using a spectrophotometer “U-4100” manufactured by Hitachi High-Technologies Corporation, as shown in FIG. 8, where the unpolarized light beam at 5 ° incidence was incident from one surface of the optical filter. And the intensity of light reflected from the back surface, and the intensity of light reflected from the front and back surfaces incident from the other surface were measured by absolute reflectance measurement.
  • the average value of the reflectance at wavelengths A to Bnm is obtained by measuring the reflectance at each wavelength of 1 nm or more from Anm to Bnm and dividing the total reflectance by the number of the measured reflectances (wavelength range, B -A + 1).
  • ⁇ Glass transition temperature> Using a differential scanning calorimeter “DSC6200” manufactured by SII Nanotechnology Co., Ltd., the temperature was measured at a rate of 20 ° C./min under a nitrogen stream.
  • G 0 represents the sensitivity of the green pixel when sunlight enters from the vertical direction of the optical filter, and more specifically, the transmittance T 0 ( ⁇ ) for each wavelength of the optical filter based on Expression (i). And the intensity I ( ⁇ ) of each wavelength of sunlight, the sensitivity G ( ⁇ ) of each wavelength of the green sensor pixel, and the transmittance DT ( ⁇ ) of each wavelength of a two-wavelength region transmission filter that transmits green and near infrared rays. The product was calculated as the sum of the calculated values for each 1 nm.
  • IR 0 represents the sensitivity of a near-infrared pixel when sunlight enters from the vertical direction of the optical filter.
  • the transmittance T 0 ( ⁇ ) of the optical filter for each wavelength is calculated based on Expression (ii). ), The intensity I ( ⁇ ) of the solar light by wavelength, the sensitivity IR ( ⁇ ) of the near-infrared sensor pixel by wavelength, and the transmittance DT ( ⁇ ) by wavelength of a two-wavelength region transmission filter that transmits green and near infrared rays. ) was calculated as the sum of the calculated values for each 1 nm of the product of
  • G 30 represents the sensitivity of the green pixel when the sunlight is incident at an angle of 30 ° from the vertical direction of the optical filter, specifically, on the basis of the formula (iii), each wavelength transmittance of the optical filter T 0 ( ⁇ ), intensity I ( ⁇ ) of each wavelength of sunlight, sensitivity G ( ⁇ ) of each wavelength of a green sensor pixel, and transmittance of each wavelength of a two-wavelength region transmission filter that transmits green and near infrared rays. It was calculated as the sum of the calculated values for each 1 nm of the product with DT ( ⁇ ).
  • IR 30 represents the sensitivity of a near-infrared pixel when sunlight is incident at an angle of 30 ° from the vertical direction of the optical filter. Specifically, based on Equation (iv), transmission of the optical filter by wavelength is performed. Rate T 0 ( ⁇ ), intensity I ( ⁇ ) of wavelength of sunlight, wavelength sensitivity IR ( ⁇ ) of near-infrared sensor pixel, and wavelength of dual-wavelength region transmission filter that transmits green and near infrared rays. It was calculated as the sum of the calculated values for each 1 nm of the product of the transmittance DT ( ⁇ ).
  • G N represents the amount of noise at a wavelength of 800 to 1200 nm in the green pixel, and specifically, based on Equation (v), the transmittance T 0 ( ⁇ ) of the optical filter and the intensity of the solar light by wavelength. Calculation of the product of I ( ⁇ ), the sensitivity IR ( ⁇ ) of each wavelength of the near-infrared sensor pixel and the transmittance DT ( ⁇ ) of each wavelength of the two-wavelength region transmission filter that transmits green light and near-infrared rays for each 1 nm. It was calculated as the sum of the values.
  • the intensity I ( ⁇ ) of the wavelength of the sunlight is obtained by comparing the irradiation data of Gifu at a certain date and time disclosed by the New Energy and Industrial Technology Development Organization of Japan with a maximum intensity of 1 The value normalized so as to be 0.0 was used.
  • the sensitivity shown in FIG. 4 was used for the sensitivity of each wavelength of the green and near-infrared sensor pixels based on the description in JP-A-2017-216678.
