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WO2017030174A1 - Filtre optique et dispositif de capture d'image - Google Patents

Filtre optique et dispositif de capture d'image Download PDF

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Publication number
WO2017030174A1
WO2017030174A1 PCT/JP2016/074148 JP2016074148W WO2017030174A1 WO 2017030174 A1 WO2017030174 A1 WO 2017030174A1 JP 2016074148 W JP2016074148 W JP 2016074148W WO 2017030174 A1 WO2017030174 A1 WO 2017030174A1
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WIPO (PCT)
Prior art keywords
wavelength
wavelength band
optical filter
resin
light
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PCT/JP2016/074148
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English (en)
Japanese (ja)
Inventor
村川　真弘
和彦 塩野
麻奈 吉岡
保高　弘樹
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2017535566A priority Critical patent/JP6642578B2/ja
Publication of WO2017030174A1 publication Critical patent/WO2017030174A1/fr
Anticipated expiration legal-status Critical
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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
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
    • H04N23/10—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from different wavelengths
    • H04N23/12—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from different wavelengths with one sensor only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F99/00—Subject matter not provided for in other groups of this subclass

Definitions

  • the present invention relates to an optical filter that transmits visible light and specific infrared light and blocks light between these two regions, and an imaging device including the optical filter.
  • imaging devices using a solid-state imaging device have been extended to devices that capture images regardless of day or night, such as surveillance cameras and in-vehicle cameras.
  • the conventional dual bandpass filter has a high-refractive index film and a low-refractive index film alternately stacked, and a near-infrared light by a reflective layer made of a dielectric multilayer film that reflects light in a specific region by light interference.
  • the dielectric multilayer film has a so-called incident angle dependency in which the spectral transmittance characteristic changes depending on the incident angle of light. For this reason, an image pickup apparatus using a conventional dual bandpass filter, particularly when acquiring an image based on visible light, is visible light close to the wavelength of near-infrared light. There was a problem that could not be faithfully reproduced.
  • Japanese Patent No. 4705342 Japanese Patent No. 5287362 Japanese Patent Laid-Open No. 56-60421 JP 2008-91753 A JP 2012-244533 A
  • the conventional dual bandpass filter realizes the blocking of near infrared light by the dielectric multilayer film, the spectral transmittance characteristic changes depending on the incident angle of light. For this reason, particularly when an image based on visible light is acquired, there is a problem that the image cannot be faithfully reproduced due to the incident angle dependency of transmittance with visible light close to the wavelength of near-infrared light.
  • the present invention provides an optical filter with good reproducibility and a clear image when acquiring an image based on visible light and near-infrared light, and an imaging apparatus using the optical filter. For the purpose of provision.
  • the optical filter according to one aspect of the present invention has a transmission wavelength band in which a transmittance with respect to light with an incident angle of 0 ° is 40% or more in a wavelength region of a wavelength of 350 nm to 1200 nm, A reflection layer having a transmittance on the longer wavelength side of the transmission wavelength band of less than 40%, and an absorption layer having an absorption maximum in the transmission wavelength band of the reflection layer, A transmission wavelength band, a first high transmission wavelength band having a higher transmittance for light having an incident angle of 0 ° than the low transmission wavelength band on a shorter wavelength side than the low transmission wavelength band, and a longer wavelength than the low transmission wavelength band And a second high transmission wavelength band having a higher transmittance with respect to light having an incident angle of 0 ° than the low transmission wavelength band.
  • An imaging apparatus includes the optical filter including a solid-state imaging device, an imaging lens, and the optical filter.
  • the incident angle dependency of the transmittance characteristic of visible light close to the wavelength of near-infrared light can be suppressed, and high transmittance of predetermined near-infrared light can be achieved.
  • an image based on each of visible light and near-infrared light can be obtained as an optical filter with good reproducibility and a clear image.
  • an image pickup apparatus having excellent image characteristics using such an optical filter can be obtained.
  • FIG. 6 is a diagram showing a spectral transmittance curve (incident angle 0 ° / 30 °) of a reflective layer used in the optical filters of Examples 1 to 3. It is a figure which shows the spectral transmittance curve (incident angle 0 degree / 30 degree) of the optical filter in Example 1.
  • FIG. It is a figure which shows the spectral transmittance curve (incident angle 0 degree / 30 degree) of the optical filter in Example 2.
  • FIG. It is a figure which shows the spectral transmittance curve (incident angle 0 degree / 30 degree) of the optical filter in Example 3.
  • FIG. 6 is a diagram showing a spectral transmittance curve (incident angle 0 ° / 30 °) of a reflective layer used in the optical filters of Examples 1 to 3.
  • FIG. It is a figure which shows the spectral transmittance curve (incident angle 0 degree / 30 degree) of the optical filter in Example 1.
  • FIG. It is
  • the near-infrared absorbing material may be referred to as “NIR absorbing material” and the ultraviolet absorbing material may be referred to as “UV absorbing material”.
  • NIR absorbing material the near-infrared absorbing material
  • UV absorbing material ultraviolet absorbing material
  • transmittance means “transmittance in a spectral transmittance curve at an incident angle of 0 °”
  • average transmittance means “average in a spectral transmittance curve at an incident angle of 0 °.
  • An optical filter according to an embodiment of the present invention (hereinafter also referred to as “the present filter”) has a reflective layer and an absorption layer.
  • the reflective layer and the absorbing layer may each have one layer in the filter, one may have two or more layers, and both may have two or more layers. When it has two or more layers, each layer may have the same structure or different.
  • one of the layers is a near-infrared reflective layer that shields near-infrared light with a wavelength of 950 to 1100 nm
  • the other reflective layer is near-infrared light with a wavelength of 1050 nm or later.
  • a near-infrared / near-ultraviolet reflecting layer that shields both near-ultraviolet light.
  • the absorption layer when it has two absorption layers, it is good also considering one layer as an absorption layer which consists of resin containing the NIR absorber mentioned later and the other layer as an absorption layer consisting of resin containing the UV absorber mentioned later. Moreover, the absorption layer itself may function as a substrate (resin substrate).
  • This filter may further have a transparent substrate.
  • the absorption layer and the reflection layer may be provided on the same main surface of the transparent substrate, or may be provided on different main surfaces.
  • the order of lamination is not particularly limited.
  • This filter may also have other functional layers.
  • other functional layers include an antireflection layer made of an inorganic film or an organic film, a protective layer having a passivation function, and the like.
  • an antireflection layer made of an inorganic film or an organic film
  • a protective layer having a passivation function and the like.
  • the absorption layer has an outermost surface configuration, transmittance loss occurs at the interface between the absorption layer and air. Therefore, it is preferable to provide an antireflection layer on the absorption layer.
  • the protective layer is not necessarily provided in that case. When the antireflection layer and the protective layer cover not only the outermost surface of the absorption layer but also the entire side surface of the absorption layer, the moisture-proof effect on the absorption layer can be enhanced.
  • FIG. 1A is a configuration example of an optical filter 10 ⁇ / b> A including the absorption layer 11 and the reflection layer 12.
