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WO2019138976A1 - Filtre optique et dispositif d'imagerie - Google Patents

Filtre optique et dispositif d'imagerie Download PDF

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Publication number
WO2019138976A1
WO2019138976A1 PCT/JP2019/000109 JP2019000109W WO2019138976A1 WO 2019138976 A1 WO2019138976 A1 WO 2019138976A1 JP 2019000109 W JP2019000109 W JP 2019000109W WO 2019138976 A1 WO2019138976 A1 WO 2019138976A1
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Prior art keywords
wavelength
optical filter
transmittance
light
spectral transmittance
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PCT/JP2019/000109
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English (en)
Japanese (ja)
Inventor
智孝 高城
新毛　勝秀
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Nippon Sheet Glass Co Ltd
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Nippon Sheet Glass Co Ltd
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Publication of WO2019138976A1 publication Critical patent/WO2019138976A1/fr
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters

Definitions

  • the present invention relates to an optical filter and an imaging device.
  • Patent Document 1 describes a near-infrared cut filter including a laminate having a resin layer containing a near-infrared absorber on at least one side of a glass plate substrate.
  • this near infrared cut filter has a dielectric multilayer film on at least one side of a laminate.
  • of the difference between the wavelength value (Ya) and the wavelength value (Yb) is less than 15 nm.
  • the value of the wavelength (Ya) is a value of the wavelength at which the transmittance is 50% when measured from the vertical direction of the near infrared cut filter in the wavelength range of 560 to 800 nm.
  • the wavelength value (Yb) is a wavelength value at which the transmittance is 50% when measured from an angle of 30 ° with respect to the vertical direction of the near infrared cut filter in the wavelength range of 560 to 800 nm.
  • Patent Document 2 describes a near-infrared cut filter provided with a near-infrared absorbing glass substrate, a near-infrared absorbing layer, and a dielectric multilayer film.
  • the near infrared absorbing layer contains a near infrared absorbing dye and a transparent resin.
  • Patent Document 2 describes a solid-state imaging device including the near-infrared cut filter and a solid-state imaging device. According to Patent Document 2, by laminating a near-infrared absorbing glass substrate and a near-infrared absorbing layer, the dielectric multilayer film inherently has an angle dependency in which the shielding wavelength is shifted depending on the incident angle of light. The effects can be almost eliminated. For example, in Patent Document 2, the transmittance (T 0 ) at an incident angle of 0 ° and the transmittance (T 30 ) at an incident angle of 30 ° in a near infrared cut filter are measured.
  • Patent Documents 3 and 4 describe an infrared cut filter provided with a dielectric substrate, an infrared reflection layer, and an infrared absorption layer.
  • the infrared reflection layer is formed of a dielectric multilayer film.
  • the infrared absorbing layer contains an infrared absorbing dye.
  • Patent Documents 3 and 4 describe an imaging device provided with this infrared cut filter.
  • Patent Documents 3 and 4 describe the transmittance spectrum of the infrared cut filter when the incident angle of light is 0 °, 25 °, and 35 °.
  • Patent Document 5 describes a near-infrared cut filter that includes an absorption layer and a reflection layer and that satisfies predetermined requirements. For example, in this near infrared cut filter, the integral T 0 (600-725) of the transmittance of light of wavelength 600 to 725 nm in the spectral transmittance curve at an incident angle of 0 ° and the spectral transmittance curve at an incident angle of 30 °. The difference
  • with the integral value T 30 (600-725) of the transmittance of light with a wavelength of 600 to 725 nm is 3% ⁇ nm or less.
  • Patent Document 5 also describes an imaging device provided with this near infrared cut filter.
  • JP 2012-103340 A International Publication No. 2014/030628 U.S. Patent Application Publication No. 2014/0300956 U.S. Patent Application Publication No. 2014/0063597 Patent No. 6119920
  • the characteristics of the optical filter when the incident angle of light is larger than 35 ° (for example, 40 °) are not specifically studied.
  • the present invention provides an optical filter having characteristics advantageous for use in an imaging device, even when the incident angle of light is large.
  • the present invention also provides an imaging device provided with this optical filter.
  • the present invention An optical filter, A light absorbing layer containing a light absorbing agent that absorbs at least part of light in the near infrared region, When light having a wavelength of 300 nm to 1200 nm is incident on the optical filter at incident angles of 0 °, 30 °, and 40 °, an optical filter satisfying the following conditions is provided.
  • the spectral transmittance at a wavelength of 390 nm is 20% or less.
  • the spectral transmittance at a wavelength of 400 nm is 45% or less.
  • the spectral transmittance at a wavelength of 450 nm is 75% or more.
  • the spectral transmittance at a wavelength of 700 nm is 3% or less.
  • the spectral transmittance at a wavelength of 715 nm is 1% or less.
  • the spectral transmittance at a wavelength of 1100 nm is 2% or less.
  • the spectral transmittance at a wavelength of 1200 nm is 15% or less.
  • the average transmittance at a wavelength of 500 to 600 nm is 80% or more.
  • the average transmittance at a wavelength of 700 to 800 nm is 0.5% or less.
  • the present invention is Lens system, An imaging element that receives light passing through the lens system; A color filter disposed in front of the imaging element and having a filter of three colors of R (red), G (green), and B (blue); And the above-mentioned optical filter disposed in front of the color filter, An imaging device is provided.
  • the above optical filter has advantageous characteristics for use in an imaging device even when the incident angle of light is large. Further, according to the above-described imaging device, even when the incident angle of light is large, an image of good image quality is easily generated.
  • FIG. 1A is a cross-sectional view showing an example of the optical filter of the present invention.
  • FIG. 1B is a cross-sectional view showing another example of the optical filter of the present invention.
  • FIG. 1C is a cross-sectional view showing still another example of the optical filter of the present invention.
  • FIG. 1D is a cross-sectional view showing still another example of the optical filter of the present invention.
  • FIG. 1E is a cross-sectional view showing still another example of the optical filter of the present invention.
  • FIG. 1F is a cross-sectional view showing still another example of the optical filter of the present invention.
  • FIG. 2 is a cross-sectional view showing an example of the imaging device of the present invention.
  • FIG. 3A is a transmittance spectrum of a semifinished product of the optical filter according to Example 1.
  • FIG. 3B is a transmittance spectrum of another semifinished product of the optical filter according to Example 1.
  • FIG. 3C is a transmittance spectrum of the laminate according to Reference Example 1.
  • FIG. 3D is a transmittance spectrum of a laminate according to Reference Example 2.
  • FIG. 3E is a transmittance spectrum of the optical filter according to the first embodiment.
  • FIG. 4A is a graph showing a difference in spectral transmittance at different incident angles of the optical filter according to Example 1.
  • FIG. 4B is a graph showing the absolute value of the difference in spectral transmittance at different incident angles of the optical filter according to Example 1.
  • FIG. 4A is a graph showing a difference in spectral transmittance at different incident angles of the optical filter according to Example 1.
  • FIG. 4B is a graph showing the absolute value of the difference in spectral transmittance at different incident angles of the optical filter according to Example
  • FIG. 4C is a graph showing the square value of the difference in spectral transmittance at different incident angles of the optical filter according to Example 1.
  • FIG. 5A is a transmittance spectrum of a laminate according to Reference Example 3.
  • FIG. 5B is a transmittance spectrum of the optical filter according to the second embodiment.
  • FIG. 6A is a graph showing a difference in spectral transmittance at different incident angles of the optical filter according to Example 2.
  • FIG. 6B is a graph showing the absolute value of the difference in spectral transmittance at different incident angles of the optical filter according to Example 2.
  • 6C is a graph showing the square value of the difference in spectral transmittance at different incident angles of the optical filter according to Example 2.
  • FIG. FIG. 7A is a transmittance spectrum of a laminate according to Reference Example 4.
  • FIG. 7B is a transmittance spectrum of the optical filter according to the third embodiment.
  • FIG. 8A is a graph showing a difference in spectral transmittance at different incident angles of the optical filter according to Example 3.
  • FIG. 8B is a graph showing the absolute value of the difference in spectral transmittance at different incident angles of the optical filter according to Example 3.
  • FIG. 8C is a graph showing the square value of the difference in spectral transmittance at different incident angles of the optical filter according to Example 3.
  • FIG. 9 is a transmittance spectrum of the optical filter according to the fourth embodiment.
  • FIG. 10A is a graph showing a difference in spectral transmittance at different incident angles of the optical filter according to Example 4.
  • FIG. 10A is a graph showing a difference in spectral transmittance at different incident angles of the optical filter according to Example 4.
  • 10B is a graph showing the absolute value of the difference in spectral transmittance at different incident angles of the optical filter according to Example 4.
  • FIG. 10C is a graph showing the square value of the difference in spectral transmittance at different incident angles of the optical filter according to Example 4.
  • 11A is a transmittance spectrum of a semifinished product of the optical filter according to Example 5.
  • FIG. 11B is a transmittance spectrum of the optical filter according to Example 5.
  • FIG. 12A is a graph showing a difference in spectral transmittance at different incident angles of the optical filter according to Example 5.
  • FIG. FIG. 12B is a graph showing the absolute value of the difference in spectral transmittance at different incident angles of the optical filter according to Example 5.
  • FIG. 12C is a graph showing the square value of the difference in spectral transmittance at different incident angles of the optical filter according to Example 5.
  • FIG. 13A is a transmittance spectrum of a semifinished product of the optical filter according to Comparative Example 1.
  • FIG. 13B is a transmittance spectrum of the laminate according to Reference Example 5.
  • FIG. 13C is a transmittance spectrum of the optical filter according to Comparative Example 1.
  • FIG. 14A is a graph showing a difference in spectral transmittance at different incident angles of the optical filter according to Comparative Example 1.
  • FIG. 14B is a graph showing the absolute value of the difference in spectral transmittance at different incident angles of the optical filter according to Comparative Example 1.
  • FIG. 14C is a graph showing the square value of the difference in spectral transmittance at different incident angles of the optical filter according to Comparative Example 1.
  • FIG. 15A is a transmittance spectrum of an infrared absorptive glass substrate of an optical filter according to Comparative Example 2.
  • FIG. 15B is a transmittance spectrum of the laminate according to Reference Example 6.
  • FIG. 15C is a transmittance spectrum of the laminate according to Reference Example 7.
  • FIG. 15D is a transmittance spectrum of the optical filter according to Comparative Example 2.
  • FIG. 16A is a graph showing a difference in spectral transmittance at different incident angles of the optical filter according to Comparative Example 2.
  • FIG. 16B is a graph showing the absolute value of the difference in spectral transmittance at different incident angles of the optical filter according to Comparative Example 2.
  • FIG. 16C is a graph showing the square value of the difference between spectral transmittances at different incident angles of the optical filter according to Comparative Example 2.
  • FIG. 17A is a transmittance spectrum of a semifinished product of the optical filter according to Comparative Example 3.
  • FIG. 17B is a transmittance spectrum of the optical filter according to Comparative Example 3.
  • FIG. 18A is a graph showing a difference in spectral transmittance at different incident angles of the optical filter according to Comparative Example 3.
  • FIG. 18B is a graph showing the absolute value of the difference in spectral transmittance at different incident angles of the optical filter according to Comparative Example 3.
  • FIG. 18C is a graph showing the square value of the difference between spectral transmittances at different incident angles of the optical filter according to Comparative Example 3.
