WO2023282184A1 - 光学フィルタ - Google Patents

光学フィルタ Download PDF

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Publication number
WO2023282184A1
WO2023282184A1 PCT/JP2022/026327 JP2022026327W WO2023282184A1 WO 2023282184 A1 WO2023282184 A1 WO 2023282184A1 JP 2022026327 W JP2022026327 W JP 2022026327W WO 2023282184 A1 WO2023282184 A1 WO 2023282184A1
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Prior art keywords
transmittance
wavelength
spectral
less
incident angle
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Ceased
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PCT/JP2022/026327
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English (en)
French (fr)
Japanese (ja)
Inventor
和彦 塩野
崇 長田
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AGC Inc
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Asahi Glass Co Ltd
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Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2023533586A priority Critical patent/JP7511103B2/ja
Priority to CN202280051049.2A priority patent/CN117716264A/zh
Publication of WO2023282184A1 publication Critical patent/WO2023282184A1/ja
Priority to US18/396,795 priority patent/US12181697B2/en
Anticipated expiration legal-status Critical
Priority to JP2024079605A priority patent/JP2024098014A/ja
Priority to US18/927,235 priority patent/US20250052934A1/en
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—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
    • 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

Definitions

  • the present invention relates to an optical filter that transmits visible light and blocks near-infrared light.
  • Imaging devices using solid-state imaging devices transmit light in the visible range (hereinafter also referred to as “visible light”) and light in the near-infrared wavelength range (hereinafter referred to as An optical filter that cuts off “near-infrared light” is used.
  • Such an optical filter is formed by alternately laminating dielectric thin films (dielectric multilayer film) having different refractive indices on one or both sides of a transparent substrate, and using light interference to reflect light to be shielded.
  • dielectric thin films dielectric multilayer film
  • Patent Documents 1 and 2 describe an optical filter having an absorption layer containing a dielectric multilayer film and a dye.
  • An optical filter with a dielectric multilayer film has a problem that the spectral transmittance curve changes with the incident angle because the optical film thickness of the dielectric multilayer film changes depending on the incident angle of light. For example, depending on the number of multilayer films, interference caused by reflected light at each layer interface causes a sharp change in the transmittance in the visible light region, a so-called ripple, which tends to occur more strongly as the incident angle of light increases. If such a filter is used, the spectral sensitivity of the solid-state imaging device may be affected by the angle of incidence. In particular, since camera modules are expected to be used under high incident angle conditions as the height of camera modules is reduced in recent years, there is a demand for an optical filter that is less affected by the incident angle.
  • An object of the present invention is to provide an optical filter that has little change in transmittance in the visible light range even at high incident angles, and that has excellent transmittance in the visible light range and shielding properties in the near-infrared light range.
  • the present invention provides an optical filter or the like having the following configuration.
  • An optical filter comprising a substrate and a dielectric multilayer film laminated as an outermost layer on at least one main surface side of the substrate,
  • the substrate comprises near-infrared absorbing glass and a resin film having a thickness of 10 ⁇ m or less laminated on at least one main surface of the near-infrared absorbing glass,
  • the resin film contains a resin and a dye (NIR1) having a maximum absorption wavelength of 680 to 740 nm in the resin,
  • the optical filter satisfies all of the following spectral characteristics (i-1) to (i-13).
  • the average transmittance T 450-600 (0 deg) AVE at a wavelength of 450 to 600 nm is 80% or more (i-2) Spectral transmission at an incident angle of 50 degrees
  • the average transmittance T 450-600 (50 deg) AVE at a wavelength of 450 to 600 nm is 80% or more (i-3) the average transmittance T 450-600 (0 deg) AVE and the average transmittance T 450-600 (50 deg)
  • the absolute value of the difference from AVE is 5% or less (i-4)
  • the transmittance T 450 (0 deg) at a wavelength of 450 nm is 80% or more (i-5)
  • Transmittance T 450 (50 deg) at a wavelength of 450 nm is 80% or more in the spectral transmittance curve at an incident angle of 50 degrees
  • the wavelength IR50 ( 50 deg) at which the transmittance is 50% is in the range of 610 to 650 nm (i-9) the wavelength IR50 (0 deg) and the absolute value of the difference between the wavelength IR50 (50 deg) is 10 nm or less (i-10)
  • the maximum transmittance T 1000-1200 ( 50 deg) at a wavelength of 1000 to 1200 nm is 5% or less (i-12) the transmittance T 450 (0deg) / maximum transmittance T 1000-1200 (0deg) MAX ⁇ 25 (i-13) the transmittance T 450 (50deg) / the maximum transmittance T 1000
  • an optical filter that has little change in transmittance in the visible light range even at high incident angles, and has excellent transmittance in the visible light range and shielding properties in the near-infrared light range.
  • FIG. 1 is a cross-sectional view schematically showing an example of an optical filter according to one embodiment.
  • FIG. 2 is a cross-sectional view schematically showing another example of the optical filter of one embodiment.
  • FIG. 3 is a cross-sectional view schematically showing another example of the optical filter of one embodiment.
  • FIG. 4 is a diagram showing spectral transmittance curves of near-infrared absorbing glass.
  • FIG. 5 is a diagram showing a spectral transmittance curve of the resin film of Example 1-1.
  • FIG. 6 is a diagram showing a spectral transmittance curve of the substrate of Example 2-1.
  • FIG. 7 is a diagram showing a spectral transmittance curve of the optical filter of Example 4-1.
  • the near-infrared absorbing dye is sometimes abbreviated as "NIR dye”
  • the ultraviolet absorbing dye is sometimes abbreviated as "UV dye”.
  • NIR dye the near-infrared absorbing dye
  • UV dye ultraviolet absorbing dye
  • the compound represented by formula (I) is referred to as compound (I).
  • a dye comprising compound (I) is also referred to as dye (I), and the same applies to other dyes.
  • the group represented by formula (I) is also referred to as group (I), and the groups represented by other formulas are the same.
  • the internal transmittance is the transmittance obtained by subtracting the influence of interface reflection from the measured transmittance, which is represented by the formula ⁇ measured transmittance/(100 ⁇ reflectance) ⁇ 100.
  • the spectroscopy of the transmittance of the resin film including the transmittance of the base material and the case where the dye is contained in the resin is all "internal transmittance" even if it is described as "transmittance”.
  • the transmittance measured by dissolving a dye in a solvent such as dichloromethane, the transmittance of a dielectric multilayer film, and the transmittance of an optical filter having a dielectric multilayer film are actually measured transmittances.
  • a transmittance of, for example, 90% or more in a specific wavelength range means that the transmittance in the entire wavelength range does not fall below 90%, that is, the minimum transmittance in the wavelength range is 90% or more.
  • a transmittance of, for example, 1% or less means that the transmittance does not exceed 1% in the entire wavelength range, that is, the maximum transmittance in the wavelength range is 1% or less.
  • the average transmittance and average internal transmittance in a particular wavelength range are the arithmetic mean of the transmittance and internal transmittance for each 1 nm of the wavelength range.
  • Optical properties can be measured using a UV-visible spectrophotometer. In the present specification, the numerical range "to" includes upper and lower limits.
  • An optical filter according to one embodiment of the present invention (hereinafter also referred to as "this filter”) comprises a substrate and a dielectric multilayer film laminated as an outermost layer on at least one main surface side of the substrate.
  • the substrate includes near-infrared absorbing glass and a resin film having a thickness of 10 ⁇ m or less laminated on at least one main surface of the near-infrared absorbing glass.
  • the resin film contains a resin and a dye (NIR1) having a maximum absorption wavelength of 680 to 740 nm in the resin.
  • the optical filter as a whole Due to the reflection properties of the dielectric multilayer film and the absorption properties of the near-infrared absorbing glass and near-infrared absorbing dye base material, the optical filter as a whole has excellent transmittance in the visible light region and excellent shielding in the near-infrared region. can achieve
  • FIG. 1 to 3 are cross-sectional views schematically showing an example of an optical filter according to one embodiment.
  • An optical filter 1A shown in FIG. 1 is an example having a dielectric multilayer film 20 on one main surface side of a substrate 10 having a near-infrared absorbing glass 11 and a resin film 12 .
  • “having a specific layer on the main surface side of the base material” is not limited to the case where the layer is provided in contact with the main surface of the base material, and another function is provided between the base material and the layer. Including cases where layers are provided.