  • FIG. 1B is a configuration example of an optical filter 10 ⁇ / b> B that includes the absorption layer 11 on one main surface of the transparent substrate 13 and the reflective layer 12 on the other main surface of the transparent substrate 13.
  • “equipped with other layers such as the absorption layer 11 and the reflective layer 12 on one main surface of the transparent substrate 13” is not limited to the case where the transparent substrate 13 is in contact with the other layers and includes the transparent substrate 13.
  • the case where another functional layer is provided between 13 and another layer is also included, and the following configurations are also the same.
  • FIG. 1C is a configuration example of an optical filter 10C having an antireflection layer 14 on the main surface of the absorption layer 11 of the optical filter 10B shown in FIG. 1B.
  • the absorption layer has the outermost surface configuration, transmittance loss occurs on the absorption layer. Therefore, it is preferable to provide an antireflection layer on the absorption layer.
  • the reflective layer, the absorption layer, the transparent substrate, the functional layer, and the like constituting the filter will be described.
  • the reflection layer has a transmission wavelength band with a transmittance of 40% or more, preferably 60% or more, and more preferably 80% or more with respect to light having an incident angle of 0 ° at a wavelength of 350 to 1200 nm. Further, the average transmittance in the transmission wavelength band is preferably 40% or more, more preferably 60% or more, and further preferably 80% or more. The higher the transmittance and the higher the average transmittance, the higher the light utilization efficiency.
  • the reflective layer has a transmittance of less than 40% on the short wavelength side and the long wavelength side of the transmission wavelength band for light having an incident angle of 0 °.
  • the transmission wavelength band includes a wavelength of 430 to 900 nm, and an average transmittance for light having an incident angle of 0 ° at the wavelength of 430 to 900 nm. Is preferably 80% or more. Further, the average transmittance for light having an incident angle of 0 ° at a wavelength of 430 to 900 nm is more preferably 85% or more, still more preferably 90% or more, still more preferably 95% or more, and particularly preferably 98% or more.
  • the reflective layer preferably has an average transmittance of 5% or less for light having an incident angle of 0 ° at a wavelength of 350 to 400 nm. % Or less is more preferable.
  • transmittance of 40% or more means that the transmittance does not fall below 40% in the specific entire wavelength region.
  • 2% or less means that the transmittance does not exceed 2% in the specific wavelength region.
  • the reflective layer is a dielectric layer in which a low refractive index dielectric film (hereinafter also abbreviated as “low refractive index film”) and a high refractive index dielectric film (hereinafter also abbreviated as “high refractive index film”) are alternately laminated.
  • low refractive index film a low refractive index dielectric film
  • high refractive index film a high refractive index dielectric film
  • the high refractive index film preferably has a refractive index of 1.6 or more, more preferably 2.2 to 2.5.
  • the material for the high refractive index film include Ta 2 O 5 , TiO 2 , Nb 2 O 5 , and ZrO 2 . Of these, TiO 2 is preferable from the viewpoints of film formability, reproducibility in refractive index, and stability.
  • the low refractive index film preferably has a refractive index of less than 1.6, more preferably 1.35 or more and less than 1.55, and even more preferably 1.40 to 1.50.
  • the material for the low refractive index film include SiO 2 , SiO x N y , and MgF 2 .
  • the refractive index refers to a refractive index with respect to light having a wavelength of 589 nm at 20 ° C.
  • a vacuum film forming process such as a CVD method, a sputtering method, a vacuum evaporation method, an ion assist evaporation method, an ion beam method, an ion plating method, or a wet method such as a spray method or a dip method.
  • a film forming process or the like can be used.
  • the reflective layer made of a dielectric multilayer film may be a single layer or a plurality of layers and have predetermined optical characteristics.
  • the reflective layer is preferably a single layer from the viewpoint of productivity, but may be provided on both sides of the absorption layer, for example, in order to prevent the optical filter from warping due to film stress.
  • the absorption layer is a layer having an absorption maximum within the transmission wavelength band of the reflection layer. From the viewpoint of obtaining a clear visible light image and infrared light image having excellent color reproducibility, the above absorption maximum may be at a wavelength of 680 to 780 nm, preferably at a wavelength of 700 to 750 nm, and preferably at a wavelength of 700 to 720 nm. More preferably.
  • the absorption layer preferably has an absorption maximum at a wavelength of 350 to 420 nm from the viewpoint of suppressing near-ultraviolet light incidence and improving color reproducibility of a visible light image.
  • the absorption maximum is more preferably at a wavelength of 390 to 420 nm, and further preferably at a wavelength of 400 to 410 nm.
  • the absorption layer is composed of a layer or a substrate in which the NIR absorber (A) is uniformly dissolved or dispersed in the transparent resin (B).
  • the absorption layer may further include a UV absorber (U).
  • the absorption layer may include a plurality of absorption layers, for example, a layer containing the NIR absorber (A) and a layer containing the UV absorber (U) as separate layers.
  • the thickness of the absorption layer is preferably 0.1 to 100 ⁇ m.
  • the total thickness of each absorption layer is preferably 0.1 to 100 ⁇ m.
  • the thickness of the absorption layer is appropriately determined according to the arrangement space in the apparatus to be used. If the thickness is less than 0.1 ⁇ m, the desired optical properties may not be sufficiently exhibited. On the other hand, if the thickness exceeds 100 ⁇ m, the flatness of the layer is lowered, and there is a possibility that in-plane variation in the absorption rate occurs.
  • the thickness of the absorption layer is more preferably 0.3 to 50 ⁇ m.
  • the thickness of the absorption layer is preferably 0.3 to 10 ⁇ m.
  • the absorption layer typically uses a near-infrared absorbing dye as the NIR absorbing material (A), and uses an ultraviolet absorbing dye as the UV absorbing material (U) as necessary, but is not limited thereto.
  • a near-infrared absorbing dye as the NIR absorbing material (A)
  • an ultraviolet absorbing dye as the UV absorbing material (U) as necessary, but is not limited thereto.
  • typically used near-infrared absorbing dyes and ultraviolet absorbing dyes will be described in detail.
  • the near-infrared absorbing dye (A) (hereinafter also referred to as the dye (A)) is a single type or a combination of two or more types, and when dissolved or dispersed in the transparent resin (B), the absorption layer has the optical characteristics described above. If it has, the kind will not be restrict
  • the dye (A) has an absorption maximum within a wavelength of 680 to 780 nm in an absorption spectrum of a wavelength of 400 to 850 nm measured using a resin film obtained by dispersing the dye (A) in the transparent resin (B). Those having a wavelength are preferred.
  • the absorption maximum wavelength is more preferably 700 to 750 nm, and even more preferably 700 to 720 nm.
  • dye (A1) the near-infrared absorbing dye having this absorption characteristic
  • ⁇ max (NIR) of the dye (A1) the absorption maximum wavelength in this absorption spectrum
  • the absorption spectrum of the dye (A1) has an absorption peak having an absorption peak at the wavelength ⁇ max (NIR) (hereinafter, referred to as “ ⁇ max (NIR) absorption peak”).
