WO2024048510A1 - 光学フィルタ - Google Patents

光学フィルタ Download PDF

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Publication number
WO2024048510A1
WO2024048510A1 PCT/JP2023/030941 JP2023030941W WO2024048510A1 WO 2024048510 A1 WO2024048510 A1 WO 2024048510A1 JP 2023030941 W JP2023030941 W JP 2023030941W WO 2024048510 A1 WO2024048510 A1 WO 2024048510A1
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Prior art keywords
optical filter
transmittance
less
spectral
degrees
Prior art date
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PCT/JP2023/030941
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English (en)
French (fr)
Japanese (ja)
Inventor
雄一朗 折田
和彦 塩野
崇 長田
貴尋 坂上
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2024544239A priority Critical patent/JPWO2024048510A1/ja
Publication of WO2024048510A1 publication Critical patent/WO2024048510A1/ja
Priority to US19/048,086 priority patent/US20250180791A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • 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
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/281—Interference filters designed for the infrared light
    • G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/80—Constructional details of image sensors
    • H10F39/806—Optical elements or arrangements associated with the image sensors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/80—Constructional details of image sensors
    • H10F39/805—Coatings
    • H10F39/8057—Optical shielding

Definitions

  • the present invention relates to an optical filter that transmits visible light and blocks near-infrared light.
  • Imaging devices using solid-state image sensors transmit light in the visible range (hereinafter also referred to as “visible light”) and transmit light in the ultraviolet wavelength range (hereinafter referred to as “ultraviolet light”) in order to reproduce color tones well and obtain clear images.
  • An optical filter is used that blocks light in the near-infrared wavelength region (hereinafter also referred to as “near-infrared light”).
  • optical filters include reflective filters that reflect the light that you want to block by utilizing light interference caused by a dielectric multilayer film in which dielectric thin films with different refractive indexes are alternately laminated on one or both sides of a transparent substrate.
  • Such optical filters have a problem in that the optical thickness of the dielectric multilayer film changes depending on the incident angle of light, so that the spectral transmittance curve and the spectral reflectance curve change depending on the incident angle.
  • interference caused by reflected light from the interfaces of each layer causes a drastic change in the transmittance in the visible light region, so-called ripple, which is more likely to occur as the incident angle of light is larger. This causes a problem in that the amount of light taken in in the visible light range changes at a high incident angle, resulting in a decrease in image reproducibility.
  • Image sensors are sensitive to near-ultraviolet light, so if near-ultraviolet light is not sufficiently blocked, there is a risk that image quality degradation due to unnecessary light called flare or ghosting may occur in the acquired visible light images. be.
  • Patent Document 1 describes an optical filter that has both near-ultraviolet light cutting ability and near-infrared light cutting ability, in which a copper phosphonate film is formed on a glass substrate.
  • Patent Document 2 describes a method for cutting near-ultraviolet light and near-infrared light, which includes an absorption layer containing a near-ultraviolet light-absorbing dye and a near-infrared light-absorbing dye in a transparent resin, and a copper phosphonate film.
  • An optical filter is described that has both of the following.
  • Patent Document 3 describes an optical filter that has both near-ultraviolet light cutting ability and near-infrared light cutting ability, which is equipped with an absorption layer containing a near-ultraviolet light absorption dye and a near-infrared light absorption dye in a transparent resin. ing.
  • the optical filter described in Patent Document 1 has room for improvement in terms of light blocking performance in the near-ultraviolet region, particularly around a wavelength of 400 nm.
  • the optical filter described in Patent Document 2 there is room for improvement in light blocking properties in the near-ultraviolet region, particularly around a wavelength of 400 nm, and the change in transmittance between the near-ultraviolet light-blocking region and the visible light transmission region is gradual. Therefore, there is room for improvement in terms of achieving both light-shielding properties and transparency.
  • the present invention suppresses ripples in the visible light region even at high incident angles, maintains high transparency of visible light, and has excellent shielding properties for near-infrared light and near-ultraviolet light, especially at wavelengths around 400 nm.
  • the purpose of the present invention is to provide an optical filter with excellent ultraviolet light shielding properties.
  • the present invention provides an optical filter having the following configuration.
  • a base material an antireflection layer 1 consisting of a dielectric multilayer film laminated as the outermost layer on one main surface side of the base material, and an antireflection layer 1 laminated as the outermost layer on the other main surface side of the base material.
  • An optical filter comprising an antireflection layer 2 made of a dielectric multilayer film
  • the base material includes near-infrared absorbing glass and a resin film laminated on at least one main surface of the near-infrared absorbing glass
  • the resin film includes a resin, a UV dye having a maximum absorption wavelength in the resin from 350 to 410 nm, and an IR dye having a maximum absorption wavelength in the resin from 700 to 850 nm
  • the optical filter satisfies all of the following spectral characteristics (i-1) to (i-7).
  • the average transmittance T 350-390 (0 deg) AVE is 1% or less in the wavelength range of 350 to 390 nm
  • Spectral transmittance at an incident angle of 0 degrees the transmittance T 400 (0deg) at a wavelength of 400 nm is 3% or less (i-3).
  • Transmittance T 430 (0deg) satisfies the following relationship T 430 (0deg) - T 400 (0deg) ⁇ 78% (i-4)
  • the average transmittance T 430-600 (0 deg) AVE for wavelengths of 430 to 600 nm is 80% or more (i-5)
  • the antireflection layer 1 side is incident Average reflectance R1 430-600 (5deg) AVE for wavelengths of 430 to 600 nm in the spectral reflectance curve at an incident angle of 5 degrees and wavelengths of 430 to 600 nm in the spectral reflectance curve at an incident angle of 50 degrees
  • Average reflectance R1 430-600 (50 deg) The absolute value of the difference between AVE is 4% or less (i-6)
  • ripples in the visible light region are suppressed even at high incident angles, and while maintaining high transparency of visible light, it has excellent shielding properties for near-infrared light and near-ultraviolet light, especially at a wavelength of 400 nm. It is possible to provide an optical filter that has excellent shielding properties for nearby ultraviolet light and an imaging device that includes the optical filter.
  • FIG. 1 is a schematic cross-sectional view of an example of an optical filter according to this embodiment.
  • FIG. 2 is a diagram showing a spectral transmittance curve of phosphate glass.
  • FIG. 3 is a diagram showing a spectral transmittance curve of the optical filter of Example 1-1.
  • FIG. 4 is a diagram showing a spectral reflectance curve (A side) of the optical filter of Example 1-1.
  • FIG. 5 is a diagram showing the spectral reflectance curve (B side) of the optical filter of Example 1-1.
  • FIG. 6 is a diagram showing the spectral transmittance curve of the optical filter of Example 1-7.
  • FIG. 7 is a diagram showing the spectral reflectance curve (A side) of the optical filter of Example 1-7.
  • FIG. 1 is a schematic cross-sectional view of an example of an optical filter according to this embodiment.
  • FIG. 2 is a diagram showing a spectral transmittance curve of phosphate glass.
  • FIG. 3 is a
  • FIG. 8 is a diagram showing the spectral reflectance curve (B side) of the optical filter of Example 1-7.
  • FIG. 9 is a diagram showing the spectral transmittance curve of the optical filter of Example 1-8.
  • FIG. 10 is a diagram showing the spectral reflectance curve (A side) of the optical filter of Example 1-8.
  • FIG. 11 is a diagram showing the spectral reflectance curve (B side) of the optical filter of Example 1-8.
  • IR dyes near-infrared absorbing dyes
  • UV dyes ultraviolet absorbing dyes
  • the compound represented by formula (I) is referred to as compound (I).
  • the dye composed of compound (I) is also referred to as dye (I), and the same applies to other dyes.
  • group represented by formula (I) is also referred to as group (I), and the same applies to groups represented by other formulas.