  • the dielectric multilayer film 20 is provided on the surface of the near-infrared absorbing glass 11, but may be provided on the surface of the resin film 12.
  • the optical filter 1B shown in FIG. 2 is an example having dielectric multilayer films 20A and 20B on both main surfaces of the substrate 10.
  • FIG. 1 is an example having dielectric multilayer films 20A and 20B on both main surfaces of the substrate 10.
  • the optical filter 1C shown in FIG. 3 is an example in which the base material 10 has resin films 12A and 12B on both main surfaces of the near-infrared absorbing glass 11, and dielectric multilayer films 20A and 20B on both main surfaces of the base material 10. is.
  • the optical filter of the present invention satisfies all of the following spectral characteristics (i-1) to (i-13).
  • i-1 In the spectral transmittance curve at an incident angle of 0 degrees, the average transmittance T 450-600 (0 deg) AVE at a wavelength of 450 to 600 nm is 80% or more (i-2) Spectral transmission at an incident angle of 50 degrees
  • the average transmittance T 450-600 (50 deg) AVE at a wavelength of 450 to 600 nm is 80% or more (i-3) the average transmittance T 450-600 (0 deg) AVE and the average transmittance T 450-600 (50 deg)
  • the absolute value of the difference from AVE is 5% or less
  • the transmittance T 450 (0 deg) at a wavelength of 450 nm is 80% or more (i-5) Transmittance T 450 (50 deg) at a
  • the wavelength IR50 ( 50 deg) at which the transmittance is 50% is in the range of 610 to 650 nm (i-9) the wavelength IR50 (0 deg) and the absolute value of the difference between the wavelength IR50 (50 deg) is 10 nm or less (i-10)
  • the maximum transmittance T 1000-1200 ( 50 deg) at a wavelength of 1000 to 1200 nm is 5% or less (i-12) the transmittance T 450 (0deg) / maximum transmittance T 1000-1200 (0deg) MAX ⁇ 25 (i-13) the transmittance T 450 (50deg) / the maximum transmittance T 1000
  • This filter which satisfies all of the spectral characteristics (i-1) to (i-13), has little change in transmittance in the visible light region even at a high incident angle of 50 degrees, and has excellent shielding properties in the near-infrared region. is a filter.
  • T 450-600 (0 deg) AVE is preferably 85% or more, more preferably 87% or more.
  • T 450-600 (50 deg) AVE is preferably 83% or more, more preferably 85% or more.
  • the difference between T 450-600 (0 deg) AVE and T 450-600 (50 deg) AVE is preferably 4.5% or less, more preferably 4% or less.
  • T 450 (0 deg) is preferably 82% or more, more preferably 85% or more.
  • T 450 (50 deg) is preferably 81% or more, more preferably 82% or more.
  • T 450-600 (0 deg) MAX is preferably 92% or more, more preferably 93% or more.
  • IR50 (0 deg) is preferably 615 to 640 nm, more preferably 615 to 635 nm.
  • IR50 (50 deg) is preferably 615-640 nm, more preferably 615-635 nm.
  • Satisfying the spectral characteristic (i-9) means that the spectral curve in the region of 610 to 650 nm is less likely to shift even at a high incident angle.
  • the absolute value of the spectral characteristic (i-9) is preferably 9 nm or less, more preferably 8 nm or less.
  • T 1000-1200 (0 deg) MAX is preferably 4% or less, more preferably 2% or less.
  • T 1000-1200 (50 deg) MAX is preferably 4% or less, more preferably 3% or less.
  • T 450 (0 deg) /T 1000-1200 (0 deg) MAX is preferably 30 or more, more preferably 40 or more.
  • T 450 (50 deg) /T 1000-1200 (50 deg) MAX is preferably 15 or more, more preferably 20 or more.
  • the optical filter of the present invention preferably further satisfies the following spectral characteristics (i-14) to (i-15).
  • spectral characteristics i-14
  • the maximum transmittance T 750-1000 (0 deg) MAX at a wavelength of 750 to 1000 nm is 1% or less
  • the maximum transmittance T 750-1000 (50 deg) MAX at a wavelength of 750-1000 nm is 1% or less
  • T 750-1000 (0 deg) MAX is preferably 4% or less, more preferably 2% or less.
  • T 750-1000 (50 deg) MAX is preferably 4% or less, more preferably 3% or less.
  • the optical filter of the present invention preferably further satisfies the following spectral characteristics (i-16) to (i-18).
  • spectral characteristics i-16
  • the wavelength UV50 (0 deg) at which the transmittance is 50% is in the range of 400 to 440 nm
  • Spectroscopy at an incident angle of 50 degrees In the transmittance curve, the wavelength UV50 (50 deg) at which the transmittance is 50% is in the range of 400 to 440 nm (i-18)
  • the absolute value of the difference between the wavelength UV50 (0 deg) and the wavelength UV50 (50 deg) is 3 nm or less
  • Satisfying the spectral characteristics (i-16) to (i-17) means that the near-ultraviolet region can be blocked and visible transmitted light can be efficiently captured. Satisfying the spectral characteristic (i-18) means that the spectral curve in the region of 400 to 440 nm is less likely to shift even at a high incident angle.
  • UV50 (0 deg) is preferably 400 to 430 nm, more preferably 410 to 430 nm.
  • UV50 (50 deg) is preferably 400-430 nm, more preferably 410-430 nm.
  • the spectral characteristic (i-18) is preferably 2.5 nm or less, more preferably 2 nm or less.
  • the optical filter of the present invention preferably further satisfies the following spectral characteristics (i-19) to (i-22).
  • spectral transmittance curve at an incident angle of 0 degrees the average transmittance T 370-400 (0 deg) AVE at a wavelength of 370 to 400 nm is 2% or less (i-20) Spectral transmission at an incident angle of 50 degrees
  • the average transmittance T 370-400 (50 deg) AVE is 2% or less (i-21) at a wavelength of 370 to 400 nm.
  • the maximum transmittance T 370-400 (50deg) MAX at a wavelength of 370-400 nm is 3% or less
  • T 370-400 (0 deg) AVE is preferably 1% or less, more preferably 0.5% or less.
  • T 370-400 (50 deg) AVE is preferably 1% or less, more preferably 0.5% or less.
  • T 370-400 (0 deg) MAX is preferably 2.5% or less, more preferably 2% or less.
  • T 370-400 (50 deg) MAX is preferably 2.5% or less, more preferably 2% or less.
  • the dielectric multilayer film is laminated as the outermost layer on at least one main surface side of the substrate.
  • the dielectric multilayer film preferably further satisfies the following spectral characteristics (v-6) to (v-8).
  • v-6 In the spectral transmittance curve at an incident angle of 0 degrees, the average transmittance T 450-600 (0 deg) AVE at a wavelength of 450 to 600 nm is 91% or more
  • v-7) Spectral transmission at an incident angle of 50 degrees
  • the average transmittance T 450-600 (50 deg) AVE at a wavelength of 450 to 600 nm is 91% or more
  • the average transmittance T 450-600 (0 deg) AVE and the average transmittance T 450-600 The absolute value of the difference from (50 deg) AVE is 5% or less
  • T 450-600 (0 deg) AVE is preferably 90% or more, more preferably 92% or more.
  • T 450-600 (50 deg) AVE is preferably 90% or more, more preferably 92% or more.
  • (v-8) is preferably 4% or less, more preferably 3.5% or less.
  • the dielectric multilayer film in the present invention moderately shield the near-infrared region as shown in the above spectral characteristics (v-4) to (v-5). If a dielectric multilayer film is designed to enhance reflection characteristics in the near-infrared region, ripples are likely to occur in the visible light region. In the present invention, by designing the dielectric multilayer film so as not to strongly shield the near-infrared region, ripples in the visible light region are suppressed as shown in the above spectral characteristics (v-1) to (v-3). .
  • the near-infrared light shielding property which cannot be completely shielded by the reflection property of the dielectric multilayer film, is supplemented by the absorption property of the base material described later, and the present invention has excellent near-infrared light shielding property as a whole optical filter.
  • At least one of the dielectric multilayer films is preferably designed as a near-infrared reflective layer (hereinafter also referred to as an NIR reflective layer).
  • the other dielectric multilayer film is preferably designed as an NIR reflective layer, a reflective layer having a reflective region other than the near-infrared region, or an antireflection layer.
  • the NIR reflective layer is a dielectric multilayer film designed to block light in the near-infrared region.
