WO2023022118A1 - 光学フィルタ - Google Patents

光学フィルタ Download PDF

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Publication number
WO2023022118A1
WO2023022118A1 PCT/JP2022/030832 JP2022030832W WO2023022118A1 WO 2023022118 A1 WO2023022118 A1 WO 2023022118A1 JP 2022030832 W JP2022030832 W JP 2022030832W WO 2023022118 A1 WO2023022118 A1 WO 2023022118A1
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WIPO (PCT)
Prior art keywords
wavelength
transmittance
dye
spectral
optical filter
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/JP2022/030832
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English (en)
French (fr)
Japanese (ja)
Inventor
雄一朗 折田
和彦 塩野
拓郎 島田
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
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Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to CN202280056595.5A priority Critical patent/CN117836678A/zh
Priority to JP2023542391A priority patent/JPWO2023022118A1/ja
Publication of WO2023022118A1 publication Critical patent/WO2023022118A1/ja
Priority to US18/444,829 priority patent/US20240255681A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/281—Interference filters designed for the infrared light
    • G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection

Definitions

  • the present invention relates to an optical filter that transmits light in the visible wavelength range and blocks light in the ultraviolet and near-infrared wavelength ranges.
  • Imaging devices using solid-state imaging devices transmit light in the visible range (hereinafter also referred to as “visible light”) and transmit light in the ultraviolet wavelength range (hereinafter referred to as “ultraviolet light”) in order to reproduce color tones well and obtain clear images. (also referred to as “near-infrared light”) and light in the near-infrared wavelength region (hereinafter also referred to as “near-infrared light”).
  • an optical filter for example, there is a reflective filter that reflects light to be shielded by utilizing light interference by a dielectric multilayer film in which dielectric thin films with different refractive indices are alternately laminated on one or both sides of a transparent substrate.
  • a dielectric multilayer film in which dielectric thin films with different refractive indices are alternately laminated on one or both sides of a transparent substrate.
  • the optical film thickness of the dielectric multilayer film changes depending on the incident angle of light. can occur.
  • the image sensor is also sensitive to near-ultraviolet light, if the near-ultraviolet light shielding property is not sufficient, there is a risk of deterioration in image quality due to unnecessary light called flare or ghost in the captured visible light image. be.
  • a near-infrared/ultraviolet light cut filter in which the spectral sensitivity of a solid-state imaging device is not affected by the incident angle.
  • near-ultraviolet light-cutting ability and near-infrared light-cutting ability are disclosed by combining an absorption layer containing a near-ultraviolet light-absorbing dye and a near-infrared light-absorbing dye in a transparent resin with a dielectric multilayer film.
  • An optical filter is described that also has an ability to cut external light.
  • the present invention has high visible light transmittance and high near-infrared light and ultraviolet light shielding properties.
  • flare and ghost are suppressed by suppressing deterioration of ultraviolet light shielding properties at high incident angles. It is an object of the present invention to provide an optical filter with a
  • the present invention provides an optical filter having the following configuration.
  • An optical filter comprising a substrate and a dielectric multilayer film laminated as an outermost layer on at least one main surface side of the substrate,
  • the substrate contains a resin, a UV dye 1 having a maximum absorption wavelength of 360 to 390 nm in the resin, and an IR dye having a maximum absorption wavelength of 680 to 800 nm in the resin, and has a thickness of 3 ⁇ m or less.
  • having a resin film of The optical filter satisfies all of the following spectral characteristics (i-1) to (i-8).
  • the absolute value of the difference between ⁇ UV 70-10(0) and ⁇ UV 70-10(30) is 2.5 nm or less (i-7).
  • the wavelength IR50 (0) at which the transmittance is 50% is in the range of 610 to 670 nm
  • the wavelength IR50 (30) at which the transmittance is 50% is in the range of 610 to 670 nm in the spectral transmittance curve with a wavelength of 600 to 700 nm and an incident angle of 30 degrees.
  • the absolute value of the difference between the wavelength IR50 (0) and the wavelength IR50 (30) is 5 nm or less.
  • the present invention has high visible light transmittance and high shielding properties for near-infrared light and ultraviolet light, and particularly suppresses deterioration of the ultraviolet light shielding properties at high incident angles, such as flare and ghost. It is possible to provide an optical filter in which the is suppressed.
  • FIG. 1 is a cross-sectional view schematically showing an example of an optical filter according to one embodiment.
  • FIG. 2 is a cross-sectional view schematically showing another example of the optical filter of one embodiment.
  • FIG. 3 is a cross-sectional view schematically showing another example of the optical filter of one embodiment.
  • FIG. 4 is a cross-sectional view schematically showing another example of the optical filter of one embodiment.
  • FIG. 5 is a diagram showing a spectral internal transmittance curve of the resin film of Example 2-19.
  • FIG. 6 is a diagram showing a spectral internal transmittance curve of the resin film of Example 2-1.
  • FIG. 7 is a diagram showing a spectral internal transmittance curve of the resin film of Example 2-8.
  • FIG. 8 is a diagram showing the spectral transmittance curve of the optical filter of Example 3-18.
  • FIG. 9 is a diagram showing a spectral transmittance curve of the optical filter of Example 3-1.
  • FIG. 10 is a diagram showing a spectral transmittance curve of the optical filter of Example 3-6.
  • the near-infrared absorbing dye is sometimes abbreviated as "NIR dye”
  • the ultraviolet absorbing dye is sometimes abbreviated as "UV dye”.
  • NIR dye the near-infrared absorbing dye
  • UV dye ultraviolet absorbing dye
  • the compound represented by formula (I) is referred to as compound (I).
  • a dye comprising compound (I) is also referred to as dye (I), and the same applies to other dyes.
  • the group represented by formula (I) is also referred to as group (I), and the groups represented by other formulas are the same.
  • the internal transmittance is the transmittance obtained by subtracting the influence of interface reflection from the measured transmittance, which is represented by the formula ⁇ measured transmittance/(100 ⁇ reflectance) ⁇ 100.
  • the absorbance is converted from the (internal) transmittance by the formula -log 10 ((internal) transmittance/100).
  • the transmittance of the substrate and the spectral transmittance when the pigment is contained in the resin are all "internal transmittance" even if they are described as "transmittance".
  • the transmittance measured by dissolving a dye in a solvent such as dichloromethane the transmittance of a dielectric multilayer film, and the transmittance of an optical filter having a dielectric multilayer film are actually measured transmittances.