  • the absorption spectrum of the dye (A1) has ⁇ max (NIR) in the wavelength range of 680 to 780 nm, has little absorption of visible light, and has a visible wavelength region side and near infrared wavelength as viewed from the absorption peak of ⁇ max (NIR). It is preferable that the slope on the region side is steep.
  • the dye (A1) is a squarylium compound, cyanine compound, phthalocyanine compound, naphthalocyanine compound, dithiol metal complex compound, diimonium compound, polymethine compound, phthalide compound, naphthoquinone compound, anthraquinone compound, indophenol. System compounds and the like.
  • squarylium compounds, cyanine compounds and phthalocyanine compounds are preferable, and squarylium compounds are more preferable.
  • the squarylium compound has little visible light absorption, and the absorption peak of ⁇ max (NIR) has a steep slope on both the visible wavelength region side and near infrared wavelength region side. Is preferable because of high.
  • a cyanine compound is preferable because it absorbs less visible light and has a high light absorptance on the long wavelength side near ⁇ max (NIR).
  • cyanine compounds are low-cost and long-term stability can be ensured by salt formation. Phthalocyanine compounds are excellent in heat resistance and weather resistance.
  • squarylium-based compound examples include at least one selected from squarylium-based compounds represented by the following formula (F1).
  • a compound represented by the formula (F1) is also referred to as a compound (F1), and dyes represented by other formulas are also described in the same manner.
  • a group represented by the formula (1n) is referred to as a group (1n), and groups represented by other formulas are also described in the same manner.
  • Compound (F1) has a structure in which a benzene ring is bonded to the left and right sides of the squarylium skeleton, a nitrogen atom is bonded to the 4-position of the benzene ring, and a saturated heterocyclic ring containing the nitrogen atom is formed.
  • A1) is a compound having light absorption characteristics.
  • a substituent of the benzene ring is used in the following range in accordance with a request such as increasing the solubility in the solvent (host solvent) or the transparent resin (B) used when forming the near infrared absorption layer. Can be adjusted as appropriate.
  • R 4 and R 6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl or alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —NR 7 R 8 (R 7 And R 8 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or —C ( ⁇ O) —R 9 (R 9 is a hydrogen atom or an optionally substituted carbon atom).
  • At least one pair of R 1 and R 2 , R 2 and R 5 , and R 1 and R 3 is connected to each other and has a nitrogen atom and a member of 5 or 6 to each of heterocycle A, heterocycle B, and heterocycle C is formed.
  • R 1 and R 2 represent an alkylene group or an alkyleneoxy group as the divalent group —Q— to which they are bonded.
  • a hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyloxy group having 1 to 10 carbon atoms which may have a substituent. May be.
  • R 2 and R 5 when the heterocyclic ring B is formed, and R 1 and R 3 when the heterocyclic ring C is formed are each a divalent group —X 1 —Y 1 — and — X 2 —Y 2 — (X 1 and X 2 on the side bonded to nitrogen), X 1 and X 2 are each a group represented by the following formula (1x) or (2x), and Y 1 and Y 2 are each It is a group represented by any one selected from the following formulas (1y) to (5y). When X 1 and X 2 are groups represented by the following formula (2x), Y 1 and Y 2 may each be a single bond.
  • Z's are each independently a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, or -NR 28 R 29 (R 28 and R 29 are each independently Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
  • R 21 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 27 is an alkyl group having 1 to 6 carbon atoms or an alkyl group having 6 to 10 carbon atoms.
  • An aryl group is shown.
  • R 7 , R 8 , R 9 , R 4 , R 6 , R 21 to R 27 , R 1 to R 3 when not forming a heterocyclic ring, and R 5 are It may combine to form a 5-membered ring or a 6-membered ring.
  • R 21 and R 26 , R 21 and R 27 may be directly bonded.
  • R 1 and R 2 are each independently a hydrogen atom, an optionally substituted alkyl group or allyl group having 1 to 6 carbon atoms, or 6 carbon atoms. Represents an aryl group or an araryl group of ⁇ 11.
  • R 3 and R 5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having 1 to 6 carbon atoms.
  • the heterocycle A may be simply referred to as ring A. The same applies to the heterocyclic rings B and C.
  • R 4 and R 6 each independently represent the above atom or group.
  • the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • the alkyl group may be linear, branched or cyclic.
  • R 4 and R 6 are preferably a combination in which either one is a hydrogen atom and the other is —NR 7 R 8 .
  • —NR 7 R 8 is introduced into either R 4 or R 6. May be. In the case where the compound (F1) has only ring B and only ring A and ring B, —NR 7 R 8 is preferably introduced into R 4 . Similarly, when it has only ring C, only ring A and ring C, each of —NR 7 R 8 is preferably introduced into R 6 .
  • R 9 is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 10 carbon atoms, or an optionally substituted group.
  • an araryl group having 7 to 18 carbon atoms which may have an oxygen atom between carbon atoms is preferable.
  • Substituents include halogen atoms such as fluorine atoms, hydroxyl groups, carboxy groups, sulfo groups, cyano groups, alkyl groups having 1 to 6 carbon atoms, fluoroalkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms. And an acyloxy group having 1 to 6 carbon atoms.
  • R 9 is a linear, branched or cyclic alkyl group having 1 to 17 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms and / or carbon which may be substituted with a fluorine atom.
  • a phenyl group which may be substituted with an alkoxy group having 1 to 6 carbon atoms, and a carbon atom having 7 to 18 carbon atoms which may have an oxygen atom between the carbon atoms, and substituted with a fluorine atom having 1 to 6 carbon atoms at the terminal A group selected from an alkyl group which may be substituted and / or an aryl group having a phenyl group which may be substituted with an alkoxy group having 1 to 6 carbon atoms is preferred.
  • one or more hydrogen atoms may be independently substituted with a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, or a cyano group, and an unsaturated bond, oxygen atom, saturated or
  • a group which is a hydrocarbon group having 5 to 25 carbon atoms and having at least one branch which may contain an unsaturated ring structure is also preferably used.
  • R 1 and R 2 , R 2 and R 5 , and R 1 and R 3 are connected to each other to form 5 or 6 members of ring A, ring B, and ring C, At least any one of these may be formed, and two or three may be formed.
  • R 1 and R 2 are each independently a hydrogen atom, an optionally substituted alkyl group or allyl group having 1 to 6 carbon atoms, or 6 to 6 carbon atoms.
  • 11 aryl groups or araryl groups are shown.
  • the alkyl group may be linear, branched or cyclic. Examples of the substituent include a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, and an acyloxy group having 1 to 3 carbon atoms.
  • R 3 and R 5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having 1 to 6 carbon atoms.
  • R 1 , R 2 , R 3 , and R 5 an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of solubility in a host solvent or a transparent resin (B). And the 2-propyl group is particularly preferred.
  • the groups R 1 to R 6 of the benzene ring bonded to the left and right of the squarylium skeleton may be different on the left and right, but are preferably the same on the left and right.