  • the inventors of the present invention have devised an optical filter according to the present invention based on new findings obtained by the following study on an optical filter.
  • an optical filter for blocking unnecessary light rays other than visible light rays is disposed.
  • the use of optical filters with light absorbing layers to block unwanted light is being considered.
  • an optical filter provided with a light absorbing layer often further includes a reflective film formed of a dielectric multilayer film.
  • the wavelength band of the transmitted light and the wavelength band of the reflected light are determined by the interference of the light beams reflected on the front and back surfaces of each layer of the reflective film. Rays can be incident on the optical filter from various angles of incidence.
  • the optical path length in the reflective film changes depending on the incident angle of light to the optical filter.
  • the wavelength bands of the transmitted and reflected light rays change to the short wavelength side. Therefore, the boundary between the wavelength band of the light beam to be shielded and the wavelength band of the light beam to be transmitted is defined by the absorption of light so that the characteristic of the transmittance of the optical filter does not greatly fluctuate depending on the incident angle of light. It can be considered that the wavelength band of the light beam to be reflected is separated from the wavelength band of the light beam to be transmitted.
  • Patent Documents 1 and 2 evaluate the light transmission characteristics of the near infrared cut filter when the incident angles of light are 0 ° and 30 °. Moreover, in patent documents 3 and 4, the transmittance
  • an optical filter provided with a reflective film formed of a dielectric multilayer film
  • the light reflectance is locally local in the wavelength band of light that is desired to suppress reflection and achieve high transmittance. It may increase. This causes a defect called ripple in which the transmittance locally decreases in the optical filter. For example, even in the case of an optical filter designed so that ripples do not occur when the incident angle of light is 0 ° to 30 °, ripples easily occur when the incident angle of light is increased to 40 °.
  • An RGB color filter is incorporated in each pixel of the image sensor provided in the imaging device, and the amount of light sensed by each pixel of the sensor is the spectral transmittance of the optical filter that blocks unnecessary light and the color filter Correlate with the product of For this reason, it is desirable that the optical filter have a characteristic that matches the characteristic of the color filter used in the imaging device.
  • spectral transmittance is transmittance when incident light of a specific wavelength is incident on an object such as a sample
  • average transmittance is spectral transmittance within a predetermined wavelength range. It is the average value of the rate.
  • transmittance spectrum is a spectrum in which the spectral transmittance at each wavelength within a predetermined wavelength range is arranged in order of wavelength.
  • IR cutoff wavelength indicates 50% spectral transmittance in a wavelength range of 600 nm or more when light having a wavelength of 300 nm to 1200 nm is incident on an optical filter at a predetermined incident angle. It means the wavelength.
  • UV cut-off wavelength means a wavelength that exhibits 50% spectral transmittance in the wavelength range of 450 nm or less when light having a wavelength of 300 nm to 1200 nm is incident on an optical filter at a predetermined incident angle. .
  • the optical filter 1 a includes a light absorption layer 10.
  • the light absorbing layer 10 contains a light absorbing agent, and the light absorbing agent absorbs at least part of light in the near infrared region.
  • the optical filter 1a satisfies the following conditions when light having a wavelength of 300 nm to 1200 nm is incident on the optical filter 1a at incident angles of 0 °, 30 °, and 40 °.
  • the spectral transmittance at a wavelength of 390 nm is 20% or less.
  • Ii-1) The spectral transmittance at a wavelength of 400 nm is 45% or less.
  • the spectral transmittance at a wavelength of 450 nm is 75% or more.
  • the spectral transmittance at a wavelength of 700 nm is 3% or less.
  • the spectral transmittance at a wavelength of 715 nm is 1% or less.
  • the spectral transmittance at a wavelength of 1100 nm is 2% or less.
  • the spectral transmittance at a wavelength of 1200 nm is 15% or less.
  • the average transmittance at a wavelength of 500 to 600 nm is 80% or more.
  • the average transmittance at a wavelength of 700 to 800 nm is 0.5% or less.
  • the optical filter 1a Since the optical filter 1a satisfies the above conditions (i-1) to (ix-1), even if the incident angle of light changes from 0 ° (perpendicular to the optical filter 1a) to 40 °, the optical filter 1a The change of the transmission characteristic of 1a is suppressed. Therefore, for example, even when incorporated in a camera module or an imaging apparatus in which a wide-angle lens is mounted, it is possible to suppress the appearance of different colors or brightness in the central portion of the image and the peripheral portion of the image, and is unnecessary. It can block light rays.
  • the optical filter 1a desirably satisfies the following conditions when light having a wavelength of 300 nm to 1200 nm is incident on the optical filter 1a at incident angles of 0 °, 30 °, and 40 °.
  • the spectral transmittance at a wavelength of 390 nm is 10% or less.
  • the spectral transmittance at a wavelength of 400 nm is 25% or less.
  • the spectral transmittance at a wavelength of 700 nm is 2.5% or less.
  • the spectral transmittance at a wavelength of 1100 nm is 1% or less.
  • the spectral transmittance at a wavelength of 1200 nm is 13% or less.
  • the average transmittance at a wavelength of 500 to 600 nm is 85% or more.
  • the optical filter 1a further satisfies the above conditions (i-2), (ii-2), (iv-2), (vi-2), (vii-2) and (viii-2), Even if the incident angle of light changes from 0 ° to 40 °, the change in the transmission characteristic of the optical filter can be suppressed more effectively.
  • the transmittance in the wavelength region (500 to 600 nm) corresponding to the center of the visible light region is higher, a brighter image can be easily obtained.
  • unnecessary light rays (light with a wavelength of 390 nm or less and light with a wavelength of 1100 to 1200 nm) which are not included in human visual sensitivity can be shielded more effectively. Since these performances are maintained in the range of the incident angle of 0 ° to 40 °, an image having higher color reproducibility is easily obtained.
  • the optical filter 1a desirably satisfies the following condition (ii-3) when light having a wavelength of 300 nm to 1200 nm is incident on the optical filter 1a at incident angles of 0 °, 30 °, and 40 °: More desirably, the following condition (ii-4) is further satisfied. Since the optical filter 1a satisfies the condition of (iii-1), the spectral transmittance at a wavelength of 450 nm is as high as 75% or more. Therefore, in the region where the wavelength is relatively short, the condition of (iii-1) is satisfied and the condition of (ii-3), more preferably the condition of (ii-4) is satisfied. A transmission characteristic appears that changes rapidly from low transmission to high transmission. Such transmission characteristics are desirable characteristics as an optical filter. (Ii-3) The spectral transmittance at a wavelength of 400 nm is 15% or less. (Ii-4) The spectral transmittance at a wavelength of 400 nm is 10% or less.
  • the optical filter 1a desirably has an IR cutoff wavelength in the wavelength range of 600 nm to 650 nm when light having a wavelength of 300 nm to 1200 nm is incident on the optical filter 1a at incident angles of 0 °, 30 °, and 40 °.
  • a wavelength corresponding to a relative luminosity of 0.5 in a wavelength range of 600 nm to 650 nm and an IR cut-off wavelength, where the maximum value of the relative luminosity is 1 in the human relative luminosity curve in the bright field And will be close. This is desirable from the viewpoint of the consistency between the transmission characteristic of the optical filter 1a and the relative luminosity curve.
  • the optical filter 1a more preferably has an IR cutoff wavelength in the wavelength range of 610 nm to 640 nm when light having a wavelength of 300 nm to 1200 nm is incident on the optical filter 1a at incident angles of 0 °, 30 ° and 40 °. Have.
  • the optical filter 1a desirably has a UV cutoff wavelength in the wavelength range of 400 nm to 430 nm when light having a wavelength of 300 nm to 1200 nm is incident on the optical filter 1a at incident angles of 0 °, 30 ° and 40 °.
  • a UV cutoff wavelength in the wavelength range of 400 nm to 430 nm when light having a wavelength of 300 nm to 1200 nm is incident on the optical filter 1a at incident angles of 0 °, 30 ° and 40 °.
  • the optical filter 1a has a UV cutoff wavelength in the wavelength range of 405 nm to 430 nm when light having a wavelength of 300 nm to 1200 nm is incident on the optical filter 1a at incident angles of 0 °, 30 °, and 40 °. Have.
  • the difference between the IR cutoff wavelength and the UV cutoff wavelength is preferably 200 nm or more .
  • the amount of light belonging to the visible light region is increased, and the brightness of the obtained image is desirably increased.
  • the spectral transmittance of the optical filter 1a at the wavelength ⁇ when the incident angle of light is ⁇ ° is expressed as T ⁇ ( ⁇ ).
  • the minimum value and the maximum value of the domain of wavelength ⁇ are denoted as ⁇ 1 [nm] and ⁇ 2 [nm], respectively.
  • IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 satisfy the conditions shown in the following Table (I).
  • it is defined by the following equation (1).
  • the incident angle of the chief ray incident on the center of the imaging device of the imaging device is close to 0 °, and the incident angle of the chief ray incident on the peripheral portion of the imaging device is large.
  • the color tone of the image may change when the image generated by the imaging device is displayed or printed There is. Therefore, when displaying or printing an image captured by the imaging device, the color of the subject that should be the same color changes from the central portion toward the peripheral portion, and may be recognized as color unevenness.
  • the optical filter 1a since the conditions shown in Table (I) are satisfied, it can be evaluated that the optical filter 1a is easily adapted to the characteristics of the color filter used in the imaging device.
  • IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 is an incident angle ⁇ 2 selected from 30 ° and 40 ° from the spectral transmittance T ⁇ 1 ( ⁇ ) at an incident angle ⁇ 1 ° selected from 0 ° and 30 °
  • the difference obtained by subtracting the spectral transmittance T ⁇ 2 ( ⁇ ) in ° ( ⁇ 1 ⁇ 2) is integrated and determined in the wavelength range of ⁇ 1 nm to ⁇ 2 nm.
  • IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 satisfy the conditions shown in the following Table (II).
  • it is defined by the following equation (2).
  • IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 is an incident angle ⁇ 2 selected from 30 ° and 40 ° from the spectral transmittance T ⁇ 1 ( ⁇ ) at an incident angle ⁇ 1 ° selected from 0 ° and 30 °
  • the absolute value of the difference obtained by subtracting the spectral transmittance T ⁇ 2 ( ⁇ ) in ° ( ⁇ 1 ⁇ 2) is determined by integration in the wavelength range of ⁇ 1 nm to ⁇ 2 nm.
  • the integrated value in the wavelength band in which the difference between T ⁇ 1 ( ⁇ ) and T ⁇ 2 ( ⁇ ) is negative is positive only in the evaluation based on IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2. It may be offset by integrated values in certain other wavelength bands, and it may be difficult to appropriately identify the characteristics of the optical filter.
  • the optical filter 1a can be more appropriately evaluated by referring also to IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 .
  • ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 satisfy the conditions shown in the following Table (III).
  • it is defined by the following equation (3).
  • ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 is an incident angle ⁇ 2 selected from 30 ° and 40 ° from the spectral transmittance T ⁇ 1 ( ⁇ ) at an incident angle ⁇ 1 ° selected from 0 ° and 30 °
  • the square value of the difference (transmittance difference) obtained by subtracting the spectral transmittance T ⁇ 2 ( ⁇ ) in ° ( ⁇ 1 ⁇ 2) is integrated in the wavelength range of ⁇ 1 nm to ⁇ 2 nm.