  • internal transmittance refers to the ratio of measured transmittance to interface reflection, which is expressed by the formula ⁇ actually measured transmittance (incident angle 0 degrees)/(100-reflectance (incident angle 5 degrees)) ⁇ 100. This is the transmittance obtained by subtracting the influence.
  • absorbance is converted from (internal) transmittance using the formula -log10 ((internal) transmittance/100).
  • the transmittance of a base material and the spectrum of the transmittance of a resin film, including the case where a dye is contained in the resin are all referred to as "internal transmittance" even when it is described as "transmittance".
  • the transmittance of an optical filter having a dielectric multilayer film is an actually measured transmittance.
  • a transmittance of 90% or more means that the transmittance is not less than 90% in the entire wavelength range, that is, the minimum transmittance is 90% or more in that wavelength range. means.
  • a transmittance of 1% or less means that the transmittance does not exceed 1% in the entire wavelength range, that is, the maximum transmittance in that wavelength range is 1% or less.
  • the average transmittance and average internal transmittance in a specific wavelength range are the arithmetic averages of the transmittance and internal transmittance for every 1 nm in the wavelength range. Spectral characteristics can be measured using an ultraviolet-visible near-infrared spectrophotometer. In this specification, " ⁇ " representing a numerical range includes the upper and lower limits.
  • An optical filter according to an embodiment of the present invention (hereinafter also referred to as "this filter”) includes a base material and an antireflection layer made of a dielectric multilayer film laminated as the outermost layer on one main surface side of the base material. 1, and an antireflection layer 2 made of a dielectric multilayer film laminated as the outermost layer on the other main surface side of the base material.
  • the base material includes near-infrared absorbing glass and a resin film laminated on at least one main surface of the near-infrared absorbing glass.
  • the resin film includes a resin, a UV dye having a maximum absorption wavelength in the resin from 350 to 410 nm, and an IR dye having a maximum absorption wavelength in the resin from 700 to 850 nm.
  • the dielectric multilayer film is an antireflection layer, its reflection properties are small, and the light-shielding properties of the optical filter are substantially ensured by the near-infrared absorbing glass and the absorption properties of the IR dye and the UV dye. Since the absorption characteristics are not affected by the incident angle of light, the optical filter as a whole suppresses ripples in the visible light region, and has excellent transparency in the visible light region and excellent shielding in the near-infrared light region and near-ultraviolet light region. You can realize your sexuality.
  • FIG. 1 is a cross-sectional view schematically showing an example of an optical filter according to an embodiment.
  • the optical filter 1B shown in FIG. 1 has a dielectric multilayer film 20A on one main surface side of a base material 10 having a near-infrared absorbing glass 11 and a resin film 12, and a dielectric multilayer film 20B on the other main surface side.
  • a base material 10 having a near-infrared absorbing glass 11 and a resin film 12
  • a dielectric multilayer film 20B on the other main surface side.
  • the optical filter according to this embodiment satisfies all of the following spectral characteristics (i-1) to (i-7).
  • i-1 In the spectral transmittance curve at an incident angle of 0 degrees, the average transmittance T 350-390 (0 deg) AVE is 1% or less in the wavelength range of 350 to 390 nm
  • i-2 Spectral transmittance at an incident angle of 0 degrees
  • the transmittance T 400 (0deg) at a wavelength of 400 nm is 3% or less (i-3).
  • Transmittance T 430 (0deg) satisfies the following relationship T 430 (0deg) - T 400 (0deg) ⁇ 78% (i-4)
  • the average transmittance T 430-600 (0 deg) AVE for wavelengths of 430 to 600 nm is 80% or more (i-5)
  • the antireflection layer 1 side is incident Average reflectance R1 430-600 (5deg) AVE for wavelengths of 430 to 600 nm in the spectral reflectance curve at an incident angle of 5 degrees and wavelengths of 430 to 600 nm in the spectral reflectance curve at an incident angle of 50 degrees
  • Average reflectance R1 430-600 (50 deg) The absolute value of the difference between AVE is 4% or less (i-6)
  • This filter which satisfies all of the spectral characteristics (i-1) to (i-7), has excellent light-shielding properties in the near-ultraviolet region, as shown in characteristics (i-1) to (i-2), and especially has the characteristic (i-7). As shown in -2), it can block a wide range of light up to around 400 nm, and as shown in property (i-4), it has excellent visible light transmittance, and as shown in property (i-7), it can block light in the near-infrared region. Excellent shielding properties. Furthermore, as shown in characteristic (i-3), the change in transmittance is steep from the near-ultraviolet region to the visible light region. Furthermore, as shown in characteristics (i-5) to (i-6), the change in reflection characteristics is small at high incident angles in any direction on the main surface of the optical filter, and ripples in the visible light region are suppressed. There is.
  • a dielectric multilayer film with suppressed reflection characteristics and to use phosphate glass or fluorophosphate glass as the near-infrared absorbing glass.
  • phosphate glass or fluorophosphate glass as the near-infrared absorbing glass.
  • the average transmittance T 350-390 (0 deg) AVE of characteristic (i-1) is 1% or less, preferably 0.8% or less, more preferably 0.5% or less.
  • the transmittance T 400 (0deg) of characteristic (i-2) is 3% or less, preferably 2.5% or less, more preferably 2% or less.
  • Characteristic (i-3) T 430 (0deg) - T 400 (0deg) is 78% or more, preferably 79% or more, more preferably 79.5% or more.
  • the average transmittance T 430-600 (0 deg) AVE of characteristic (i-4) is 80% or more, preferably 81% or more, more preferably 82% or more.
  • the absolute value of the difference between the average reflectance R1 430-600 (5deg) AVE and the average reflectance R1 430-600 (50deg) AVE is 4% or less, preferably 3.5% or less, or more. Preferably it is 3% or less.
  • the absolute value of the difference between the average reflectance R2 430-600 (5deg) AVE and the average reflectance R2 430-600 (50deg) AVE is 4% or less, preferably 3.5% or less, or more. Preferably it is 3% or less.
  • the average transmittance T 750-1100 (0 deg) AVE is 2% or less, preferably 1.5% or less, more preferably 1% or less.
  • the optical filter according to this embodiment preferably further satisfies the following spectral characteristic (i-8).
  • i-8 In the spectral transmittance curve at an incident angle of 50 degrees, the transmittance T 400 (50 deg) at a wavelength of 400 nm is 3% or less.This makes an optical filter with excellent light blocking properties around 400 nm even at a high incident angle. is obtained.
  • the transmittance T 400 (50deg) is more preferably 2.5% or less, even more preferably 2% or less.
  • the optical filter according to this embodiment preferably further satisfies the following spectral characteristic (i-9).
  • i-9 spectral characteristic
  • the average transmittance T 350-390 (50 deg) AVE for wavelengths of 350 to 390 nm is 1.5% or less.
  • An optical filter having excellent light-shielding properties can be obtained.
  • the average transmittance T 350-390 (50 deg) AVE is more preferably 1.3% or less, even more preferably 1% or less.
  • the optical filter according to this embodiment preferably further satisfies the following spectral characteristics (i-10) and (i-11).
  • i-10) In the spectral transmittance curve at an incident angle of 0 degrees, the minimum wavelength T (0 deg) UV50 at which the transmittance is 50% in the wavelength range of 350 to 430 nm and the incident direction on the antireflection layer 1 side Then, in the spectral reflectance curve at an incident angle of 5 degrees, the maximum wavelength R1 (5deg)UV50 at which the reflectance is 50% in the wavelength range of 350 to 430nm satisfies the following relationship T (0deg)UV50 -R1 (5deg) UV50 >10nm (i-11) When the T (0deg) UV50 and the antireflection layer 2 side are the incident direction, the reflectance is 50% in the wavelength range of 350 to 430 nm in the spectral reflectance curve at an incident angle of 5 degrees.