  • the compound (F1) includes the compound (F1-1) represented by the formula (F1-1) having a resonance structure having the structure represented by the general formula (F1).
  • compound (F1) a compound represented by the following formula (F11) having only ring B as a ring structure, a compound represented by the following formula (F12) having only ring A as a ring structure, ring B And a compound represented by the following formula (F13) having two of ring C as a ring structure.
  • the compound represented by the following formula (F11) is the same compound as the compound (F1) having only ring C as a ring structure and R 6 being —NR 7 R 8 .
  • the compound represented by the following formula (F11) and the compound represented by the following formula (F13) are compounds described in US Pat. No. 5,543,086.
  • X 1 is preferably an ethylene group in which the hydrogen atom represented by (2x) above may be substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • the substituent is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • X 1 represents — (CH 2 ) 2 —, —CH 2 —C (CH 3 ) 2 —, —CH (CH 3 ) —C (CH 3 ) 2 —, —C (CH 3 ) 2 — And C (CH 3 ) 2 — and the like.
  • —NR 7 R 8 is —NH—C ( ⁇ O) —CH 3 , —NH—C ( ⁇ O) —C 6 H 13 , —NH—C ( ⁇ O) —C 6 H. 5 , —NH—C ( ⁇ O) —CH (C 2 H 5 ) —C 4 H 9 , —NH—C ( ⁇ O) —C (CH 3 ) 2 —C 2 H 5 , —NH—C ( ⁇ O) —C (CH 3 ) 2 —C 3 H 7 , —NH—C ( ⁇ O) —C (CH 3 ) 2 — (CH 2 ) 3 —O—C 6 H 3 (CH 3 ) 2 etc.
  • Y 1 is 0 to 1 oxygen atom or sulfur atom.
  • Examples of the compound (F11) include compounds represented by the following formulas (F11-1) to (F11-7). Among these, the compounds (F11-2) to (F11-7) are more preferable because of their high solubility in the host solvent and the transparent resin (B).
  • Q may be a hydrogen atom substituted with an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyloxy group having 1 to 10 carbon atoms which may have a substituent.
  • the oxygen position is preferably other than next to N.
  • Q is preferably a butylene group which may be substituted with an alkyl group having 1 to 3 carbon atoms, particularly a methyl group.
  • —NR 7 R 8 is —NH—C ( ⁇ O) — (CH 2 ) m —CH 3 (m is 0 to 19), —NH—C ( ⁇ O) —Ph—R. 10
  • —Ph— represents a phenylene group
  • R 10 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms in which the hydrogen atom may be substituted with a fluorine atom, or an alkoxy group having 1 to 3 carbon atoms, respectively. .) Etc. are preferred.
  • the compound (F12) has a ⁇ max (NIR) on the relatively long wavelength side in the above wavelength region, the visible light transmission region can be widened by using the compound (F12).
  • the compound (F12) include compounds represented by the following formulas (F12-1) to (F12-3).
  • X 1 and X 2 independently represent an ethylene group in which the hydrogen atom represented by the above (2x) may be substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms Is preferred.
  • the substituent is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • X 1 and X 2 are — (CH 2 ) 2 —, —CH 2 —C (CH 3 ) 2 —, —CH (CH 3 ) —C (CH 3 ) 2 —, —C (CH 3 ) 2 -C (CH 3 ) 2- and the like.
  • Y 1 and Y 2 are independently —CH 2 —, —C (CH 3 ) 2 —, —CH (C 6 H 5 ) —, —CH ((CH 2 ) m CH 3 ) — (m is 0 To 5).
  • —NR 7 R 8 is —NH—C ( ⁇ O) —C m H 2m + 1 (m is 1 to 20, and C m H 2m + 1 is linear, branched, or cyclic.
  • —NH—C ( ⁇ O) —Ph—R 10 (—Ph— represents a phenylene group, R 10 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, 1 carbon atom) An alkoxy group having 1 to 3 carbon atoms or a perfluoroalkyl group having 1 to 3 carbon atoms, respectively).
  • Examples of the compound (F13) include compounds represented by the following formulas (F13-1) and (F13-2).
  • Formula (F6) represents a compound in which none of rings A to C is formed in Formula (F1) (wherein R 1 to R 6 are as follows).
  • R 1 and R 2 each independently represents a hydrogen atom, an optionally substituted alkyl group or allyl group having 1 to 12 carbon atoms, or an aryl group or aryl group having 6 to 11 carbon atoms.
  • R 3 and R 5 each independently represents a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 6 carbon atoms.
  • R 4 and R 6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl or alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —NR 7 R 8 (R 7 And R 8 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or —C ( ⁇ O) —R 9 (R 9 is a hydrogen atom or an optionally substituted carbon atom).
  • Examples of the compound (F6) include compounds represented by the formula (F6-1) and the formula (F6-2).
  • a squarylium compound represented by the following formula (F7) can be used as the dye (A1).
  • the compounds (F1) such as the compounds (F11) to (F13) and the compounds (F6) and (F7) can be produced by a conventionally known method.
  • Compound (F11) such as compound (F11-1) can be produced, for example, by the method described in US Pat. No. 5,543,086.
  • the compound (F12) is, for example, J.I. Org. Chem. 2005, 70 (13), 5164-5173.
  • the cyanine compound specifically includes at least one selected from cyanine compounds represented by the following formula (F5).
  • R 11 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an alkylsulfone group, or an anionic species thereof.
  • R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • Z represents PF 6 , ClO 4 , R f —SO 2 , (R f —SO 2 ) 2 —N (R f represents an alkyl group having 1 to 8 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. shown.), or an BF 4.
  • R 14 , R 15 , R 16 and R 17 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms.
  • n represents an integer of 1 to 6.
  • R 11 in the compound (F5) is preferably an alkyl group having 1 to 20 carbon atoms
  • R 12 and R 13 are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 14 , R 15 , R 16 and R 17 are each independently preferably a hydrogen atom, and the number of n is preferably 1 to 4.
  • the left and right structures sandwiching n repeating units may be different, but the same structure is preferred.
  • examples of the compound (F5) include compounds represented by the following formulas (F51) and (F52).
  • Z - is an anion shown Z in the above (F5) - is the same as.
  • Cyanine compounds are ADS680HO (trade name, manufactured by American dye), S0830 (trade name, manufactured by FEW Chemicals), S2137 (trade name, manufactured by FEW Chemicals), ADS760MP (trade name, manufactured by American Diesor, Inc.)
  • Commercial products such as DLS745B and DLS757A (both are trade names, manufactured by Crystal-Lyn Chemical company) can be used.
  • the phthalocyanine compounds are commercially available such as FB22 (trade name, manufactured by Yamada Chemical Co., Ltd.), TXEX720 (trade name, manufactured by Nippon Shokubai Co., Ltd.), PC142c (trade name, manufactured by Yamada Chemical Industries, Ltd.), and the like. Goods can be used.
  • Table 1 is a table showing ⁇ max (NIR) of each compound used as the dye (A1) exemplified above together with the type of the transparent resin (B) used at the time of measurement.