  • the NIR reflective layer has, for example, wavelength selectivity of transmitting visible light and mainly reflecting light in the near-infrared region.
  • the reflective region of the NIR reflective layer may include a light shielding region in the near-infrared region of the resin film.
  • the NIR reflective layer is not limited to NIR reflective properties, and may be appropriately designed to further block light in a wavelength range other than the near-infrared range, for example, the near-ultraviolet range.
  • the NIR reflective layer is composed of, for example, a dielectric multilayer film in which dielectric films having different refractive indices are alternately laminated.
  • the dielectric film include a low refractive index dielectric film (low refractive index film), a medium refractive index dielectric film (middle refractive index film), and a high refractive index dielectric film (high refractive index film). It is preferable to combine and laminate two or more of these dielectric films. Above all, it is preferable to have at least a medium refractive index film from the viewpoint of enhancing light shielding properties in the infrared region to the extent that ripples do not occur in the visible region.
  • the high refractive index film preferably has a refractive index of 2.2 or more, more preferably 2.2 to 2.5.
  • materials for the high refractive index film include Ta 2 O 5 , TiO 2 , TiO, Ti 2 O 3 and Nb 2 O 5 .
  • Other commercial products available from Canon Optron include OS50 ( Ti3O5 ), OS10 ( Ti4O7 ), OA500 ( mixture of Ta2O5 and ZrO2), and OA600 ( mixture of Ta2O5 and TiO2 ). etc.
  • TiO 2 is preferable from the viewpoints of film formability, reproducibility in refractive index and stability, and the like.
  • the medium refractive index film preferably has a refractive index of 1.6 to 2.1.
  • 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), and the like.
  • 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 of refractive index, and stability.
  • the low refractive index film preferably has a refractive index of 1.5 or less, more preferably 1.4 to 1.5.
  • materials for the low refractive index film include SiO 2 , SiO x N y and MgF 2 .
  • Other commercially available products include S4F and S5F (a mixture of SiO2 and AlO2 ) manufactured by Canon Optron. Of these, SiO 2 is preferred from the viewpoints of reproducibility in film formation, stability, economy, and the like.
  • Spectroscopic characteristics (v-1) to (v-5) that is, a dielectric multilayer film that satisfies mild light shielding characteristics in the near-infrared region and low ripple characteristics in the visible light region, requires transmission of the desired wavelength band. , combining several types of dielectric films with different spectral characteristics when selecting. Specifically, the reflection ripple in the visible light region can be suppressed by reducing the difference in refractive index between the materials of the medium refractive index layer and the low refractive index layer. In a conventional infrared cut filter, a low refractive index material and a high refractive index material such as SiO 2 /TiO 2 are used to enhance the light shielding property in the near-infrared region. likely to occur.
  • the optical filter of the present invention it is possible to reduce the transmittance in the near-infrared region due to the absorption characteristics of the base material (dye and absorbing glass). / There is no need to use a combination of high refractive index layers.
  • the total lamination number of dielectric multilayer films constituting the reflective layer is preferably 20 layers or more, more preferably 30 layers or more, and still more preferably 35 layers or more. However, if the total number of laminations increases, warping or the like occurs or the film thickness increases. Therefore, the total number of laminations is preferably 100 or less, more preferably 75 or less, and even more preferably 60 or less. Further, the film thickness of the reflective layer is preferably 2 to 10 ⁇ m as a whole.
  • a vacuum film formation process such as a CVD method, a sputtering method, or a vacuum deposition method, or a wet film formation process such as a spray method or a dip method can be used.
  • the NIR reflective layer may provide predetermined optical properties with one layer (one group of dielectric multilayer films), or may provide predetermined optical properties with two layers.
  • each reflective layer may have the same structure or a different structure.
  • it is usually composed of a plurality of reflective layers with different reflection bands.
  • one is a near-infrared reflective layer that shields light in the short wavelength band of the near infrared region, and the other is both the long wavelength band and the near ultraviolet region of the near infrared region. It may be a near-infrared/near-ultraviolet reflective layer that shields the light.
  • the antireflection layer examples include a dielectric multilayer film, an intermediate refractive index medium, and a moth-eye structure in which the refractive index changes gradually.
  • a dielectric multilayer film is preferable from the viewpoint of optical efficiency and productivity.
  • the antireflection layer is obtained by alternately laminating dielectric multilayer films in the same manner as the reflective layer.
  • the substrate has near-infrared absorbing glass and a resin film with a thickness of 10 ⁇ m or less.
  • the resin film contains a resin and a dye (NIR1) having a maximum absorption wavelength of 680 to 740 nm in the resin, and is laminated on at least one main surface of the near-infrared absorbing glass.
  • the substrate preferably satisfies all of the following spectral characteristics (ii-1) to (ii-7).
  • (ii-1) average internal transmittance T 450-600 AVE at wavelength 450-600 nm is 85% or more
  • maximum internal transmittance T 450-600 MAX at wavelength 450-600 nm is 92% or more
  • Internal transmittance T 450 at 450 nm is 82% or more
  • the wavelength IR50 at which the internal transmittance is 50% is in the range of 610 to 650 nm
  • Average internal transmittance T at wavelengths 750 to 1000 nm 750-1000AVE is 1.5% or less
  • Maximum internal transmittance T 1000-1200MAX at wavelength 1000-1200nm is 5% or less
  • T 450-600 AVE is preferably 93% or higher, more preferably 95% or higher.
  • T 450-600 MAX is preferably 87% or more, more preferably 88% or more.
  • T 450 is preferably 83% or higher, more preferably 84% or higher.
  • Satisfying the spectral characteristics (ii-4) means that the near-infrared region can be blocked and visible transmitted light can be efficiently captured.
  • the IR50 is preferably in the range 615-640 nm, more preferably 615-635 nm.
  • Satisfying spectral characteristics (ii-5) means excellent light shielding properties in the near-infrared region of 750 to 1000 nm.
  • T 750-1000 AVE is preferably 1% or less, more preferably 0.8% or less.
  • Satisfying the spectral characteristics (ii-6) means excellent light shielding properties in the infrared region of 1000 to 1200 nm.
  • T 1000-1200MAX is preferably 4.8% or less, more preferably 4.5% or less.
  • Internal transmittance T 450 /maximum internal transmittance T 1000-1200MAX is preferably 17 or more, more preferably 18 or more.
  • the substrate preferably further satisfies the following spectral characteristics (ii-8).
  • spectral characteristics ii-8.
  • the maximum internal transmittance T 750-1000MAX at a wavelength of 750 to 1000 nm is 2% or less Satisfying the spectral characteristics (ii-8) means that the light shielding property in the near infrared region of 750 to 1000 nm is excellent. do.
  • T 750-1000MAX is preferably 1.2% or less, more preferably 0.8% or less.
  • the substrate preferably further satisfies the following spectral characteristics (ii-9) to (ii-11).
  • the wavelength UV50 at which the internal transmittance is 50% is in the range of 400 to 440 nm (ii-10)
  • the average internal transmittance T 370-400AVE at a wavelength of 370 to 400 nm is 3% or less (ii-11 )
  • the maximum internal transmittance T 370-400MAX at a wavelength of 370 to 400 nm is 5% or less Satisfying the spectral characteristics (ii-9) means that the near-ultraviolet region can be blocked and visible transmitted light can be efficiently captured.
  • the UV50 is preferably in the range 400-430 nm, more preferably 410-430 nm.
  • T 370-400 AVE is preferably 2% or less, more preferably 1% or less.
  • T 370-400MAX is preferably 4.5% or less, more preferably 4% or less.
  • the substrate has transparency in the visible light region as shown in the above spectral characteristics (ii-1) to (ii-3), and spectral characteristics (ii-5) to (ii-6) as shown in In addition, it has excellent light shielding properties in the near-infrared light region and the infrared light region, and as shown in the spectral characteristics (ii-7), it has both the transparency and light shielding properties.
  • the high light shielding properties in the near-infrared light region and the infrared light region can compensate for the light shielding property of the dielectric multilayer film described above.
  • the substrate has both the absorptivity of near-infrared absorbing glass and the absorptive ability of a resin film containing a near-infrared absorbing dye (NIR1).
  • NIR1 near-infrared absorbing dye
  • the near-infrared absorbing glass preferably satisfies all of the following spectral characteristics (iii-1) to (iii-6).
  • Satisfying spectral characteristics (iii-1) means excellent transmittance in the visible light region of 450 to 600 nm, and satisfying spectral characteristics (iii-2) means excellent transparency in the blue light region.