  • the maximum wavelength R2 (5deg)UV50 satisfies the following relationship T (0deg)UV50 -R2 (5deg)UV50 >10nm
  • T (0deg)UV50 -R2 5deg)UV50 >10nm
  • an optical filter can be obtained in which the difference between the transmittance and the reflectance at the cut end is large, that is, the reflection property is small and the absorption property ensures the light-shielding property.
  • T (0deg)UV50 -R1 (5deg)UV50 >11 nm still more preferably T (0deg)UV50 -R1 (5deg)UV50 >12 nm.
  • T (0deg)UV50 -R2 5deg)UV50 >11 nm
  • T (0deg)UV50 -R2 5deg)UV50 >12nm.
  • the optical filter according to this embodiment preferably further satisfies the following spectral characteristics (i-12) to (i-14).
  • i-12 The T (0deg) UV50 is in the wavelength range of 400 to 430 nm.
  • i-13 In the spectral transmittance curve at an incident angle of 50 degrees, the transmittance is 50% in the wavelength range of 350 to 430 nm.
  • the wavelength T (0 deg) UV50 is more preferably 405 to 430 nm, and even more preferably 410 to 425 nm.
  • the wavelength T (50 deg) UV50 is more preferably 405 to 430 nm, and even more preferably 410 to 425 nm.
  • the absolute value of the difference between T (0deg) UV50 and T (50deg) UV50 is more preferably 3 nm or less, and even more preferably 2 nm or less.
  • the optical filter according to this embodiment preferably further satisfies the following spectral characteristic (i-15).
  • Average transmittance at 600 nm T 430-600 (50 deg) AVE satisfies the following relationship T 430-600 (0 deg) AVE - T 430-600 (50 deg) AVE ⁇ 4.5%
  • T 430-600 (0deg) AVE - T 430-600 (50 deg) AVE is more preferably 4.3% or less, even more preferably 4% or less.
  • the optical filter according to this embodiment preferably further satisfies the following spectral characteristics (i-16) and (i-17).
  • i-16 When the anti-reflection layer 1 side is the incident direction, in the spectral reflectance curve at an incident angle of 5 degrees, the average reflectance R1 750-1100 (5 deg) AVE at wavelengths of 750 to 1100 nm is 15% or less
  • the average reflectance R2 750-1100 (5 deg) AVE for wavelengths of 750 to 1100 nm is 15% or less
  • an optical filter having low reflection characteristics in the near-infrared region can be obtained.
  • the average reflectance R1 750-1100 (5 deg) AVE is more preferably 13% or less, even more preferably 12% or less.
  • the average reflectance R2 750-1100 (5 deg) AVE is more preferably 13% or less, even more preferably 12% or less.
  • the optical filter according to this embodiment preferably further satisfies the following spectral characteristics (i-18) to (i-20).
  • the minimum transmittance T 430-600 (0 deg) MIN is 60% or more for the wavelength 430-600 nm (i-19) Spectral transmission at an incident angle of 0 degrees
  • the maximum transmittance T in the wavelength range of 430 to 600 nm 430-600 (0deg) MAX is 90% or more
  • the maximum transmittance T in the wavelength range of 750 to 1100 nm 750-1100 (0deg) MAX is 3% or less
  • T 430-600 (0deg) MIN is more preferably 62% or more, still more preferably 64% or more.
  • T 430-600 (0deg) MAX is more preferably 91% or more, even more preferably 93% or more.
  • T 750-1100 (0deg) MAX is more preferably 2.5% or less, even more preferably 2% or less.
  • the base material includes near-infrared absorbing glass and a resin film.
  • the resin film is laminated on at least one main surface of the near-infrared absorbing glass, and includes a resin, a UV dye having a maximum absorption wavelength in the range of 350 to 410 nm in the resin, and a UV dye having a maximum absorption wavelength in the resin of 700 to 850 nm. and an IR dye.
  • the base material has both the absorption ability of near-infrared absorbing glass and the absorption ability of a resin film containing UV dye and IR dye.
  • the near-infrared absorbing glass preferably satisfies all of the following spectral characteristics (ii-1) and (ii-2).
  • (ii-1) Average internal transmittance T 450-600AVE for wavelengths 450-600 nm is 80% or more
  • Average internal transmittance T 750-1100AVE for wavelengths 750-1100 nm is 5% or less
  • the material has both high transmittance in the visible light region and light blocking properties in the near-infrared region over a wide range of 750 to 1100 nm.
  • the average internal transmittance T 450-600AVE is more preferably 81% or more, even more preferably 82% or more.
  • the average internal transmittance T 750-1100AVE is more preferably 4% or less, even more preferably 3% or less.
  • the near-infrared absorbing glass is not limited as long as it can obtain the above-mentioned spectral characteristics, and examples thereof include absorption type glass containing copper ions such as fluorophosphate glass and phosphate glass. Among these, phosphate glass is preferable from the viewpoint that the above spectral characteristics can be easily obtained. Note that "phosphate glass” also includes silicate glass in which a part of the glass skeleton is composed of SiO 2 .
  • the phosphate glass contains components constituting the following glasses.
  • each content ratio of the following glass constituent components is expressed as a mass percentage on an oxide basis.
  • P 2 O 5 is a main component forming glass, and is a component for improving near-infrared ray cutting properties. If the P 2 O 5 content is 40% or more, the effect can be sufficiently obtained, and if it is 80% or less, problems such as glass becoming unstable and weather resistance decreasing are unlikely to occur. Therefore, it is preferably 40 to 80%, more preferably 45 to 78%, still more preferably 50 to 77%, even more preferably 55 to 76%, and most preferably 60 to 75%. be.
  • Al 2 O 3 is a main component forming glass, and is a component for increasing the strength of glass and weather resistance of glass. If the Al 2 O 3 content is 0.5% or more, the effect can be sufficiently obtained, and if it is 20% or less, problems such as the glass becoming unstable and the near-infrared cut property decreasing occur. Hateful. Therefore, it is preferably 0.5 to 20%, more preferably 1.0 to 20%, even more preferably 2.0 to 18%, even more preferably 3.0 to 17%, Particularly preferably 4.0 to 16%, most preferably 5.0 to 15.5%.
  • R 2 O (wherein R 2 O is one or more components selected from Li 2 O, Na 2 O, K 2 O, Rb 2 O, and Cs 2 O) lowers the melting temperature of the glass. It is a component that lowers the liquidus temperature of glass and stabilizes glass. If the total amount of R 2 O ( ⁇ R 2 O) is 0.5% or more, the effect can be sufficiently obtained, and if it is 20% or less, the glass is less likely to become unstable, which is preferable. Therefore, it is preferably 0.5 to 20%, more preferably 1.0 to 19%, even more preferably 1.5 to 18%, even more preferably 2.0 to 17%, Particularly preferably from 2.5 to 16%, most preferably from 3 to 15.5%.
  • Li 2 O is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, and stabilizing glass.
  • the content of Li 2 O is preferably 0 to 15%. It is preferable that the Li 2 O content is 15% or less, since problems such as the glass becoming unstable and the near-infrared cut property being lowered are less likely to occur. More preferably 0 to 8%, still more preferably 0 to 7%, even more preferably 0 to 6%, and most preferably 0 to 5%.
  • Na 2 O is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, and stabilizing glass.
  • the content of Na 2 O is preferably 0 to 15%. It is preferable that the Na 2 O content is 15% or less because the glass is less likely to become unstable. More preferably, it is 0.5 to 14%, still more preferably 1 to 13%, even more preferably 2 to 13%, and most preferably 3 to 13%.
  • K 2 O is a component that has effects such as lowering the melting temperature of glass and lowering the liquidus temperature of glass.
  • the content of K 2 O is preferably 0 to 20%. It is preferable that the content of K 2 O is 20% or less because the glass is less likely to become unstable. More preferably 0.5 to 19%, still more preferably 1 to 18%, even more preferably 2 to 17%, and most preferably 3 to 16%.