  • a two-wavelength range transmission filter that transmits green light and near-infrared light is formed on a surface of a glass substrate (D263, manufactured by SCHOTT, 0.1 mm thick) using an ion-assisted vacuum deposition apparatus at a deposition temperature of 120 ° C. 2 (0) [dielectric material in which a silica (SiO 2 : refractive index of 1.46 at 550 nm) layer and a titania (TiO 2 : refractive index of 2.48 at 550 nm) layer are alternately laminated] Obtained by forming a multilayer film.
  • FIG. 5 shows the wavelength-dependent transmittance DT ( ⁇ ) of the two-wavelength region transmission filter.
  • the optical filter satisfying both of the following requirements (Xa) and (Xb) has a small change in sensitivity even at a high incident angle in a green pixel, and has a wavelength of 800 to 1200 nm at which human visibility is low. And the green sensitivity was ⁇ .
  • Those that were not optical filters that satisfied both requirements (Xa) and (Xb) were rated green sensitivity x. Requirement (Xa) 0.8 ⁇ G 30 / G 0 ⁇ 1.2 Requirement (Xb) G N / G 0 ⁇ 0.05
  • an optical filter that satisfies both of the following requirements (Y) and (Z) has a high near-infrared sensitivity relative to a green pixel and a small amount of change in near-infrared sensitivity even at a wide viewing angle. did. If the requirement (Y) is not satisfied, it is necessary to increase the sensor sensitivity of IR 0 by about 5 times or more compared to G 0, and it is expected that the noise amount also increases by 5 times or more. When the requirement (Z) is not satisfied, the sensitivity of the IR 30 is 0.2 times higher than that of the IR 0 .
  • Requirement (Y) IR 0 / G 0 is 0.21 or more Requirement (Z) 0.8 ⁇ IR 30 / IR 0 ⁇ 1.2
  • ⁇ Ghost evaluation> An imaging device including the obtained optical filter was constructed between a lens and a sensor used in an imaging device (“KBCR-M04VG” manufactured by Shikino High-Tech Co., Ltd.). In an environment where surrounding stray light is blocked, if the image is divided horizontally into five rows and left to right with 1 to 5 rows, and vertically divided into 5 rows from top to bottom with 1 to 5 columns, halogen The image was taken so that the light source ("ALA-100" manufactured by Asahi Spectroscopy Co., Ltd.) was positioned at 2 rows and 4 columns. At that time, in the ghost generated in the area of 1 row-5 column, the area where the red sensitivity was 80 or more was defined as the ghost area, and the area was evaluated. The ghost performance ⁇ was 20% or less of the region of 1 row-5 column, and the ghost performance x was more than 20%.
  • ALA-100 manufactured by Asahi Spectroscopy Co., Ltd.
  • a compound (14) represented by the following formula (14) (absorption maximum wavelength: 887 nm, 100 parts by mass of a norbornene resin “ARTON” manufactured by JSR Corporation (refractive index: 1.52, glass transition temperature: 160 ° C.), 887 nm; Absolute value of difference between Aa) and (Ab): 94 nm, absorbance ⁇ 700 / absorbance ⁇ max : 0.08, absorbance ⁇ 751 / absorbance ⁇ max : 0.31) 0.078 parts by mass, and phenolic antioxidant (ADEKA CORPORATION, “ADK STAB AO-20”) was added in an amount of 0.05 part by mass, and methylene chloride was further added and dissolved to obtain a solution having a solid content of 30% by mass.
  • ADK STAB AO-20 phenolic antioxidant
  • the resulting solution was cast on a smooth glass plate, dried at 50 ° C. for 8 hours, and further dried under reduced pressure at 100 ° C. for 1 hour and then peeled off.
  • a substrate having a thickness of 0.1 mm, a side of 60 mm, and an in-plane retardation Ro of 5 nm was obtained.
  • “(950 ⁇ shortest absorption maximum wavelength) ⁇ dye concentration ⁇ dye medium thickness” of the obtained base material was 1.3, which satisfied the condition (c).
  • near-infrared reflective films composed of a dielectric multilayer film were formed on both surfaces of the obtained base material at a deposition temperature of 120 ° C. by design (1) and design (2) [silica (SiO 2 ), respectively. : 550 nm refractive index 1.46) layer and titania (TiO 2 : 550 nm refractive index 2.48) layer are alternately laminated to obtain an optical filter having a thickness of 0.107 mm. .
  • Table 2 shows the designs (1) and (2). The reflectance at a wavelength of 700 nm was 10% or less on both surfaces.