  • the transmittance difference between the incident angles changes rapidly due to the occurrence of ripples in the narrow wavelength range and when it changes gently over a wide wavelength range.
  • rapid change in transmittance is emphasized by using ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 as an index, which is determined by integrating the squared value of the transmittance difference, and the latter pattern having a greater influence on image quality is identified and excluded. it can. Therefore, the optical filter 1a can be evaluated more appropriately.
  • the light absorbing agent contained in the light absorbing layer 10 absorbs at least a part of light in the near infrared region, and in particular as long as the optical filter 1a satisfies the above conditions (i-1) to (ix-1). It is not restricted.
  • the light absorbing agent contained in the light absorbing layer 10 is (i-2), (ii-2), (iv-2), (vi-2), (vii-2) for the optical filter 1a. And (viii-2) are further determined.
  • the light absorbing agent contained in the light absorbing layer 10 is desirably determined so that the optical filter 1a satisfies the conditions shown in at least one of Table (I), Table (II), and Table (III). Be done.
  • the light absorber is formed of, for example, phosphonic acid and copper ions.
  • the light absorption layer 10 can absorb light in the near infrared region and a wide wavelength band of the visible light region adjacent to the near infrared region. For this reason, even if the optical filter 1a is not provided with a reflective film, desired characteristics can be exhibited. Further, even when the optical filter 1a includes a reflective film, the optical filter 1a can be designed so that the wavelength band of the light beam reflected by the reflective film is sufficiently separated from the wavelength band of the light beam to be transmitted.
  • the wavelength band of the light beam reflected by the reflective film can be set to a wavelength band longer by 100 nm or more from the wavelength band of the transition region in which the transmittance sharply decreases as the wavelength increases.
  • the incident angle of light is large and the wavelength band of the light beam reflected by the reflection film is shifted to the short wavelength side, it overlaps with the wavelength band of the light beam absorbed by the light absorption layer 10, and the transition of the optical filter 1a
  • the transmittance characteristics in the region hardly change with respect to the change of the incident angle of light.
  • the light absorbing layer 10 can absorb light in a wide range of the wavelength band of the ultraviolet region.
  • the phosphonic acid contains, for example, a first phosphonic acid having an aryl group.
  • the aryl group is attached to the phosphorus atom.
  • the aryl group which the first phosphonic acid has is, for example, a phenyl group, a benzyl group, a toluyl group, a nitrophenyl group, a hydroxyphenyl group, a halogenated phenyl group in which at least one hydrogen atom in the phenyl group is substituted by a halogen atom, Alternatively, it is a halogenated benzyl group in which at least one hydrogen atom in the benzene ring of the benzyl group is substituted by a halogen atom.
  • the phosphonic acid desirably further comprises a second phosphonic acid having an alkyl group.
  • the alkyl group is attached to the phosphorus atom.
  • the alkyl group possessed by the second phosphonic acid is, for example, an alkyl group having 6 or less carbon atoms.
  • the alkyl group may have either linear or branched chain.
  • the light absorbing layer 10 includes a light absorbing agent formed of phosphonic acid and copper ions
  • the light absorbing layer 10 desirably further includes a phosphate ester for dispersing the light absorbing agent and a matrix resin.
  • the phosphate ester contained in the light absorption layer 10 is not particularly limited as long as the light absorber can be appropriately dispersed, but for example, a phosphate diester represented by the following formula (c1) and a table by the following formula (c2) And / or at least one of the following phosphoric monoesters.
  • R 21 , R 22 and R 3 are each a monovalent functional group represented by — (CH 2 CH 2 O) n R 4 and n Is an integer of 1 to 25 and R 4 is an alkyl group having 6 to 25 carbon atoms.
  • R 21 , R 22 and R 3 are functional groups of the same or different type from one another.
  • the phosphoric acid ester is not particularly limited.
  • Plysurf A208N polyoxyethylene alkyl (C12, C13) ether phosphoric acid ester
  • Plysurf A208 F polyoxyethylene alkyl (C8) ether phosphoric acid ester
  • Plysurf A208 B Polyoxyethylene lauryl ether phosphate
  • Plysurf A 219 B Polyoxyethylene lauryl ether phosphate
  • Plysurf AL Polyoxyethylene styrenated phenyl ether phosphate
  • Plysurf A 212 C Polyoxyethylene tridecyl ether phosphate
  • Plysurf A 215 C polyoxyethylene tridecyl ether phosphate ester.
  • NIKKOL DDP-2 polyoxyethylene alkyl ether phosphate
  • NIKKOL DDP-4 polyoxyethylene alkyl ether phosphate
  • NIKKOL DDP-6 polyoxyethylene alkyl ether phosphate possible.
  • the matrix resin contained in the light absorbing layer 10 is, for example, a resin capable of dispersing a light absorbing agent and capable of being thermally cured or ultraviolet curable. Furthermore, when a resin layer of 0.1 mm is formed of the resin as a matrix resin, the transmittance of the resin layer to light with a wavelength of 350 nm to 900 nm is, for example, 80% or more, preferably 85% or more, More preferably, a resin of 90% or more can be used, but it is not particularly limited as long as the above conditions (i-1) to (ix-1) are satisfied in the optical filter 1a.
  • the matrix resin is preferably such that the optical filter 1a is any one of (i-2), (ii-2), (iv-2), (vi-2), (vii-2) and (viii-2) described above. It is decided to satisfy the conditions further. Also, the matrix resin is desirably determined so that the optical filter 1a satisfies the conditions shown in at least one of Table (I), Table (II), and Table (III).
  • the content of phosphonic acid in the light absorption layer 10 is, for example, 3 to 180 parts by mass with respect to 100 parts by mass of the matrix resin.
  • the matrix resin contained in the light absorption layer 10 is not particularly limited as long as the above-mentioned properties are satisfied, but, for example, (poly) olefin resin, polyimide resin, polyvinyl butyral resin, polycarbonate resin, polyamide resin, polysulfone resin, polyether sulfone Resin, polyamide imide resin, (modified) acrylic resin, epoxy resin, or silicone resin.
  • the matrix resin may contain an aryl group such as a phenyl group, and is preferably a silicone resin containing an aryl group such as a phenyl group.
  • the light absorbing layer 10 When the light absorbing layer 10 is hard (is rigid) and the thickness of the light absorbing layer 10 is increased, cracks easily occur due to curing shrinkage during the manufacturing process of the optical filter 1a.
  • the matrix resin is a silicone resin containing an aryl group
  • the light absorption layer 10 tends to have good crack resistance.
  • the light absorber does not easily aggregate when it contains the light absorber formed of the above phosphonic acid and copper ion.
  • the phosphoric acid ester contained in the light absorbing layer 10 may be a phosphoric acid ester represented by Formula (c1) or Formula (c2) It is desirable to have a flexible linear organic functional group such as an oxyalkyl group. This is because the light absorber is less likely to aggregate due to the interaction based on the combination of the above-mentioned phosphonic acid, the silicone resin containing an aryl group, and the phosphate ester having a linear organic functional group such as an oxyalkyl group, and It is because the light absorption layer can be provided with good rigidity and good flexibility.
  • silicone resins used as matrix resins include KR-255, KR-300, KR-2621-1, KR-211, KR-311, KR-216, KR-212, and KR-251. be able to. All of these are silicone resins manufactured by Shin-Etsu Chemical Co., Ltd.
  • the optical filter 1a further includes, for example, a transparent dielectric substrate 20.
  • a transparent dielectric substrate 20 One main surface of the transparent dielectric substrate 20 is covered with the light absorption layer 10.
  • the characteristics of the transparent dielectric substrate 20 are not particularly limited as long as the above conditions (i-1) to (ix-1) are satisfied in the optical filter 1a.
  • the transparent dielectric substrate 20 desirably has the optical filters 1a (i-2), (ii-2), (iv-2), (vi-2), (vii-2), and (viii-2). It has the characteristic to further satisfy the condition of
  • the transparent dielectric substrate 20 desirably has such a property that the optical filter 1a satisfies the conditions shown in at least one of Table (I), Table (II), and Table (III).
  • the transparent dielectric substrate 20 is, for example, a dielectric substrate having high average transmittance (for example, 80% or more, preferably 85% or more, more preferably 90% or more) at 450 nm to 600 nm.
  • the transparent dielectric substrate 20 is made of, for example, glass or resin.
  • the glass contains, for example, borosilicate glass such as D263 T eco, soda lime glass (blue plate), white sheet glass such as B270, alkali-free glass, or copper.
  • Infrared absorbing glass such as phosphate glass or fluorophosphate glass containing copper.
  • the transparent dielectric substrate 20 is an infrared absorbing glass such as copper containing phosphate glass or copper containing fluorophosphate glass, the infrared absorption performance and light of the transparent dielectric substrate 20
  • the combination with the infrared absorption performance of the absorption layer 10 can provide the optical filter 1a with a desired infrared absorption performance.
  • Such infrared absorbing glass is, for example, BG-60, BG-61, BG-62, BG-63, or BG-67 manufactured by SCHOTT, 500EXL manufactured by Nippon Electric Glass Co., Ltd., or Hoya Company CM5000, CM500, C5000, or C500S.
  • the transparent dielectric substrate 20 may have an ultraviolet absorbing property.
  • the transparent dielectric substrate 20 may be a crystalline substrate having transparency, such as magnesium oxide, sapphire, or quartz.
  • sapphire is hard to scratch because of its high hardness.
  • plate-shaped sapphire is disposed on the front surface of a camera module or lens provided in a smartphone or a portable terminal such as a mobile phone as a scratch-resistant protective material (sometimes called a protect filter or cover glass). May be By forming the light absorption layer 10 on such plate-like sapphire, it is possible to effectively cut off light with a wavelength of 650 nm to 1100 nm together with the protection of the camera module and the lens.
  • an optical filter having infrared ray shielding properties at a wavelength of 650 nm to 1100 nm it is not necessary to dispose an optical filter having infrared ray shielding properties at a wavelength of 650 nm to 1100 nm around an imaging device such as a CCD (Charge-Coupled Device) sensor and a CMOS (Complementary Metal Oxide Semiconductor) sensor or inside a camera module.
  • an imaging device such as a CCD (Charge-Coupled Device) sensor and a CMOS (Complementary Metal Oxide Semiconductor) sensor or inside a camera module.
  • the light absorption layer 10 is formed on plate-shaped sapphire, it can contribute to shortening of a camera module or an imaging device.
  • the resin is, for example, (poly) olefin resin, polyimide resin, polyvinyl butyral resin, polycarbonate resin, polyamide resin, polysulfone resin, polyether sulfone resin, polyamide imide resin, (Modified) Acrylic resin, epoxy resin, or silicone resin.
  • the optical filter 1a can be manufactured, for example, by applying a coating solution for forming the light absorption layer 10 on one main surface of the transparent dielectric substrate 20 to form a coating, and drying the coating.
  • the method of preparing the coating solution and the method of manufacturing the optical filter 1a will be described by taking, as an example, the case where the light absorbing layer 10 contains a light absorbing agent formed of phosphonic acid and copper ions.
  • a copper salt such as copper acetate monohydrate is added to a predetermined solvent such as tetrahydrofuran (THF) and stirred to obtain a solution of copper salt.