  • B-OKP2, OKP-850, Byron (registered trademark) 103 is a polyester resin
  • SP3810 is a polycarbonate resin
  • EA-F5003 is an acrylic resin used as the transparent resin (B) in the above. Details will be described later. It is.
  • the dye (A) preferably contains one or more of the dyes (A1).
  • the dye (A) may contain other near-infrared absorbing dyes in addition to the dye (A1) as necessary.
  • the absorption spectrum at a wavelength of 400 to 850 nm measured with respect to a resin film prepared by dispersing the near infrared absorbing dye in the transparent resin (B) is combined so as to have an absorption maximum within the wavelength of 680 to 780 nm. It is good to use.
  • a near-infrared absorbing dye is used so that the visible light absorption is small and the slopes of the visible wavelength region side and the near-infrared wavelength region side are both steep from the absorption peak of ⁇ max (NIR). Use in combination.
  • the content of the dye (A) in the absorbing layer is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the transparent resin (B). If it is 0.1 parts by mass or more, a desired light absorption ability is obtained, and if it is 30 parts by mass or less, a decrease in light absorption ability, an increase in haze value, and the like are suppressed. From these viewpoints, 0.5 to 25 parts by mass is more preferable, and 1 to 20 parts by mass is further preferable.
  • UV absorbing dye (U) As the ultraviolet absorbing dye (U) (hereinafter also referred to as the dye (U)), a wavelength of 300 to 850 nm measured using a resin film obtained by dispersing the dye (U) in the transparent resin (B). In the absorption spectrum, it is preferable that the absorption maximum be within a wavelength of 350 to 420 nm. The absorption maximum is more preferably a wavelength of 390 to 420 nm, and further preferably a wavelength of 400 to 410 nm.
  • the ultraviolet absorbing dye having this absorption characteristic is referred to as a dye (U1).
  • the absorption maximum wavelength in this absorption spectrum is referred to as ⁇ max (UV) of the dye (U1).
  • the absorption spectrum of the dye (U1) has an absorption peak having an absorption peak at the wavelength ⁇ max (UV) (hereinafter referred to as “ ⁇ max (UV) absorption peak”).
  • the absorption spectrum of the dye (U1) has ⁇ max (UV) within a wavelength range of 350 to 420 nm, has little absorption of visible light, and has a steep slope on the visible wavelength region side as seen from the absorption peak of ⁇ max (UV). There should be.
  • the dye (U1) is an oxazole compound, merocyanine compound, cyanine compound, naphthalimide compound, oxadiazole compound, oxazine compound, oxazolidine compound, naphthalic acid compound, styryl compound, anthracene compound, Cyclic carbonyl compounds, triazole compounds, benzotriazole compounds, benzophenone compounds, triazine compounds, coumarin compounds, imidazoline compounds, imidazole compounds, imidazolone compounds, thiazole compounds, carbazole compounds, pyrazoline compounds, Pyrene compounds, pyridine compounds, acridine compounds, quinolone compounds, cyanoacrylate compounds, salicylate compounds, benzoate compounds, cyclic imino ester compounds Indole-based compounds, formamidine compounds, benzoxazinone based compounds, nickel complex compounds, inorganic ultraviolet absorbers, and the like.
  • the dye (U1) one kind selected from a plurality of
  • the dye (U) preferably contains one or more of the dyes (U1).
  • the dye (U) may contain other ultraviolet absorbing dyes as necessary as long as the effect of the dye (U1) is not impaired. Even in this case, in the absorption spectrum at a wavelength of 300 to 850 nm measured for a resin film prepared by dispersing an ultraviolet absorbing dye in the transparent resin (B), the ultraviolet absorption is performed so that the absorption maximum is within the wavelength of 350 to 420 nm. A combination of dyes may be used. Further, in the absorption spectrum, it is preferable to use a combination of ultraviolet absorbing dyes so that the absorption of visible light is small and the inclination on the visible wavelength region side is steep as seen from the absorption peak of ⁇ max (UV).
  • the content of the dye (U) in the absorbing layer is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the transparent resin (B). If it is 0.1 parts by mass or more, a desired ultraviolet absorbing ability is obtained, and if it is 30 parts by mass or less, a decrease in ultraviolet absorbing ability, an increase in haze value, and the like are suppressed.
  • the content is more preferably 0.5 to 25 parts by mass, and further preferably 1 to 20 parts by mass.
  • the transparent resin (B) may have a refractive index of 1.45 or more, more preferably 1.5 or more, and more preferably 1.6 or more.
  • the transparent resin (B) has no particular upper limit on the refractive index, but preferably has a refractive index of about 1.72 due to availability.
  • the transparent resin (B) is specifically acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyarylene ether. Examples thereof include phosphine oxide resin, polyamide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, and polyester resin.
  • Transparent resin (B) can be used individually by 1 type from these resins or in mixture of 2 or more types.
  • the transparent resin (B) is an acrylic resin, a polyester resin, a polycarbonate resin, an ene thiol resin, an epoxy resin, a polyamide resin, a polyimide resin. , One or more selected from polyamideimide resins and cyclic olefin resins are preferred. Furthermore, the transparent resin (B) is more preferably at least one selected from acrylic resins, polyester resins, polycarbonate resins, polyamide resins, polyimide resins, polyamideimide resins, and cyclic olefin resins. As the polyester resin, polyethylene terephthalate resin, polyethylene naphthalate resin and the like are preferable. In addition, the refractive index of transparent resin (B) can be adjusted to the said range by adjusting the molecular structure of a raw material component so that it may have a specific structure in a polymer principal chain or a side chain, for example.
  • the transparent resin (B) a commercially available acrylic resin obtained by curing acrylate monomer Ogsol (registered trademark) EA-F5003 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index: 1.59) can be used.
  • Commercial products of acrylic resins such as polymethyl methacrylate (refractive index: 1.49) and polyisobutyl methacrylate (refractive index: 1.48) manufactured by Tokyo Chemical Industry Co., Ltd. can be used.
  • the transparent resin (B) is manufactured by Osaka Gas Chemical Co., Ltd. OKPH4HT (refractive index: 1.64), OKPH4 (refractive index: 1.61), B-OKP2 (refractive index: 1.63), OKP850.
  • Commercially available polyester resins such as (refractive index: 1.64) and Byron (registered trademark) 103 (made by Toyobo Co., Ltd., refractive index: 1.58) can be used.
  • the transparent resin (B) is a commercial product of polycarbonate resin such as SP3810 (manufactured by Teijin Chemicals Ltd., refractive index: 1.64), LeXan (registered trademark) ML9103 (manufactured by sabic, refractive index 1.59). Can be used. Further, the transparent resin (B) is commercially available such as Panlite (registered trademark) AM-8 series (manufactured by Teijin Chemicals Ltd.) or xylex (registered trademark) 7507 (manufactured by sabic), which is a polymer alloy of polycarbonate and polyester. Goods can be used.