  • Rb 2 O is a component that has effects such as lowering the melting temperature of glass and lowering the liquidus temperature of glass.
  • the content of Rb 2 O is preferably 0 to 15%. It is preferable that the Rb 2 O content is 15% or less because the glass is less likely to become unstable. More preferably, it is 0.5 to 14%, still more preferably 1 to 13%, even more preferably 2 to 13%, and most preferably 3 to 13%.
  • Cs 2 O is a component that has effects such as lowering the melting temperature of glass and lowering the liquidus temperature of glass.
  • the content of Cs 2 O is preferably 0 to 15%. It is preferable that the Cs 2 O content is 15% or less because the glass is less likely to become unstable. More preferably, it is 0.5 to 14%, still more preferably 1 to 13%, even more preferably 2 to 13%, and most preferably 3 to 13%.
  • the phosphate glass of this embodiment preferably contains two or more components selected from Li 2 O, Na 2 O, K 2 O, Rb 2 O, and Cs 2 O.
  • the total amount ( ⁇ R 2 O) of R 2 O is more than 7%18 % or less is preferable. If the total amount of R 2 O is more than 7%, the effect will be sufficiently obtained, and if it is less than 18%, the glass will become unstable, the near-infrared cut property will decrease, the strength of the glass will decrease, etc. This is preferable because it is less likely to cause problems. Therefore, ⁇ R 2 O is preferably more than 7% and 18% or less, more preferably 7.5% to 17%, still more preferably 8% to 16%, and even more preferably 8.5% to 15%. and most preferably 9 to 14%.
  • R'O (where R'O is one or more components selected from CaO, MgO, BaO, SrO, and ZnO) lowers the melting temperature of glass, lowers the liquidus temperature of glass, and improves glass. It is a component used to stabilize and increase the strength of glass.
  • the total amount of R'O ( ⁇ R'O) is preferably 0 to 40%. It is preferable that the total amount of R'O is 40% or less because problems such as the glass becoming unstable, the near-infrared cut property decreasing, and the strength of the glass decreasing are unlikely to occur. More preferably 0 to 35%, still more preferably 0 to 30%. Even more preferably it is 0 to 25%, particularly preferably 0 to 20%, and most preferably 0 to 15%.
  • CaO is a component that lowers the melting temperature of glass, lowers the liquidus temperature of glass, stabilizes glass, and increases the strength of glass.
  • the content of CaO is preferably 0 to 10%. It is preferable that the CaO content is 10% or less because problems such as the glass becoming unstable and the near-infrared cut property being lowered are less likely to occur. More preferably, it is 0 to 8%, still more preferably 0 to 6%, even more preferably 0 to 5%, and most preferably 0 to 4%.
  • MgO is a component that lowers the melting temperature of glass, lowers the liquidus temperature of glass, stabilizes glass, and increases the strength of glass.
  • the content of MgO is preferably 0 to 15%. It is preferable that the MgO content is 15% or less because problems such as glass becoming unstable and near-infrared cut properties are less likely to occur. More preferably 0 to 13%, still more preferably 0 to 10%, even more preferably 0 to 9%, and most preferably 0 to 8%.
  • BaO is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, and stabilizing glass.
  • the BaO content is preferably 0 to 40%. It is preferable that the BaO content is 40% or less, since problems such as glass becoming unstable and near-infrared cut properties are less likely to occur. More preferably 0 to 30%, still more preferably 0 to 20%, even more preferably 0 to 10%, and most preferably 0 to 5%.
  • SrO is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, and stabilizing glass.
  • the content of SrO is preferably 0 to 10%. It is preferable that the SrO content is 10% or less, since problems such as glass becoming unstable and near-infrared cut-off properties are less likely to occur. More preferably, it is 0 to 8%, still more preferably 0 to 7%, and most preferably 0 to 6%.
  • ZnO has effects such as lowering the melting temperature of glass and lowering the liquidus temperature of glass.
  • the content of ZnO is preferably 0 to 15%. If the content of ZnO is 15% or less, problems such as the glass becoming unstable, the solubility of the glass deteriorating, and the near-infrared cut property decreasing are less likely to occur, so it is preferable. More preferably 0 to 13%, still more preferably 0 to 10%, even more preferably 0 to 9%, and most preferably 0 to 8%.
  • CuO is a component for improving near-infrared ray cutting properties.
  • the content of CuO is preferably 0.5 to 40%. If the CuO content is 0.5% or more, the effect can be sufficiently obtained, and if it is 40% or less, devitrification foreign matter will occur in the glass, the transmittance of light in the visible region will decrease, etc. This is preferable because it is less likely to cause problems. More preferably 1.0 to 35%, still more preferably 1.5 to 30%, even more preferably 2.0 to 25%, most preferably 2.5 to 20%.
  • F may be contained in a range of 10% or less in order to improve weather resistance. If the content of F is 10% or less, problems such as a decrease in near-infrared cutting properties and generation of devitrification foreign matter in the glass are less likely to occur, so it is preferable. It is more preferably 9% or less, still more preferably 8% or less, even more preferably 7% or less, particularly preferably 6% or less, and most preferably 5% or less.
  • B 2 O 3 may be contained in a range of 10% or less in order to stabilize the glass. It is preferable that the content of B 2 O 3 is 10% or less, since problems such as deterioration of the weather resistance of the glass and deterioration of the near-infrared cut property are unlikely to occur. It is more preferably 9% or less, still more preferably 8% or less, even more preferably 7% or less, particularly preferably 6% or less, and most preferably 5% or less.
  • SiO2 , GeO2 , ZrO2, SnO2 , TiO2 , CeO2 , MoO3 , WO3 , Y2O3 , La2O3 , Gd2O3 , Yb2O3 , Nb 2 O 5 may be contained in an amount of 5% or less in order to improve the weather resistance of the phosphate glass. If the content of these components is 5% or less, problems such as generation of devitrification foreign matter in the glass and deterioration of near-infrared cut properties are less likely to occur, which is preferable. Preferably it is 4% or less, more preferably 3% or less, still more preferably 2% or less, even more preferably 1% or less.
  • substantially not containing a specific component means that it is not intentionally added, and does not contain a specific component that is unavoidably mixed in from raw materials etc. and does not affect the intended properties. It is not something to be excluded.
  • the thickness of the near-infrared absorbing glass is preferably 0.5 mm or less, more preferably 0.3 mm or less, from the viewpoint of reducing the height of the camera module, and preferably 0.15 mm or more from the viewpoint of element strength.
  • Phosphate glass can be produced, for example, as follows. First, raw materials are weighed and mixed so that the composition falls within the above composition range (mixing step). This raw material mixture is placed in a platinum crucible and heated and melted at a temperature of 700 to 1400°C in an electric furnace (melting step). After sufficient stirring and clarification, it is poured into a mold, cut and polished, and formed into a flat plate with a predetermined thickness (molding process).
  • the highest temperature of the glass during glass melting is 1400°C or less. If the highest temperature of the glass during glass melting exceeds the above temperature, the transmittance characteristics may deteriorate.
  • the temperature is more preferably 1350°C or lower, still more preferably 1300°C or lower, even more preferably 1250°C or lower.
  • the temperature in the above melting step is too low, problems such as devitrification occurring during melting and a long time required for melting through may occur, so it is preferably 700°C or higher, more preferably 800°C or higher. It is.
  • the UV dye is not limited as long as it is a compound that has a maximum absorption wavelength in the range of 350 to 410 nm in the resin, but includes merocyanine compounds that have the maximum absorption wavelength in the resin in the range of 370 to 410 nm, and UV dyes that have the maximum absorption wavelength in the range of 350 to 380 nm in the resin. It is preferable to include at least one of the zeromethine compounds having the above, and it is more preferable to include both from the viewpoint of efficiently blocking a wide near-ultraviolet light region.