  • a phosphate diester represented by the formula (c1) or a phosphate ester compound such as a phosphate monoester represented by the formula (c2) is added to the copper salt solution and stirred to prepare a solution A.
  • the first phosphonic acid is added to a predetermined solvent such as THF and stirred to prepare a solution B.
  • solution B is added to solution A and stirred for a predetermined time.
  • a predetermined solvent such as toluene is added to the solution and stirred to obtain a solution C.
  • a desolvation process is performed for a predetermined time while heating the solution C to obtain the solution D.
  • a solvent such as THF and a component generated by dissociation of a copper salt such as acetic acid (boiling point: about 118 ° C.) are removed, and a light absorbing agent is generated by the first phosphonic acid and the copper ion.
  • the temperature for heating solution C is determined based on the boiling point of the component to be removed which has been dissociated from the copper salt.
  • a solvent such as toluene (boiling point: about 110 ° C.) used to obtain the liquid C also evaporates. Since it is desirable that the solvent remains to some extent in the coating solution, it is preferable from this viewpoint that the amount of the solvent added and the time for the desolvation treatment be defined.
  • o-xylene (boiling point: about 144 ° C.) can be used instead of toluene. In this case, since the boiling point of o-xylene is higher than the boiling point of toluene, the amount of addition can be reduced to about one fourth of the amount of addition of toluene.
  • a matrix resin such as silicone resin is added to solution D and stirred to prepare a coating solution.
  • the coating solution is applied to one of the main surfaces of the transparent dielectric substrate 20 to form a coating.
  • the coating liquid is applied to one main surface of the transparent dielectric substrate 20 by die coating, spin coating, or application by a dispenser to form a coating.
  • this coating film is subjected to a predetermined heat treatment to cure the coating film.
  • the coating is exposed to an environment at a temperature of 50 ° C. to 200 ° C. for a predetermined time.
  • the light absorption layer 10 may be formed as a single layer or may be formed as a plurality of layers.
  • the light absorbing layer 10 may be, for example, a first layer containing a light absorbing agent formed of a first phosphonic acid and a copper ion, and a second layer It has a second layer containing a light absorber formed by phosphonic acid and copper ions.
  • the coating solution for forming the first layer can be prepared as described above.
  • the second layer is formed using a coating solution prepared separately from the coating solution for forming the first layer.
  • the coating liquid for forming the second layer can be prepared, for example, as follows.
  • a copper salt such as copper acetate monohydrate is added to a predetermined solvent such as tetrahydrofuran (THF) and stirred to obtain a solution of copper salt.
  • a phosphate diester represented by the formula (c1) or a phosphate ester compound such as a phosphate monoester represented by the formula (c2) is added to the solution of the copper salt and stirred to prepare a solution E.
  • a phosphate ester compound such as a phosphate monoester represented by the formula (c2)
  • secondary phosphonic acid is added to a predetermined solvent such as THF and stirred to prepare solution F.
  • the solution F is added to the solution E and stirred for a predetermined time.
  • a predetermined solvent such as toluene is added to the solution and stirred, and the solvent is further evaporated to obtain a G liquid.
  • a matrix resin such as silicone resin is added to solution G and stirred to obtain a coating solution for forming a second layer.
  • a coating solution for forming the first layer and a coating solution for forming the second layer are applied to form a coating, and the coating is subjected to a predetermined heat treatment to cure the coating.
  • the first layer and the second layer can be formed.
  • the coating is exposed to an environment at a temperature of 50 ° C. to 200 ° C. for a predetermined time.
  • the order in which the first layer and the second layer are formed is not particularly limited, and the first layer and the second layer may be formed in different periods or may be formed in the same period.
  • a protective layer may be formed between the first layer and the second layer.
  • the protective layer is formed of, for example, a vapor deposited film of SiO 2 .
  • the optical filter 1a can be changed from various viewpoints.
  • the optical filter 1a may be changed to the optical filters 1b to 1f shown in FIGS. 1B to 1F, respectively.
  • the optical filters 1b to 1f are configured in the same manner as the optical filter 1a, unless otherwise specified.
  • the components of the optical filters 1b to 1f which are the same as or correspond to the components of the optical filter 1a are designated by the same reference numerals, and the detailed description thereof is omitted.
  • the description on the optical filter 1a also applies to the optical filters 1b to 1f unless technically contradictory.
  • the light absorption layer 10 is formed on both main surfaces of the transparent dielectric substrate 20.
  • the above conditions (i-1) to (ix-1) are satisfied not by one light absorbing layer 10 but by two light absorbing layers 10, and preferably, the above (i-2) , (Ii-2), (iv-2), (vi-2), (vii-2), and (viii-2) are further satisfied, and desirably, Table (I), Table (II) And the conditions shown in at least one of Table (III) are satisfied.
  • the thickness of the light absorption layer 10 on both main surfaces of the transparent dielectric substrate 20 may be the same or different.
  • the light absorbing layer is formed on both main surfaces of the transparent dielectric substrate 20 so that the thickness of the light absorbing layer 10 necessary for the optical filter 1b to obtain the desired optical characteristics may be evenly or unevenly distributed. 10 are formed. Thereby, the thickness of each light absorption layer 10 formed on one main surface of the transparent dielectric substrate 20 of the optical filter 1b is smaller than that of the optical filter 1a. By forming the light absorption layer 10 on both main surfaces of the transparent dielectric substrate 20, warping of the optical filter 1b is suppressed even when the transparent dielectric substrate 20 is thin.
  • Each of the two light absorption layers 10 may be formed as a plurality of layers.
  • the light absorption layer 10 is formed on both main surfaces of the transparent dielectric substrate 20.
  • the optical filter 1 c includes the anti-reflection film 30.
  • the anti-reflection film 30 is a film formed to form an interface between the optical filter 1c and air, for reducing reflection of light in the visible light region.
  • the antireflective film 30 is a film formed of, for example, a resin, an oxide, and a dielectric such as a fluoride.
  • the antireflective film 30 may be a multilayer film formed by laminating two or more types of dielectrics having different refractive indexes.
  • the antireflective film 30 may be a dielectric multilayer film made of a low refractive index material such as SiO 2 and a high refractive index material such as TiO 2 or Ta 2 O 5 . In this case, Fresnel reflection at the interface between the optical filter 1c and the air is reduced, and the amount of light in the visible light region of the optical filter 1c can be increased.
  • the anti-reflection film 30 may be formed on both sides of the optical filter 1c, or may be formed on one side of the optical filter 1c.
  • the light absorption layer 10 is formed on both main surfaces of the transparent dielectric substrate 20.
  • the optical filter 1 d further includes a reflective film 40.
  • the reflective film 40 reflects infrared light and / or ultraviolet light.
  • the reflective film 40 is, for example, a film formed by vapor deposition of a metal such as aluminum, or a dielectric multilayer film in which a layer made of a high refractive index material and a layer made of a low refractive index material are alternately stacked. is there.
  • the high refractive index material a material having a refractive index of 1.7 to 2.5 such as TiO 2 , ZrO 2 , Ta 2 O 5 , Nb 2 O 5 , ZnO, and In 2 O 3 is used.
  • the low refractive index material materials having a refractive index of 1.2 to 1.6, such as SiO 2 , Al 2 O 3 and MgF 2 are used.
  • the method of forming the dielectric multilayer film is, for example, a chemical vapor deposition (CVD) method, a sputtering method, or a vacuum evaporation method.
  • such a reflective film may be formed so that it may make both the main surfaces of an optical filter (illustration omitted). When the reflective film is formed on both main surfaces of the optical filter, the stress is balanced on both the front and back sides of the optical filter, and the merit that the optical filter is hardly warped is obtained.
  • the optical filter 1 e is constituted only by the light absorption layer 10.
  • the optical filter 1e is formed by, for example, applying a coating solution to a predetermined substrate such as a glass substrate, a resin substrate, a metal substrate (for example, a steel substrate or a stainless steel substrate) to form a coating and curing the coating. It can be manufactured by peeling from a substrate.
  • the optical filter 1e may be manufactured by a casting method.
  • the optical filter 1 e is thin because it does not include the transparent dielectric substrate 20. Therefore, the optical filter 1e can contribute to the shortening of the height of the imaging device.
  • the optical filter 1 f includes the light absorption layer 10 and a pair of anti-reflection films 30 disposed on both sides thereof.
  • the optical filter 1 f can contribute to reducing the height of the imaging device, and can increase the amount of light in the visible light region as compared to the optical filter 1 e.
  • Each of the optical filters 1a to 1f may be changed to include an infrared absorption layer (not shown) separately from the light absorption layer 10, as necessary.
  • the infrared absorbing layer contains, for example, an organic infrared absorber such as a cyanine type, phthalocyanine type, squarylium type, diimmonium type, or azo type, or an infrared absorber made of a metal complex.
  • the infrared absorption layer contains, for example, one or more infrared absorbers selected from these infrared absorbers. This organic infrared absorber has a small wavelength range (absorption band) of absorbable light and is suitable for absorbing light in a specific range of wavelengths.
  • Each of the optical filters 1a to 1f may be changed to include an ultraviolet absorbing layer (not shown) separately from the light absorbing layer 10, as necessary.
  • the ultraviolet absorbing layer contains, for example, ultraviolet absorbers such as benzophenone type, triazine type, indole type, merocyanine type, and oxazole type.
  • the ultraviolet absorbing layer contains, for example, one or more ultraviolet absorbers selected from these ultraviolet absorbers.
  • UV absorbers may be included, for example, those that absorb UV light of around 300 nm to 340 nm, emit light (fluorescent light) having a wavelength longer than the absorbed wavelength, and function as a fluorescent agent or a brightening agent,
  • the ultraviolet absorbing layer can reduce the incidence of ultraviolet light that causes deterioration of the material used for the optical filter such as resin.
  • the above-mentioned infrared ray absorbing agent and / or ultraviolet ray absorbing agent may be previously contained in a transparent dielectric substrate 20 made of resin to form a substrate having a property of absorbing infrared rays and / or ultraviolet rays.
  • the resin needs to be able to appropriately dissolve or disperse the infrared absorber and / or the ultraviolet absorber and be transparent.
  • Such resins include (poly) olefin resins, polyimide resins, polyvinyl butyral resins, polycarbonate resins, polyamide resins, polysulfone resins, polyether sulfone resins, polyamideimide resins, (modified) acrylic resins, epoxy resins, and silicone resins Can be illustrated.
  • the optical filter 1 a is used, for example, to manufacture an imaging device 100 (camera module).
  • the imaging device 100 includes a lens system 2, an imaging device 4, a color filter 3, and an optical filter 1 a.
  • the imaging element 4 receives light that has passed through the lens system 2.
  • the color filter 3 is disposed in front of the imaging device 4 and has three color filters of R (red), G (green), and B (blue).
  • the optical filter 1 a is disposed in front of the color filter 3.
  • the light absorption layer 10 is formed in contact with the surface of the transparent dielectric substrate 20 close to the lens system 2.
  • a high hardness material such as sapphire for the transparent dielectric substrate 20
  • the effect of protecting the lens system 2 or the imaging device 4 is enhanced.
  • the color filter 3 filters of three colors of R (red), G (green), and B (blue) are arranged in a matrix, and R (red) right above each pixel of the imaging device 4, A filter of any of G (green) and B (blue) is disposed.