  • Table 1 and FIG. 12 show the results of the requirements (A) to (E) and (Za) obtained by measuring the transmittance and the reflectance of the obtained optical filter.
  • the sensitivity of this optical filter was evaluated. As a result, the sensitivity was green ( ⁇ ) and near infrared ( ⁇ ⁇ ). As a result of ghost evaluation, the ghost performance was ⁇ .
  • the obtained optical filter was suitable for a solid-state imaging device having sensitivity to near infrared rays.
  • Example 2 Compound (15) represented by the following formula (15) (absorption maximum wavelength: 898 nm, absolute value of the difference between (Aa) and (Ab): 110 nm, absorbance ⁇ 700 / absorbance ⁇ ) max : 0.05, absorbance ⁇ 751 / absorbance ⁇ max : 0.1)
  • a substrate was obtained in the same procedure except that the amount was changed to 0.05 part by mass. “(950 ⁇ shortest absorption maximum wavelength) ⁇ dye concentration ⁇ dye medium thickness” of the obtained base material was 0.74, which satisfied the condition (c).
  • a near-infrared reflective film composed of a dielectric multilayer film was designed on both sides of the obtained base material at a deposition temperature of 120 ° C.
  • (2) [Silica (SiO 2 : refractive index of 550 nm 1. 46) layer and a titania (TiO 2: and the 550nm refractive index 2.48) layer is formed by those obtained by laminating alternately, to obtain an optical filter having a thickness of 0.107 mm.
  • Table 2 shows the design (2).
  • Table 1 shows the results of the requirements (A) to (E) and (Za) obtained by measuring the transmittance and the reflectance of the obtained optical filter.
  • the reflectance at a wavelength of 700 nm was 10% or less on both surfaces.
  • the obtained optical filter was suitable for a solid-state imaging device having sensitivity to near infrared rays.
  • Example 3 Compound (14) in Example 1 was converted to compound (16) represented by the following formula (16) (absorption maximum wavelength: 897 nm, absolute value of difference between (Aa) and (Ab): 134 nm, absorbance ⁇ 700 / absorbance ⁇ max : 0.1, absorbance ⁇ 751 / absorbance ⁇ max : 0.2) A substrate was obtained in the same procedure except that the amount was changed to 0.064 parts by mass. “(950-shortest absorption maximum wavelength) ⁇ dye concentration ⁇ dye medium thickness” of the obtained base material was 0.32, which satisfied the condition (c).
  • a near-infrared reflective film composed of a dielectric multilayer film was designed on both surfaces of the obtained substrate at an evaporation temperature of 120 ° C. using an ion-assisted vacuum evaporation apparatus (3) [Silica (SiO 2 : refractive index of 550 nm 1. 46) and a layer of titania (TiO 2 : 550 nm, refractive index: 2.48) laminated alternately] to obtain an optical filter having a thickness of 0.104 mm.
  • Table 2 shows the design (3).
  • Table 1 shows the results of the requirements (A) to (E) and (Za) obtained by measuring the transmittance and the reflectance of the obtained optical filter.
  • the reflectance at a wavelength of 700 nm was 10% or less on both surfaces.
  • the obtained optical filter was suitable for a solid-state imaging device having sensitivity to near infrared rays.
  • Example 4 Compound (14) in Example 1 was converted to compound (17) represented by the following formula (17) (absorption maximum wavelength: 844 nm, absolute value of difference between (Aa) and (Ab): 84 nm, absorbance ⁇ 700 / absorbance ⁇ max : 0.08, absorbance ⁇ 751 / absorbance ⁇ max : 0.26) A substrate was obtained in the same procedure except that the amount was changed to 0.05 parts by mass. “(950 ⁇ Shortest absorption maximum wavelength) ⁇ dye concentration ⁇ dye medium thickness” of the obtained base material was 0.54, which satisfied the condition (c).
  • a near-infrared reflective film composed of a dielectric multilayer film was designed on both surfaces of the obtained substrate at an evaporation temperature of 120 ° C. using an ion-assisted vacuum evaporation apparatus (3) [Silica (SiO 2 : refractive index of 550 nm 1. 46) and a layer of titania (TiO 2 : 550 nm, refractive index: 2.48) laminated alternately] to obtain an optical filter having a thickness of 0.104 mm.
  • Table 2 shows the design (3).