  • the resin is a resin used for the resin film in the optical filter according to this embodiment.
  • merocyanine compound As the merocyanine compound, a compound represented by the following formula (M) is preferred.
  • the compound represented by the following formula (M) is preferable because the dye compound itself has excellent light resistance and is resistant to photodeterioration. It is also preferable in that it does not affect the light resistance of the IR dye even when used in combination with the IR dye.
  • R 21 represents a monovalent hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.
  • R 22 to R 25 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • Y20 represents a methylene group or an oxygen atom substituted with R26 and R27 .
  • X 20 represents any of the divalent groups represented by the following formulas (X1) to (X5).
  • R 28 and R 29 each independently represent a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent
  • R 30 to R 39 each independently represent a hydrogen atom, or Represents a monovalent hydrocarbon group having 1 to 12 carbon atoms that may have a substituent.
  • R 21 represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
  • substituent an alkoxy group, an acyl group, an acyloxy group, a cyano group, a dialkylamino group, or a chlorine atom is preferable.
  • the number of carbon atoms in the alkoxy group, acyl group, acyloxy group and dialkylamino group is preferably 1 to 6.
  • R 21 is an alkyl group having 1 to 6 carbon atoms, in which some of the hydrogen atoms may be substituted with a cycloalkyl group or a phenyl group.
  • Particularly preferred R 21 is an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, etc. It will be done.
  • R 22 to R 25 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • the number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 6, more preferably 1 to 4.
  • At least one of R 22 and R 23 is preferably an alkyl group, and both are more preferably an alkyl group. When R 22 and R 23 are not alkyl groups, hydrogen atoms are more preferred. R 22 and R 23 are both particularly preferably an alkyl group having 1 to 6 carbon atoms.
  • At least one of R 24 and R 25 is preferably a hydrogen atom, and more preferably both are hydrogen atoms.
  • R 24 and R 25 are preferably alkyl groups having 1 to 6 carbon atoms.
  • Y20 represents a methylene group or an oxygen atom substituted with R26 and R27 .
  • R 26 and R 27 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • X 20 represents any of the divalent groups represented by the above formulas (X1) to (X5).
  • R 28 and R 29 each independently represent a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent
  • R 30 to R 39 each independently represent a hydrogen atom, or Represents a monovalent hydrocarbon group having 1 to 12 carbon atoms that may have a substituent.
  • substituents for R 28 to R 39 include the same substituents as the substituent for R 21 , and preferred embodiments are also the same.
  • R 28 to R 39 are hydrocarbon groups having no substituents, the same embodiment as R 21 having no substituents can be mentioned.
  • R 28 and R 29 are both alkyl groups having 1 to 6 carbon atoms in which some of the hydrogen atoms may be substituted with a cycloalkyl group or a phenyl group.
  • Particularly preferable R 28 and R 29 are both alkyl groups having 1 to 6 carbon atoms, and specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. group, t-butyl group, etc.
  • R 30 and R 31 are both preferably alkyl groups having 1 to 6 carbon atoms, and particularly preferably the same alkyl group.
  • R 32 and R 35 are both preferably hydrogen atoms or unsubstituted alkyl groups having 1 to 6 carbon atoms.
  • the two groups R 33 and R 34 bonded to the same carbon atom are preferably both hydrogen atoms or both alkyl groups having 1 to 6 carbon atoms.
  • the two groups R 36 and R 37 and R 38 and R 39 bonded to the same carbon atom are preferably both hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.
  • Examples of the compound represented by formula (M) include compounds in which Y 20 is an oxygen atom and X 20 is a group (X1), a group (X2), or a group (X5), and Y 20 is an unsubstituted methylene
  • Y 20 is an oxygen atom and X 20 is a group (X1), a group (X2), or a group (X5)
  • Y 20 is an unsubstituted methylene
  • a compound in which X 20 is a group (X1), a group (X2) or a group (X5) is preferred.
  • compound (M) examples include the compounds shown in the table below.
  • Compounds (M) include Compounds (M-2), Compounds (M-8), Compounds (M-9), and Compounds (M-13) from the viewpoint of appropriate solubility in resin and maximum absorption wavelength. , Compound (M-20) is preferred.
  • Compound (M) can be produced, for example, by a known method described in Japanese Patent No. 6504176.
  • (Zeromethine compound) As the zeromethine compound, a compound represented by the following formula (I) is preferable.
  • the compound represented by the following formula (I) is preferable because the dye compound itself has excellent light resistance and is resistant to photodeterioration. It is also preferable in that it does not affect the light resistance of the IR dye even when used in combination with the IR dye.
  • R 1 is an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • R 2 to R 5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and an alkoxy group having 1 to 10 carbon atoms which may have a substituent. , a nitro group, an amino group, or an amide group.
  • A represents any of the divalent groups represented by the following formulas (A1) to (A4).
  • Y is an oxygen atom or a sulfur atom
  • R 6 to R 13 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. It is. ]
  • X is an oxygen atom, a sulfur atom, NR 14 , or CR 15 R 16 .
  • R 14 to R 16 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and examples of the substituent which may have include an alkoxy group, an acyl group, acyloxy group, cyano group, dialkylamino group, or chlorine atom.
  • R 14 to R 16 are preferably each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.
  • X is preferably an oxygen atom, a sulfur atom, or CR 15 R 16 , more preferably an oxygen atom or a sulfur atom. That is, the compound (I) is more preferably a compound represented by the following formula (I)'.
  • X' is an oxygen atom or a sulfur atom
  • R 1 is an alkyl group having 1 to 6 carbon atoms which may have a substituent
  • R 2 to R 5 are each independently is a hydrogen atom, a halogen atom, an alkyl group or alkoxy group having 1 to 10 carbon atoms which may have a substituent, a nitro group, an amino group, or an amide group
  • A is the above formula (A1) to ( Represents any of the divalent groups represented by A4).
  • R 1 is an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • substituents include an alkoxy group, an acyl group, an acyloxy group, a cyano group, a dialkylamino group, and a chlorine atom.
  • R 1 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.
  • R 2 to R 5 each independently represent a hydrogen atom, a halogen atom, an alkyl group or alkoxy group having 1 to 10 carbon atoms which may have a substituent, It is a nitro group, an amino group, or an amide group.
  • substituents include an alkoxy group, an acyl group, an acyloxy group, a cyano group, a dialkylamino group, and a chlorine atom.
  • R 2 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and more preferably a hydrogen atom.
  • R 3 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 4 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and more preferably a hydrogen atom.
  • R 5 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and more preferably a hydrogen atom.
  • A represents any of the divalent groups represented by formulas (A1) to (A4) above, and A represents a divalent group represented by formula (A1) or (A3). Groups are preferred.
  • Y is an oxygen atom or a sulfur atom.
  • X in formula (I) or X' in formula (I)' is a sulfur atom
  • Y is preferably an oxygen atom.
  • X is preferably an oxygen atom, NR 14 or CR 15 R 16 , more preferably an oxygen atom
  • X' is preferably an oxygen atom.
  • at least one of X or X' and Y is preferably an oxygen atom.
  • R 6 to R 13 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or It is a phenyl group.
  • substituents include an alkoxy group, an acyl group, an acyloxy group, a cyano group, a dialkylamino group, and a chlorine atom.
  • R 6 and R 7 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • R 8 and R 9 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • R 10 and R 11 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • R 12 and R 13 are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom.
  • Examples of compound (I) or compound (I)' include compounds in which the atoms or groups bonded to each skeleton are shown in Table 2 below.
  • i-Bu means an isobutyl group
  • t-Bu means a tertiary butyl group
  • Ph means a phenyl group.
  • the method for producing compound (I) or compound (I)' is not particularly limited, but for example, by reacting 2-(methylthio)benzothiazole and methyl p-toluenesulfonate, an intermediate represented by the following formula can be produced. Get 1.