  • a transmittance of, for example, 90% or more in a specific wavelength range means that the transmittance in the entire wavelength range does not fall below 90%, that is, the minimum transmittance in the wavelength range is 90% or more.
  • a transmittance of, for example, 1% or less means that the transmittance does not exceed 1% in the entire wavelength range, that is, the maximum transmittance in the wavelength range is 1% or less.
  • the average transmittance and average internal transmittance in a particular wavelength range are the arithmetic mean of the transmittance and internal transmittance for each 1 nm of the wavelength range.
  • Spectroscopic properties can be measured using an ultraviolet-visible-near-infrared spectrophotometer.
  • the numerical range "to" includes upper and lower limits.
  • An optical filter according to one embodiment of the present invention (hereinafter also referred to as “this filter”) comprises a base material and a dielectric multilayer film laminated as an outermost layer on at least one main surface side of the base material. It is an optical filter that satisfies specific spectral characteristics that
  • the substrate contains a resin, a UV dye 1 having a maximum absorption wavelength of 360 to 390 nm in the resin, and an IR dye having a maximum absorption wavelength of 680 to 800 nm in the resin, and has a thickness of 3 ⁇ m or less.
  • the optical filter As a whole achieves excellent transparency in the visible light region and excellent shielding properties in the near-ultraviolet and near-infrared regions. can.
  • the substrate contains an ultraviolet-absorbing dye or a near-infrared-absorbing dye
  • changes in the spectral characteristics of the dielectric multilayer film at high incident angles such as the occurrence of light leakage in the ultraviolet region or the near-infrared region, can be suppressed by the substrate.
  • FIG. 1 are cross-sectional views schematically showing an example of an optical filter according to one embodiment.
  • An optical filter 1A shown in FIG. 1 is an example having a dielectric multilayer film 30 on one main surface side of a base material 10 .
  • "having a specific layer on the main surface side of the base material” is not limited to the case where the layer is provided in contact with the main surface of the base material, and another function is provided between the base material and the layer. Including cases where layers are provided.
  • the optical filter 1B shown in FIG. 2 is an example having dielectric multilayer films 30 on both main surface sides of the substrate 10 .
  • the optical filter 1C shown in FIG. 3 is an example in which the substrate 10 has a support 11 and a resin film 12 laminated on one main surface side of the support 11 .
  • the optical filter 1C further has a dielectric multilayer film 30 on the resin film 12 and on the main surface side of the support 11 on which the resin film 12 is not laminated.
  • the optical filter 1D shown in FIG. 4 is an example in which the base material 10 has a support 11 and resin films 12 laminated on both main surface sides of the support 11 .
  • Optical filter 1D further has dielectric multilayer film 30 on each resin film 12 .
  • the optical filter of the present invention satisfies all of the following spectral characteristics (i-1) to (i-8).
  • (i-1) Average transmittance T 360-400 (0) AVE of 0.5% or less in the spectral transmittance curve at a wavelength of 360 to 400 nm and an incident angle of 0 degree (i-2) A wavelength of 350 to 390 nm and an incident angle of 50 Average transmittance T 350-390 (50) AVE in the spectral transmittance curve of 0.5% or less (i-3)
  • Average transmittance T 400- 430 (0) AVE is 35% or more
  • Average transmittance T 430-500 (0) AVE of 88% or more i-5) wavelength in spectral transmittance curve at wavelength 430-500 nm and incident angle 0 degree
  • the wavelength UV50 (0) at which the transmittance is 50% is in 400 to 430 nm
  • Spectral transmission of wavelength 350 Average transmittance T 360-400 (0) AVE of 0.5% or less in the spect
  • the absolute value of the difference between ⁇ UV 70-10(0) and ⁇ UV 70-10(30) is 2.5 nm or less (i-7).
  • the wavelength IR50 (0) at which the transmittance is 50% is in the range of 610 to 670 nm
  • the wavelength IR50 (30) at which the transmittance is 50% is in the range of 610 to 670 nm in the spectral transmittance curve with a wavelength of 600 to 700 nm and an incident angle of 30 degrees.
  • the absolute value of the difference between the wavelength IR50 (0) and the wavelength IR50 (30) is 5 nm or less.
  • This filter which satisfies all of the spectral characteristics (i-1) to (i-8), has good visible light transmittance, especially blue light transmittance as shown in characteristics (i-3) to (i-4). While maintaining the above, the optical filter suppresses the deterioration of the ultraviolet light shielding ability especially at high incident angles as shown in the characteristics (i-1) to (i-2).
  • spectral characteristics (i-1) means that the light shielding property in the ultraviolet light region with a wavelength of 360 to 400 nm is high.
  • T 360-400(0) AVE is preferably 0.4% or less.
  • the use of a dye having a high absorbability in the near-ultraviolet region can be mentioned.
  • Satisfying the spectral characteristic (i-2) means that in the ultraviolet light region with a wavelength of 350 to 390 nm, light leakage is unlikely to occur even at a high incident angle, and light shielding properties are high.
  • T 350-390(50)AVE is preferably 0.4% or less.
  • the use of a dye having a high absorbability in the near-ultraviolet region can be mentioned.
  • Satisfying the spectral characteristics (i-3) means having excellent blue light transmittance before the UV absorption start band with a wavelength of 400 to 430 nm.
  • the T 400-430(0) AVE is preferably 37% or higher, more preferably 38% or higher.
  • a UV dye with excellent sharpness or an IR dye with high blue band transmittance can be used.
  • Satisfying the spectral characteristics (i-4) means having excellent transmittance in the visible light range, particularly in the blue range.
  • the T 430-500(0) AVE is preferably 89% or higher, more preferably 90% or higher.
  • UV dyes and IR dyes with high transmittance in the visible light band are used.
  • Satisfying the spectral characteristics (i-5) means excellent light shielding properties in the ultraviolet region and excellent transmittance in the visible light region.
  • the wavelength UV50 (0) is preferably between 400 and 430 nm.
  • ⁇ UV 70-10(0) and ⁇ UV 70-10(30) in the spectral characteristic (i-6) are the transmittance curves around the UV absorption onset band with wavelengths of 350 to 450 nm at incident angles of 0 and 30 degrees. Represents steepness (how it rises). Satisfying the spectral characteristics (i-6) means that the sharpness of the transmittance curve shift is small and the color reproducibility is excellent even at a high incident angle in the UV absorption start band of wavelength 350 to 450 nm.
  • the absolute value of the difference between ⁇ UV 70-10(0) and ⁇ UV 70-10(30) is preferably 2.0 nm or less.