  • Table 1 shows the results of the requirements (A) to (E) and (Za) obtained by measuring the transmittance and the reflectance of the obtained optical filter.
  • the reflectance at a wavelength of 700 nm was 10% or less on both surfaces.
  • the obtained optical filter was suitable for a solid-state imaging device having sensitivity to near infrared rays.
  • Example 5 A substrate was obtained in the same procedure as in Example 1, except that the amount of the compound (14) was changed to 0.07 parts by mass. “(950 ⁇ shortest absorption maximum wavelength) ⁇ dye concentration ⁇ dye medium thickness” of the obtained base material was 1.1, which satisfied the condition (c).
  • near-infrared reflective films composed of a dielectric multilayer film were designed (4) and (5) on both surfaces of the obtained substrate at an evaporation temperature of 120 ° C. [silica (SiO 2 : A 550 nm refractive index 1.46) layer and a titania (TiO 2 : 550 nm refractive index 2.48) layer laminated alternately] to obtain an optical filter having a thickness of 0.104 mm.
  • Table 2 shows the designs (4) and (5).
  • the obtained optical filter was suitable for a solid-state imaging device having sensitivity to near infrared rays.
  • Example 6 The following resin composition (1) is applied to a glass plate (D263, manufactured by SCHOTT) having a thickness of 0.1 mm by spin coating, and then heated at 80 ° C. for 2 minutes on a hot plate to cure by volatilizing and removing the solvent. A layer was formed. At this time, the application conditions of the spin coater were adjusted so that the thickness of the cured layer was about 0.8 ⁇ m.
  • Resin composition (1) 30 parts of isocyanuric acid ethylene oxide-modified triacrylate (trade name: ARONIX M-315, manufactured by Toa Gosei Chemical Co., Ltd.), 20 parts of 1,9-nonanediol diacrylate, 20 parts of methacrylic acid, 30 parts of glycidyl methacrylate, 5 parts of 3-glycidoxypropyltrimethoxysilane, 5 parts of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemical Co., Ltd.) and the main agent of San-Aid SI-110 (Sanshin A solution obtained by mixing 1 part of a chemical industry (manufactured by Chemical Industry Co., Ltd.), dissolving in propylene glycol monomethyl ether acetate so as to have a solid content concentration of 50% by mass, and filtering through a Millipore filter having a pore size of 0.2 ⁇ m.
  • near-infrared reflective films composed of a dielectric multilayer film were formed on both surfaces of the obtained base material at a deposition temperature of 120 ° C. by designing (4) and designing (5) [silica (SiO 2 ), respectively. : 550 nm refractive index 1.46) layer and titania (TiO 2 : 550 nm refractive index 2.48) layer alternately laminated] to obtain an optical filter having a thickness of 0.104 mm. .
  • Table 2 shows the designs (4) and (5).
  • the obtained optical filter was suitable for a solid-state imaging device having sensitivity to near infrared rays.
  • Near-infrared reflective films composed of a dielectric multilayer film were formed on both surfaces of the obtained base material at a deposition temperature of 120 ° C. using an ion-assisted vacuum vapor deposition device, respectively, by design (7) and design (6) [silica (SiO 2 : 550 nm refractive index 1.46) layer and titania (TiO 2 : 550 nm refractive index 2.48) layer alternately laminated] to obtain an optical filter having a thickness of 0.106 mm. .
  • Table 2 shows the designs (6) and (7).
  • Table 1 and FIG. 14 show the measurement results of the transmittance and the reflectance of the obtained optical filter and the results of the requirements (A) to (E) and (Za).
  • the reflectance at a wavelength of 700 nm was 10% or less on both surfaces.
  • the resulting solution was cooled to 5 ° C. using an ice water bath. While maintaining the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 0.50 g (0.005 mol) of triethylamine as an imidization catalyst were added all at once to the solution. did. After the addition was completed, the temperature was raised to 180 ° C. and refluxed for 6 hours while distilling off the distillate as needed.
  • the mixture was air-cooled until the internal temperature reached 100 ° C., diluted with 143.6 g of N, N-dimethylacetamide, and cooled with stirring to obtain a polyimide resin solution 264 having a solid content concentration of 20% by mass. .16 g were obtained.
  • a part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide resin.