  • Ts in the formula represents a tosyl group.
  • Compound (I) or compound (I)' can be obtained by reacting the above intermediate 1 with a compound corresponding to a divalent group represented by formulas (A1) to (A4) in the presence of a solvent.
  • the above 2-(methylthio)benzothiazole may be changed to a 2-(methylthio)benzothiazole derivative in which the hydrogen atoms corresponding to R 1 to R 5 are replaced with substituents, or 2-(methylthio)benzoxazole or 2-(methylthio)benzoxazole or By changing to a -(methylthio)indole derivative or the like, compound (I) or compound (I)' having a desired structure can be obtained.
  • the content of the UV dye in the resin film is such that the product of the content in mass % of the UV dye and the thickness of the resin film is preferably 20.0 (mass %/ ⁇ m) or less, more preferably 19.0 (mass %/ ⁇ m) or less. % ⁇ m) or less, particularly preferably 18.0 (mass% ⁇ m) or less.
  • the above product is preferably 3.0 (mass %/ ⁇ m) or more, and more preferably 5.0 (mass %/ ⁇ m) or more.
  • the product of the total content of the plurality of UV dyes and the thickness of the resin film satisfies the above range.
  • the content of the UV dye in the resin film is preferably 3.0 parts by mass or more based on 100 parts by mass of the resin. It is more preferably 0 parts by mass or more, more preferably 15.0 parts by mass or less, and more preferably 14.0 parts by mass or less. In addition, even when using a plurality of compounds as UV dyes, it is preferable that the total content of the plurality of UV dyes satisfies the above range.
  • the IR dye is not limited as long as it is a compound having a maximum absorption wavelength in the range of 700 to 850 nm in the resin, but examples include squarylium dyes, cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, dithiol metal complex dyes, azo dyes, and polymethine dyes.
  • phthalide dyes naphthoquinone dyes, anthraquinone dyes, indophenol dyes, pyrylium dyes, thiopyrylium dyes, croconium dyes, tetradehyde ocholine dyes, triphenylmethane dyes, aminium dyes and diimmonium dyes, It is more preferable that at least one dye selected from the group consisting of squarylium dyes, phthalocyanine dyes, and cyanine dyes is included.
  • squarylium dyes and cyanine dyes are preferred from a spectroscopic viewpoint, and phthalocyanine dyes are preferred from a durability viewpoint.
  • the content of the IR dye in the resin film is preferably 3.0 parts by mass or more, more preferably 5.0 parts by mass or more, and preferably 25.0 parts by mass or less, based on 100 parts by mass of the transparent resin. More preferably, it is 0 parts by mass or less.
  • the resin contained in the resin film is not particularly limited as long as it is a transparent resin that transmits visible light with a wavelength of 400 to 700 nm.
  • Transparent resins include, for example, polyester resins, acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, and polyarylene ether phosphine oxides.
  • Examples include resins, polyamide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyurethane resins, polystyrene resins, and the like.
  • These transparent resins may be used alone or in combination of two or more.
  • polyimide resins are preferred from the viewpoints of excellent visible transmittance, high resin glass transition temperature, and resistance to thermal deterioration of dyes.
  • the optical filter may have one layer of resin film, or may have two or more layers of the resin film. When having two or more layers, each resin film may have the same structure or may have different structures.
  • the thickness of the resin film is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, from the viewpoint of obtaining a uniform film with a small film thickness distribution. Further, from the viewpoint of obtaining desired spectral characteristics, the thickness of the resin film is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more. When the optical filter according to this embodiment includes two or more layers of resin films, it is preferable that the thickness of each resin film satisfies the above range.
  • each dielectric multilayer film is laminated as the outermost layer on both principal surfaces of the base material. Further, each dielectric multilayer film is designed as an antireflection layer that has low reflection characteristics in the ultraviolet light region, visible light region, and near-infrared light region.
  • the antireflection layer is, for example, a dielectric film with a low refractive index (low refractive index film), a dielectric film with an intermediate refractive index (medium refractive index film), or a dielectric film with a high refractive index (high refractive index film). It is composed of a dielectric multilayer film made by laminating two or more layers.
  • the antireflection layer means a layer that does not have a wavelength band with a width of 100 nm or more in which the reflectance is 90% or more in a spectral reflectance curve at a wavelength of 750 to 1200 nm and an incident angle of 5 degrees
  • a reflective layer is a layer having a wavelength band of 100 nm or more in width with a reflectance of 90% or more in a spectral reflectance curve with a wavelength of 750 to 1200 nm and an incident angle of 5 degrees, or a laminated antireflection layer of an optical filter.
  • the absolute value of the difference between the average reflectance for wavelengths 430 to 600 nm in the spectral reflectance curve at an incident angle of 5 degrees and the average reflectance for wavelengths 430 to 600 nm in the spectral reflectance curve at an incident angle of 50 degrees is It means a layer designed to have a concentration of 4% or less.
  • the high refractive index film preferably has a refractive index of 1.6 or more, more preferably 2.2 to 2.5.
  • the material for the high refractive index film include Ta 2 O 5 , TiO 2 , TiO, and Nb 2 O 5 .
  • Other commercially available products are manufactured by Canon Optron, OS50 (Ti 3 O 5 ), OS10 (Ti 4 O 7 ), OA500 (mixture of Ta 2 O 5 and ZrO 2 ), OA600 (mixture of Ta 2 O 5 and TiO 2 ). Examples include. Among these, TiO 2 is preferred in terms of film formability, reproducibility in refractive index, stability, and the like.
  • the medium refractive index film preferably has a refractive index of 1.6 or more and less than 2.2.
  • Materials for the medium refractive index film include, for example, ZrO 2 , Nb 2 O 5 , Al 2 O 3 , HfO 2 , and OM-4 and OM-6 (Al 2 O 3 and ZrO 2 OA-100, H4 sold by Merck, M2 (alumina lanthania), etc.
  • Al 2 O 3 -based compounds and mixtures of Al 2 O 3 and ZrO 2 are preferred from the viewpoint of film formability, reproducibility in refractive index, stability, and the like.
  • the low refractive index film preferably has a refractive index of less than 1.6, more preferably 1.45 or more and less than 1.55.
  • Examples of the material of the low refractive index film include SiO 2 , SiO x N y, MgF 2 and the like.
  • Other commercially available products include S4F and S5F (mixture of SiO 2 and Al 2 O 3 ) manufactured by Canon Optron. Among these, SiO 2 is preferred from the viewpoint of reproducibility in film formation, stability, economic efficiency, and the like.
  • the total number of dielectric multilayer films in the antireflection layer is preferably 20 or less, more preferably 18 or less, even more preferably 15 or less, and preferably 5 or more.
  • the overall thickness of the antireflection layer is preferably 1 ⁇ m or less, more preferably 0.9 ⁇ m or less, and more preferably 0.2 ⁇ m or more. Note that it is preferable that both the antireflection layer 1 and the antireflection layer 2 satisfy the above-mentioned number of laminated layers and film thickness, respectively.
  • a vacuum film forming process such as a CVD method, a sputtering method, a vacuum evaporation method, or a wet film forming process such as a spray method or a dip method can be used.
  • the antireflection layer may have one layer (a group of dielectric multilayer films) that provides predetermined optical properties, or two layers that provide predetermined optical properties. When having two or more layers, each antireflection layer may have the same structure or different structures.
  • the optical filter according to the present embodiment may further include a functional layer having another function as another component, as long as the effects of the present invention are not impaired.
  • Examples of other functional layers include a functional layer that provides absorption using inorganic fine particles that control transmission and absorption of light in a specific wavelength range.
  • Examples of the inorganic fine particles include ITO (Indium Tin Oxides), ATO (Antimony-doped Tin Oxides), cesium tungstate, and lanthanum boride.