  • T 450-600 AVE is preferably 94% or higher, more preferably 95% or higher.
  • T 450 is preferably 83% or higher, more preferably 85% or higher.
  • the IR50 is preferably in the range 625-645 nm, more preferably 625-640 nm.
  • T 750-1000 AVE is preferably 2% or less, more preferably 1.2% or less.
  • Satisfying the spectral characteristics (iii-5) means excellent light shielding properties in the infrared region of 1000 to 1200 nm.
  • T 1000-1200MAX is preferably 4.8% or less, more preferably 4.5% or less.
  • T 450 /T 1000-1200MAX is preferably 15 or more, more preferably 18 or more.
  • the near-infrared absorbing glass absorbs near-infrared light from a region of 625 to 650 nm, as shown in the above property (iii-3), and reaches 750 nm, as shown in the above property (iii-4). After that, it is preferable to exhibit a high light-shielding property. As a result, a substrate can be obtained that can compensate for the light-shielding properties of the dielectric multilayer film described above.
  • the near-infrared absorption glass is not limited as long as it can obtain the above spectral characteristics, and examples thereof include absorption type glass containing copper ions in fluorophosphate-based glass, phosphate-based glass, and the like. Among them, phosphate-based glass is preferable from the viewpoint of easily obtaining the above spectral characteristics.
  • phosphate-based glass also includes silicate phosphate glass in which a part of the skeleton of the glass is composed of SiO 2 .
  • the phosphate-based glass contains the following glass-constituting components.
  • each content rate of the following glass constituents is a mass % display of oxide conversion.
  • P 2 O 5 is a main component (glass-forming oxide) that forms glass, and is an essential component for enhancing near-infrared cutting properties. If it exceeds, the melting temperature rises and the transmittance in the visible region decreases, which is not preferable. It is preferably 67-73%, more preferably 68-72%.
  • Al 2 O 3 is an essential component for improving weather resistance, but if it is less than 5%, the effect is not sufficiently obtained, and if it exceeds 10%, the melting temperature of the glass increases, and the near-infrared cut property and visible range are improved. It is not preferable because it lowers the permeability. It is preferably 6 to 10%, more preferably 7 to 9%.
  • B 2 O 3 is an essential component for lowering the melting temperature of the glass, but if it is less than 0.5%, the effect is not sufficiently obtained, and if it exceeds 3%, the near-infrared shielding property is lowered, which is not preferable. . It is preferably 0.7 to 2.5%, more preferably 0.8 to 2.0%.
  • Li 2 O is not an essential component, it has the effect of lowering the melting temperature of the glass. It is preferably 0 to 5%, more preferably 0 to 3%.
  • Na 2 O is an essential component for lowering the melting temperature of the glass, but if it is less than 3%, the effect is not sufficiently obtained, and if it exceeds 10%, the glass becomes unstable, which is not preferable. It is preferably 4 to 9%, more preferably 5 to 9%.
  • Li 2 O and Na 2 O are essential components for lowering the melting temperature of the glass, but if the content is less than 3%, the effect is not sufficient, and if the content exceeds 15%, the glass becomes unstable, which is undesirable. It is preferably 4 to 13%, more preferably 5 to 10%.
  • MgO is not an essential component, it has the effect of increasing the stability of the glass. It is preferably 1% or less, more preferably not contained. Although CaO is not an essential component, it has the effect of increasing the stability of the glass. It is preferably 1.5% or less, more preferably not contained. Although SrO is not an essential component, it has the effect of increasing the stability of the glass. It is preferably 0 to 4%, more preferably 0 to 3%. BaO is an essential component for lowering the melting temperature of the glass, but if it is less than 3%, the effect is not sufficiently obtained, and if it exceeds 9%, the glass becomes unstable, which is not preferable. It is preferably 3 to 8%, more preferably 4 to 8%. MgO + CaO + SrO + BaO are essential components for increasing the stability of the glass and lowering the melting temperature of the glass. I don't like it. It is preferably 3 to 12%, more preferably 4 to 10%.
  • CuO is an essential component for enhancing near-infrared shielding properties, but if the content is less than 0.5%, the effect cannot be sufficiently obtained, and if it exceeds 20%, the visible region transmittance decreases, which is not preferable. It is preferably 1 to 15%, more preferably 2 to 10%. Most preferably 3 to 9%.
  • K 2 O is not substantially contained in the phosphate glass.
  • K 2 O is known to have the effect of lowering the melting temperature of glass.
  • the melting temperature of the glass is lower than that when only Na 2 O is contained without containing K 2 O. resulted in an increase in The reason for this is as follows.
  • the liquidus temperature when equimolar mixture of P 2 O 5 and Na 2 O is about 628° C. from the phase diagram of the two-component system.
  • P 2 O 5 and K 2 O are equimolarly mixed, the liquidus temperature exceeds 800° C. from the phase diagram of the two-component system.
  • substantially free means not intended to be used as a raw material, and it is assumed that unavoidable impurities mixed in from raw material components and manufacturing processes are not substantially contained. Considering the inevitable impurities, “substantially free” means that the content is 0.05% or less.
  • copper ions in the glass component must absorb in the ultraviolet region and reduce the transmittance in the visible region. It is important to allow Cu 2+ , which has absorption in the near-infrared region, to exist as much as possible rather than Cu + , which is a factor in lowering the density. Copper in the glass component tends to be reduced as the melting temperature of the glass increases, that is, Cu 2+ is reduced to Cu + . Therefore, it is effective to lower the melting temperature of the glass as much as possible in order to allow a large amount of Cu 2+ to exist.
  • the melting temperature of the near-infrared cut filter glass of the present invention is preferably 1150° C. or lower, more preferably 1100° C. or lower, and even more preferably 1080° C. or lower. Therefore, the ratio of BaO and B 2 O 3 , which have the effect of lowering the melting temperature of the glass, to Al 2 O 3 , which has the effect of raising the melting temperature of the glass, is increased.
  • the balance in these glass components can be achieved by increasing (BaO+B 2 O 3 )/Al 2 O 3 , but if it is too large, it will lead to a decrease in weather resistance, so the ratio of these is 0.3 to 2.4. is in the range of Furthermore, these ratios are preferably 0.3 to 2.0, more preferably 0.5 to 1.5.
  • phosphate glass in order to obtain spectral characteristics with high transmittance in the visible region and low transmittance in the near-infrared region, specifically, sharp cutoff characteristics for light in the vicinity of 600 to 700 nm, glass It is important to reduce the distortion of the 6-coordinated structure of Cu 2+ in the glass and move the absorption peak of Cu 2+ to the longer wavelength side, that is, to further enhance the absorption of light in the near-infrared region by Cu 2+ in the glass. is.
  • the balance of network oxides contained in the glass is in the range of 6.5-10 for P 2 O 5 /Al 2 O 3 . Furthermore, these ratios are preferably 7 to 10, more preferably 7 to 9.5.
  • the balance of the modified oxides contained in the glass should be Na 2 O/(Li 2 O + MgO + CaO + SrO + BaO). ⁇ 3. Further, the ratio of these is preferably 0.5-2.5, more preferably 0.7-2.
  • alkali metal ions with a small ionic radius e.g., Li ions and Na ions
  • Chemically strengthened glass obtained by exchanging large alkali ions for example, Na ions or K ions for Li ions, and K ions for Na ions may be used.
  • 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 device strength.
  • the resin film preferably satisfies all of the following spectral characteristics (iv-1) to (iv-5).
  • (iv-1) average internal transmittance T 450-600 AVE at wavelength 450-600 nm is 93% or more
  • maximum internal transmittance T 450-600 MAX at wavelength 450-600 nm is 95% or more
  • Internal transmittance T 450 at 450 nm is 86% or more
  • IR50 (S) is the shortest wavelength at which the internal transmittance is 50% in the spectral transmittance curve of wavelengths 650 to 900 nm, and IR50 ( S) is the longest wavelength.
  • L) when IR50 (L) -IR50 (S) ⁇ 90 nm
  • Minimum internal transmittance T 700-800MIN at wavelength 700-800 nm is 10% or less
  • T 450-600 AVE is preferably 94% or higher, more preferably 95% or higher.
  • T 450-600 MAX is preferably 96% or higher, more preferably 97% or higher.
  • T 450 is preferably 87% or higher, more preferably 88% or higher.