  • the filtered polyimide resin was washed with methanol, it was dried in a vacuum drier at 100 ° C. for 24 hours to obtain a white powdery polyimide resin.
  • the glass transition temperature of the obtained polyimide resin was 310 ° C.
  • a diimmonium-based absorbent (absorption maximum wavelength: 1094 nm; absolute value of difference between (Aa) and (Ab): 124 nm) 0.0005 quality
  • N, N-dimethylacetamide was added and dissolved to obtain a solution having a solid content of 30% by mass.
  • the obtained solution is cast-formed on a smooth glass plate, dried at 50 ° C. for 8 hours, further dried at 140 ° C. under reduced pressure for 1 hour, and peeled off to obtain a base material having a thickness of 0.05 mm and a side of 60 mm.
  • “(950 ⁇ shortest absorption maximum wavelength) ⁇ dye concentration ⁇ dye medium thickness” of the obtained base material was 0.45, which satisfied the condition (c).
  • An acrylate-based ultraviolet-curable hard coat agent (“Desolite Z-7524" manufactured by JSR Corporation) containing 2 parts by mass of a polymerization initiator was diluted with methyl ethyl ketone on both surfaces of the obtained base material to give a solid concentration of 45.
  • the solution having the mass% was applied by a coater bar (automatic film applicator manufactured by Yasuda Seiki Seisakusho, model number 542-AB). After drying at 80 ° C.
  • UV curing was performed using a UV conveyor ultraviolet curing device “US2-X040560 Hz” manufactured by Eye Graphics Co., under a nitrogen atmosphere, a metal halide lamp illuminance of 270 mW / cm 2 , and an accumulated light amount of 150 mJ / cm 2.
  • a laminate having a thickness of 0.052 mm and having a hard coat layer having a thickness of 1 ⁇ m on both surfaces of the resin film was obtained.
  • Near-infrared reflective films composed of a dielectric multilayer film were formed on both surfaces of the obtained laminate at an evaporation temperature of 120 ° C. using an ion-assisted vacuum evaporation apparatus, by designing (8) and designing (6) [silica (SiO 2 : 550 nm refractive index 1.46) layer and titania (TiO 2 : 550 nm refractive index 2.48) layer alternately laminated] to obtain an optical filter having a thickness of 0.056 mm. .
  • Table 2 shows the designs (8) and (6).
  • Table 1 shows the measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the requirements (A) to (E) and (Za).
  • the reflectance at a wavelength of 700 nm was 10% or less on both surfaces.
  • thermometer a thermometer, a stirrer, a three-way cock equipped with a nitrogen inlet tube, a Dean-Stark tube, and a cooling tube were attached to the four-necked flask.
  • the obtained solution was reacted at 140 ° C. for 3 hours, and generated water was removed from the Dean-Stark tube as needed.
  • the temperature was gradually raised to 160 ° C., and the reaction was continued at the same temperature for 6 hours.
  • the generated salt was removed with a filter paper, and the filtrate was reprecipitated by throwing it into methanol, and the filtrate (residue) was isolated by filtration.
  • the obtained residue was vacuum-dried at 60 ° C. overnight to obtain a polyether resin.
  • the resulting polyether resin had a refractive index of 1.60 and a glass transition temperature of 285 ° C.
  • a solution having a thickness of 0.1 mm By forming a resin layer of 01 mm, a base material having a side of 60 mm including a glass plate and a resin layer was obtained.
  • the in-plane retardation Ro of the obtained base material was 8 nm.
  • near-infrared reflective films composed of a dielectric multilayer film were designed at a deposition temperature of 120 ° C. using an ion-assisted vacuum deposition apparatus (7) and (6) [Silica (SiO) 2 : a layer in which a 550 nm refractive index 1.46) layer and a titania (TiO 2 : 550 nm refractive index 2.48) layer are alternately laminated] to obtain an optical filter having a thickness of 0.116 mm.
  • Table 2 shows the designs (7) and (6).
  • Table 3 shows the measurement results of the transmittance and the reflectance of the obtained optical filter and the results of the requirements (A) to (E) and (Za).
  • the reflectance at a wavelength of 700 nm was 10% or less on both surfaces.
  • the obtained solution is cast on a smooth glass plate, dried at 50 ° C. for 8 hours, and further dried at 140 ° C. under reduced pressure for 3 hours, and then peeled to obtain a base material having a thickness of 0.1 mm and a side of 60 mm.