  • ITO fine particles and cesium tungstate fine particles have high visible light transmittance and have light absorption properties over a wide range of infrared wavelengths exceeding 1200 nm, so they can be used when such infrared light shielding properties are required. .
  • the optical filter according to this embodiment when used in an imaging device such as a digital still camera, it can provide an imaging device with excellent color reproducibility. That is, it is preferable that the imaging device according to the present embodiment includes the present optical filter, and more specifically, the solid-state image sensor, the imaging lens, and the present optical filter.
  • This optical filter can be used, for example, by being placed between an imaging lens and a solid-state imaging device, or by being directly attached to a solid-state imaging device, imaging lens, etc. of an imaging device via an adhesive layer.
  • the resin film in the optical filter according to the present embodiment is prepared by dissolving or dispersing the resin or its raw material components, UV dye and IR dye, and other components blended as necessary in a solvent and applying a coating liquid. It can be formed by preparing it, coating it on a support, drying it, and further curing it if necessary. If the support at this time is the near-infrared absorbing glass used for the optical filter according to this embodiment, the base material can be manufactured as is. If the support is a peelable support used only when forming a resin film, the base material can be manufactured by integrating the obtained resin film with near-infrared absorbing glass by thermocompression bonding or the like.
  • the solvent in the coating liquid may be any dispersion medium or solvent in which each component can be stably dispersed or dissolved.
  • the coating liquid may also contain a surfactant to improve voids caused by minute bubbles, dents caused by adhesion of foreign matter, repellency during the drying process, and the like.
  • a dip coating method, a cast coating method, a spin coating method, or the like can be used to apply the coating liquid.
  • Curing is performed, for example, by a curing treatment such as thermal curing or photocuring.
  • the resin membrane can also be manufactured into a film shape by extrusion molding.
  • the base material can be manufactured by laminating the obtained film-like resin film on near-infrared absorbing glass and integrating it by thermocompression bonding or the like.
  • the optical filter according to the present embodiment is obtained by forming an antireflection layer 1 and an antireflection layer 2 made of a dielectric multilayer film on the outermost layer on both main surfaces of the obtained base material. Moreover, it may be an optical filter in which other functional layers are further formed as desired.
  • a base material an antireflection layer 1 consisting of a dielectric multilayer film laminated as the outermost layer on one main surface side of the base material, and an antireflection layer 1 laminated as the outermost layer on the other main surface side of the base material.
  • An optical filter comprising an antireflection layer 2 made of a dielectric multilayer film
  • the base material includes near-infrared absorbing glass and a resin film laminated on at least one main surface of the near-infrared absorbing glass
  • the resin film includes a resin, a UV dye having a maximum absorption wavelength in the resin from 350 to 410 nm, and an IR dye having a maximum absorption wavelength in the resin from 700 to 850 nm
  • the optical filter satisfies all of the following spectral characteristics (i-1) to (i-7).
  • the average transmittance T 350-390 (0 deg) AVE is 1% or less in the wavelength range of 350 to 390 nm
  • Spectral transmittance at an incident angle of 0 degrees the transmittance T 400 (0deg) at a wavelength of 400 nm is 3% or less (i-3).
  • Transmittance T 430 (0deg) satisfies the following relationship T 430 (0deg) - T 400 (0deg) ⁇ 78% (i-4)
  • the average transmittance T 430-600 (0 deg) AVE for wavelengths of 430 to 600 nm is 80% or more (i-5)
  • the antireflection layer 1 side is incident Average reflectance R1 430-600 (5deg) AVE for wavelengths of 430 to 600 nm in the spectral reflectance curve at an incident angle of 5 degrees and wavelengths of 430 to 600 nm in the spectral reflectance curve at an incident angle of 50 degrees
  • Average reflectance R1 430-600 (50 deg) The absolute value of the difference between AVE is 4% or less (i-6)
  • the absolute value is 4% or less (i-7)
  • the average transmittance T 750-1100 (0 deg) AVE is 2% or less at a wavelength of 750 to 1100 nm [2]
  • the optical filter The optical filter according to [1], which further satisfies the following spectral characteristic (i-8).
  • the transmittance T 400 (50deg) at a wavelength of 400 nm is 3% or less [3]
  • the optical filter further satisfies the following spectral characteristic (i-9), The optical filter according to [1] or [2].
  • the average transmittance T 350-390 (50 deg) AVE for wavelengths 350-390 nm is 1.5% or less [4]
  • the optical filter has the following spectral characteristics ( The optical filter according to any one of [1] to [3], which further satisfies i-10) and (i-11).
  • the maximum wavelength R2 (5deg)UV50 satisfies the following relationship T (0deg)UV50 -R2 (5deg)UV50 >10nm [5]
  • the T (0deg) UV50 is in the wavelength range of 400 to 430 nm.
  • the transmittance is 50% in the wavelength range of 350 to 430 nm.
  • the minimum wavelength T (50deg) UV50 is in the wavelength range of 400 to 430 nm (i-14)
  • the absolute value of the difference between the T (0deg) UV50 and the T (50deg) UV50 is 4 nm or less [6]
  • R 21 represents a monovalent hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.
  • R 22 to R 25 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • Y20 represents a methylene group or an oxygen atom substituted with R26 and R27 .
  • X 20 represents any of the divalent groups represented by the following formulas (X1) to (X5).
  • R 28 and R 29 each independently represent a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent
  • R 30 to R 39 each independently represent a hydrogen atom, or Represents a monovalent hydrocarbon group having 1 to 12 carbon atoms that may have a substituent.
  • R 1 is an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • R 2 to R 5 each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted alkoxy group having 1 to 10 carbon atoms. , a nitro group, an amino group, or an amide group.
  • A represents any of the divalent groups represented by the following formulas (A1) to (A4).
  • Y is an oxygen atom or a sulfur atom
  • R 6 to R 13 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. It is. ] [12] The optical filter according to any one of [1] to [11], wherein the antireflection layer 1 and the antireflection layer 2 each have a thickness of 1 ⁇ m or less. [13] The optical filter according to any one of [1] to [12], wherein the number of layers of the antireflection layer 1 and the antireflection layer 2 is 20 or less.
  • An ultraviolet-visible near-infrared spectrophotometer manufactured by Hitachi High-Technologies Corporation, model UH-4150 was used to measure each optical property. Note that, unless the incident angle is specified, the spectral characteristics are values measured at an incident angle of 0 degrees (perpendicular to the main surface).
  • the dyes used in each example are as follows. Note that compounds 1 to 8 are UV dyes, and compounds 9 to 11 are IR dyes.
  • Compounds 1 and 2 Synthesized with reference to Japanese Patent No. 6020746.
  • Compounds 3 and 4 Each was synthesized by the method shown below.
  • Compound 5 D5730 manufactured by Tokyo Kasei Kogyo Co., Ltd. was used.
  • Compound 6 B2728 manufactured by Tokyo Kasei Kogyo Co., Ltd. was used.
  • Compound 7 Tinuvin 460 manufactured by BASF Japan was used.
  • Compound 8 Synthesized with reference to Japanese Patent No. 6256335.
  • Compound 9 Synthesized with reference to Japanese Patent No. 7014272.
  • Compound 10 Synthesized with reference to Dyes and Pigments 73 (2007) 344-352.
  • Compound 11 Synthesized with reference to Japanese Patent No. 6197940.
  • Compound 1 was added to the polyimide resin solution prepared above in an amount of 7.0 parts by mass based on 100 parts by mass of the resin, and the mixture was stirred for 2 hours while being heated to 50°C.
  • the dye-containing resin solution was spin-coated onto a glass substrate (alkali glass, Schott D263) to obtain a coating film with a thickness of 1 ⁇ m. Coating films were similarly prepared for Compounds 2 to 11.
  • Transmission spectroscopy (incident angle of 0 degrees) and reflection spectroscopy (incident angle of 5 degrees) in the wavelength range of 350 nm to 1200 nm was measured for each of the obtained coated glass substrates using a spectrophotometer.