  • the image sensor 4 receives light from an object that has passed through the lens system 2, the optical filter 1 a, and the color filter 3.
  • the imaging device 100 generates an image based on the information related to the charge generated by the light received by the imaging device 4.
  • the color image sensor may be configured by integrating the color filter 3 and the imaging device 4.
  • the imaging device 100 since the above conditions (i-1) to (ix-1) are satisfied, the imaging device 100 provided with such an optical filter 1a can generate an image of good image quality. In the optical filter 1a, if the above conditions (i-2), (ii-2), (iv-2), (vi-2), (vii-2) and (viii-2) are further satisfied. The imaging device 100 can generate an image having high color reproducibility. If the conditions shown in at least one of Table (I), Table (II), and Table (III) are satisfied in the optical filter 1a, even if the incident angle of light changes, the shape of the spectral transmittance curve changes Can effectively prevent the occurrence of color unevenness in the image generated by the imaging device 100.
  • the transmittance spectrum when light having a wavelength of 300 nm to 1200 nm is made incident on the optical filters according to the examples and comparative examples, the semi-finished products thereof, or the laminate according to the reference example is an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation) Product name: measured using V-670).
  • the incident angles of incident light are set to 0 °, 30 °, and 40 ° with respect to the optical filters of Examples and Comparative Examples, some semi-finished products, and laminates according to some Reference Examples
  • the transmittance spectrum of was measured.
  • permeability spectrum at the time of setting the incident angle of incident light to 0 degree was measured with respect to the laminated body which concerns on other semi-finished products and other reference examples.
  • Example 1 The coating solution IRA1 was prepared as follows. A mixture of 1.1 g of copper acetate monohydrate and 60 g of tetrahydrofuran (THF) was stirred for 3 hours, and a phosphate ester (product name: Plysurf A208F, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added to the obtained solution. 3 g was added and stirred for 30 minutes to obtain solution A. 10 g of THF was added to 0.6 g of phenylphosphonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and stirred for 30 minutes to obtain solution B. Solution B was added while stirring solution A, and stirred at room temperature for 1 minute.
  • THF tetrahydrofuran
  • the coating liquid IRA2 was prepared as follows. A mixture of 2.25 g of copper acetate monohydrate and 120 g of tetrahydrofuran (THF) was stirred for 3 hours, and the obtained solution was treated with 1.8 g of phosphoric ester (product name: Plysurf A208F, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). Was added and stirred for 30 minutes to obtain solution E. 20 g of THF was added to 1.35 g of butylphosphonic acid and stirred for 30 minutes to obtain a solution F.
  • THF tetrahydrofuran
  • Solution F was added while stirring solution E and stirred at room temperature for 3 hours, 40 g of toluene was added, and then the solvent was evaporated in an environment of 85 ° C. for 7.5 hours to obtain solution G.
  • a 8.8 g silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., product name: KR-300 was added to solution G, and the mixture was stirred for 3 hours to obtain a coating solution IRA2.
  • the coating solution IRA1 is applied to one main surface of a transparent glass substrate (manufactured by SCHOTT, product name: D263 T eco) by a die coater, dried in an oven at 85 ° C for 3 hours, then at 125 ° C for 3 hours, then at 150 ° C.
  • the coating film was cured by heat treatment at 170 ° C. for 3 hours to form an infrared absorbing layer ira11.
  • the coating liquid IRA1 was applied also to the opposite principal surface of the transparent glass substrate, and heat treatment was performed under the same conditions as described above to cure the coating, thereby forming the infrared absorption layer ira12.
  • a semi-finished product ⁇ of the optical filter according to Example 1 was obtained.
  • the thickness of the infrared absorption layer ira11 and the infrared absorption layer ira12 was 0.2 mm in total.
  • the transmission spectrum of the semifinished product ⁇ at an incidence angle of 0 ° is shown in FIG. 3A.
  • the semi-finished product ⁇ had the following characteristics ( ⁇ 1) to ( ⁇ 10).
  • ⁇ 5 The spectral transmittance at a wavelength of 715 nm was 0.9%.
  • ⁇ 6 The spectral transmittance at a wavelength of 1100 nm was 12.1%.
  • ⁇ 7 The spectral transmittance at a wavelength of 1200 nm was 49.1%.
  • ⁇ 8 The average transmittance at a wavelength of 500 to 600 nm was 88.0%.
  • ⁇ 9 The average transmittance at a wavelength of 700 to 800 nm was 0.5% or less.
  • ⁇ 10 The IR cutoff wavelength is 632 nm, the UV cutoff wavelength is 394 nm, and the difference between the IR cutoff wavelength and the UV cutoff wavelength is considered to be the full width at half maximum of the transmission region. The total width was 238 nm.
  • a deposited film (protective layer p1) of SiO 2 having a thickness of 500 nm was formed on the infrared absorption layer ira11 of the semifinished product ⁇ using a vacuum deposition apparatus.
  • a 500 nm thick SiO 2 vapor deposition film (protective layer p 2) was formed on the infrared absorption layer ira 12 of the semifinished product ⁇ .
  • the coating solution IRA2 is applied to the surface of the protective layer p1 by a die coater, and heat treated in an oven at 85 ° C. for 3 hours, then at 125 ° C. for 3 hours, then at 150 ° C. for 1 hour, then at 170 ° C.
  • the coating was cured to form an infrared absorbing layer ira21.
  • the coating liquid IRA2 was also applied to the surface of the protective layer p2 by a die coater, and the coating was cured under the same heating conditions to form an infrared absorption layer ira22.
  • a semi-finished product ⁇ was obtained.
  • the thicknesses of the infrared absorbing layer ira21 and the infrared absorbing layer ira22 were 50 ⁇ m in total.
  • the transmission spectrum of the semifinished product ⁇ at an incidence angle of 0 ° is shown in FIG. 3B.
  • the semifinished product ⁇ had the following characteristics ( ⁇ 1) to ( ⁇ 10).
  • ⁇ 1 The spectral transmittance at a wavelength of 390 nm was 38.2%.
  • ⁇ 2 The spectral transmittance at a wavelength of 400 nm was 62.1%.
  • ⁇ 3 The spectral transmittance at a wavelength of 450 nm was 84.0%.
  • ⁇ 4 The spectral transmittance at a wavelength of 700 nm was 1.8%.
  • ⁇ 5 The spectral transmittance at a wavelength of 715 nm was 0.6%.
  • ⁇ 6 The spectral transmittance at a wavelength of 1100 nm was 1.2%.
  • ⁇ 7 The spectral transmittance at a wavelength of 1200 nm was 10.1%.
  • the average transmittance at a wavelength of 500 to 600 nm was 87.2%.
  • the average transmittance at a wavelength of 700 to 800 nm was 0.5% or less.
  • the IR cutoff wavelength is 632 nm, the UV cutoff wavelength is 394 nm, and the difference between the IR cutoff wavelength and the UV cutoff wavelength is considered to be the full width at half maximum of the transmission region. The full width was 237 nm.
  • a deposited film (protective layer p3) of SiO 2 having a thickness of 500 nm was formed on the infrared absorption layer ira22 of the semifinished product ⁇ using a vacuum deposition apparatus.
  • Coating solution UVA1 was prepared as follows.
  • As the ultraviolet absorbing material a benzophenone-based ultraviolet absorbing material which has low light absorption in the visible light region and is soluble in MEK (methyl ethyl ketone) was used.
  • the ultraviolet absorbing material was dissolved in MEK as a solvent, and 60% by weight of polyvinyl butyral (PVB) of solid content was added, and the mixture was stirred for 2 hours to obtain a coating solution UVA1.
  • the coating liquid UVA1 was applied by spin coating on the protective layer p3 and cured by heating at 140 ° C. for 30 minutes to form an ultraviolet absorbing layer uva1.
  • the thickness of the ultraviolet absorbing layer uva1 was 6 ⁇ m.
  • a UV absorbing layer having a thickness of 6 ⁇ m was formed on the surface of a transparent glass substrate (manufactured by SCHOTT, product name: D263 T eco) by spin coating using a coating solution UVA1 to obtain a laminate according to Reference Example 1 .
  • permeability spectrum of the laminated body which concerns on the reference example 1 is shown to FIG. 3C.
  • the laminate according to Reference Example 1 had the following characteristics (r1) to (r3).
  • R2 The transmittance at a wavelength of 400 nm is 12.9%, the transmittance at 410 nm is 51.8%, the transmittance at 420 nm is 77.1%, and the transmittance at 450 nm is 89.8% Met.
  • R3 The average transmittance at a wavelength of 450 to 750 nm was 91.0%.
  • Antireflection film ar1 was formed on infrared absorption layer ira21 using a vacuum evaporation system. Further, an antireflective film ar2 was formed on the ultraviolet absorbing layer uva1 by using a vacuum evaporation system.
  • the antireflective film ar1 and the antireflective film ar2 have the same specifications, and are films in which SiO 2 and TiO 2 are alternately stacked, and the number of layers in the antireflective film ar1 and the antireflective film ar2 is seven.
  • the layer thickness was about 0.4 ⁇ m. Thus, an optical filter according to Example 1 was obtained.
  • An antireflection film was formed on one side of a transparent glass substrate (manufactured by SCHOTT, product name: D263 T eco) under the same conditions as the film formation of the antireflection film ar1, and a laminate according to Reference Example 2 was obtained.
  • permeability spectrum of the laminated body which concerns on the reference example 2 is shown to FIG. 3D.
  • the laminate according to Reference Example 2 had the following characteristics (s1) to (s4). (S1): When the incident angle of light is 0 °, the transmittance at a wavelength of 350 nm is 73.4%, the transmittance at a wavelength of 380 nm is 88.9%, and the transmittance at a wavelength of 400 nm is 95.
  • the transmittance spectrum of the optical filter according to Example 1 is shown in FIG. 3E and Table 4.
  • the optical filter according to Example 1 had the characteristics shown in Table 5.
  • the relationship between the difference in the spectral transmittance of the optical filter according to Example 1 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 4A.
  • the relationship between the absolute value of the difference in the spectral transmittance of the optical filter according to Example 1 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 4B.
  • FIG. 4C The relationship between the square value of the difference of the spectral transmittance of the optical filter according to Example 1 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 4C.
  • IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 From the transmittance spectra of the optical filter according to Example 1 at incident angles of 0 °, 30 °, and 40 °, according to the above equations (1) to (3), IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 , IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 and ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 were determined.
  • Tables 6-8 The results are shown in Tables 6-8.
  • Example 2 In the same manner as in Example 1, a coating solution IRA1 and a coating solution IRA2 were prepared.
  • the coating solution IRA1 is applied to one main surface of a transparent glass substrate (manufactured by SCHOTT, product name: D263 T eco) by a die coater, dried in an oven at 85 ° C for 3 hours, then at 125 ° C for 3 hours, then at 150 ° C.
  • the coating film was cured by heat treatment at 170 ° C. for 3 hours to form an infrared absorbing layer ira11.
  • the coating liquid IRA1 was applied also to the opposite principal surface of the transparent glass substrate, and heat treatment was performed under the same conditions as described above to cure the coating, thereby forming the infrared absorption layer ira12.
  • the thickness of the infrared absorption layer ira11 and the infrared absorption layer ira12 was 0.2 mm in total.