  • a UV dye having a maximum absorption wavelength in an appropriate wavelength range and excellent sharpness can be used.
  • spectral characteristics (i-7) and spectral characteristics (i-8) it has excellent light shielding properties in the near-infrared region and excellent transparency in the visible light region, and has a high angle of incidence before and after the near-infrared absorption start band. However, it means that the shift of the transmittance curve is small and the color reproducibility is excellent.
  • the wavelength IR50 (0) is preferably between 620 and 660 nm.
  • the wavelength IR50 (30) is preferably between 620 and 660 nm.
  • the absolute value of the difference between the wavelength IR50 (0) and the wavelength IR50 (30) is preferably 4 nm or less. Satisfying spectral characteristics (i-7) and (i-8) includes, for example, using an IR dye having a maximum absorption wavelength in the appropriate wavelength range.
  • the optical filter of the present invention preferably further satisfies the following spectral characteristics (i-9).
  • spectral characteristics i-9.
  • the absolute value of the difference between the wavelength UV10 (0) and the wavelength UV70 (0) is 13 nm or less.
  • the slope of the spectral transmittance curve over a certain visible light region is steep, which means that high shielding properties in the near-ultraviolet light region and high transmittance in the visible light region are compatible.
  • the absolute value of the difference between the wavelength UV10 (0) and the wavelength UV70 (0) is more preferably 12 nm or less. In order to satisfy the spectral characteristics (i-9), for example, use of a UV dye having excellent sharpness is mentioned.
  • the optical filter of the present invention preferably further satisfies the following spectral characteristics (i-10) and (i-11).
  • (i-10) Maximum transmittance T 360-400 (0) MAX is 5% or less in the spectral transmittance curve at a wavelength of 360 to 400 nm and an incident angle of 0 degrees (i-11) At a wavelength of 350 to 390 nm and an incident angle of 50 degrees
  • the maximum transmittance T 350-390 (50) MAX in the spectral transmittance curve is 5% or less
  • spectral characteristics (i-10) means that the light shielding property in the ultraviolet light region with a wavelength of 360 to 400 nm is high.
  • T 360-400(0) MAX is preferably 4% or less.
  • the use of a dye having a high absorbability in the near-ultraviolet region can be used.
  • spectral characteristic (i-11) means that in the ultraviolet light region with a wavelength of 350 to 390 nm, light leakage is less likely to occur even at high incident angles, and light shielding properties are high.
  • T 350-390(50) MAX is preferably 4% or less.
  • the use of a dye having a high absorbability in the near-ultraviolet region can be used.
  • the base material is provided with an ability to absorb ultraviolet light and near-infrared light, and the above spectral characteristics (i-1) to (i -8).
  • the substrate has a resin film containing resin, UV dye 1, and IR dye.
  • the resin film preferably satisfies all of the following spectral characteristics (iii-1) to (iii-9).
  • Internal transmittance T 370 at a wavelength of 370 nm is 10% or less
  • Internal transmittance T 380 at a wavelength of 380 nm is 4%
  • the average internal transmittance T 360-400AVE in the spectral transmittance curve at a wavelength of 360 to 400 nm is 15% or less
  • the average internal transmittance in the spectral transmittance curve at a wavelength of 400 to 430 nm T 400- 430AVE is 40% or more
  • Average internal transmittance T in the spectral transmittance curve of wavelength 430-500nm 430-500AVE is 90% or more
  • the internal transmittance T360 is more preferably 20% or less.
  • the internal transmittance T 370 is more preferably 7% or less.
  • the internal transmittance T380 is more preferably 3.5% or less. More preferably, the average internal transmittance T 360-400AVE is 13% or less.
  • T 400-430 AVE is more preferably 42% or more.
  • T 430-500 AVE is more preferably 92% or more.
  • the absolute value of the difference between the wavelength UV10 and the wavelength UV70 is more preferably 15 nm or less.
  • the internal transmittance T700 is more preferably 3% or less.
  • the wavelength IR50 more preferably lies between 620 and 670 nm.
  • a compound represented by the formula (S) described below may be used as a UV dye.
  • the use of a squarylium compound, which will be described later, can be used as the IR dye.
  • UV dye 1 is a near-ultraviolet absorbing dye having a maximum absorption wavelength of 360 to 390 nm in resin. Ultraviolet light can be effectively cut by containing such a dye.
  • the UV dye 1 preferably has specific spectral properties in the resin. Specifically, the spectral internal transmittance curve of a coating film obtained by dissolving UV dye 1 in a resin and coating it on an alkali glass plate satisfies all of the following spectral characteristics (ii-1) to (ii-3). is preferred.
  • the resin is preferably the same as the resin contained in the substrate.
  • the absorbance at the maximum absorption wavelength is 0.1 (/% by mass ⁇ m) or more (ii-2)
  • the average internal transmittance T 350-400AVE at a wavelength of 350 to 400 nm is 13% or less
  • the absolute value of the difference between the wavelength UV10 when the internal transmittance is 10% at a wavelength of 350 to 450 nm and the wavelength UV70 when the internal transmittance is 70% is 10 nm or less.
  • the absorbance is the absorbance per 1 ⁇ m film thickness with a dye content of 1% by mass.
  • the absorbance is 0.1 or more, it means that the UV dye 1 has a high absorption ability, and sufficient light shielding properties can be achieved even with a small content.
  • the absorbance is preferably 0.12 (/mass % ⁇ m) or more.
  • the spectral characteristic (ii-2) means that a wide range of wavelengths from 350 to 400 nm can be absorbed.
  • T 350-400 AVE is preferably 11% or less.
  • the spectral characteristic (ii-3) means that the slope of the spectral transmittance curve from the near-ultraviolet light region, which is the light shielding region, to the visible light region, which is the transmission region, is steep.
  • the absolute value of the difference between the wavelength UV10 and the wavelength UV70 is preferably 9.5 nm or less.
  • a cyanine compound represented by the following formula (S) is preferable from the viewpoint of easily satisfying the spectral characteristics (ii-1) to (ii-3) and from the viewpoint of having an effect of suppressing deterioration of the IR dye. .
  • IR dyes generally tend to deteriorate when used in combination with UV dyes, but this can be prevented by using the cyanine compound represented by the formula (S) as the UV dye in combination.
  • R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms.
  • R 3 to R 10 each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phenyl group, or an optionally substituted alkyl group having 1 to 10 carbon atoms.
  • R 1 and R 2 are each independently preferably a methyl group or an ethyl group.