  • polycarbonate resin such as SP3810 (manufactured by Teijin Chemicals Ltd., refractive index: 1.64), LeXan (registered trademark) ML9103 (manufactured by sabic, refractive index 1.59). Can be used.
  • the transparent resin (B) is commercially available such as Panlite (register
  • the absorption layer may further contain various optional components that this type of absorption layer normally contains in addition to the above-described dye (A) and dye (U) as long as the effects of the present invention are not impaired.
  • the optional component include a color tone correction dye, a leveling agent, an antistatic agent, a heat stabilizer, a light stabilizer, an antioxidant, a dispersant, a flame retardant, a lubricant, and a plasticizer.
  • the absorption layer is prepared by dissolving or dispersing at least the pigment (A), the transparent resin (B), and each component blended as necessary in a solvent or a dispersion medium to prepare a coating liquid. It can be formed by coating on a material, drying, and further curing as necessary.
  • the absorbing layer may dissolve or disperse the dye (U) in addition to the dye (A), or may be formed using the raw material component of the transparent resin (B).
  • the base material may be a transparent substrate applicable as a constituent member of the present filter, or may be a base material used only at the time of forming the absorption layer, for example, a peelable base material.
  • the coating solution can contain a surfactant.
  • a surfactant By including the surfactant, it is possible to improve the appearance, in particular, voids due to fine bubbles, dents due to adhesion of foreign matters, and repelling in the drying process.
  • the surfactant known ones such as cationic, anionic and nonionic surfactants can be arbitrarily used.
  • the solid content concentration of the pigment (A), the pigment (U), the transparent resin (B), etc. in the coating solution is generally 10 to 60% by mass, although it depends on the coating method of the coating solution. If the solid content concentration is too low, uneven coating tends to occur, and if the solid content concentration is too high, the coating appearance tends to be poor.
  • a coating method of the coating liquid a spinner coating method, an ink jet method or the like can be used.
  • a bar coater method, a screen printing method, a flexographic printing method, etc. can also be used.
  • the absorbent layer is obtained by applying the above coating liquid onto a substrate and then drying it.
  • a drying method a known method such as heat drying or hot air drying can be used.
  • the coating liquid contains the raw material component of the transparent resin, a curing treatment is further performed.
  • the curing process is a thermosetting process, drying and curing can be performed simultaneously.
  • a curing process may be provided separately from the drying.
  • the releasable substrate on which the coating liquid is applied may be either a film or a plate, and the material is not limited as long as it has releasability. Specifically, a glass plate, a release-treated plastic film, a stainless steel plate or the like can be used.
  • the base material can be pretreated for coating the coating liquid.
  • Pretreatment agents include (3-ureidopropyl) trimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane N-phenyl-3-aminopropylmethoxysilane, tris- (trimethoxysilylpropyl) isocyanate, 3-mercaptopropyl Trimethoxysilane or the like can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • the absorbent layer may be produced in a film form by extrusion, and a plurality of films thus produced may be laminated and integrated by thermocompression bonding or the like.
  • the material of the transparent substrate is not particularly limited as long as it has visible light permeability. Examples thereof include inorganic materials such as glass and crystal materials, and organic materials such as resins.
  • the material of the transparent substrate is more preferably an inorganic material from the viewpoint of long-term reliability such as optical properties and mechanical properties as an optical filter, optical stability, shape stability, handling properties at the time of manufacture, and glass from the viewpoint of workability. preferable.
  • the thickness of the transparent substrate is preferably 30 ⁇ m to 5 mm, more preferably 50 ⁇ m to 1 mm.
  • Resins that can be used for transparent substrates are polyester resin, polyolefin resin, norbornene resin, acrylic resin, polyamide resin, polyimide resin, polyamideimide resin, urethane resin, vinyl chloride resin, fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin Etc.
  • the glass that can be used for the transparent substrate examples include silicate glass such as soda lime glass and white plate glass, borosilicate glass, alkali-free glass, quartz glass, fluorophosphate glass, and phosphate glass.
  • the phosphate glass includes silicic acid phosphate glass in which a part of the glass skeleton is composed of SiO 2 .
  • the crystal material that can be used for the transparent substrate include birefringent crystals such as quartz, lithium niobate, and sapphire.
  • the functional layer examples include an antireflection layer and a protective layer having a passivation function.
  • the antireflection layer is a layer for the purpose of increasing the light utilization efficiency, and can be formed by a known method such as a sputtering method or a vacuum deposition method.
  • the antireflection layer is composed of one or more films such as SiO 2 , TiO 2 , Ta 2 O 5 , MgF 2 , ZrO 2 , Al 2 O 3 , a silicate system formed by a sol-gel method, a coating method, a silicone system, It is composed of a film such as fluorinated methacrylate.
  • the thickness of the antireflection layer is usually 0.1 to 2 ⁇ m.
  • the protective layer has a function of suppressing deterioration of various properties when the absorption layer or the like is located on the outermost surface and the surface is exposed.
  • an absorption layer containing a dye when the dye comes into contact with oxygen or air, its molecular structure or the like may change and properties such as absorption characteristics may be impaired. Therefore, when an absorption layer exists in the outermost surface, it is good to provide the protective layer which covers this absorption layer.
  • the protective layer either an inorganic material or an organic material can be used, and the thickness is usually 0.2 to 20 ⁇ m.
  • the materials mentioned in the antireflection layer can be used as appropriate.
  • the protective layer is a thermosetting resin and an energy ray curable resin, for example, a composition containing those polymerizable precursor compounds is dropped on the main surface where the absorption layer is exposed, and a mold is released thereon. A treated glass plate can be placed and cured by energy beam irradiation or the like. When the glass plate is released after curing, a (organic) protective film having a smooth and uniform thickness is obtained.
  • the components mentioned as other additives that can be added to the absorption layer described above can be added as appropriate.
  • the functional layer is not limited to one layer, and a plurality of functional layers may be provided, and can be appropriately arranged according to a required function.
  • This filter includes a reflection layer and an absorption layer, and has two high transmission wavelength bands with a low transmission wavelength band sandwiched between transmission wavelength bands of the reflection layer. That is, the filter includes a low transmission wavelength band, a first high transmission wavelength band having a higher transmittance for light having an incident angle of 0 ° than the low transmission wavelength band on a shorter wavelength side than the low transmission wavelength band, and the low transmission wavelength band. And a second high transmission wavelength band having a higher transmittance for light having an incident angle of 0 ° than the low transmission wavelength band on the longer wavelength side than the transmission wavelength band.
  • the first and second high transmission wavelength bands may have a transmittance with respect to light having an incident angle of 0 ° of 40% or more, preferably 60% or more, and more preferably 80% or more.
  • the low transmission wavelength band should just have the transmittance
  • This filter may satisfy the following requirement (1).
  • the incident angles are all 0 °.
  • the ratio of the minimum transmittance T min % in the low transmission wavelength band to the maximum transmittance T max (I)% in the first high transmission wavelength band, and T min % / T max (I)% is 0 .5 or less
  • the ratio of the minimum transmittance T min % in the low transmission wavelength band to the maximum transmittance T max (II)% in the second high transmission wavelength band is T min % / T max (II)%. 0.5 or less.
