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WO2022034739A1 - Filtre optique - Google Patents

Filtre optique Download PDF

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Publication number
WO2022034739A1
WO2022034739A1 PCT/JP2021/022940 JP2021022940W WO2022034739A1 WO 2022034739 A1 WO2022034739 A1 WO 2022034739A1 JP 2021022940 W JP2021022940 W JP 2021022940W WO 2022034739 A1 WO2022034739 A1 WO 2022034739A1
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WO
WIPO (PCT)
Prior art keywords
wavelength
dye
less
group
wavelength range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/022940
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English (en)
Japanese (ja)
Inventor
和彦 塩野
崇 長田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2022542588A priority Critical patent/JPWO2022034739A1/ja
Priority to CN202180055527.2A priority patent/CN116075751A/zh
Publication of WO2022034739A1 publication Critical patent/WO2022034739A1/fr
Anticipated expiration legal-status Critical
Priority to JP2025158330A priority patent/JP2025178366A/ja
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting 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

  • An image sensor using a solid-state image sensor has optics that transmit light in the visible band (visible light) and block light in the near-infrared region (near-infrared light) in order to reproduce color tones well and obtain clear images.
  • a filter is used.
  • an optical filter for example, a near-infrared light cut filter in which a base material containing a dye and a resin and a dielectric multilayer film is provided on a glass substrate is known.
  • the number of layers having at least a layer made of resin A (layer A) and a layer made of resin B (layer B) is 30 or more.
  • an optical filter comprising the laminated film of the above, having an average reflectance of 60% or more in the near infrared band having a wavelength of 850 to 1000 nm, and satisfying the following formulas a and b.
  • This filter satisfies all of the following (i-1) to (i-9).
  • (I-1) In the spectral transmittance curve with an incident angle of 0 °, It has a maximum value of 1 (0 deg) in the wavelength range of 430 nm or more and less than 490 nm. It has a maximum value of 2 (0 deg) in the wavelength range of 490 nm or more and less than 590 nm. It has a maximum value of 3 (0 deg) in the wavelength range of 590 nm or more and less than 650 nm.
  • the wavelength range of the minimum value 1 (30 deg) or the wavelength range in which the transmittance is 1% or less is preferably 400 nm or more and less than 430 nm, and more preferably 410 nm or more and less than 420 nm.
  • the wavelength range of the minimum value 2 (30 deg) or the wavelength range in which the transmittance is 1% or less is preferably 450 nm or more and less than 530 nm, and more preferably 460 nm or more and less than 520 nm.
  • the average transmittance (30 deg) is preferably 1% or less, more preferably 0.5% or less, still more preferably 0.2% or less.
  • wavelength ⁇ 1 (0deg) , wavelength ⁇ 1 (30deg) , wavelength ⁇ 2 (0deg) , wavelength ⁇ 2 (30deg) , wavelength ⁇ 3 (0deg) , wavelength ⁇ 3 (30deg) , wavelength ⁇ 4 (0deg) , wavelength ⁇ 4 ( 30deg). ) Is a value obtained by the following formula.
  • this filter reduces the change in the amount of light in the RGB band due to the incident angle.
  • IR80b (dye 4) -IR10 (dye 4) is preferably 79 nm or less, more preferably 77 nm or less.
  • the dye A has an absorption maximum wavelength in a wavelength range of 400 nm or more and less than 700 nm in the spectral transmittance curve of the coating film obtained by dissolving the dye A in a resin and applying the dye A on a glass substrate.
  • the dye 3 In the spectral transmittance curve of the coating film obtained by dissolving the dye 3 in the resin and coating the glass substrate, the dye 3 has an absorption maximum wavelength in a wavelength range of 540 nm or more and less than 600 nm. .. (Ii-4) In the spectral transmittance curve of the coating film obtained by dissolving the dye 4 in the resin and coating the glass substrate, the dye 4 has an absorption maximum wavelength in a wavelength range of 600 nm or more and less than 720 nm. ..
  • the dye 1 preferably has an absorption maximum wavelength in the wavelength range of 395 nm or more and less than 430 nm, and more preferably has an absorption maximum wavelength in the wavelength range of 395 nm or more and less than 420 nm.
  • the dye 2 preferably has an absorption maximum wavelength in a wavelength range of 460 nm or more and less than 530 nm, and more preferably has an absorption maximum wavelength in a wavelength range of 470 nm or more and less than 520 nm.
  • the resin layer When the resin layer has dye 1, dye 2, dye 3, dye 4, and resin, the resin layer preferably satisfies all of the following (iii-1) to (iii-3).
  • the wavelength range of the maximum value 10 is preferably 430 nm or more and less than 480 nm, and more preferably 430 nm or more and less than 455 nm.
  • the wavelength range of the maximum value 11 is preferably 490 nm or more and less than 550 nm, and more preferably 500 nm or more and less than 540 nm.