  • Substituents for R 3 to R 10 include an alkyl group, a halogen atom and a phenyl group from the viewpoint of ease of synthesis, and among them, a t-butyl group is preferred from the viewpoint of solubility in resins. .
  • the number of carbon atoms in the substituent is included in each of R 3 to R 10 .
  • R 3 is preferably a hydrogen atom from the viewpoint of ease of synthesis.
  • R 8 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogen atom or a phenyl group from the viewpoint of ease of synthesis and maximum absorption wavelength range.
  • R 9 and R 10 are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, from the viewpoint of ease of synthesis and maximum absorption wavelength range.
  • X and Y are preferably O from the viewpoint that the maximum absorption wavelength of the dye (S) is in an appropriate wavelength region.
  • An - is preferably PF 6 - , [Rf-SO 2 ] - , [N(Rf-SO 2 ) 2 ] - or BF 4 - .
  • Rf represents an alkyl group substituted with at least one fluorine atom, preferably a perfluoroalkyl group having 1 to 8 carbon atoms, particularly preferably -CF 3 .
  • a UV dye compound (S) having excellent light resistance can be obtained because the anion has such a structure.
  • the compound (S) As the compound (S), the compound (S-7) whose anion is BF 4 ⁇ , PF 6 ⁇ , or N(SO 2 CF 3 ) 2 ⁇ and a compound (S-8) is preferred, and the compound (S-8) whose anion is BF 4 ⁇ , PF 6 ⁇ , or N(SO 2 CF 3 ) 2 — , and the compound (S-7) whose anion is PF 6 — is particularly preferred.
  • the compound (S) can be produced by known methods described, for example, in Japanese Patent Application Laid-Open No. 2011-102841 and Japanese Patent No. 4702731.
  • the UV dye in the resin film may be used alone, or two or more kinds may be used in combination. It is preferable to use two or more different types in combination.
  • the resin film preferably further contains a UV dye 2 having a maximum absorption wavelength of 390 to 405 nm in the resin and having a maximum absorption wavelength longer than that of the UV dye 1 by 10 nm or more.
  • UV dye 2 a merocyanine dye represented by the following formula (M) is particularly preferable.
  • R 1 represents an optionally substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.
  • Preferred substituents are alkoxy groups, acyl groups, acyloxy groups, cyano groups, dialkylamino groups and chlorine atoms.
  • the alkoxy group, acyl group, acyloxy group and dialkylamino group preferably have 1 to 6 carbon atoms.
  • R 1 having no substituent examples include an alkyl group having 1 to 12 carbon atoms in which a portion of the hydrogen atoms may be substituted with an aliphatic ring, an aromatic ring or an alkenyl group, and a portion of the hydrogen atoms. is optionally substituted by an aromatic ring, an alkyl group or an alkenyl group, and a cycloalkyl group having 3 to 8 carbon atoms, and a portion of the hydrogen atoms may be substituted by an aliphatic ring, an alkyl group or an alkenyl group.
  • Aryl groups having 6 to 12 carbon atoms are preferred.
  • R 1 is an unsubstituted alkyl group
  • the alkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms.
  • R 1 is an alkyl group having 1 to 12 carbon atoms partially substituted with an aliphatic ring, an aromatic ring or an alkenyl group, a cycloalkyl group having 3 to 6 carbon atoms and 1 to 1 carbon atoms 4 alkyl groups, phenyl-substituted alkyl groups having 1 to 4 carbon atoms are more preferred, and phenyl-substituted alkyl groups having 1 or 2 carbon atoms are particularly preferred.
  • An alkyl group substituted with an alkenyl group means an alkenyl group as a whole but having no unsaturated bond between the 1- and 2-positions, such as an allyl group or a 3-butenyl group.
  • R 1 is an alkyl group having 1 to 6 carbon atoms in which part of the hydrogen atoms may be substituted with a cycloalkyl group or a phenyl group.
  • Particularly preferred Q 1 is an alkyl group having 1 to 6 carbon atoms, and specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. be done.
  • R 2 to R 5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • the number of carbon atoms in the alkyl group and alkoxy group is preferably 1-6, more preferably 1-4.
  • At least one of R 2 and R 3 is preferably an alkyl group, more preferably both are alkyl groups. Hydrogen atoms are more preferred if R 2 and R 3 are not alkyl groups. Both R 2 and R 3 are particularly preferably C 1-6 alkyl groups.
  • At least one of R 4 and R 5 is preferably a hydrogen atom, and both are more preferably hydrogen atoms.
  • R 4 or R 5 is not a hydrogen atom, an alkyl group having 1 to 6 carbon atoms is preferred.
  • Y represents a methylene group or an oxygen atom substituted with R6 and R7 .
  • R 6 and R 7 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • X represents any of the divalent groups represented by the following formulas (X1) to (X5).
  • R 8 and R 9 each independently represent an optionally substituted monovalent hydrocarbon group having 1 to 12 carbon atoms
  • R 10 to R 19 each independently represent a hydrogen atom, or It represents an optionally substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.
  • Substituents for R 8 to R 19 include the same substituents as those for R 1 , and preferred embodiments are also the same. When R 8 to R 19 are hydrocarbon groups having no substituents, the same embodiments as R 1 having no substituents can be mentioned.
  • R 8 and R 9 may be different groups, but are preferably the same group.
  • R 8 and R 9 are unsubstituted alkyl groups, they may be linear or branched, and preferably have 1 to 6 carbon atoms.
  • R 8 and R 9 are both C 1-6 alkyl groups in which some of the hydrogen atoms may be substituted with cycloalkyl groups or phenyl groups. Particularly preferred R 8 and R 9 are both alkyl groups having 1 to 6 carbon atoms, and specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl. group, t-butyl group, and the like.
  • both R 10 and R 11 are more preferably alkyl groups having 1 to 6 carbon atoms, particularly preferably the same alkyl group.
  • both R 12 and R 15 are preferably hydrogen atoms or unsubstituted alkyl groups having 1 to 6 carbon atoms.
  • Two groups, R 13 and R 14 , which are bonded to the same carbon atom, are preferably both hydrogen atoms or both C 1-6 alkyl groups.
  • Two groups R 16 and R 17 and R 18 and R 19 bonded to the same carbon atom in formula (X4) are both hydrogen atoms, or both preferably C 1-6 alkyl groups.
  • Compounds represented by formula (M) include compounds in which Y is an oxygen atom and X is group (X1), group (X2) or group (X5), and compounds in which Y is an unsubstituted methylene group. , X is the group (X1), the group (X2) or the group (X5) are preferred.