  • a 500 nm thick SiO 2 vapor deposition film (protective layer p1) was formed using a vacuum vapor deposition apparatus.
  • a deposited film (protective layer p2) of SiO 2 having a thickness of 500 nm was formed on the infrared absorption layer ira12.
  • the coating solution IRA2 is applied to the surface of the protective layer p1 by a die coater, and heat treated in an oven at 85 ° C. for 3 hours, then at 125 ° C. for 3 hours, then at 150 ° C. for 1 hour, then at 170 ° C. for 3 hours The coating was cured to form an infrared absorbing layer ira21.
  • the coating liquid IRA2 was also applied to the surface of the protective layer p2 by a die coater, and the coating was cured under the same heating conditions to form an infrared absorption layer ira22.
  • the thicknesses of the infrared absorbing layer ira21 and the infrared absorbing layer ira22 were 50 ⁇ m in total.
  • a 500 nm-thick SiO 2 vapor deposition film (protective layer p3) was formed using a vacuum vapor deposition apparatus.
  • a coating solution UVIRA1 containing an infrared absorbing dye and an ultraviolet absorbing dye was prepared as follows.
  • the infrared absorbing dye was a combination of a cyanine-based organic dye and a squalilium-based organic dye, which has an absorption peak at a wavelength of 680 to 780 nm and hardly absorbs light in the visible light range.
  • the ultraviolet absorbing dye was a dye made of an ultraviolet absorbing material of benzophenone type which hardly absorbs light in the visible light range.
  • the infrared absorbing dye and the ultraviolet absorbing dye were soluble in MEK.
  • An infrared absorbing dye and an ultraviolet absorbing dye were added to MEK as a solvent, and PVB as a matrix material was further added, and then stirred for 2 hours to obtain a coating solution UVIRA1.
  • the compounding ratio of the infrared absorbing dye in the coating solution UVIRA1 and the compounding ratio of the ultraviolet absorbing dye were determined so that the laminate according to Reference Example 3 exhibited the transmittance spectrum shown in FIG. 5A.
  • the laminate according to Reference Example 3 is obtained by applying the coating solution UVIRA1 by spin coating on a transparent glass substrate (manufactured by SCHOTT, product name: D263 T eco), and heating the coating film at 140 ° C. for 30 minutes.
  • the mass ratio of the infrared absorbing dye to the solid content of PVB was about 1: 199. Further, the mass ratio of the ultraviolet absorbing dye to the solid content of PVB (mass of ultraviolet absorbing dye: mass of solid content of PVB) was about 40:60.
  • the laminate according to Reference Example 3 had the following characteristics (t1) to (t5). (T1): The transmittance at a wavelength of 700 nm was 8.7%, the transmittance at a wavelength of 715 nm was 13.6%, and the average transmittance at a wavelength of 700 to 800 nm was 66.2%.
  • T2 The transmittance at a wavelength of 1100 nm was 92.1%.
  • T3 The transmittance at a wavelength of 400 nm was 11.8%, the transmittance at 450 nm was 85.3%, and the average transmittance at wavelengths of 500 to 600 nm was 89.1%.
  • T4 The IR cutoff wavelength at a wavelength of 600 nm to 700 nm was 669 nm, the IR cutoff wavelength at a wavelength of 700 nm to 800 nm was 729 nm, and their difference was 60 nm. The wavelength (maximum absorption wavelength) showing the lowest transmittance at wavelengths of 600 nm to 800 nm was 705 nm.
  • T5 The UV cutoff wavelength at a wavelength of 350 nm to 450 nm was 411 nm.
  • the coating liquid UVIRA1 was applied on the protective layer p3 by spin coating, and the coated film was cured by heating at 140 ° C for 30 minutes to form an infrared / ultraviolet absorbing layer uvira1.
  • the thickness of the infrared and ultraviolet absorbing layer uvira 1 was 7 ⁇ m.
  • Antireflection film ar1 was formed on infrared absorption layer ira21 using a vacuum evaporation system. Further, an antireflective film ar2 was formed on the infrared / ultraviolet absorbing layer uvira1 using a vacuum vapor deposition apparatus.
  • the antireflective film ar1 and the antireflective film ar2 have the same specifications, and are films in which SiO 2 and TiO 2 are alternately stacked, and the number of layers in the antireflective film ar1 and the antireflective film ar2 is seven.
  • the layer thickness was about 0.4 ⁇ m. Thus, an optical filter according to Example 2 was obtained.
  • the transmittance spectrum of the optical filter according to Example 2 is shown in FIG. 5B and Table 9.
  • the optical filter according to Example 2 had the characteristics shown in Table 10.
  • the relationship between the difference in the spectral transmittance of the optical filter according to Example 2 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 6A.
  • the relationship between the absolute value of the difference in spectral transmittance of the optical filter according to Example 2 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 6B.
  • FIG. 6C The relationship between the square value of the difference of the spectral transmittance of the optical filter according to Example 2 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 6C.
  • IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 From the transmittance spectra of the optical filter according to Example 2 at incident angles of 0 °, 30 °, and 40 °, according to the above equations (1) to (3), IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 , IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 and ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 were determined.
  • Example 3 In the same manner as in Example 1, a coating solution IRA1 was prepared. Apply to one of the main surfaces of a transparent glass substrate (SCHOTT, product name: D263 T eco) by a die coater, use an oven at 85 ° C for 3 hours, then 125 ° C for 3 hours, then 150 ° C for 1 hour, then A heat treatment was performed at 170 ° C. for 3 hours to cure the coating, thereby forming an infrared absorption layer ira11. Similarly, the coating liquid IRA1 was applied also to the opposite principal surface of the transparent glass substrate, and heat treatment was performed under the same conditions as described above to cure the coating, thereby forming the infrared absorption layer ira12. The thickness of the infrared absorption layer ira11 and the infrared absorption layer ira12 was 0.2 mm in total.
  • a transparent glass substrate SCHOTT, product name: D263 T eco
  • an infrared reflective film irr1 was formed on the infrared absorption layer ira11 using a vacuum evaporation system.
  • 16 layers of SiO 2 and TiO 2 were alternately laminated.
  • An infrared ray reflective film was formed on one main surface of a transparent glass substrate (manufactured by SCHOTT, product name: D263 T eco) under the same conditions as the formation of the infrared ray reflective film irr1, and a laminate according to Reference Example 4 was produced.
  • permeability spectrum of the laminated body which concerns on the reference example 4 is shown to FIG. 7A.
  • the laminate according to Reference Example 4 had the following characteristics (u1) to (u3).
  • a deposited film (protective layer p2) of SiO 2 having a thickness of 500 nm was formed on the infrared absorption layer ira12.
  • the coating solution UVA1 used in Example 1 was applied by spin coating, and the coated film was cured by heating at 140 ° C. for 30 minutes to form an ultraviolet absorbing layer uva1.
  • the thickness of the ultraviolet absorbing layer uva1 was 6 ⁇ m.
  • An antireflective film ar2 was formed on the ultraviolet absorbing layer uva1 using a vacuum evaporation system.
  • the antireflective film ar2 is a film in which SiO 2 and TiO 2 are alternately stacked, and in the antireflective film ar2, the number of layers is 7, and the total film thickness is about 0.4 ⁇ m. Thus, an optical filter according to Example 3 was obtained.
  • Transmittance spectra of the optical filter according to Example 3 are shown in FIG. 7B and Table 14.
  • the optical filter according to Example 3 had the characteristics shown in Table 15.
  • the relationship between the difference in the spectral transmittance of the optical filter according to Example 3 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 8A.
  • the relationship between the absolute value of the difference in spectral transmittance of the optical filter according to Example 3 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 8B.
  • FIG. 8C The relationship between the square value of the difference of the spectral transmittance of the optical filter according to Example 3 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 8C. From the transmittance spectra of the optical filter according to Example 3 at incident angles of 0 °, 30 °, and 40 °, according to the above equations (1) to (3), IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 , IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 and ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 were determined.
  • Tables 16-18 The results are shown in Tables 16-18.
  • Example 4 In the same manner as in Example 1, a coating solution IRA1 was prepared. Apply to one of the main surfaces of a transparent glass substrate (SCHOTT, product name: D263 T eco) by a die coater, use an oven at 85 ° C for 3 hours, then 125 ° C for 3 hours, then 150 ° C for 1 hour, then A heat treatment was performed at 170 ° C. for 3 hours to cure the coating, thereby forming an infrared absorption layer ira11. Similarly, the coating liquid IRA1 was applied also to the opposite principal surface of the transparent glass substrate, and heat treatment was performed under the same conditions as described above to cure the coating, thereby forming the infrared absorption layer ira12. The thickness of the infrared absorption layer ira11 and the infrared absorption layer ira12 was 0.2 mm in total.
  • a transparent glass substrate SCHOTT, product name: D263 T eco
  • an infrared reflection film irr1 was formed on the infrared absorption layer ira11 using a vacuum evaporation system.
  • the infrared reflective film irr1 16 layers of SiO 2 and TiO 2 were alternately laminated.
  • a deposited film (protective layer p2) of SiO 2 having a thickness of 500 nm was formed on the infrared absorption layer ira12.
  • the coating solution UVIRA1 used in Example 2 is applied under the same conditions as in Example 2, and the coating film is cured by heating at 140 ° C. for 30 minutes to form an infrared / ultraviolet absorbing layer uvira1. did.
  • the thickness of the infrared and ultraviolet absorbing layer uvira 1 was 7 ⁇ m.
  • An antireflective film ar2 was formed on the infrared / ultraviolet absorbing layer uvira1 using a vacuum evaporation system.
  • the antireflective film ar2 is a film in which SiO 2 and TiO 2 are alternately stacked, and in the antireflective film ar2, the number of layers is 7, and the total film thickness is about 0.4 ⁇ m. Thus, an optical filter according to Example 4 was obtained.
  • the transmittance spectrum of the optical filter according to Example 4 is shown in FIG. 9 and Table 19.
  • the optical filter according to Example 4 had the characteristics shown in Table 20.
  • the relationship between the difference in the spectral transmittance of the optical filter according to Example 4 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 10A.
  • the relationship between the absolute value of the difference in spectral transmittance of the optical filter according to Example 4 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 10B.
  • FIG. 10C The relationship between the square value of the difference of the spectral transmittance of the optical filter according to Example 4 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 10C.
  • IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 From the transmittance spectra of the optical filter according to Example 4 at incident angles of 0 °, 30 °, and 40 °, according to the above equations (1) to (3), IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 , IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 and ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 were determined.
  • Tables 21-23 The results are shown in Tables 21-23.
  • Example 5 In the same manner as in Example 1, a coating solution IRA1 and a coating solution IRA2 were prepared. Apply to one of the main surfaces of a transparent glass substrate (SCHOTT, product name: D263 T eco) by a die coater, use an oven at 85 ° C for 3 hours, then 125 ° C for 3 hours, then 150 ° C for 1 hour, then A heat treatment was performed at 170 ° C. for 3 hours to cure the coating, thereby forming an infrared absorption layer ira11. Similarly, the coating liquid IRA1 was applied also to the opposite principal surface of the transparent glass substrate, and heat treatment was performed under the same conditions as described above to cure the coating, thereby forming the infrared absorption layer ira12. The thickness of the infrared absorption layer ira11 and the infrared absorption layer ira12 was 0.4 mm in total.