  • the wavelength range of the maximum value 12 is preferably 590 nm or more and less than 640 nm, and more preferably 590 nm or more and less than 630 nm.
  • the maximum value among the maximum value 10, the maximum value 11 and the maximum value 12 is preferably 55% or more, more preferably 60% or more.
  • the dye 1 is preferably a compound represented by the following formula (1).
  • R 1 represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
  • substituent an alkoxy group, an acyl group, an acyloxy group, a cyano group, a dialkylamino group or a chlorine atom is preferable.
  • the alkoxy group, acyl group, acyloxy group and dialkylamino group preferably have 1 to 6 carbon atoms.
  • R 1 is an alkyl group having 1 to 6 carbon atoms in which a part of the hydrogen atom may be substituted with a cycloalkyl group or a phenyl group.
  • Particularly preferable Q 1 is an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. Be done.
  • R 2 to R 5 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • At least one of R 2 and R 3 is preferably an alkyl group, and it is more preferable that both are alkyl groups. When R 2 and R 3 are not alkyl groups, a hydrogen atom is more preferred. As R 2 and R 3 , an alkyl group having 1 to 6 carbon atoms is particularly preferable.
  • R8 and R9 each independently represent a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
  • R 10 to R 19 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
  • R 8 to R 19 examples include the same substituents as the substituents in R 1 , and the preferred embodiments are also the same.
  • R 8 to R 19 are hydrocarbon groups having no substituent, the same embodiment as that of R 1 having no substituent can be mentioned.
  • both R 10 and R 11 are more preferably alkyl groups having 1 to 6 carbon atoms, and particularly preferably the same alkyl group.
  • the alkyl group may be linear or branched, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group or a t-butyl group.
  • the compound (3) may have the same group having two pyrrole rings or different groups, but preferably the group having two pyrrole rings is the same and is a symmetrical squarylium system. It is preferably a compound.
  • the compound (3) include compounds in which the atom or group bonded to each skeleton is the atom or group shown in the table below.
  • the dye 4 is preferably a compound represented by the following formula (4).
  • Y 1 and Y 2 may be single bonds, respectively, and in that case, oxygen atoms may be provided between carbon atoms. ..
  • R 37 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • R 24 is preferably -NH-SO 2 -R 30 from the viewpoint of increasing the transmittance of visible light, particularly the transmittance of light having a wavelength of 430 to 550 nm.
  • the base material is preferably a resin base material containing dye A and a resin. Further, the resin base material can further contain a UV dye.
  • the base material preferably has a structure in which a resin layer containing the dye A and the resin is laminated on at least one main surface of the support. At this time, the support is preferably made of the transparent resin or the transparent inorganic material. Further, the resin layer can further contain a UV dye.
  • the transparent inorganic material glass or a crystalline material is preferable.
  • the glass include absorbent glass (near infrared absorber glass) containing copper ions in fluoride-based glass, phosphate-based glass and the like, soda lime glass, borosilicate glass, non-alkali glass, quartz glass and the like. ..
  • absorbent glass is preferable depending on the purpose, and phosphate-based glass and fluoride-based glass are preferable from the viewpoint of absorbing infrared light.
  • phosphate-based glass also includes silicate glass in which a part of the skeleton of the glass is composed of SiO 2 .
  • an inorganic material is preferable, and glass and sapphire are particularly preferable, from the viewpoint of shape stability related to long-term reliability such as optical properties and mechanical properties, and handleability at the time of filter manufacturing.
  • the base material is a resin base material having a single-layer structure containing a transparent resin and dye A
  • it can be produced by, for example, the following method.
  • the resin base material can be produced by melt-extruding a transparent resin or a mixture of a transparent resin and an arbitrary component and molding it into a film. Further, a transparent resin and, if necessary, an arbitrary component are dissolved in a solvent to prepare a coating liquid, which is applied to a peelable base material for producing a resin base material to a desired thickness, dried, and further. After curing, if necessary, the resin base material can be peeled off from the base material for production.
  • the solvent used for the coating liquid may be a dispersion medium capable of stably dispersing the transparent resin or a solvent capable of dissolving the transparent resin.