  • the compound (M), the compound (M-2), the compound (M-8), the compound (M-9), and the compound (M-13) are suitable in terms of the solubility in the resin and the maximum absorption wavelength. , the compound (M-20) is preferred.
  • Compound (M) can be produced, for example, by a known method described in Japanese Patent No. 6504176.
  • the product of the content of the UV dye 1 and the thickness of the resin film is preferably 15 (mass% ⁇ m) or less, more preferably 14.5 (mass% ⁇ m) or less. , and particularly preferably 14.0 (% by mass ⁇ m) or less. If the amount of the UV dye 1 added is too large, the resin characteristics may be deteriorated, and as a result, the adhesion to the dielectric multilayer film or glass may be deteriorated. In addition, the glass transition temperature of the resin is lowered, and there is concern about the heat resistance. Such a problem can be prevented if the product of the dye content and the thickness of the resin film is within the above range. Moreover, from the viewpoint of satisfying desired spectral characteristics, the product of the content and the thickness is preferably 3.0 (mass % ⁇ m) or more, more preferably 5.0 (mass % ⁇ m) or more.
  • the content of the UV dye 1 in the resin film is preferably 2.0 to 15.0 parts by mass, more preferably 3.0 to 14.0 parts by mass with respect to 100 parts by mass of the resin. . Within this range, the above problem can be avoided without deteriorating the resin properties.
  • the product of the total content of UV dye 1 and UV dye 2 and the thickness of the resin film is 15 (% by mass ⁇ ⁇ m) or less. It is preferable to set the content of the UV dye 2 so as to be within a range of preferably 14.5 (mass % ⁇ m) or less, particularly preferably 14.0 (mass % ⁇ m) or less.
  • the content of the UV dye 2 in the resin film is preferably 2.0 to 13.0 parts by mass, more preferably 3.0 to 11.0 parts by mass with respect to 100 parts by mass of the resin.
  • the total content of the UV dye 1 and the UV dye 2 in the resin film is preferably 3.0 to 15.0 parts by mass, more preferably 5.0 to 14.0 parts by mass with respect to 100 parts by mass of the resin. .
  • An IR dye is a near-infrared absorbing dye that has a maximum absorption wavelength of 680 to 800 nm in resin. Infrared light can be effectively cut by containing such a dye.
  • IR dyes include squarylium dyes, cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, dithiol metal complex dyes, azo dyes, polymethine dyes, phthalide dyes, naphthoquinone dyes, anthraquinone dyes, indophenol dyes, pyrylium dyes, thiopyrylium dyes, At least one dye selected from the group consisting of cucochonium dyes, tetradehydocholine dyes, triphenylmethane dyes, aminium dyes and diimmonium dyes is preferred.
  • the IR dye preferably contains at least one dye selected from squarylium dyes, phthalocyanine dyes, and cyanine dyes.
  • squarylium dyes and cyanine dyes are preferred from the viewpoint of spectroscopy, and phthalocyanine dyes are preferred from the viewpoint of durability.
  • the content of the NIR dye in the resin film is preferably 5 to 25 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the resin.
  • the substrate in this filter may have a single-layer structure or a multilayer structure.
  • the material of the base material is not particularly limited and may be either an organic material or an inorganic material as long as it is a transparent material that transmits visible light of 400 to 700 nm.
  • the base material has a single-layer structure, it is preferably a resin base material comprising a resin film containing a resin, a UV dye, and an NIR dye.
  • the substrate has a multi-layer structure, it preferably has a structure in which a resin film containing a UV dye and an NIR dye is laminated on at least one main surface of the support.
  • the support is preferably made of a transparent resin or a transparent inorganic material.
  • transparent resins are preferable, and examples include polyester resins, acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, poly Arylene ether phosphine oxide resins, polyamide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyurethane resins, polystyrene resins, and the like. These resins may be used individually by 1 type, and may be used in mixture of 2 or more types. Among them, polyimide resins are preferable from the viewpoint of making it difficult for dyes to thermally deteriorate due to excellent visible transmittance and high glass transition temperature of resins.
  • glass and crystalline materials are preferable.
  • glass that can be used for the support include fluorophosphate glass, phosphate glass, and the like that contain copper ions (near-infrared absorbing glass), soda lime glass, borosilicate glass, alkali-free glass, and quartz. Glass etc. are mentioned.
  • absorption glass is preferable according to the purpose, and from the viewpoint of absorbing infrared light, phosphoric acid glass and fluorophosphate glass are preferable.
  • Alkaline glass, non-alkali glass, and quartz glass are preferable when it is desired to take in a large amount of red light (600 to 700 nm).
  • phosphate-based glass also includes silicate phosphate glass in which a part of the skeleton of the glass is composed of SiO 2 .
  • alkali metal ions with a small ionic radius e.g., Li ions, Na ions
  • alkali ions with a larger ionic radius e.g., Li ions are Na ions or K ions, and Na ions are K ions.
  • Crystal materials that can be used for the support include birefringent crystals such as quartz, lithium niobate, and sapphire.
  • inorganic materials are 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 during filter production.
  • a resin film is prepared by dissolving or dispersing a dye, a resin or a raw material component of the resin, and each component to be blended as necessary in a solvent to prepare a coating solution, coating the solution on a support, and drying it. It can be formed by curing and, if necessary, curing.
  • the support may be the support included in the present filter, or may be a peelable support that is used only when forming the resin film.
  • the solvent may be a dispersion medium capable of stably dispersing or a solvent capable of dissolving.
  • the coating liquid may contain a surfactant to improve voids caused by microbubbles, dents caused by adhesion of foreign matter, repellency during the drying process, and the like.
  • a surfactant to improve voids caused by microbubbles, dents caused by adhesion of foreign matter, repellency during the drying process, and the like.
  • dip coating, cast coating, spin coating, or the like can be used for the application of the coating liquid.
  • a resin film is formed by coating the above coating liquid on a support and then drying it.
  • the coating liquid contains a raw material component of the transparent resin, it is further subjected to a curing treatment such as heat curing or photocuring.
  • the resin film can also be produced in the form of a film by extrusion molding.
  • the base material has a single-layer structure (resin base material) composed of a resin film containing a dye
  • the resin film can be used as it is as the base material.
  • the base material has a multilayer structure (composite base material) having a support and a resin film laminated on at least one main surface of the support, the film is laminated on the support and integrated by thermocompression bonding or the like.
  • the substrate can be produced by allowing
  • the resin film may have one layer in the optical filter, or may have two or more layers. When it has two or more layers, each layer may have the same configuration or different configurations.