  • a transparent glass substrate SCHOTT, product name: D263 T eco
  • a 500 nm thick SiO 2 vapor deposition film (protective layer p1) was formed using a vacuum vapor deposition apparatus.
  • a deposited film (protective layer p2) of SiO 2 having a thickness of 500 nm was formed on the infrared absorption layer ira12.
  • the coating solution IRA2 is applied to the surface of the protective layer p1 by a die coater, and heat treated in an oven at 85 ° C. for 3 hours, then at 125 ° C. for 3 hours, then at 150 ° C. for 1 hour, then at 170 ° C. for 3 hours The coating was cured to form an infrared absorbing layer ira21.
  • the coating liquid IRA2 was also applied to the surface of the protective layer p2 by a die coater, and the coating was cured under the same heating conditions to form an infrared absorption layer ira22, to obtain a semifinished product ⁇ .
  • the transmission spectrum of the semifinished product ⁇ at an incidence angle of 0 ° C. is shown in FIG. 11A.
  • the semifinished product ⁇ had the following characteristics ( ⁇ 1) to ( ⁇ 10).
  • ( ⁇ 1) The spectral transmittance at a wavelength of 390 nm was 15.8%.
  • ⁇ 4 The spectral transmittance at a wavelength of 700 nm was 0.5% or less.
  • ⁇ 5) The spectral transmittance at a wavelength of 715 nm was 0.5% or less.
  • ⁇ 6 The spectral transmittance at a wavelength of 1100 nm was 0.5% or less.
  • ⁇ 7 The spectral transmittance at a wavelength of 1200 nm was 1.1%.
  • ⁇ 8 The average transmittance at a wavelength of 500 to 600 nm was 82.7%.
  • ⁇ 9 The average transmittance at a wavelength of 700 to 800 nm was 0.5% or less.
  • the IR cutoff wavelength is 613 nm
  • the UV cutoff wavelength is 404 nm
  • the difference between the IR cutoff wavelength and the UV cutoff wavelength is considered to be the full width at half maximum of the transmission region.
  • the full width was 209 nm.
  • Antireflection film ar1 was formed on infrared absorption layer ira21 using a vacuum evaporation system. Further, an antireflective film ar2 was formed on the infrared absorption layer ira22 using a vacuum evaporation system.
  • the antireflective film ar1 and the antireflective film ar2 have the same specifications, and are films in which SiO 2 and TiO 2 are alternately stacked, and the number of layers in the antireflective film ar1 and the antireflective film ar2 is seven.
  • the layer thickness was about 0.4 ⁇ m. Thus, an optical filter according to Example 5 was obtained.
  • the transmittance spectrum of the optical filter according to Example 5 is shown in FIG. 11B and Table 24.
  • the optical filter according to Example 5 had the characteristics shown in Table 25.
  • the relationship between the difference in the spectral transmittance of the optical filter according to Example 5 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 12A.
  • the relationship between the absolute value of the difference between the spectral transmittances of the optical filter according to Example 5 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 12B.
  • FIG. 12C The relationship between the square value of the difference of the spectral transmittance of the optical filter according to Example 5 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 12C. From the transmittance spectra of the optical filter according to Example 5 at incident angles of 0 °, 30 °, and 40 °, according to the above equations (1) to (3), IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 , IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 and ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 were determined.
  • Comparative Example 1 An infrared ray reflective film irr2 is formed by alternately laminating 24 layers of SiO 2 and TiO 2 on one main surface of a transparent glass substrate (manufactured by SCHOTT, product name: D263 T eco) using a vacuum deposition apparatus to form a semifinished product I got ⁇ .
  • the transmittance spectrum of the semifinished product ⁇ is shown in FIG. 13A.
  • the semifinished product ⁇ had the following characteristics ( ⁇ 1) to ( ⁇ 3).
  • the transmittance at a wavelength of 380 nm is 13.1%
  • the transmittance at a wavelength of 400 nm is 90.5%
  • the average transmittance at a wavelength of 450 to 600 nm is 92.1%
  • the lowest value of the transmittance at a wavelength of 450 to 600 nm is 87.6%
  • the transmittance at a wavelength of 700 nm is 2.0%
  • the transmittance at a wavelength of 715 nm is 0.8%
  • the average transmittance at a wavelength of 700 to 800 nm was 0.5% or less
  • the transmittance at a wavelength of 1100 nm was 5.4%
  • the IR cut-off wavelength was 661 nm
  • the UV cut-off length was 386 nm.
  • Coating solution IRA3 containing an infrared absorbing dye was prepared as follows.
  • the infrared absorbing dye was a combination of a cyanine-based organic dye soluble in MEK and a squarylium-based organic dye.
  • An infrared absorbing dye was added to MEK as a solvent, and PVB as a matrix material was further added, and then stirred for 2 hours to obtain a coating solution IRA3.
  • the content of the matrix material in the solid content of the coating solution IRA3 was 99% by mass.
  • the coating liquid IRA3 was applied by spin coating to the other principal surface of the transparent glass substrate of the semifinished product ⁇ , the coating was heated at 140 ° C. for 30 minutes to be cured to form an infrared absorption layer ira3.
  • an infrared absorption layer is formed on one main surface of a transparent glass substrate (manufactured by SCHOTT, product name: D263 T eco) under the same conditions as the formation conditions of the infrared absorption layer ira3, and the laminate according to Reference Example 5 is obtained. Obtained.
  • permeability spectrum of the laminated body which concerns on the reference example 5 in the incident angle of 0 degree is shown to FIG. 13B.
  • the laminate according to Reference Example 5 had the following characteristics (v1) to (v4).
  • V1 The transmittance at a wavelength of 700 nm was 2.0%, the transmittance at a wavelength of 715 nm was 2.6%, and the average transmittance at a wavelength of 700 to 800 nm was 15.9%.
  • V2 The transmittance at a wavelength of 1100 nm was 91.1%.
  • V3 The transmittance at a wavelength of 400 nm was 78.2%, the transmittance at 450 nm was 83.8%, and the average transmittance at wavelengths of 500 to 600 nm was 86.9%.
  • V4 The IR cut-off wavelength at a wavelength of 600 nm to 700 nm is 637 nm, the IR cut-off wavelength at a wavelength of 700 nm to 800 nm is 800 nm, and the difference between these IR cut-off wavelengths is 163 nm.
  • the maximum absorption wavelength was 706 nm.
  • An antireflection film ar1 was formed on the infrared absorption layer ira3 in the same manner as in Example 1 using a vacuum vapor deposition apparatus, to obtain an optical filter according to Comparative Example 1.
  • the transmittance spectrum of the optical filter according to Comparative Example 1 is shown in FIG. 13C and Table 29.
  • the optical filter according to Comparative Example 1 had the characteristics shown in Table 30.
  • the relationship between the difference between the spectral transmittance of the optical filter according to Comparative Example 1 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 14A.
  • the relationship between the absolute value of the difference of the spectral transmittance of the optical filter according to Comparative Example 1 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 14B.
  • FIG. 14C The relationship between the square value of the difference of the spectral transmittance of the optical filter according to Comparative Example 1 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 14C.
  • IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 From the transmittance spectra of the optical filter according to Comparative Example 1 at incident angles of 0 °, 30 °, and 40 °, according to the above equations (1) to (3), IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 , IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 and ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 were determined.
  • Tables 31-33 The results are shown in Tables 31-33.
  • G6 The spectral transmittance at a wavelength of 1100 nm was 32.5%.
  • G7 The spectral transmittance at a wavelength of 1200 nm was 44.5%.
  • G8 The average transmittance at a wavelength of 500 to 600 nm was 86.5%.
  • G9 The average transmittance at a wavelength of 700 to 800 nm was 19.1%.
  • G10 The IR cutoff wavelength was 653 nm, and the wavelength showing a transmittance of 20% at wavelengths of 600 to 800 nm was 738 nm.
  • the laminate according to Reference Example 6 had the following characteristics (w1) to (w3).
  • the IR cut-off wavelength is 702 nm
  • the UV cut-off wavelength is 411 nm.
  • W2 When the incident angle of light is 30 °, the transmittance at a wavelength of 380 nm is 1.7%, the transmittance at a wavelength of 400 nm is 77.7%, and the average transmittance at a wavelength of 450 to 600 nm is 94.1%, the lowest value of the transmittance at a wavelength of 450 to 600 nm is 93.0%, the average transmittance at a wavelength of 700 to 800 nm is 1.1%, and the transmittance at a wavelength of 1100 nm is 1.2 %, The IR cut-off wavelength was 680 nm, and the UV cut-off wavelength was 397 nm.
  • a coating solution UVIRA2 containing an infrared absorbing dye and an ultraviolet absorbing dye was prepared as follows.
  • the ultraviolet absorbing dye was a dye made of an ultraviolet absorbing material of benzophenone type which hardly absorbs light in the visible light range.
  • the infrared absorbing dye was a combination of a cyanine-based organic dye and a squarylium-based organic dye.
  • the infrared absorbing dye and the ultraviolet absorbing dye were soluble in MEK.
  • An infrared absorbing dye and an ultraviolet absorbing dye were added to MEK as a solvent, and PVB as a matrix material was further added, and then stirred for 2 hours to obtain a coating solution UVIRA2.
  • the content of PVB in the solid content of the coating solution UVIRA2 was 60% by mass.
  • the coating solution UVIRA2 was applied to the other principal surface of the semifinished product, and the coating was heated and cured to form an infrared / ultraviolet absorbing layer uvira2.
  • the thickness of the infrared and ultraviolet absorbing layer uvira 2 was 7 ⁇ m.
  • An infrared / ultraviolet absorbing layer is formed on one main surface of a transparent glass substrate (SCHOTT's product name: D263 T eco) using the coating solution UVIRA2 under the same conditions as the forming conditions of the infrared / ultraviolet absorbing layer uvira 2
  • the laminate according to Reference Example 7 was obtained.
  • permeability spectrum of the laminated body which concerns on the reference example 7 in the incident angle of 0 degree is shown to FIG. 15C.
  • the laminate according to Reference Example 7 had the following characteristics (p1) to (p5).
  • P1 The transmittance at a wavelength of 700 nm was 4.9%, the transmittance at a wavelength of 715 nm was 8.4%, and the average transmittance at a wavelength of 700 to 800 nm was 63.9%.
  • P2 The transmittance at a wavelength of 1100 nm was 92.3%.
  • P3 The transmittance at a wavelength of 400 nm was 12.6%, the transmittance at 450 nm was 84.4%, and the average transmittance at wavelengths of 500 to 600 nm was 88.7%.
  • An antireflective film ar1 was formed on the infrared / ultraviolet absorbing layer uvira 2 in the same manner as in Example 1 using a vacuum evaporation system.
  • the antireflective film ar1 is a film in which SiO 2 and TiO 2 are alternately stacked, and in the antireflective film ar1, the number of layers is 7, and the total film thickness is about 0.4 ⁇ m.
  • the optical filter according to Comparative Example 2 was obtained.
  • the transmittance spectrum of the optical filter according to Comparative Example 2 is shown in FIG. 15D and Table 34.
  • the optical filter according to Comparative Example 2 had the characteristics shown in Table 35.
  • the relationship between the difference between the spectral transmittance of the optical filter according to Comparative Example 2 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 16A.
  • the relationship between the absolute value of the difference in the spectral transmittance of the optical filter according to Comparative Example 2 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 16B.