  • IR50 (L) -IR50 (S) is preferably 95 nm or more, more preferably 105 nm or more.
  • T 700-800 MIN is preferably 9% or less, more preferably 7% or less.
  • the resin film preferably further satisfies the following spectral characteristics (iv-6) to (iv-7).
  • the wavelength IR50 (S) at which the internal transmittance is 50% is in the range of 650 to 700 nm (iv-7)
  • the wavelength IR50 (L) at which the internal transmittance is 50% is 740 to 850 nm
  • the IR50 (S) is preferably 650-690 nm, more preferably 660-690 nm.
  • IR50 (L) is preferably between 750 and 830 nm, more preferably between 760 and 830 nm.
  • the resin film preferably further satisfies the following spectral characteristics (iv-8).
  • spectral characteristics (iv-8) Average internal transmittance T 700-800AVE at a wavelength of 700 to 800 nm is 30% or less Satisfying spectral characteristics (iv-8) means excellent light shielding properties in the near-infrared region of 700 to 800 nm. do.
  • T 700-800 AVE is preferably 2.8% or less, more preferably 2.5% or less.
  • the resin film preferably further satisfies the following spectral characteristics (iv-9) to (iv-11).
  • the wavelength UV50 at which the internal transmittance is 50% is in the range of 400 to 440 nm (iv-10)
  • the average internal transmittance T 370-400AVE at a wavelength of 370 to 400 nm is 3% or less (iv-11 )
  • the maximum internal transmittance T 370-400MAX at a wavelength of 370 to 400 nm is 5% or less.
  • the UV50 is preferably in the range 400-430 nm, more preferably 410-430 nm.
  • T 370-400 AVE is preferably 2% or less, more preferably 1% or less.
  • T 370-400MAX is preferably 4.8% or less, more preferably 4.6% or less.
  • the resin film in the present invention contains a dye (NIR1) having a maximum absorption wavelength of 680 to 740 nm, so that near-infrared light near 700 nm as shown in the above characteristics (iv-4) and (iv-5) It is particularly excellent in light-shielding properties over a wide area.
  • NIR1 dye having a maximum absorption wavelength of 680 to 740 nm, so that near-infrared light near 700 nm as shown in the above characteristics (iv-4) and (iv-5) It is particularly excellent in light-shielding properties over a wide area.
  • the near-infrared light region around 700 nm which is slightly light-shielding with infrared-absorbing glass, can be shielded by the absorption characteristics of the dye.
  • the dye (NIR1) has a maximum absorption wavelength in the resin between 680 and 740 nm, preferably between 700 and 730 nm.
  • the resin refers to the resin forming the resin film.
  • the NIR dye may consist of one kind of compound or may contain two or more kinds of compounds.
  • the resin film in the present invention preferably further contains other near-infrared absorbing dyes having different maximum absorption wavelengths in addition to the dye (NIR1). As a result, the resin film can obtain a wide range of light shielding properties in the near-infrared region around 700 nm, and the characteristic (iv-4) can be easily obtained.
  • a dye (NIR2) having a maximum absorption wavelength in the resin that is 20 to 60 nm longer than that of the dye (NIR1) is preferred.
  • the maximum absorption wavelength of the dye (NIR2) is preferably 700 to 800 nm.
  • the dye (NIR1) a squarylium compound is preferable from the viewpoints of maximum absorption wavelength range, visible light transmittance, solubility in resin, and durability.
  • the maximum absorption wavelength of the squarylium compound that is the dye (NIR1) is preferably 680 to 740 nm.
  • the dye (NIR2) a squarylium compound and a cyanine compound are preferable from the viewpoints of maximum absorption wavelength region, visible light transmittance, solubility in resin, and durability.
  • the maximum absorption wavelength of the squarylium compound, which is the dye (NIR2) is preferably 740 to 770 nm.
  • the maximum absorption wavelength of the cyanine compound that is the dye (NIR2) is preferably 740 to 800 nm.
  • the squarylium compound that is the dye (NIR1) is preferably a compound represented by the following formula (I).
  • NIR1 a compound represented by the following formula (I).
  • R 21 and R 22 , R 22 and R 25 , and R 21 and R 23 are linked together to form 5- or 6-membered heterocyclic ring A, heterocyclic ring B, and heterocyclic ring C, respectively, with the nitrogen atom; good too.
  • R 21 and R 22 are, as the divalent group -Q- to which they are bonded, a hydrogen atom having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or It represents an alkylene group optionally substituted by an optionally substituted acyloxy group having 1 to 10 carbon atoms, or an alkyleneoxy group.
  • R 22 and R 25 when the heterocyclic ring B is formed, and R 21 and R 23 when the heterocyclic ring C is formed are respectively the divalent groups —X 1 —Y 1 — and — to which they are attached.
  • X 2 -Y 2 - (X 1 and X 2 are on the nitrogen-bonding side)
  • X 1 and X 2 are groups represented by the following formula (1x) or (2x)
  • Y 1 and Y 2 are each A group represented by any one of the following formulas (1y) to (5y).
  • each of X 1 and X 2 is a group represented by the following formula (2x)
  • each of Y 1 and Y 2 may be a single bond, in which case an oxygen atom may be present between the carbon atoms. .
  • Zs are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, or -NR 38 R 39 (R 38 and R 39 are each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
  • R 31 to R 36 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 37 represents an alkyl group having 1 to 6 carbon atoms or a represents an aryl group.
  • R 27 , R 28 , R 29 , R 31 to R 37 , R 21 to R 23 when not forming a heterocyclic ring, and R 25 are combined with any other of these to form a 5-membered ring Or you may form a 6-membered ring.
  • R 31 and R 36 and R 31 and R 37 may be directly bonded.
  • R 21 , R 22 , R 23 and R 25 when not forming a heterocyclic ring are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl or alkoxy group having 1 to 20 carbon atoms, or 1 to 10 acyloxy groups, 6 to 11 carbon atoms aryl groups, or optionally substituted and optionally having oxygen atoms between carbon atoms 7 to 18 araryl groups .
  • Examples of the compound (I) include compounds represented by any one of formulas (I-1) to (I-3), and solubility in resins, heat resistance and light resistance in resins, From the viewpoint of the visible light transmittance of the contained resin layer, the compound represented by formula (I-1) is particularly preferred.
  • X 1 is preferably group (2x), and Y 1 is preferably a single bond or group (1y).
  • R 31 to R 36 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
  • -Y 1 -X 1 - specifically includes divalent organic groups represented by formulas (11-1) to (12-3).
  • R 21 is independently represented by the formula (Groups represented by 4-1) or (4-2) are more preferred.
  • R 71 to R 75 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
  • R 24 is preferably —NR 27 R 28 .
  • a compound (I-1) in which R 24 is —NH—C( ⁇ O)—R 29 is represented by formula (I-11).
  • R 23 and R 26 are each preferably a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having 1 to 6 carbon atoms, each of which is more preferably a hydrogen atom.
  • R 29 is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 10 carbon atoms, or an optionally substituted
  • An araryl group having 7 to 18 carbon atoms which may have an oxygen atom between carbon atoms is preferred.
  • substituents include hydroxyl group, carboxy group, sulfo group, cyano group, alkyl group having 1 to 6 carbon atoms, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and alkoxy group having 1 to 6 carbon atoms.
  • An acyloxy group and the like can be mentioned.
  • R 29 is a linear, branched or cyclic alkyl group having 1 to 17 carbon atoms, a phenyl group optionally substituted with an alkoxy group having 1 to 6 carbon atoms, and an oxygen atom between carbon atoms.
  • a group selected from araryl groups having 7 to 18 carbon atoms which may be substituted is preferred.
  • one or more hydrogen atoms may be independently substituted with a hydroxyl group, a carboxy group, a sulfo group, or a cyano group, and an unsaturated bond between carbon atoms, an oxygen atom, a saturated or unsaturated
  • a group which is a hydrocarbon group having at least one or more branches and having 5 to 25 carbon atoms and which may contain a ring structure can also be preferably used.
  • Compound (I-11) more specifically includes the compounds shown in the table below.
  • the symbols on the left and right sides of the squarylium skeleton have the same meaning.
  • the compound (I-11) among these, compounds (1-11-1) to (1-11-12) and compounds (1-11-17) to (1-11-28) are added to the resin From the viewpoint of solubility, maximum absorption wavelength, light resistance, heat resistance, and high absorbance, especially compounds (1-11-1) to (1-11-12) are light resistance and heat resistance. is preferred.