  • the thickness of the resin film is 3 ⁇ m or less, preferably 2.5 ⁇ m or less. If the thickness of the resin film is within such a range, a uniform film with a narrow film thickness distribution can be easily obtained. Moreover, it is preferably 1.0 ⁇ m or more from the viewpoint of obtaining desired spectral characteristics. When the resin film consists of multiple layers, the thickness of each layer preferably satisfies the above range.
  • the shape of the substrate is not particularly limited, and may be block-shaped, plate-shaped, or film-shaped.
  • the thickness of the substrate is preferably 300 ⁇ m or less, more preferably 50 to 300 ⁇ m, particularly preferably 50 to 300 ⁇ m, particularly preferably from the viewpoint of warping deformation that occurs when reliability fluctuates when a dielectric multilayer film is formed, or from the viewpoint of handling. 70 to 300 ⁇ m.
  • the substrate is a resin substrate containing a resin and a dye
  • the substrate thickness is preferably 120 ⁇ m or less from the merit of lowering the height, and 50 ⁇ m or more from the viewpoint of reducing warpage during multilayer film formation. preferable.
  • the thickness is preferably 70 ⁇ m to 110 ⁇ m.
  • the dielectric multilayer film is laminated as the outermost layer on at least one main surface side of the substrate.
  • At least one of the dielectric multilayer films is preferably designed as a near-infrared reflective layer (hereinafter also referred to as an NIR reflective layer).
  • the other dielectric multilayer film is preferably designed as an NIR reflective layer, a reflective layer having a reflective region other than the near-infrared region, or an antireflection layer.
  • the NIR reflective layer is a dielectric multilayer film designed to block light in the near-infrared region.
  • the NIR reflective layer has, for example, wavelength selectivity of transmitting visible light and mainly reflecting light in the near-infrared region other than the light-shielding region of the resin film.
  • the reflective region of the NIR reflective layer may include a light shielding region in the near-infrared region of the resin film.
  • the NIR reflective layer is not limited to NIR reflective properties, and may be appropriately designed to further block light in a wavelength range other than the near-infrared range, for example, the near-ultraviolet range.
  • the NIR reflective layer preferably satisfies the following spectral characteristics.
  • (v-1) Average transmittance T 360-400 in the spectral transmittance curve at a wavelength of 360 to 400 nm and an incident angle of 0 degree (0) AVE is 1% or less
  • Average transmittance T 430-500 (0) in the spectral transmittance curve AVE is 90% or more
  • v-3 Average transmittance T 750-1000 (0) in the spectral transmittance curve at a wavelength of 750 to 1000 nm and an incident angle of 0 degree AVE is 2% or less
  • the wavelength UV50 at which the transmittance is 50% is in the range of 380-430 nm
  • the NIR reflective layer is, for example, a dielectric film with a low refractive index (low refractive index film), a dielectric film with a medium refractive index (medium refractive index film), or a dielectric film with a high refractive index (high refractive index film). It is composed of a dielectric multilayer film in which two or more layers are laminated.
  • the high refractive index film preferably has a refractive index of 1.6 or more, more preferably 2.2 to 2.5. Examples of materials for the high refractive index film include Ta 2 O 5 , TiO 2 , TiO, and Nb 2 O 5 .
  • TiO 2 is preferable from the viewpoints of film formability, reproducibility in refractive index and stability, and the like.
  • the medium refractive index film preferably has a refractive index of 1.6 or more and less than 2.2.
  • Materials for the medium refractive index film include, for example, ZrO 2 , Nb 2 O 5 , Al 2 O 3 , HfO 2 , and OM-4 and OM-6 (Al 2 O 3 and ZrO 2 ), OA-100, H4 sold by Merck, M2 (alumina lanthania), and the like.
  • Al 2 O 3 -based compounds and mixtures of Al 2 O 3 and ZrO 2 are preferred from the viewpoint of film formability, reproducibility of refractive index, and stability.
  • the low refractive index film preferably has a refractive index of less than 1.6, more preferably 1.45 or more and less than 1.55.
  • Materials for the low refractive index film include, for example, SiO 2 , SiO x N y and MgF 2 .
  • Other commercially available products include S4F and S5F (a mixture of SiO2 and AlO2 ) manufactured by Canon Optron. Of these, SiO 2 is preferred from the viewpoints of reproducibility in film formation, stability, economy, and the like.
  • the transmittance of the NIR reflective layer sharply changes in the boundary wavelength region between the transmission region and the light blocking region.
  • the total number of laminated dielectric multilayer films constituting the reflective layer is preferably 15 layers or more, more preferably 25 layers or more, and even more preferably 30 layers or more.
  • the total number of laminations is preferably 100 or less, more preferably 75 or less, and even more preferably 60 or less.
  • the film thickness of the reflective layer is preferably 2 to 10 ⁇ m as a whole.
  • the NIR reflective layer satisfies the requirements for miniaturization and can suppress the incident angle dependence while maintaining high productivity.
  • a vacuum film forming process such as a CVD method, a sputtering method, or a vacuum deposition method, or a wet film forming process such as a spray method or a dipping method can be used.
  • the NIR reflective layer may provide predetermined optical properties with one layer (one group of dielectric multilayer films), or may provide predetermined optical properties with two layers.
  • each reflective layer may have the same structure or a different structure.
  • it is usually composed of a plurality of reflective layers with different reflection bands.
  • one is a near-infrared reflective layer that shields light in the short wavelength band of the near infrared region, and the other is both the long wavelength band and the near ultraviolet region of the near infrared region. It may be a near-infrared/near-ultraviolet reflective layer that shields the light.
  • antireflection layers examples include dielectric multilayer films, intermediate refractive index media, and moth-eye structures in which the refractive index changes gradually.
  • a dielectric multilayer film is preferable from the viewpoint of optical efficiency and productivity.
  • the antireflection layer is obtained by alternately laminating dielectric films in the same manner as the reflective layer.
  • the present filter may include, as other constituent elements, for example, a constituent element (layer) that provides absorption by inorganic fine particles or the like that controls the transmission and absorption of light in a specific wavelength range.
  • a constituent element layer
  • inorganic fine particles include ITO (indium tin oxides), ATO (antimony-doped tin oxides), cesium tungstate, and lanthanum boride.
  • ITO fine particles and cesium tungstate fine particles have high visible light transmittance and absorb light over a wide range of infrared wavelengths exceeding 1200 nm, so they can be used when such infrared light shielding properties are required. .
