WO2017146413A2 - Article optique et filtre optique le comprenant - Google Patents

Article optique et filtre optique le comprenant Download PDF

Info

Publication number
WO2017146413A2
WO2017146413A2 PCT/KR2017/001688 KR2017001688W WO2017146413A2 WO 2017146413 A2 WO2017146413 A2 WO 2017146413A2 KR 2017001688 W KR2017001688 W KR 2017001688W WO 2017146413 A2 WO2017146413 A2 WO 2017146413A2
Authority
WO
WIPO (PCT)
Prior art keywords
group
absorption
optical filter
carbon atoms
wavelength
Prior art date
Application number
PCT/KR2017/001688
Other languages
English (en)
Korean (ko)
Other versions
WO2017146413A3 (fr
Inventor
최정옥
정준호
정진호
김주영
양선호
Original Assignee
주식회사 엘엠에스
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170007027A external-priority patent/KR101904500B1/ko
Application filed by 주식회사 엘엠에스 filed Critical 주식회사 엘엠에스
Priority to US16/078,728 priority Critical patent/US10767030B2/en
Priority to CN201780022221.0A priority patent/CN109416420B/zh
Publication of WO2017146413A2 publication Critical patent/WO2017146413A2/fr
Publication of WO2017146413A3 publication Critical patent/WO2017146413A3/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters

Definitions

  • the present invention relates to an optical article and an optical filter including the same, and more particularly, to an optical article and an optical filter including the same that can suppress light transmittance in the wavelength range of 800 nm to 1,000 nm.
  • An imaging device using a solid-state imaging device such as a CMOS image sensor (CIS) blocks light in the range of 800 nm to 1,000 nm in the near infrared region detected by the sensor in order to obtain a natural color image as seen by a human eye.
  • CIS CMOS image sensor
  • optical components include reflective near-infrared cut off filters containing a multilayer dielectric film or absorption near-infrared cut off filters using fluorinated phosphate-based glass containing divalent copper ions as coloring components.
  • An object of the present invention is not only to prevent ghosting by selectively and / or effectively block light in the wavelength range of 800 nm to 1,000 nm while having excellent transmittance for light having a wavelength in the visible light range, It is to provide an easy optical component.
  • Another object of the present invention is to provide an optical filter including the optical component.
  • Still another object of the present invention is to provide an imaging device including the optical component.
  • the present invention includes a transparent substrate containing at least one pigment for absorbing near infrared rays in one embodiment, the absorption spectrum measured using a spectrophotometer in the wavelength range of 380nm to 1,200nm (The absorbance spectrum has two or more absorption peaks including the following first and second absorption peaks, the first absorption peak has an absorption maximum lambda max1 in the wavelength range of 650 nm to 750 nm, and the second absorption peak is 830 nm.
  • Absorption value (OD2) at the absorption maximum of the second absorption peak when having an absorption maximum ( ⁇ max2) in the wavelength range of 980 nm and normalizing the absorbance value (OD1) at the absorption maximum of the first absorption peak to be 1. ) Provides an optical article satisfying the following formula 1:
  • Equation 1 0.03 ⁇ OD2 ⁇ 0.36.
  • the present invention provides an optical filter including the optical article.
  • the optical filter according to the present invention includes an optical article having at least two absorption peaks containing at least one near infrared absorption pigment and having first and second absorption peaks in a wavelength range of 380 nm to 1,200 nm, thereby providing a visible light region. It exhibits high transmittance with respect to light having a wavelength and suppresses ghost phenomenon by suppressing transmittance with respect to light having a wavelength in the range of 800 nm to 1,000 nm to 0.6% or less. The production cost is reduced by increasing the yield and productivity at.
  • FIG. 1 is a cross-sectional view showing the structure of an optical article according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing the structure of an optical filter according to another embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing a bent state of the optical filter:
  • a to C and (a) to (g) are as follows.
  • a and B test specimen in the (-) direction
  • C test specimen in the (+) direction
  • Figure 4 is a graph showing the absorbance curve of each of the optical article according to the content of the near infrared absorber according to an embodiment of the present invention.
  • 5 and 6 are graphs showing the spectral transmittances of the first and second selective wavelength reflecting layers according to the exemplary embodiment of the present invention, respectively.
  • FIG. 11 is an image photographed using an image pickup device equipped with an optical filter according to Example 7 and Comparative Example 6 according to an embodiment of the present disclosure.
  • the "visible light” is light in the wavelength region that can be detected by the human eye among electromagnetic waves, and means light in the wavelength range of 380 nm to 750 nm.
  • “near-infrared ray” is an electromagnetic wave which is located outside the end of the red line and has a wavelength longer than visible light, and means light in the wavelength range of 750 nm to 3 ⁇ m.
  • the degree of blocking of the "near-infrared” may be expressed as absorbance with respect to the near-infrared.
  • the "absorption band” means a wavelength range in which light is absorbed, that is, a wavelength having maximum absorbance at the absorption band.
  • the "degree of warpage” is a measure of the degree of warpage of the optical filter, and is formed by connecting the ends of the specimens b in a straight line as shown in FIGS. 3A and 3B. It means the height of the point (f) having the largest value among the heights for any point existing on the inner surface of the specimen (b).
  • the "inner surface of the specimen” refers to a surface of which both sides of the specimen are warped with the smaller length, and the opposite surface is referred to as the "outer surface of the specimen”. The higher the value is, the greater the degree of warpage (c) of the specimen (b).
  • a "bending direction” means the direction to which an optical filter bends, and can represent it in a (+) direction or a (-) direction.
  • the bending point c is the largest on the inner surface of the specimen b based on the surface e formed by connecting the ends of the specimen b in a straight line. If f) is present between the horizontal plane (a) and the center plane (d), it can be said that the deflection of the specimen (b) has a negative direction.
  • the "middle surface (d)" is a surface (e) formed by connecting the end of the specimen (b) with the point (f or g) with the largest deflection degree (c) on the inner surface of the specimen (b) in a straight line (e)
  • a plane existing between) means a plane parallel to plane e at a position where the height of the point f or g is 1/2.
  • the "horizontal plane (a)" is a plane on which the specimen is supported when measuring the degree of warpage of the specimen (b), and is a specimen of a three-dimensional surface measuring apparatus such as an ultra-accuracy 3-D profilometer. And a fixed surface.
  • alkyl group means a substituent derived from a saturated hydrocarbon in a linear or branched form.