  • the dielectric multilayer film has a moderate light-shielding property in the ultraviolet region, so the lightfastness of the dye is particularly important.
  • the squarylium compound that is the dye (NIR2) is preferably a compound represented by the following formula (II).
  • Each ring Z is independently a 5- or 6-membered ring having 0 to 3 heteroatoms in the ring, and the hydrogen atoms of ring Z may be substituted.
  • the carbon atoms or heteroatoms constituting R 1 and R 2 , R 2 and R 3 , and R 1 and ring Z are linked together to form heterocycle A1, heterocycle B1 and heterocycle C1 together with the nitrogen atom, respectively. in which case the hydrogen atoms of heterocycle A1, heterocycle B1 and heterocycle C1 may be substituted.
  • R 1 and R 2 when not forming a hetero ring each independently contain a hydrogen atom, a halogen atom, or an unsaturated bond between carbon atoms, a hetero atom, or a saturated or unsaturated ring structure It often represents a hydrocarbon group which may have a substituent.
  • R 4 and R 3 when not forming a hetero ring are each independently a hydrogen atom, a halogen atom, or an optionally substituted alkyl group or Indicates an alkoxy group.
  • Examples of compound (II) include compounds represented by any one of formulas (II-1) to (II-3). From the viewpoint of solubility in resins and visible light transmission in resins, Compounds of formula (II-3) are particularly preferred.
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 15 carbon atoms.
  • R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 10 carbon atoms.
  • R 1 , R 4 , and R 9 to R 12 each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 15 carbon atoms.
  • R 7 and R 8 each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 5 carbon atoms.
  • R 1 and R 2 in compound (II-1) and compound (II-2) are preferably independently alkyl groups having 1 to 15 carbon atoms from the viewpoint of solubility in resins, visible light transmittance, etc. , more preferably an alkyl group having 7 to 15 carbon atoms, at least one of R 1 and R 2 more preferably a branched alkyl group having 7 to 15 carbon atoms, and both R 1 and R 2 having 8 carbon atoms Alkyl groups with ⁇ 15 branches are particularly preferred.
  • R 1 in the compound (II-3) is independently preferably an alkyl group having 1 to 15 carbon atoms, and an alkyl group having 1 to 10 carbon atoms, from the viewpoint of solubility in transparent resins, visible light transmittance, etc. is more preferred, and an ethyl group and an isopropyl group are particularly preferred.
  • R 4 is preferably a hydrogen atom or a halogen atom, particularly preferably a hydrogen atom, from the viewpoint of visible light transmittance and ease of synthesis.
  • R 7 and R 8 are each preferably a hydrogen atom, a halogen atom, or an optionally halogen-substituted alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a halogen atom, or a methyl group.
  • R 9 to R 12 is preferably independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may be substituted with a halogen atom.
  • —CR 9 R 10 —CR 11 R 12 — includes divalent organic groups represented by the following groups (13-1) to (13-5).
  • Compound (II-3) more specifically includes the compounds shown in the table below.
  • the symbols on the left and right sides of the squarylium skeleton have the same meaning.
  • compounds (II-3) among these, compounds (II-3-1) to (II-3-4) have solubility in resin, high absorption coefficient, light resistance, and heat resistance. preferred from
  • Compounds (I) to (II) can be produced by known methods.
  • Compound (I) can be produced by the methods described in US Pat. .
  • Compound (II) can be produced by the method described in International Publication No. 2017/135359.
  • cyanine compound preferably a compound represented by the following formula (III).
  • R 101 to R 109 each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 15 carbon atoms, or an aryl group having 5 to 20 carbon atoms.
  • R 110 to R 114 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 15 carbon atoms.
  • X- represents a monovalent anion .
  • n1 is 0 or 1;
  • a hydrogen atom bonded to a carbocyclic ring containing —(CH 2 ) n1 — is substituted with a halogen atom, an optionally substituted alkyl group having 1 to 15 carbon atoms or an aryl group having 5 to 20 carbon atoms; good too.
  • the alkyl group (including the alkyl group possessed by the alkoxy group) may be linear, or may contain a branched structure or a saturated ring structure.
  • An aryl group refers to a group bonded through a carbon atom constituting an aromatic ring of an aromatic compound, such as a benzene ring, naphthalene ring, biphenyl, furan ring, thiophene ring, pyrrole ring, and the like.
  • Substituents for optionally substituted alkyl or alkoxy groups having 1 to 15 carbon atoms or aryl groups having 5 to 20 carbon atoms include halogen atoms and alkoxy groups having 1 to 10 carbon atoms. .
  • R 101 is preferably an alkyl group having 1 to 15 carbon atoms or an aryl group having 5 to 20 carbon atoms. ⁇ 15 alkyl groups are more preferred.
  • R 102 to R 105 , R 108 , and R 109 are each independently preferably a hydrogen atom, an alkyl group or alkoxy group having 1 to 15 carbon atoms, or an aryl group having 5 to 20 carbon atoms.
  • a hydrogen atom is more preferable from the viewpoint of obtaining light transmittance.
  • each of R 110 to R 114 is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and more preferably a hydrogen atom from the viewpoint of obtaining high visible light transmittance.
  • R 106 and R 107 are each independently preferably a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 5 to 20 carbon atoms (which may include a chain, cyclic or branched alkyl group), A hydrogen atom or an alkyl group having 1 to 15 carbon atoms is more preferable. Moreover, R 106 and R 107 are preferably the same group.
  • X ⁇ includes I ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , anions represented by formulas (X1) and (X2), etc., preferably BF 4 ⁇ or PF 6 ⁇ be.
  • R 101 to R 114 and X - are the same as in formula (III).
  • R 115 to R 120 each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl or alkoxy group having 1 to 15 carbon atoms, or an aryl group having 5 to 20 carbon atoms.
  • R 115 to R 120 are each independently preferably a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 5 to 20 carbon atoms (which may include a chain, cyclic or branched alkyl group), A hydrogen atom or an alkyl group having 1 to 15 carbon atoms is more preferable.
  • R 115 to R 120 are preferably the same group.
  • the atoms or groups bonded to each skeleton are atoms or groups shown in the table below. compound.
  • R 101 to R 109 are all the same on the left and right sides of the formula.
  • R 110 to R 114 in the table below represent atoms or groups bonded to the central benzene ring in each formula, and when all five are hydrogen atoms, they are described as "H".
  • R 110 to R 114 is a substituent and the other is a hydrogen atom, only the combination of the symbol of the substituent and the substituent is described.
  • R 112 —C(CH 3 ) 3 indicates that R 112 is —C(CH 3 ) 3 and otherwise a hydrogen atom.
  • R 115 -R 120 in the table below represent atoms or groups bonded to the central cyclohexane ring in formula (III-1), and when all six are hydrogen atoms, they are described as "H".
  • R 115 to R 120 is a substituent and the other is a hydrogen atom, only the combination of the symbol of the substituent and the substituent is described.
  • the dye (III-1) among these, the dyes (III-1-1) to (III-1-12 ) and the like are preferable.
  • the dyes (III-1-1), (III-1-5) and (III-1-9) are particularly preferred in terms of ease of synthesis.
  • Dyes (III) are described, for example, in Dyes and pigments 73 (2007) 344-352 and J.P. It can be produced by the method described in Heterocyclic chem, 42, 959 (2005).
  • the content of the NIR dye in the resin film is preferably 0.1 to 25 parts by mass, more preferably 0.3 to 15 parts by mass, per 100 parts by mass of the resin. In addition, when combining 2 or more types of compounds, the said content is sum total of each compound. Further, when the dye (NIR1) and the dye (NIR2) are used together, the content of the dye (NIR1) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin, and the content of the dye (NIR2) is 100 parts by mass of the resin. It is preferably 0.1 to 10 parts by mass.
  • the resin film may contain other dyes in addition to the NIR dyes described above.
  • a dye (UV) having a maximum absorption wavelength in the resin of 370 to 440 nm is preferable. Thereby, the near-ultraviolet region can be efficiently shielded.
  • Dyes include oxazole dyes, merocyanine dyes, cyanine dyes, naphthalimide dyes, oxadiazole dyes, oxazine dyes, oxazolidine dyes, naphthalic acid dyes, styryl dyes, anthracene dyes, cyclic carbonyl dyes, triazole dyes, and the like. be done.
  • merocyanine dyes are particularly preferred.