  • “(950 ⁇ shortest absorption maximum wavelength) ⁇ dye concentration ⁇ dye medium thickness” of the obtained base material was 1.26, which satisfied the condition (c).
  • Table 1 and FIG. 15 show the measurement results of the transmittance and the reflectance of the obtained optical filter and the results of the requirements (A) to (E) and (Za). Note that the reflectance at a wavelength of 700 nm exceeded 10%.
  • the sensitivity of green was ⁇
  • the sensitivity of near-infrared was ⁇
  • the ghost performance was x.
  • the performance of the obtained optical filter was insufficient for a solid-state imaging device having sensitivity to near infrared rays.
  • the obtained solution is cast-molded on a smooth glass plate, dried at 50 ° C. for 3 hours and further dried at 100 ° C. for 3 hours under reduced pressure and peeled off to obtain a base material having a thickness of 0.1 mm and a side of 60 mm.
  • “(950 ⁇ shortest absorption maximum wavelength) ⁇ dye concentration ⁇ dye medium thickness” of the obtained base material was 1.15, which satisfied the condition (c).
  • near-infrared reflective films composed of a dielectric multilayer film were formed on both surfaces of the obtained base material at a deposition temperature of 120 ° C. by design (2) and design (10) [silica (SiO 2 : A layer in which a 550 nm refractive index of 1.45 and a film thickness of 37 to 194 nm) and a titania (TiO 2 : 550 nm refractive index of 2.45 and a film thickness of 11 to 108 nm) layer are alternately laminated. An optical filter having a thickness of 0.106 mm was obtained.
  • Table 1 shows the measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the requirements (A) to (E) and (Za). Note that the reflectance at a wavelength of 700 nm exceeded 10%.
  • the sensitivity of green was ⁇
  • the sensitivity of near-infrared was ⁇
  • the ghost performance was x.
  • the performance of the obtained optical filter was insufficient for a solid-state imaging device having sensitivity to near infrared rays.
  • the resulting solution is cast on a smooth glass plate, dried at 50 ° C. for 3 hours and further dried at 100 ° C. for 3 hours under reduced pressure, and then peeled off to obtain an optical filter having a thickness of 0.1 mm and a side of 60 mm.
  • an optical filter having a thickness of 0.1 mm and a side of 60 mm.
  • Table 1 shows the measurement results of the transmittance and the reflectance of the obtained optical filter, and the results of the requirements (A) to (E) and (Za).
  • the reflectance at a wavelength of 700 nm was 10% or less on both surfaces.
  • the sensitivity of green was ⁇ and the sensitivity of near infrared was ⁇ .
  • the ghost performance was ⁇ .
  • the performance of the obtained optical filter was insufficient for a solid-state imaging device having sensitivity to near infrared rays.
  • the optical filter of the present invention is useful as a sensitivity correction for a solid-state imaging device having near-infrared sensitivity with a wavelength of 700 to 750 nm, such as a camera module CCD or CMOS.
  • a solid-state imaging device having near-infrared sensitivity with a wavelength of 700 to 750 nm, such as a camera module CCD or CMOS.
  • digital still cameras mobile phone cameras, smartphone cameras, digital video cameras, PC cameras, surveillance cameras, car cameras, televisions, car navigation systems, personal digital assistants, personal computers, video game machines, portable game machines, fingerprint authentication systems , Iris authentication system, face authentication system, distance measurement sensor, distance measurement camera, digital music player, vegetation sensing system, cerebral blood flow sensing system, etc.
  • An example of the optical filter according to the present invention 10 Base material 11: Support 12: Resin layer 13: Other functional film 21: Near infrared reflective film 1 22: Near infrared reflective film 2 201: detector 301: lens 302: sensor 303: band pass filter 304: normality detection unit 305: ghost 306: ghost 400: camera module 401: light source 402: ghost

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PCT/JP2019/035476 2018-09-12 2019-09-10 光学フィルターおよびその用途 WO2020054695A1 (ja)

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WO2022016524A1 (en) * 2020-07-24 2022-01-27 Huawei Technologies Co., Ltd. Infrared cut filter, infrared cut lens and camera module
WO2022064984A1 (ja) * 2020-09-25 2022-03-31 三菱瓦斯化学株式会社 シアニン化合物及び光電変換素子

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