  • the coating liquid may contain a surfactant for improving voids due to minute bubbles, dents due to adhesion of foreign substances, repellency in the drying step, and the like. Further, for the coating of the coating liquid, for example, a dip coating method, a cast coating method, a die coating method, a spin coating method and the like can be used.
  • the thickness of the resin layer is preferably 0.3 to 15 ⁇ m. ..
  • the total thickness of the resin layers is preferably 0.3 to 15 ⁇ m.
  • the coating liquid may contain a surfactant for improving voids due to minute bubbles, dents due to adhesion of foreign substances, repelling in the drying process, and the like.
  • a dip coating method, a cast coating method, a spin coating method or the like can be used for the coating of the coating liquid.
  • a resin layer is formed by applying the above coating liquid onto a substrate and then drying it.
  • further curing treatment such as heat curing and photocuring is performed.
  • the resin layer can be manufactured in the form of a film by extrusion molding, and this film may be laminated on another member and integrated by thermocompression bonding or the like.
  • this film may be attached on a support.
  • This filter may have one resin layer or two or more layers. When the filter has two or more resin layers, each layer may have the same configuration or may be different.
  • the thickness of the base material is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, from the viewpoint of reducing the height of the filter.
  • the thickness of the base material is preferably 30 ⁇ m or more, more preferably 50 ⁇ m or more from the viewpoint of process handling.
  • This filter has a dielectric multilayer film.
  • the dielectric multilayer film is laminated as an outermost layer on at least one main surface side of the base material.
  • the dielectric multilayer film When the dielectric multilayer film is laminated as the outermost layer on both main surface sides of the substrate, at least one of the dielectric multilayer films is designed as a near-infrared reflective layer (hereinafter, also referred to as NIR reflective layer). Is preferable.
  • the other side of the dielectric multilayer film is preferably designed as a NIR reflective layer, a reflective layer having a reflective region other than the near infrared region, or an antireflection layer.
  • the base material has a single-layer structure, it is preferable to form NIR reflective layers on both sides of the base material from the viewpoint of preventing warping.
  • the NIR reflective layer is a dielectric multilayer film designed to shield light in the near infrared region.
  • the NIR reflective layer has, for example, wavelength selectivity that transmits visible light and mainly reflects light in the near infrared region other than the light shielding region of the absorption layer.
  • the reflection region of the NIR reflection layer may include a light-shielding region in the near-infrared region of the absorption layer.
  • the NIR reflection layer is not limited to the NIR reflection characteristic, and may be appropriately designed to have specifications for further blocking light in a wavelength range other than the near infrared region, for example, the near ultraviolet region.
  • the low refractive index film preferably has a refractive index of less than 1.6, more preferably 1.45 or more and less than 1.55.
  • the material of the low refractive index film include SiO 2 , SiO x N y and the like. SiO 2 is preferable from the viewpoint of reproducibility, stability, economy and the like in terms of film forming property.
  • the transmittance of the NIR reflective layer changes sharply in the boundary wavelength region between the transmissive region and the light-shielding region.
  • the total number of laminated dielectric multilayer films constituting the reflective layer is preferably 15 or more, more preferably 25 or more, and even more preferably 30 or more.
  • the total number of layers is preferably 100 layers or less, more preferably 75 layers or less, and even more preferably 60 layers or less.
  • the film thickness of the reflective layer is preferably 2 to 10 ⁇ m as a whole.
  • the antireflection layer examples include a dielectric multilayer film, an intermediate refractive index medium, and a moth-eye structure in which the refractive index gradually changes. Of these, a dielectric multilayer film is preferable from the viewpoint of optical efficiency and productivity.
  • the antireflection layer is obtained by alternately laminating dielectric films like the reflection layer.
  • the dielectric multilayer film satisfies all of the following (vi-1) to (vi-7) in the spectral transmittance curve of the incident angle of 5 ° and the spectral transmittance curve of 30 °.
  • (Vi-1) The average reflectance of light having a wavelength of 430 nm or more and less than 490 nm is 30% or less.
  • (Vi-2) The average reflectance of light having a wavelength of 490 nm or more and less than 590 nm is 30% or less.
  • Vi-3) The average reflectance of light having a wavelength of 590 nm or more and less than 650 nm is 30% or less.