  • T min % / T max (I)% is preferably 0.1 or less, more preferably 0.05 or less, and further preferably 0.02 or less. Further, T min % / T max (II)% is more preferably 0.05 or less, and further preferably 0.02 or less.
  • the low transmission wavelength band includes a wavelength of 680 to 720 nm, and an average transmittance for light having an incident angle of 0 ° with the wavelength of 680 to 720 nm is 20% or less.
  • the first high transmission wavelength band includes a wavelength of 420 to 650 nm, and an average transmittance for light having an incident angle of 0 ° with the wavelength of 420 to 650 nm is 50% or more.
  • the second high transmission wavelength band includes a wavelength of 820 to 900 nm, and an average transmittance for light having an incident angle of 0 ° with the wavelength of 820 to 900 nm is 40% or more.
  • ⁇ Satisfying requirement (2) can block near-infrared light that affects visible light images and enhance color reproducibility of visible light images. Moreover, the transmittance
  • the average transmittance for light having an incident angle of 0 ° at a wavelength of 680 to 720 nm is more preferably 10% or less, and further preferably 5% or less.
  • the average transmittance of the filter for light having an incident angle of 0 ° at a wavelength of 420 to 650 nm is more preferably 60% or more, and further preferably 70% or more. The higher the average transmittance for light with a wavelength of 420 to 650 nm, the higher the transmittance of visible light, and a clear visible light image can be obtained.
  • the average transmittance of this filter for light having an incident angle of 0 ° at a wavelength of 820 to 900 nm is more preferably 55% or more, and further preferably 70% or more.
  • This filter more preferably satisfies the following requirement (5).
  • of the difference between the wavelengths of 30 and 15 is 15 nm or less.
  • is more preferably 10 nm or less, and further preferably 5 nm or less.
  • is an index indicating the incident angle dependency of light of the present filter at wavelengths of 350 to 420 nm, and the smaller the value, the lower the incident angle dependency.
  • the second high transmission wavelength band includes a wavelength of 750 to 900 nm, and the average transmittance for light having an incident angle of 0 ° with the wavelength of 750 to 900 nm is 40% or more.
  • the average transmittance is more preferably 50% or more, and further preferably 60% or more. The higher the average transmittance at a wavelength of 750 to 900 nm, the clearer the image by near infrared light is obtained.
  • This filter is particularly preferably used in a solid-state imaging device that captures images day and night, such as surveillance cameras and vehicle-mounted cameras.
  • this filter is disposed, for example, between the imaging lens and the solid-state imaging device.
  • this filter can be used even if it sticks directly to the solid-state image sensor, imaging lens, etc. of an imaging device through an adhesive layer.
  • Spectral transmittance curves of the optical filter and the reflective layer in the examples and comparative examples were measured using a spectrophotometer (model name U4100 manufactured by Hitachi, Ltd.).
  • Example 1 As a transparent substrate, SiO 2 and TiO 2 are alternately laminated on one main surface of white plate glass by a vacuum deposition method to form a reflective layer (34 layers) having a thickness of about 3.45 ⁇ m.
  • FIG. 2 shows a spectral transmittance curve (incident angle 0 ° / 30 °) of this reflective layer with a wavelength of 350 to 1000 nm.
  • a polyester resin (trade name “B-OKP2”, refractive index 1.63, manufactured by Osaka Gas Chemical Co., Ltd.) is dissolved in a mixed solvent (mass ratio 1: 1) of cyclohexanone and N-methyl-2-pyrrolidone (NMP).
  • a squarylium compound (compound (F11-3); absorption maximum wavelength 705 nm) as an NIR absorber is added at a ratio of 4.0 parts by mass with respect to 100 parts by mass of the polyester resin, and stirred and mixed at room temperature.
  • This coating solution is applied to the surface of the glass plate on which the reflective layer is formed using a spin coater, and the solvent is dried and the resin is baked and cured to obtain an absorption layer having a thickness of 3 ⁇ m. .
  • SiO 2 and TiO 2 are alternately laminated on the upper surface of the absorption layer by vacuum deposition, and an MgF 2 layer is provided on the outermost layer (interface with air), and an antireflection layer (7 layers) having a thickness of 340 nm. ) To obtain an optical filter.
  • Example 2 In a solution of B-OKP2 dissolved in a mixed solvent of cyclohexanone and NMP (mass ratio 1: 1), a squarylium compound (compound (F11-3)) and a cyanine compound (produced by Crystal-Lyn Chemical company) are used as NIR absorbers. “DLS745B” (absorption maximum wavelength 755 nm) is added at a ratio of 1.0 part by mass and 3.3 parts by mass with respect to 100 parts by mass of the polyester resin, respectively, followed by stirring and mixing at room temperature to obtain a coating solution.
  • NMP mass ratio 1: 1
  • a squarylium compound compound (F11-3)
  • a cyanine compound produced by Crystal-Lyn Chemical company
  • the coating liquid is applied to the surface opposite to the reflective layer of the white glass provided with the reflective layer in the same manner as in Example 1 to obtain an absorbing layer having a thickness of 3 ⁇ m.
  • An antireflection layer having the same configuration as that of Example 1 is formed to obtain an optical filter.
  • Example 3 In a solution prepared by dissolving B-OKP2 in a mixed solvent of cyclohexanone and NMP (mass ratio 1: 1), a squarylium compound (compound (F11-3) as an NIR absorber, and an oxazole compound (manufactured by BASF) as a UV absorber.
  • a squarylium compound compound (F11-3) as an NIR absorber
  • an oxazole compound manufactured by BASF
  • the name “Uvitex (registered trademark) OB” (absorption maximum wavelength 380 nm) is added at a ratio of 4 parts by mass and 5 parts by mass with respect to 100 parts by mass of the polyester resin, respectively, and stirred at room temperature to obtain a coating solution.
  • This coating liquid is formed on the surface of the white plate glass provided with the reflective layer on the side opposite to the reflective layer in the same manner as in Example 1 to form an absorption layer having a thickness of 3 ⁇ m.
  • An antireflection layer having the same configuration as that of Example 1 is formed on the upper surface to obtain an optical filter.
  • FIG. 3 (Example 1)
  • FIG. 4 (Example 2)
  • FIG. 5 (Example 3) show the spectral transmittance curves of the optical filters obtained in the above Examples.
  • the average transmittance at a wavelength of 420 to 650 nm is 70% or more
  • the average transmittance at a wavelength of 680 to 720 nm is 5% or less
  • a wavelength of 820 to 900 nm is 70% or more
  • the average transmittance at 70 nm or more at a wavelength of 750 to 900 nm is 70% or more, and the transmittance sharply changes (increases) between wavelengths of 730 to 760 nm.
  • the optical filter has no incident angle dependence in the transmittance characteristics of the region where the transition is made from transmission to cutoff in the vicinity of 700 nm at the boundary between the visible wavelength region and the near-infrared wavelength region. Therefore, the optical filter of Example 1 provides a clear color image based on visible light and excellent color reproducibility, and a clear black and white image based on infrared light.