  • an imaging device using this filter includes a solid-state imaging device, an imaging lens, and this filter.
  • the present filter can be used, for example, by being placed between an imaging lens and a solid-state imaging device, or by being directly attached to a solid-state imaging device, an imaging lens, or the like of an imaging device via an adhesive layer.
  • An optical filter comprising a substrate and a dielectric multilayer film laminated as an outermost layer on at least one main surface side of the substrate,
  • the substrate contains a resin, a UV dye 1 having a maximum absorption wavelength of 360 to 390 nm in the resin, and an IR dye having a maximum absorption wavelength of 680 to 800 nm in the resin, and has a thickness of 3 ⁇ m or less.
  • having a resin film of The optical filter satisfies all of the following spectral characteristics (i-1) to (i-8).
  • the absolute value of the difference between ⁇ UV 70-10(0) and ⁇ UV 70-10(30) is 2.5 nm or less (i-7).
  • the wavelength IR50 (0) at which the transmittance is 50% is in the range of 610 to 670 nm
  • the wavelength IR50 (30) at which the transmittance is 50% is in the range of 610 to 670 nm in the spectral transmittance curve with a wavelength of 600 to 700 nm and an incident angle of 30 degrees.
  • the absolute value of the difference between the wavelength IR50 (0) and the wavelength IR50 (30) is 5 nm or less [2]
  • the optical filter described in [1] further satisfies the following spectral characteristics (i-9) optical filters.
  • the absolute value of the difference between the wavelength UV10 (0) and the wavelength UV70 (0) is 13 nm or less
  • the product of the content of the UV dye 1 in the resin film and the thickness of the resin film is The optical filter according to [1] or [2], which is 15 (mass % ⁇ m) or less.
  • the resin film further includes a UV dye 2 having a maximum absorption wavelength of 390 to 405 nm in the resin and having a maximum absorption wavelength greater than that of the UV dye 1 by 10 nm or more,
  • the product of the total content of the UV dye 1 and the UV dye 2 in the resin film and the thickness of the resin film is 15 (% by mass ⁇ m) or less, according to any one of [1] to [3].
  • the UV dye 1 has the following spectral characteristics (ii-1) to (ii) in the spectral internal transmittance curve of a coating film obtained by dissolving the UV dye 1 in the resin and coating it on an alkali glass plate.
  • the optical filter according to any one of [1] to [4], which satisfies all of -3).
  • UV dye 1 is a cyanine compound represented by the following formula (S).
  • R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms.
  • R 3 to R 10 each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phenyl group, or an optionally substituted alkyl group having 1 to 10 carbon atoms.
  • X and Y each independently represent O, S, or -C(CH 3 ) 2 .
  • An ⁇ represents a monovalent anion.
  • [7] The optical filter of [6], wherein X and Y are O in the cyanine compound represented by the formula (S).
  • [8] The optical filter according to any one of [1] to [7], wherein the resin film satisfies all of the following spectral characteristics (iii-1) to (iii-9).
  • the resin is a transparent resin.
  • An imaging device comprising the optical filter according to any one of [1] to [12].
  • the dyes used in each example are as follows.
  • Compounds 1 to 18 are UV dyes, and compound 19 is an NIR dye.
  • Compounds 1 to 4 (cyanine compounds): Synthesized by the method described below with reference to Japanese Patent Application Laid-Open No. 2011-102841 and Japanese Patent No. 4702731.
  • Compound 5 (azo compound): Synthesized with reference to Japanese Patent No. 6256335.
  • Compound 6 triazine compound
  • Compound 7 Tinuvin460 manufactured by BASF Japan
  • Compounds 8 to 12 (merocyanine compounds): Synthesized with reference to Japanese Patent No. 6504176.
  • Compound 13 Nikkafluor U1 manufactured by Nippon Kagaku Kogyo Co., Ltd.
  • Compound 14 Nikkafluor MCT manufactured by Nippon Kagaku Kogyo Co., Ltd.
  • Compound 15 (cyanine compound) SMP-416 manufactured by Hayashibara Chemical Co., Ltd.
  • Compound 16 (cyanine compound) SMP-370 manufactured by Hayashibara Chemical Co., Ltd.
  • Compound 17 Kayalight B manufactured by Nippon Kayaku Co., Ltd.
  • Compound 18 Kayalight 408 manufactured by Nippon Kayaku Co., Ltd.
  • Compound 19 squarylium compound: Synthesized with reference to Japanese Patent No. 6,197,940.
  • Examples 1-2 to 1-18 Coating films were prepared in the same manner as in Example 1-1 except that Compounds 2 to 18 were used instead of Compound 1. (However, only compound 5 was added so as to be 4 parts by mass with respect to 100 parts by mass of resin.)
  • transmission spectroscopy (incidence angle of 0 degrees) and reflection spectroscopy (incidence angle of 5 degrees) in the wavelength range of 350 nm to 1200 nm were measured for each of the obtained glass substrates with a coating film.
  • a spectral internal transmittance curve was calculated, and further, the absorbance at the maximum absorption wavelength when the amount of dye added was 1% by mass, and the internal at the maximum absorption wavelength A spectral transmittance curve normalized so that the transmittance was 1% was obtained.
  • the results are shown in the table below. Examples 1-1 to 1-18 are reference examples.
  • the coating films of Examples 1-1 to 1-4 containing any of Compounds 1 to 4 as the UV dye have a dye maximum absorption wavelength of 360 to 390 nm and an absorbance of 0.1 or more. Because it has a high absorptivity, and the average internal transmittance T 350-400AVE is 13% or less, it has excellent light blocking properties in the near-ultraviolet region, and the wavelength UV10 when the internal transmittance is 10% and the internal transmittance Since the absolute value of the difference from the wavelength UV70 at 70% is 10 nm or less, the rise (slope) of the transmittance curve from the near-ultraviolet region to the visible light region is steep, that is, the transmittance in the blue band is high. I understand.
  • a glass substrate alkali glass, D263 manufactured by Schott
  • Examples 2-2 to 2-23 A resin film was formed in the same manner as in Example 2-1, except that instead of compound 1, a dye compound described in the table below was used at a concentration shown in the table below, and the film thickness of the resin film was set to the value shown in the table below. Obtained.
  • the resin films of Examples 2-1 to 2-5 and Examples 2-19 to 2-23 exhibited excellent spectral characteristics in the near-ultraviolet region.
  • Examples 2-19 to 2-22 in which two types of UV dyes having different maximum wavelength regions were used in combination, realized wide absorption.