  • the maximum absorption wavelength was calculated from the spectral internal transmittance curve obtained using the spectral transmittance curve and the spectral reflectance curve. The results are shown in Table 3 below.
  • Phosphate glass having the composition shown in the table below was prepared as a near-infrared absorbing glass.
  • the spectral transmittance curve of the phosphate glass in the wavelength range of 350 to 1200 nm was measured using an ultraviolet-visible spectrophotometer. From the obtained spectral property data, the spectral properties shown in Table 4 below were calculated. Note that the spectral characteristics shown in Table 4 below were evaluated based on internal transmittance in order to avoid the influence of reflection at the air interface and glass interface.
  • the spectral transmittance curve of phosphate glass is shown in FIG.
  • the near-infrared absorbing glass used has high transmittance in the visible light region and excellent light-shielding properties in the near-infrared region.
  • 5.0 parts by mass of compound 1, 4.7 parts by mass of compound 3, 1.5 parts by mass of compound 8, and 1.6 parts by mass of compound 9 are added to 100 parts by mass of resin. and stirred for 2 hours while heating to 50°C.
  • This dye-containing resin solution was spin-coated on the phosphoric acid glass having a thickness of 0.28 mm to obtain a glass substrate having a resin film having a thickness of 1.6 ⁇ m.
  • An antireflection layer consisting of a dielectric multilayer film with a total thickness of 0.37 ⁇ m and 7 layers in which SiO 2 and TiO 2 are alternately laminated on the resin film side (B side) of the resin film-coated glass substrate.
  • An antireflection layer consisting of a dielectric multilayer film with a total thickness of 0.81 ⁇ m and 15 layers is formed on the glass surface (on the A surface) where there is no resin film (on the A surface) by laminating SiO 2 and TiO 2 alternately. The film was coated to obtain an optical filter of Example 1-1.
  • Example 1-2 to 1-5 An optical filter was obtained in the same manner as in Example 1-1 except that the thickness of the resin film and the type and content of the dye compound were changed as shown in Table 5 below.
  • Example 1-6 An optical filter was obtained in the same manner as in Example 1-1 except that the dielectric multilayer film formed on the B side was an antireflection layer having a total thickness of 0.81 ⁇ m and 15 layers.
  • Example 1-7 In the same manner as Example 1-1, except that the dielectric multilayer film formed on the A side was a reflective layer with a total thickness of 5.0 ⁇ m and 42 layers, which was made by laminating SiO 2 and TiO 2 alternately. An optical filter was obtained.
  • Example 1-8 to 1-11 An optical filter was obtained in the same manner as in Example 1-1 except that the thickness of the resin film and the type and content of the dye compound were changed as shown in Table 5 below.
  • Example 1-12 An optical filter was obtained in the same manner as in Example 1-1 except that borosilicate glass (manufactured by SCHOTT, D263 alkali glass) was used instead of phosphate glass.
  • borosilicate glass manufactured by SCHOTT, D263 alkali glass
  • spectral transmittance curves at incident angles of 0 degrees and 50 degrees and spectral reflectance curves at incident angles of 5 degrees and 50 degrees in the wavelength range of 350 to 1200 nm were measured using a UV-visible spectrophotometer.
  • the configuration of the optical filter was dielectric multilayer film 1 (side A)/near infrared absorbing glass/resin film/dielectric multilayer film 2 (side B). From the obtained spectral characteristic data, each characteristic shown in Table 6 below was calculated. Further, the spectral transmittance curve, spectral reflectance curve (A side), and spectral reflectance curve (B side) of the optical filter of Example 1-1 are shown in FIGS. 3 to 5, respectively.
  • the spectral transmittance curve, spectral reflectance curve (A side), and spectral reflectance curve (B side) of the optical filter of Example 1-7 are shown in FIGS. 6 to 8, respectively.
  • the spectral transmittance curve, spectral reflectance curve (A side), and spectral reflectance curve (B side) of the optical filter of Example 1-8 are shown in FIGS. 9 to 11, respectively. Note that Examples 1-1 to 1-6 are examples, and Examples 1-7 to 1-12 are comparative examples.
  • the optical filters of Examples 1-1 to 1-6 have high transmittance in the visible light region, high shielding properties in the near-infrared region over a wide range of 700 to 1100 nm, and high shielding properties in the near-ultraviolet region. Moreover, the change in visible light transmittance is small even at high incident angles, indicating that the filter suppresses ripple generation. Furthermore, the change in transmittance from the ultraviolet light blocking region to the visible light transmitting region is steep, indicating that the filter can sufficiently capture the necessary visible light. Since the optical filter of Example 1-7 uses a reflective layer, spectral fluctuations are large at high incident angles, and fluctuations in visible reflectance and visible transmittance are large.
  • optical filters of Examples 1-8 to 1-11 had insufficient UV dye absorption characteristics, resulting in light leakage in the near-ultraviolet region that should be blocked, and poor oblique incidence characteristics. Since the optical filter of Example 1-12 uses non-absorbing glass (borosilicate glass), the light shielding property in the near-infrared region was low.
  • D263 glass manufactured by SCHOTT
  • an antireflection layer consisting of a dielectric multilayer film with a total thickness of 0.37 ⁇ m and 7 layers, which is made by laminating SiO 2 and TiO 2 alternately, is formed to improve light resistance.
  • An evaluation filter was obtained.
  • Example 2-2 to 2-4 A filter for light resistance evaluation was obtained in the same manner as Example 2-1 except that the type and content of the dye compound in the resin film were as shown in Table 7.
  • the fluctuation rate is 20% or less.
  • Compound 2 and Compound 3 have excellent durability as UV dyes themselves, and even when used in combination with IR dyes, they do not affect the light resistance of the IR dyes. I understand. From the results of Examples 2-1 and 2-3, it can be seen that newly adding Compound 6 accelerated the photodegradation of the IR dye because the fluctuation rate in the IR region increased. From the results of Example 2-4, it can be seen that although Compound 8 did not affect the light resistance of the IR dye, its own photodeterioration was accelerated because of the large fluctuation rate in the UV region.
  • the optical filter of the present invention suppresses ripples and stray light in the visible light region even at high incident angles, and has spectral characteristics with excellent transparency in the visible light region and shielding properties in the near-infrared light region. In recent years, it is useful for use in imaging devices such as cameras and sensors for transportation aircraft, whose performance has been increasing in recent years.
  • Optical filter 10
  • Base material 11
  • Near-infrared absorbing glass 12
  • Resin film 20A, 20B

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Publication number Priority date Publication date Assignee Title
JP2009209126A (ja) * 2007-08-16 2009-09-17 Fujifilm Corp ヘテロ環化合物
JP2010059235A (ja) * 2008-09-01 2010-03-18 Fujifilm Corp 紫外線吸収剤組成物
JP2019066746A (ja) * 2017-10-03 2019-04-25 日本板硝子株式会社 光学フィルタ及び撮像装置
WO2022024826A1 (ja) * 2020-07-27 2022-02-03 Ａｇｃ株式会社 光学フィルタ
WO2022065678A1 (ko) * 2020-09-22 2022-03-31 주식회사 창강화학 광학 필터

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009209126A (ja) * 2007-08-16 2009-09-17 Fujifilm Corp ヘテロ環化合物
JP2010059235A (ja) * 2008-09-01 2010-03-18 Fujifilm Corp 紫外線吸収剤組成物
JP2019066746A (ja) * 2017-10-03 2019-04-25 日本板硝子株式会社 光学フィルタ及び撮像装置
WO2022024826A1 (ja) * 2020-07-27 2022-02-03 Ａｇｃ株式会社 光学フィルタ
WO2022065678A1 (ko) * 2020-09-22 2022-03-31 주식회사 창강화학 광학 필터

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