  • one type may be used alone, or two or more types may be used in combination.
  • a merocyanine dye represented by the following formula (M) is particularly preferable.
  • R 1 represents an optionally substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.
  • Preferred substituents are alkoxy groups, acyl groups, acyloxy groups, cyano groups, dialkylamino groups and chlorine atoms.
  • the alkoxy group, acyl group, acyloxy group and dialkylamino group preferably have 1 to 6 carbon atoms.
  • R 1 having no substituent examples include an alkyl group having 1 to 12 carbon atoms in which a portion of the hydrogen atoms may be substituted with an aliphatic ring, an aromatic ring or an alkenyl group, and a portion of the hydrogen atoms. is optionally substituted by an aromatic ring, an alkyl group or an alkenyl group, and a cycloalkyl group having 3 to 8 carbon atoms, and a portion of the hydrogen atoms may be substituted by an aliphatic ring, an alkyl group or an alkenyl group.
  • Aryl groups having 6 to 12 carbon atoms are preferred.
  • R 1 is an unsubstituted alkyl group
  • the alkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms.
  • R 1 is an alkyl group having 1 to 12 carbon atoms partially substituted with an aliphatic ring, an aromatic ring or an alkenyl group, a cycloalkyl group having 3 to 6 carbon atoms and 1 to 1 carbon atoms 4 alkyl groups, phenyl-substituted alkyl groups having 1 to 4 carbon atoms are more preferred, and phenyl-substituted alkyl groups having 1 or 2 carbon atoms are particularly preferred.
  • An alkyl group substituted with an alkenyl group means an alkenyl group as a whole but having no unsaturated bond between the 1- and 2-positions, such as an allyl group or a 3-butenyl group.
  • R 1 is an alkyl group having 1 to 6 carbon atoms in which part of the hydrogen atoms may be substituted with a cycloalkyl group or a phenyl group.
  • Particularly preferred R 1 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 and t-butyl group. be done.
  • At least one of R 2 and R 3 is preferably an alkyl group, more preferably both are alkyl groups. Hydrogen atoms are more preferred if R 2 and R 3 are not alkyl groups. Both R 2 and R 3 are particularly preferably C 1-6 alkyl groups.
  • At least one of R 4 and R 5 is preferably a hydrogen atom, and both are more preferably hydrogen atoms.
  • R 4 or R 5 is not a hydrogen atom, an alkyl group having 1 to 6 carbon atoms is preferred.
  • Y represents a methylene group or an oxygen atom substituted with R6 and R7 .
  • R 6 and R 7 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 represents any of the divalent groups represented by the following formulas (X1) to (X5).
  • R 8 and R 9 each independently represent an optionally substituted monovalent hydrocarbon group having 1 to 12 carbon atoms
  • R 10 to R 19 each independently represent a hydrogen atom, or It represents an optionally substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.
  • Substituents for R 8 to R 19 include the same substituents as those for R 1 , and preferred embodiments are also the same. When R 8 to R 19 are hydrocarbon groups having no substituents, the same embodiments as R 1 having no substituents can be mentioned.
  • R 8 and R 9 may be different groups, but are preferably the same group.
  • R 8 and R 9 are unsubstituted alkyl groups, they may be linear or branched, and preferably have 1 to 6 carbon atoms.
  • R 8 and R 9 are both C 1-6 alkyl groups in which some of the hydrogen atoms may be substituted with cycloalkyl groups or phenyl groups. Particularly preferred R 8 and R 9 are both alkyl groups having 1 to 6 carbon atoms, and specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl. group, t-butyl group, and the like.
  • both R 10 and R 11 are more preferably alkyl groups having 1 to 6 carbon atoms, particularly preferably the same alkyl group.
  • both R 12 and R 15 are preferably hydrogen atoms or unsubstituted alkyl groups having 1 to 6 carbon atoms.
  • Two groups, R 13 and R 14 , which are bonded to the same carbon atom, are preferably both hydrogen atoms or both C 1-6 alkyl groups.
  • Two groups R 16 and R 17 and R 18 and R 19 bonded to the same carbon atom in formula (X4) are both hydrogen atoms, or both preferably C 1-6 alkyl groups.
  • the compound (M) can be produced by a known method.
  • the content of the dye (UV) in the resin film is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the resin. Within this range, deterioration of resin properties is less likely to occur.
  • the substrate in this filter is a composite substrate in which a resin film is laminated on at least one main surface of near-infrared absorbing glass.
  • Resins are not limited as long as they are transparent resins, and include polyester resins, acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, and polyparaphenylene.
  • One or more transparent resins selected from resins, polyarylene ether phosphine oxide resins, polyamide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyurethane resins, polystyrene resins, and the like are used. These resins may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • One or more resins selected from polyimide resins, polycarbonate resins, polyester resins, and acrylic resins are preferable from the viewpoint of spectral characteristics, glass transition point (Tg), and adhesion of the resin film.
  • a resin film is prepared by dissolving or dispersing a pigment, a resin or a raw material component of the resin, and each component to be blended as necessary in a solvent to prepare a coating solution, coating the solution on a support, and drying it. It can be formed by curing and, if necessary, curing.
  • the support in this case may be the near-infrared absorbing glass used in the present filter, or may be a peelable support used only when forming the resin film.
  • the solvent may be a dispersion medium capable of stably dispersing or a solvent capable of dissolving.
  • the coating liquid may contain a surfactant to improve voids caused by microbubbles, dents caused by adhesion of foreign matter, repellency during the drying process, and the like.
  • a surfactant to improve voids caused by microbubbles, dents caused by adhesion of foreign matter, repellency during the drying process, and the like.
  • dip coating, cast coating, spin coating, or the like can be used for the application of the coating liquid.
  • a resin film is formed by coating the above coating liquid on a support and then drying it.
  • the coating liquid contains a raw material component of the transparent resin, it is further subjected to a curing treatment such as heat curing or photocuring.
  • the resin film can also be produced in the form of a film by extrusion molding.
  • a substrate can be produced by laminating the obtained film-like resin film on a near-infrared absorbing glass and integrating them by thermocompression bonding or the like.
  • the resin film may have one layer in the optical filter, or may have two or more layers. When it has two or more layers, each layer may have the same configuration or different configurations.
  • the thickness of the resin film is 10 ⁇ m or less, preferably 5 ⁇ m or less from the viewpoint of the in-plane film thickness distribution in the substrate after coating and the appearance quality, and from the viewpoint of expressing desired spectral characteristics at an appropriate dye concentration. is preferably 0.5 ⁇ m or more.
  • the total thickness of each resin film is preferably within the above range.
  • the shape of the substrate is not particularly limited, and may be block-shaped, plate-shaped, or film-shaped.
  • the present filter may include, as other constituent elements, for example, a constituent element (layer) that provides absorption by inorganic fine particles or the like that controls the transmission and absorption of light in a specific wavelength range.
  • a constituent element layer
  • 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 absorb light over a wide range of infrared wavelengths exceeding 1200 nm, so they can be used when such infrared light shielding properties are required. .
  • An optical filter comprising a substrate and a dielectric multilayer film laminated as an outermost layer on at least one main surface side of the substrate,
  • the substrate comprises near-infrared absorbing glass and a resin film having a thickness of 10 ⁇ m or less laminated on at least one main surface of the near-infrared absorbing glass,
  • the resin film contains a resin and a dye (NIR1) having a maximum absorption wavelength of 680 to 740 nm in the resin,
  • NIR1 dye having a maximum absorption wavelength of 680 to 740 nm in the resin
  • the average transmittance T 450-600 (0 deg) AVE at a wavelength of 450 to 600 nm is 80% or more (i-2) Spectral transmission at an incident angle of 50 degrees
  • the average transmittance T 450-600 (50 deg) AVE at a wavelength of 450 to 600 nm is 80% or more (i-3) the average transmittance T 450-600 (0 deg) AVE and the average transmittance T 450-600 (50 deg)
  • the absolute value of the difference from AVE is 5% or less (i-4)
  • the transmittance T 450 (0 deg) at a wavelength of 450 nm is 80% or more (i-5)
  • Transmittance T 450 (50 deg) at a wavelength of 450 nm is 80% or more in the spectral transmittance curve at an incident angle of 50 degrees
  • the wavelength IR50 ( 50 deg) at which the transmittance is 50% is in the range of 610 to 650 nm (i-9) the wavelength IR50 (0 deg) and the absolute value of the difference between the wavelength IR50 (50 deg) is 10 nm or less (i-10)
  • the maximum transmittance T 1000-1200 ( 50 deg) at a wavelength of 1000 to 1200 nm is 5% or less (i-12) the transmittance T 450 (0deg) / maximum transmittance T 1000-1200 (0deg) MAX ⁇ 25 (i-13) the transmittance T 450 (50deg) / the maximum transmittance T 1000
  • the maximum transmittance T 750-1000 (0 deg) MAX at a wavelength of 750 to 1000 nm is 1% or less
  • the maximum transmittance T 750-1000 (50 deg) MAX at a wavelength of 750 to 1000 nm is 1% or less [3]
  • the substrate satisfies all of the following spectral characteristics (ii-1) to (ii-7).