  • the resin films of Examples 2-2 and 2-21 have a large amount of UV dye added, and the resin film of Example 2-22 has a large film thickness. As a result, the product of the thickness of the film and the thickness of the film is large.
  • the resin films of Examples 2-7 to 2-14 contain only UV dyes whose maximum absorption wavelength region is outside the range of 360 to 390 nm, and thus have shielding properties in the near-ultraviolet light region of 360 to 400 nm and 400 Low transmission in the blue light region of ⁇ 430 nm resulted.
  • the resin films of Examples 2-6 and 2-15 to 2-18 have low absorbance in the resin, that is, contain UV dyes with weak absorption, resulting in low shielding properties in the near-ultraviolet light region of 360 to 400 nm. became.
  • Example 3-1 A dielectric multilayer film (reflective film) in which 42 layers of SiO 2 and TiO 2 were alternately laminated was formed on one main surface of a glass substrate (alkali glass, D263 manufactured by Schott) by vapor deposition. Spectral characteristics are shown in the table below. A resin film was formed on the other surface of the glass substrate in the same manner as in Example 2-1, using the dye compound in the amount shown in the table below. After that, a dielectric multilayer film (antireflection film) was formed by alternately laminating SiO 2 and TiO 2 on the resin film to form an optical filter.
  • a dielectric multilayer film antireflection film
  • Examples 3-2 to 3-21 An optical filter was produced in the same manner as in Example 3-1, except that the type and content of the dye compound and the thickness of the resin film were changed to the values shown in the table below.
  • the optical filters of Examples 3-1 to 3-3 and Examples 3-18 to 3-20 have high visible light transmittance and high near-infrared light and ultraviolet light shielding properties. Even at a high incident angle of 100 degrees, the ultraviolet light shielding performance did not deteriorate, and good spectral characteristics were exhibited.
  • the optical filters of Examples 3-18 to 3-20 in which two types of UV dyes having different maximum absorption wavelength regions are used in combination, are the optical filters of Examples 3-1 to 3-3, in which one type of UV dye is used, and those in which a dye is added. It was shown that the near-ultraviolet light region can be shielded more broadly and deeply than Examples 3-1 to 3-3, even if the amount is about the same.
  • the optical filters of Examples 3-5 to 3-8 and Examples 3-10 to 3-13 have a resin film 2 that has low shielding properties in the near-ultraviolet light region of 360 to 400 nm and low transparency in the blue light region of 400 to 430 nm.
  • any one of -7 to 2-14 at least one of the shielding property in the near-ultraviolet light region and the transmittance in the visible light region at a high incident angle was low.
  • the optical filter of Example 3-9 resulted in a large difference in steepness between incident angles of 0 degrees and 30 degrees. This is because the steepness of the optical filter 3-9 depends greatly on the steepness of the dielectric multilayer film at an incident angle of 0 degrees, and is therefore excellent in steepness.
  • the optical filters of Examples 3-4 and 3-14 to 3-17 are any of the resin films of Examples 2-6 and 2-15 to 2-18, which have low shielding properties in the near-ultraviolet region of 360 to 400 nm. By using , the shielding performance in the near-ultraviolet region at high incident angles was low. Since the film thickness of the resin film of the optical filter of Example 3-21 exceeds 3 ⁇ m, it is considered that a resin film having a uniform film thickness cannot be obtained from the results of film thickness distribution evaluation described later.
  • Example 4-1 A dielectric multilayer film (reflective film) in which 42 layers of SiO 2 and TiO 2 were alternately laminated was formed on one main surface of a glass substrate (alkali glass, D263 manufactured by Schott) by vapor deposition. A resin film was formed on the other surface of the glass substrate in the same manner as in Example 2-1, using the dye compound in the amount shown in the table below. After that, a dielectric multilayer film (antireflection film) was formed by alternately laminating SiO 2 and TiO 2 on the resin film to form an optical filter.
  • a dielectric multilayer film antireflection film
  • Example 4-2 to 4-6 An optical filter was produced in the same manner as in Example 4-1, except that the type and content of the dye compound were changed to the values shown in the table below.
  • Each optical filter obtained was subjected to a weather resistance test using a super xenon weather meter manufactured by Suga Test Instruments Co., Ltd.
  • the residual ratio of the IR dye was calculated from the absorption coefficient at 700 nm before and after the weather resistance test.
  • Incidence surface from the side of the anti-reflection film side, irradiation light amount: Irradiated so that the integrated light amount was 80000 J/mm 2 in the wavelength band of 300 to 2450 nm.
  • Examples 4-1 to 4-6 are reference examples.
  • an IR dye residual rate of 60% or more As a guideline for maintaining the performance of the optical filter, it is considered necessary to have an IR dye residual rate of 60% or more. Also, an IR dye retention rate of 60% or more could be achieved. It was found that the UV dye compounds 1 to 4 do not accelerate the deterioration of the IR dyes, since the same level of dye residual rate was obtained as compared with Example 4-6 in which the UV dye was not coexisted. On the other hand, the optical filter of Example 4-5 in which the UV dye compound 5 was coexisted accelerated the deterioration of the IR dye, and the IR dye retention rate was greatly reduced.
  • Example 5-2 to 5-4 A resin film was obtained in the same manner as in Example 5-1, except that the rotational speed was changed to that shown in the table below.
  • the film thickness was measured at 9 points in the center of each of the 9 equally divided surfaces. Calculate the average value of the nine measurement results, and if the ratio to the average value ((actual value/average value) ⁇ 100) is 95% to 105%, the film thickness is uniform and the film thickness distribution is good. I decided there was. The results are shown in the table below. Examples 5-1 to 5-4 are reference examples.
  • Example 5-1 to 5-3 in which the film thickness average value is 3 ⁇ m or less, all measured values are within 95 to 105% of the average value, indicating that uniform film formation is possible.
  • Example 5-4 in which the film thickness average value exceeded 3 ⁇ m, all measured values exceeded the average value by 95 to 105%, resulting in a large film thickness distribution. From the above results, it was found that a uniform resin film can be obtained if the film thickness is 3 ⁇ m or less.
  • the optical filter of the present invention has good ultraviolet light shielding properties such as near-infrared light shielding properties, visible light transmittance, and deterioration of ultraviolet light shielding properties at high incident angles.
  • ultraviolet light shielding properties such as near-infrared light shielding properties, visible light transmittance, and deterioration of ultraviolet light shielding properties at high incident angles.
  • it is useful for information acquisition devices such as cameras and sensors for transport planes, which have become highly sophisticated in recent years.

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