  • FIG. 16C The relationship between the square value of the difference of the spectral transmittance of the optical filter according to Comparative Example 2 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 16C.
  • IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 From the transmittance spectra of the optical filter according to Comparative Example 2 at incident angles of 0 °, 30 °, and 40 °, according to the above equations (1) to (3), IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 , IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 and ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 were determined.
  • Tables 36-38 The results are shown in Tables 36-38.
  • Example 3 In the same manner as in Example 1, a coating solution IRA1 and a coating solution IRA2 were prepared.
  • the coating solution IRA1 is applied to one main surface of a transparent glass substrate (manufactured by SCHOTT, product name: D263 T eco) by a die coater, dried in an oven at 85 ° C for 3 hours, then at 125 ° C for 3 hours, then at 150 ° C.
  • the coating film was cured by heat treatment at 170 ° C. for 3 hours to form an infrared absorbing layer ira11.
  • the coating liquid IRA1 was applied also to the opposite principal surface of the transparent glass substrate, and heat treatment was performed under the same conditions as described above to cure the coating, thereby forming the infrared absorption layer ira12.
  • a semifinished product ⁇ of the optical filter according to Comparative Example 3 was obtained.
  • the thickness of the infrared absorption layer ira11 and the infrared absorption layer ira12 was 0.2 mm in total.
  • the transmission spectrum of semifinished product ⁇ at an incidence angle of 0 ° is shown in FIG. 17A.
  • the semifinished product ⁇ had the following characteristics ( ⁇ 1) to ( ⁇ 10).
  • the average transmittance at a wavelength of 700 to 800 nm was 0.5% or less.
  • the IR cutoff wavelength is 629 nm
  • the UV cutoff wavelength is 395 nm
  • the difference between the IR cutoff wavelength and the UV cutoff wavelength is the full width at half maximum of the transmission region. The full width was 234 nm.
  • a vapor deposited film (protective layer p2) of SiO 2 having a thickness of 500 nm was formed on the infrared absorption layer ira12 of the semifinished product ⁇ .
  • the coating solution UVA1 used in Example 1 was applied by spin coating, and the coated film was cured by heating at 140 ° C. for 30 minutes to form an ultraviolet absorbing layer uva1.
  • the thickness of the ultraviolet absorbing layer uva1 was 6 ⁇ m.
  • Antireflection film ar1 was formed on infrared absorption layer ira11 using a vacuum evaporation system. Further, an antireflective film ar2 was formed on the ultraviolet absorbing layer uva1 by using a vacuum evaporation system.
  • the antireflective film ar1 and the antireflective film ar2 have the same specifications, and are films in which SiO 2 and TiO 2 are alternately stacked, and the number of layers in the antireflective film ar1 and the antireflective film ar2 is seven.
  • the layer thickness was about 0.4 ⁇ m. Thus, the optical filter according to Comparative Example 3 was obtained.
  • the transmittance spectrum of the optical filter according to Comparative Example 3 is shown in FIG. 17B and Table 39.
  • the optical filter according to Comparative Example 3 had the characteristics shown in Table 40.
  • the relationship between the difference in the spectral transmittance of the optical filter according to Comparative Example 3 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 18A.
  • the relationship between the absolute value of the difference of the spectral transmittance of the optical filter according to Comparative Example 3 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 18B.
  • FIG. 18C The relationship between the square value of the difference of the spectral transmittance of the optical filter according to Comparative Example 3 and the wavelength at two incident angles selected from 0 °, 30 °, and 40 ° is shown in FIG. 18C. From the transmittance spectra of the optical filter according to Comparative Example 3 at incident angles of 0 °, 30 °, and 40 °, according to the above equations (1) to (3), IE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 , IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 and ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 were determined.
  • Tables 41-43 The results are shown in Tables 41-43.
  • the above conditions (i-1) to (ix-1) were satisfied.
  • the transmittance in the wavelength range of 700 nm or more was sufficiently low, and it was shown that the optical filters according to Examples 1 to 5 can well shield near infrared rays.
  • the optical filter according to Example 2 exhibited lower transmittance in the wavelength range of 700 nm or more, as compared to the optical filter according to Example 1.
  • the transmittance of the visible light region was about 2 points lower than that of the optical filter according to Example 1 due to the inclusion of the infrared absorbing dye.
  • the transmittance near the wavelength of 400 nm was higher than that of the optical filters of the other examples, but was 44.9% or less.
  • the values of IAE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 and ISE ⁇ 1 / ⁇ 2 ⁇ 1 to ⁇ 2 are with respect to the upper limit values of Table (II) and Table (III) It was small enough.
  • the boundary between the wavelength band for transmitting light with an incident angle of 40 ° and the wavelength band for reflecting light with an incident angle of 40 ° is around 850 nm. It was set.
  • the spectral transmittances of the optical filters according to Examples 3 and 4 at incident angles of 0 °, 30 °, and 40 ° on the long wavelength side (600 nm to 800 nm wavelength range) in the wavelength range of 350 nm to 800 nm are It hardly changed.
  • the transmittance near the wavelength of 400 nm was higher as the incident angle of light was larger.
  • this effect is caused by IE 0/30 380 to 530 , IE 0/40 380 to 530 , IAE 0/30 380 to 530 , IAE 0/40 380 to 530 , ISE 0 / 30 380-530, and had appeared in ISE 0/40 380-530.
  • the spectral transmittance in the vicinity of a wavelength of 530 nm at an incident angle of 30 ° of the optical filters according to Examples 3 and 4 is around a wavelength of 530 nm at an incident angle of 0 ° and an incident angle of 40 ° in the optical filters according to Examples 3 and 4.
  • the infrared absorbing layer ira3 defines the boundary between the wavelength band for transmitting light and the wavelength band for shielding light in the region adjacent to the near infrared region of the visible light region and the near infrared region. It is done. However, since the absorption band of the infrared absorption layer ira3 is narrow, in the transmittance spectrum of the optical filter according to Comparative Example 1, the reflection band of the infrared reflection film shifts to the short wavelength side as the incident angle of light increases. I was affected.
  • the light absorbing ability in the ultraviolet region of the optical filter according to Comparative Example 1 is insufficient, and the optical filter according to Comparative Example 1 substantially shields the light in the ultraviolet region by the infrared reflection film irr2 alone. . Therefore, the optical filter according to Comparative Example 1 is strongly affected by the shift of the reflection band to the short wavelength side depending on the incident angle of light in the ultraviolet region. For this reason, the optical filter according to Comparative Example 1 does not satisfy the above conditions (i-1), (ii-1), (vi-1), and (vii-1), and the optical filter according to Comparative Example 1 is further included.
  • the spectral transmittance in the vicinity of 400 nm of such an optical filter largely fluctuates between an incident angle of 0 ° and an incident angle of 30 °.
  • the spectral transmittance in the vicinity of 650 nm of the optical filter according to Comparative Example 1 largely fluctuates between the incident angle of 0 ° and the incident angle of 40 °.
  • the spectral transmittance in the range of 450 nm to 650 nm of the optical filter according to Comparative Example 1 is between the incident angle of 0 ° and the incident angle of 40 ° and between the incident angle of 30 ° and the incident angle of 40 °. There was a large local variation between the two.
  • IAE 30/40 350 ⁇ 800, ISE 30/40 380 ⁇ 800, IAE 30/40 380 ⁇ 530, ISE 30/40 380 ⁇ 530, IE 30/40 450 ⁇ 650, IAE 30/40 450 ⁇ 650, IE 30 / 40 530 ⁇ 750, IAE 30/40 530 ⁇ 750, and ISE 30/40 530 ⁇ 750 were not within the range shown in Table (I) ⁇ (III). Therefore, when the optical filter according to Comparative Example 1 is incorporated into an imaging device, there is concern that strong color unevenness may occur in a narrow range of the obtained image.
  • the boundary between the wavelength band transmitting light and the wavelength band shielding the light is infrared / ultraviolet absorption Was determined by layer uvira2.
  • IE 30/40 350 to 800 show large values.
  • the transmittance spectrum of the optical filter according to Comparative Example 2 at the incident angle of 40 ° local fluctuation (ripple) of the spectral transmittance was recognized in the visible light region.
  • IE 30/40 350 ⁇ 800, IAE 30/40 350 ⁇ 800, ISE 30/40 350 ⁇ 800, IE 30/40 380 ⁇ 530, IAE 30/40 380 ⁇ 530, IE 30/40 450 ⁇ 650, IAE 30/40 450 ⁇ 650 , IE 30/40 530 ⁇ 750, and IAE 30/40 530 ⁇ 750 had become a large value.
  • the optical filter according to Comparative Example 2 is incorporated in an imaging device, there is concern that strong color unevenness may occur in a narrow range of the obtained image.
  • the optical filter according to Comparative Example 3 has desirable characteristics in the wavelength range of 1100 to 1200 nm.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Glass Compositions (AREA)
  • Burglar Alarm Systems (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un filtre optique (1a) pourvu d'une couche d'absorption de lumière (10). Lorsqu'une lumière ayant une longueur d'onde comprise entre 300 et 1200 nm est rendue incidente sur le filtre optique aux angles d'incidence de 0°, 30° et 40°, (i-1) la transmittance spectrale à une longueur d'onde de 390 nm, (ii-1) la transmittance spectrale à une longueur d'onde de 400 nm, (iii-1) la transmittance spectrale à une longueur d'onde de 450 nm, (iv-1) la transmittance spectrale à une longueur d'onde de 700 nm, (v-1) la transmittance spectrale à une longueur d'onde de 715 nm, (vi-1) la transmittance spectrale à une longueur d'onde de 1100 nm, (vii-1) la transmittance spectrale à une longueur d'onde de 1200 nm, (viii-1) la transmittance moyenne d'une longueur d'onde comprise entre 500 et 600 nm, et (ix-1) la transmittance moyenne d'une longueur d'onde comprise entre 700 et 800 nm, satisfont une condition prescrite.
PCT/JP2019/000109 2018-01-09 2019-01-07 Filtre optique et dispositif d'imagerie Ceased WO2019138976A1 (fr)

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CN119148276A (zh) * 2023-06-16 2024-12-17 白金科技股份有限公司 滤光片
JP2024180373A (ja) * 2023-06-16 2024-12-26 白金科技股▲分▼有限公司 複合感光構造及びその製造方法

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JP2021124569A (ja) * 2020-02-04 2021-08-30 日本板硝子株式会社 光吸収性組成物、光吸収膜、及び光学フィルタ
JP7631465B2 (ja) 2020-02-04 2025-02-18 日本板硝子株式会社 光吸収性組成物、光吸収膜、光吸収膜の製造方法、及び光学フィルタ
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JP2021152612A (ja) * 2020-03-24 2021-09-30 日本板硝子株式会社 光吸収性組成物、光吸収膜、及び光学フィルタ
JP2022077314A (ja) * 2020-11-11 2022-05-23 Ａｇｃ株式会社 光学フィルタ
JP7552271B2 (ja) 2020-11-11 2024-09-18 Ａｇｃ株式会社 光学フィルタ
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CN119148276A (zh) * 2023-06-16 2024-12-17 白金科技股份有限公司 滤光片
JP2024180373A (ja) * 2023-06-16 2024-12-26 白金科技股▲分▼有限公司 複合感光構造及びその製造方法
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