  • the optical filter according to [1] or [2].
  • the maximum internal transmittance T 750-1000MAX at a wavelength of 750 to 1000 nm is 2% or less [5]
  • the near-infrared absorbing glass satisfies all of the following spectral characteristics (iii-1) to (iii-6).
  • the resin film further contains a dye (NIR2), The optical system according to any one of [1] to [6], wherein the dye (NIR2) has a maximum absorption wavelength in the resin that is 20 to 60 nm larger than the maximum absorption wavelength in the resin of the dye (NIR1). filter.
  • the minimum transmittance T 450-600 (0 deg) MIN is 90% or more at a wavelength of 450 to 600 nm
  • the minimum transmittance T 450-600 (50 deg) MIN at a wavelength of 450 to 600 nm is 90% or more
  • the minimum transmittance T 450-600 (0 deg) MIN and the minimum transmittance T 450-600 (50 deg) The absolute value of the difference from MIN is 5% or less (v-4)
  • the average transmittance at a wavelength of 700 to 1200 nm T 700-1200 (0 deg) AVE is 30 ⁇ 75%
  • the resin film contains a squarylium compound as a dye (NIR1) having a maximum absorption wavelength of 680 to 740 nm in the resin, [1] to [9] further comprising at least one of a squarylium compound and a cyanine compound as a dye (NIR2) having a maximum absorption wavelength in the resin that is 20 to 60 nm larger than the maximum absorption wavelength of the dye (NIR1) in the resin; ]
  • the optical filter according to any one of .
  • the optical filter according to any one of [1] to [10] wherein the resin film further contains a dye (UV) having a maximum absorption wavelength of 370 to 440 nm in the resin.
  • An imaging device comprising the optical filter according to any one of [1] to [11].
  • the dyes used in each example are as follows.
  • Compound 1 (squarylium compound): Synthesized based on WO2014/088063 and WO2016/133099.
  • Compound 2 (merocyanine compound): Synthesized according to German Patent Publication No. 10109243.
  • Compound 3 (squarylium compound): Synthesized based on International Publication No. 2017/135359.
  • Compound 4 (cyanine compound): Synthesized according to the method described in Dyes and Pigments, 73, 344-352 (2007).
  • Compound 5 (cyanine compound): Synthesized according to the method described in Dyes and Pigments, 73, 344-352 (2007).
  • Compound 6 (diimmonium compound): Synthesized according to the method described in Japanese Patent No. 4800769.
  • the resulting coating solution was applied to an alkali glass (D263 glass manufactured by SCHOTT, thickness 0.2 mm) by a spin coating method to form a coating film having a thickness of approximately 1.0 ⁇ m.
  • the spectral transmittance curve in the wavelength range of 350 to 1200 nm was measured for the obtained coating film using an ultraviolet-visible spectrophotometer.
  • the spectral properties of each of the compounds 1 to 6 in the polyimide resin are shown in the table below. Note that the spectral characteristics shown in the table below were evaluated based on internal transmittance in order to avoid the influence of reflection at the air interface and the glass interface.
  • Phosphate glass manufactured by AGC, SP50T was prepared as the near-infrared absorbing glass.
  • a spectral transmittance curve in the wavelength range of 350 to 1200 nm was measured for the near-infrared absorbing glass using an ultraviolet-visible spectrophotometer.
  • FIG. 4 shows the spectral transmission curve of the near-infrared absorbing glass.
  • the near-infrared absorbing glass used has high transmittance in the visible light region and excellent light-shielding properties in the near-infrared region.
  • Spectral characteristics of resin film Any one of the dyes of compounds 1 to 6 is mixed with the polyimide resin solution prepared in the same manner as when calculating the spectral characteristics of the above compounds at the concentrations shown in the table below, and stirred and dissolved at 50 ° C. for 2 hours. Thus, a coating liquid was obtained. The resulting coating liquid was applied to alkali glass (D263 glass manufactured by SCHOTT, thickness 0.2 mm) by a spin coating method to form a resin film having a thickness of 3.0 ⁇ m. The spectral transmittance curve in the wavelength range of 350 to 1200 nm was measured for the obtained resin film using an ultraviolet-visible spectrophotometer.
  • alkali glass D263 glass manufactured by SCHOTT, thickness 0.2 mm
  • the average internal transmittance T 450-600AVE at a wavelength of 450 to 600 nm, the maximum internal transmittance T 450-600MAX , the internal transmittance T 450 at a wavelength of 450 nm, and the spectral transmittance curve at a wavelength of 650 to 900 nm The difference between the shortest wavelength IR50 (S) and the longest wavelength IR50 (L) at which the internal transmittance is 50%, the average internal transmittance T 700-800AVE at a wavelength of 700-800 nm, the minimum internal transmittance T 700-800MIN , an average internal transmittance T 370-400AVE and a maximum internal transmittance T 370-400MAX at a wavelength UV50 at which the internal transmittance is 50%, a wavelength of 370 to 400 nm, and T 370-400MAX were calculated.
  • FIG. 5 shows the spectral transmittance curve of the resin film of Example 1-1.
  • Examples 1-1 to 1-5 are reference examples.
  • FIG. 6 shows the spectral transmittance curve of the substrate of Example 2-1.
  • Examples 2-1 to 2-5 are reference examples.
  • the substrate in the present invention has a high ratio of visible light transmittance to near-infrared light transmittance (T 450 /T 1000-1200MAX ), so that visible light transmittance and near-infrared shielding properties are compatible.
  • the multilayer film has high transmittance in the range of 450 to 600 nm at incident angles of 0 deg and 50 deg, and the transmittance does not easily change, that is, the multilayer film has high transmittance in the visible light region and does not easily generate ripples. . Also, it can be seen from the transmittance of 700 to 1200 nm that the near-infrared light region is moderately shielded.
  • the optical filters of Examples 4-1 to 4-3, 4-5, 4-6, and 4-9 generate less ripple in the visible light region even at high incident angles. It can be seen that the transparency and the light shielding property in the near-infrared region of 700 to 1200 nm are excellent.
  • the optical filter of Example 4-4 has a large difference between the average transmittance T 450-600 (0 deg) AVE and the average transmittance T 450-600 (50 deg) AVE, and the change in visible light transmittance is large at high incident angles. .
  • Example 4-4 the transmittance T 450 (50 deg) at a wavelength of 450 nm at an incident angle of 50 degrees and the average transmittance T 450-600 (50 deg) AVE at a wavelength of 450 to 600 nm are also low.
  • the dielectric multilayer film used in Example 4-4 is excellent in light shielding properties in the near-infrared region, ripples are likely to occur in the visible light region at high incident angles. It can be seen that the optical filters of Examples 4-7 and 4-8 have a low transmittance T 450 (50 deg) at a wavelength of 450 nm and an incident angle of 50 degrees.
  • the maximum transmittance T 450-600 (0 deg) MAX at a wavelength of 450-600 nm at an incident angle of 0 degree is low.
  • the maximum absorption wavelength of the dye compound used in combination with Compound 1 having a maximum absorption wavelength of 722 nm is 845 nm (using compound 5) in Example 4-7, and 1112 nm (compound 6 use).
  • the longer the maximum absorption wavelength the lower the transmittance in the visible light region.
  • the optical filter of the present invention has excellent visible light transmittance, little change in transmittance in the visible light range even at high incident angles, and spectral characteristics with excellent shielding properties in the near-infrared light range. For example, it is useful for use in imaging devices such as cameras and sensors for transport aircraft, which have recently become highly sophisticated.
  • 1A, 1B, 1C optical filter, 10... base material, 11... near-infrared absorbing glass, 12, 12A, 12B... resin film, 20, 20A, 20B... dielectric multilayer film

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