  • the optical filter of Example 2 has an incident angle dependency in the transmittance of the region where the transition is made from transmission to cutoff at around 700 nm at the boundary between the visible wavelength region and the near-infrared wavelength region. I can't. Therefore, the optical filter of Example 2 provides a clear color image based on visible light and excellent color reproducibility, and a clear black and white image based on infrared light.
  • the average transmittance at a wavelength of 420 to 650 nm is 70% or more
  • the average transmittance at a wavelength of 680 to 720 nm is 5% or less
  • a wavelength of 820 The average transmittance at ⁇ 900 nm is 70% or more
  • the average transmittance at wavelengths 750 to 900 nm is 70% or more
  • the optical filter of Example 3 has an incident angle dependency in the transmittance of the region where the transition is made from transmission to cutoff near the wavelength of 700 nm at the boundary between the visible wavelength region and the near infrared wavelength region. I can't. In addition, no dependency on the incident angle is observed in the transmittance of the region where the transition from blocking to transmission occurs in the vicinity of the wavelength of 400 nm at the boundary between the ultraviolet wavelength region and the visible wavelength region. Therefore, Example 3 provides a clear color image based on visible light and excellent color reproducibility, particularly a color image with improved color reproducibility on the ultraviolet wavelength side compared to Examples 1 and 2, and infrared light. A clear black-and-white image based on is obtained.
  • the optical filter of the present invention can suppress the incident angle dependency of the transmittance characteristic of visible light close to the infrared wavelength region, and can achieve high transmittance in a predetermined infrared wavelength region. Therefore, it can be suitably used as an optical filter for use in an imaging device that acquires (color) images based on visible light and (black and white) images based on infrared light, for example, surveillance cameras and vehicle-mounted cameras.
  • 10A to 10C optical filter
  • 11 absorption layer
  • 12 reflection layer
  • 13 transparent substrate
  • 14 antireflection layer

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Abstract

L'invention concerne un filtre optique qui permet d'obtenir des images vives présentant une reproductibilité avantageuse, lors de l'acquisition d'images basée à la fois sur la lumière visible et sur la lumière proche infrarouge. Le filtre optique comprend : une couche réfléchissante qui comporte, dans une région de longueur d'onde entre des longueurs d'onde de 350 à 1 200 nm, une bande de longueur d'onde de transmission dans laquelle le taux de transmission de la lumière à un angle d'incidence de 0° est d'au moins 40 %, le taux de transmission au niveau du côté longueur d'onde plus court que la bande de longueur d'onde de transmission et au niveau du côté longueur d'onde plus long que la bande de longueur d'onde de transmission étant inférieur à 40 % ; et une couche d'absorption présentant un maximum d'absorption à l'intérieur de la bande de longueur d'onde de transmission de la couche réfléchissante. Dans la bande de longueur d'onde de transmission, le filtre optique comprend : une bande de longueur d'onde de transmission faible ; une première bande de longueur d'onde de transmission élevée qui est au niveau du côté de longueur d'onde plus court que la bande de longueur d'onde de transmission faible et dans laquelle le taux de transmission de la lumière à un angle d'incidence de 0° est supérieur à celui de la bande de longueur d'onde de transmission faible ; et une seconde bande de longueur d'onde de transmission élevée qui est au niveau du côté de longueur d'onde plus long que la bande de longueur d'onde de transmission faible et, dans laquelle le taux de transmission de la lumière à un angle d'incidence de 0° est supérieur à celui de la bande de longueur d'onde de transmission faible.
PCT/JP2016/074148 2015-08-20 2016-08-18 Filtre optique et dispositif de capture d'image Ceased WO2017030174A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017151176A (ja) * 2016-02-22 2017-08-31 株式会社日本触媒 光選択透過フィルター
WO2018043500A1 (fr) * 2016-08-31 2018-03-08 株式会社大真空 Filtre optique
JP2018163327A (ja) * 2017-03-27 2018-10-18 プラチナム オプティクス テクノロジー （スーチョウ） インコーポレイテッドＰｌａｔｉｎｕｍ Ｏｐｔｉｃｓ Ｔｅｃｈｎｏｌｏｇｙ （Ｓｕｚｈｏｕ） Ｉｎｃ． フィルタ
WO2019054281A1 (fr) 2017-09-15 2019-03-21 富士フイルム株式会社 Composition, film, stratifié, filtre de transmission infrarouge, dispositif d'imagerie à semi-conducteurs et capteur infrarouge
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JPWO2018043500A1 (ja) * 2016-08-31 2019-06-24 株式会社大真空 光学フィルタ
WO2018043500A1 (fr) * 2016-08-31 2018-03-08 株式会社大真空 Filtre optique
JP2018163327A (ja) * 2017-03-27 2018-10-18 プラチナム オプティクス テクノロジー （スーチョウ） インコーポレイテッドＰｌａｔｉｎｕｍ Ｏｐｔｉｃｓ Ｔｅｃｈｎｏｌｏｇｙ （Ｓｕｚｈｏｕ） Ｉｎｃ． フィルタ
KR102303331B1 (ko) 2017-07-27 2021-09-16 니혼 이타가라스 가부시키가이샤 광학 필터 및 카메라가 달린 정보 단말
KR20200030602A (ko) * 2017-07-27 2020-03-20 니혼 이타가라스 가부시키가이샤 광학 필터 및 카메라가 달린 정보 단말
WO2019054281A1 (fr) 2017-09-15 2019-03-21 富士フイルム株式会社 Composition, film, stratifié, filtre de transmission infrarouge, dispositif d'imagerie à semi-conducteurs et capteur infrarouge
WO2020059509A1 (fr) 2018-09-20 2020-03-26 富士フイルム株式会社 Composition durcissable, film durci, filtre de transmission infrarouge, stratifié, élément d'imagerie à l'état solide, capteur, et procédé de formation de motif
KR102068516B1 (ko) * 2018-12-28 2020-01-21 주식회사 옵트론텍 광학 필터
JP2021162631A (ja) * 2020-03-31 2021-10-11 日本電波工業株式会社 光学フィルタ
JP7396950B2 (ja) 2020-03-31 2023-12-12 日本電波工業株式会社 光学フィルタ
WO2023012989A1 (fr) * 2021-08-05 2023-02-09 ソニーセミコンダクタソリューションズ株式会社 Dispositif d'imagerie
WO2023127670A1 (fr) * 2021-12-27 2023-07-06 Ａｇｃ株式会社 Filtre optique
WO2023210474A1 (fr) * 2022-04-27 2023-11-02 Ａｇｃ株式会社 Filtre optique
WO2023234095A1 (fr) 2022-06-01 2023-12-07 富士フイルム株式会社 Élément de photodétection, capteur d'image et procédé de fabrication d'élément de photodétection
WO2023234096A1 (fr) 2022-06-01 2023-12-07 富士フイルム株式会社 Élément de détection de lumière, capteur d'image et procédé de production d'élément de détection de lumière
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