  • the average transmittance is preferably 18% or less, more preferably 15% or less.
  • the internal transmittance at a wavelength of 350 nm to 1200 nm was calculated based on the following formula.
  • Internal transmittance ⁇ T 0 deg / (100-R 5 deg ) ⁇ x 100
  • T 0 deg means the measured transmittance of 0 °
  • R 5 deg means the reflectance of 5 °.
  • Test Example 1a-1 The same operation as in Test Example 1a-1 was performed except that the type of the dye compound, the content of the dye compound, the type of the resin, and the thickness of the coating film were set as shown in Table 5. The results are shown in Table 5.
  • IR80a The longest wavelength with an internal transmittance of 80% in the wavelength range of 450 nm or more and less than 540 nm
  • IR80b The shortest wavelength with an internal transmittance of 80% in the wavelength range of 450 nm or more and less than 540 nm
  • IR10 Wavelength of 450 nm or more and less than 540 nm Wavelength with internal transmittance of 10% in the range
  • Test Example 1a-1 The same operation as in Test Example 1a-1 was performed except that the type of the dye compound, the content of the dye compound, the type of the resin, and the thickness of the coating film were set as shown in Table 6. The results are shown in Table 6.
  • Test Example 1a-1 The same operation as in Test Example 1a-1 was performed except that the type of the dye compound, the content of the dye compound, the type of the resin, and the thickness of the coating film were set as shown in Table 7. The results are shown in Table 7.
  • IR80a The longest wavelength with an internal transmittance of 80% in the wavelength range of 600 nm or more and less than 720 nm
  • IR80b The shortest wavelength with an internal transmittance of 80% in the wavelength range of 600 nm or more and less than 720 nm
  • IR10 Wavelength of 600 nm or more and less than 720 nm Wavelength with internal transmittance of 10% in the range
  • the obtained coated film was measured for transmission spectroscopy in the incident direction at 0 ° with respect to the incident direction in the wavelength range of 350 nm to 1200 nm with an ultraviolet-visible near-infrared spectrophotometer "UH4150" manufactured by Hitachi High-Tech Science. The results are shown in Table 8.
  • Test Example 3 A 48-layer dielectric multilayer film composed of SiO 2 and TiO 2 was formed on D263 (alkaline glass) manufactured by Schott by vapor deposition. The obtained dielectric multilayer film is measured for transmission spectroscopy in the incident direction of 5 ° and 30 ° with respect to the incident direction in the wavelength range of 350 nm to 1200 nm with the ultraviolet-visible near-infrared spectrophotometer "UH4150" manufactured by Hitachi High-Tech Science. did. The results are shown in Table 9.
  • Test Example 4 ⁇ Test Example 4-1 (Example)> Dye compound 1-2 (2% by mass), Dye compound 2-5 (2.8% by mass), Dye compound 3-3 (2.5% by mass), Dye compound 4-2 (4.5% by mass), C-3G30G (manufactured by Mitsubishi Gas Chemicals, polyimide varnish) diluted with cyclohexanone was mixed, and the dye compound and the polyimide resin solution were sufficiently dissolved to obtain a resin solution.
  • the dielectric multilayer film obtained in Test Example 3 was formed by thin film deposition on D263 (alkaline glass, thickness 0.2 mm) manufactured by Schott.
  • a resin solution obtained by using a spin coat is applied to D263 (alkaline glass) on which a dielectric multilayer film is formed, and the coating film is sufficiently heated to remove the organic solvent to obtain a coating film having a thickness of 3 ⁇ m. Made. A seven-layer antireflection film composed of SiO 2 and TiO 2 was formed by thin film deposition on the obtained coating film.
  • the coated film with the antireflection film vapor-deposited is subjected to transmission spectroscopy in the incident direction of 0 ° and 30 ° with respect to the incident direction in the wavelength range of 350 nm to 1200 nm with the ultraviolet visible near infrared spectrophotometer "UH4150" manufactured by Hitachi High-Tech Science. It was measured. The results are shown in Table 10.
  • Test Example 4-2 (Example)> The same operation as in Test Example 4-1 was performed except that D263 (alkaline glass) was changed to borosilicate glass (manufactured by AGC) that cuts infrared rays. The results are shown in Table 11 and FIG.
  • Example 4-3> A 34-layer dielectric multilayer film composed of SiO 2 and TiO 2 through which light in the blue band, light in the green band, and light in the red band is transmitted to D263 (alkaline glass, thickness 0.2 mm) manufactured by shotto. A film was formed by vapor deposition.
  • the obtained film was measured for transmission spectroscopy at 0 ° and 30 ° with respect to the incident direction in the wavelength range of 350 nm to 1200 nm with an ultraviolet-visible near-infrared spectrophotometer "UH4150" manufactured by Hitachi High-Tech Science. The results are shown in Table 12.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)

Abstract

La présente invention concerne un filtre optique comprenant un matériau de base et un film multicouche diélectrique stratifié en tant que couche la plus à l'extérieur sur au moins un côté de surface principale du matériau de base, le matériau de base ayant une couche de résine comprenant une résine et un colorant A ayant une longueur d'onde maximale d'absorption dans une plage de longueur d'onde de 400 nm ou plus et inférieure à 700 nm, et a une valeur maximale dans une plage de longueurs d'onde de 430 nm ou plus et inférieure à 490 nm, une plage de longueurs d'onde de 490 nm ou plus et inférieure à 590 nm, et une plage de longueurs d'onde de 590 nm ou plus et inférieure à 650 nm.
PCT/JP2021/022940 2020-08-14 2021-06-16 Filtre optique Ceased WO2022034739A1 (fr)

Priority Applications (3)

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JP2022542588A JPWO2022034739A1 (fr) 2020-08-14 2021-06-16
CN202180055527.2A CN116075751A (zh) 2020-08-14 2021-06-16 滤光片
JP2025158330A JP2025178366A (ja) 2020-08-14 2025-09-24 光学フィルタ

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JP2020-137088 2020-08-14
JP2020137088 2020-08-14

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001183522A (ja) * 1999-12-27 2001-07-06 Mitsubishi Chemicals Corp プラズマディスプレイパネル用フィルター
JP2006126315A (ja) * 2004-10-27 2006-05-18 Toray Ind Inc 光学フィルター
JP2013011840A (ja) * 2011-06-02 2013-01-17 Ito Kogaku Kogyo Kk 防眩光学要素
JP6197940B2 (ja) * 2015-02-18 2017-09-20 旭硝子株式会社 スクアリリウム系色素、樹脂膜、光学フィルタおよび撮像装置
JP6504176B2 (ja) * 2014-09-19 2019-04-24 Ａｇｃ株式会社 光学フィルタ
JP2020038369A (ja) * 2018-08-30 2020-03-12 Jsr株式会社 光学フィルター、その製造方法およびその用途

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070084940A (ko) * 2006-02-22 2007-08-27 삼성코닝 주식회사 디스플레이 필터 및 이를 포함한 디스플레이 장치
JP2008203436A (ja) * 2007-02-19 2008-09-04 Fujifilm Corp 光学フィルター
JP6202230B1 (ja) * 2015-12-01 2017-09-27 旭硝子株式会社 光学フィルタおよび撮像装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001183522A (ja) * 1999-12-27 2001-07-06 Mitsubishi Chemicals Corp プラズマディスプレイパネル用フィルター
JP2006126315A (ja) * 2004-10-27 2006-05-18 Toray Ind Inc 光学フィルター
JP2013011840A (ja) * 2011-06-02 2013-01-17 Ito Kogaku Kogyo Kk 防眩光学要素
JP6504176B2 (ja) * 2014-09-19 2019-04-24 Ａｇｃ株式会社 光学フィルタ
JP6197940B2 (ja) * 2015-02-18 2017-09-20 旭硝子株式会社 スクアリリウム系色素、樹脂膜、光学フィルタおよび撮像装置
JP2020038369A (ja) * 2018-08-30 2020-03-12 Jsr株式会社 光学フィルター、その製造方法およびその用途

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CN116075751A (zh) 2023-05-05
JP2025178366A (ja) 2025-12-05
JPWO2022034739A1 (fr) 2022-02-17

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