  • alkyl group for example, methyl group (ethyl group), ethyl group (ethyl group), n-propyl group (n-propyl group), isopropyl group (iso-propyl group), n-butyl group (n -butyl group, sec-butyl group, t-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group (1,1- dimethylpropyl group), 1,2-dimethylpropyl group (1,2-dimethylpropyl group), 2,2-dimethylpropyl group (2,2-dimethylpropyl group), 1-ethylpropyl group (1-ethylpropyl group), 2- 2-ethylpropyl group, n-hexyl group, 1-methyl-2-ethylpropyl group, 1-ethyl-2-methylpropyl group (1-ethyl-2-methylpropyl group (1-ethyl
  • alkyl group may have 1 to 20 carbon atoms, for example, 1 to 12 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • cycloalkyl group means a substituent derived from a monocyclic saturated hydrocarbon.
  • cycloalkyl group for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group ( cycloheptyl group), cyclooctyl group, and the like.
  • cycloalkyl group may have 3 to 20 carbon atoms, for example, 3 to 12 carbon atoms, or 3 to 6 carbon atoms.
  • aryl group means a monovalent substituent derived from an aromatic hydrocarbon.
  • the "aryl group” for example, a phenyl group (phenyl group), naphthyl group (naphthyl group), anthracenyl group (anthracenyl group), phenanthryl group naphthacenyl group (naphthacenyl group), pyrenyl group (pyrenyl group), tolyl group (tolyl group), biphenyl group (biphenyl group), terphenyl group (terphenyl group), chrycenyl group (chrycenyl group), spirobifluorenyl group (spirobifluorenyl group), fluoranthenyl group ( fluoranthenyl group, fluorenyl group, fluorenyl group, perylenyl group, indenyl group, azulenyl group, heptarenyl group, heptalenyl group, phenalenyl group And phenanthrenyl
  • the "aryl group” may have 6 to 30 carbon atoms, for example, 6 to 10 carbon atoms, 6 to 14 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms.
  • heteroaryl group means “aromatic heterocycle” or “heterocyclic” derived from a monocyclic or condensed ring.
  • the “heteroaryl group” is at least one of nitrogen (N), sulfur (S), oxygen (O), phosphorus (P), selenium (Se) and silicon (Si) as a hetero atom, for example, one, two Dogs, three or four.
  • the "heteroaryl group” for example, pyrrolyl group (pyrrolyl group), pyridyl group (pyridyl group), pyridinyl group (pyridinyl group), pyridazinyl group, pyrimidinyl group (pyrimidinyl group) ), Pyrazinyl group, triazolyl group, tetrazolyl group, tetrazolyl group, benzotriazolyl group, pyrazolyl group, imidazolyl group ), Benzimidazolyl group (benzimidazolyl group), indolyl group (indolyl group), indolinyl group (indolinyl group), isoindolyl group, indolinzinyl group (indolizinyl group), purinyl group ), Inindazolyl group, quinolyl group, isoquinolinyl group, isoquinolinyl group, quinolizinyl
  • thiazolyl group (thiazolyl group), isothiazolyl group (isothiazolyl group), benzothiazolyl group (benzothiazolyl group), benzothiadiazolyl group (benzothiadiazolyl group), phenothia Phenothiazinyl group, isoxazolyl group, furazanyl group, furazanyl group, phenoxazinyl group, oxazolyl group, oxazolyl group, benzoxazolyl group, Oxadiazolyl group, pyrazoloxazolyl group, imidazothiazolyl group, thienofuranyl group, furopyrrolyl group, pyridoxazinyl group and compounds containing at least two heteroatoms such as (pyridoxazinyl group).
  • heteroaryl group may have 2 to 20 carbon atoms, for example, 4 to 19 carbon atoms, 4 to 15 carbon atoms, or 5 to 11 carbon atoms.
  • the heteroaryl group may have a ring member of 5 to 21.
  • aralkyl group means a saturated hydrocarbon substituent having a monovalent substituent derived from an aromatic hydrocarbon at the hydrogen site of the terminal hydrocarbon. That is, the “aralkyl group” refers to an alkyl group in which the chain terminal is substituted with an aryl group, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthalenylmethyl group. ) And a naphthalenylethyl group.
  • the present invention includes a transparent base material containing at least one pigment for absorbing near infrared rays
  • the absorption spectrum measured by using a spectrophotometer in the wavelength range of 380nm to 1,200nm is the first and second Having at least two absorption peaks including an absorption peak, the first absorption peak having an absorption maximum lambda max1 in the wavelength range of 650 nm to 750 nm, and the second absorption peak having an absorption maximum lambda max2 in the wavelength range of 830 nm to 980 nm.
  • the absorbance value (OD1) at the absorption maximum of the first absorption peak is normalized to be 1
  • the absorbance value (OD2) at the absorption maximum of the second absorption peak satisfies Equation 1 below.
  • Equation 1 0.03 ⁇ OD2 ⁇ 0.36.
  • An imaging device using a solid-state imaging device blocks light in the range of 800 nm to 1,000 nm in the near-infrared region sensed by the sensor and obtains 400 nm corresponding to the visible ray region in order to obtain an image of natural color as seen by a human eye.
  • Such optical products may include optical filters such as a near-infrared blocking filter or an absorbing near-infrared blocking filter. In the case of the near-infrared blocking filter, the ghost phenomenon may be caused by internal reflection between the optical filter and the CIS microlens.
  • the optical article according to the present invention may include at least one pigment for absorbing near infrared rays.
  • the optical article includes one or more near-infrared absorbing pigments, exhibits high transmittance with respect to light having a wavelength in the visible light region, and is provided in the optical filter by suppressing transmittance with respect to light having a wavelength in the range of 800 nm to 1,000 nm. Since the thickness of the selective wavelength reflecting layer can be reduced, there is an advantage in that the thickness of the optical filter can be easily reduced.
  • the optical article may have one or more absorption peaks in the wavelength range of 650 nm to 750 nm and the wavelength range of 830 nm to 980 nm, respectively, and the absorption peak may include first and second absorption peaks having absorption maxima ⁇ max1 and ⁇ max2. have.
  • the absorbance value (OD1) at the absorption maximum of the first absorption peak when normalizing the absorbance value (OD1) at the absorption maximum of the first absorption peak to be 1, the absorbance value (OD2) at the absorption maximum of the second absorption peak may be greater than 0.03 and less than 0.36, Specifically 0.035 to 0.05; 0.08 to 0.12; 0.18 to 0.24; 0.34 to 0.35; 0.04 to 0.35; 0.05 to 0.3; 0.1 to 0.3; 0.15 to 0.25; Alternatively, the formula 1 may be satisfied by 0.2 to 0.30.
  • the absorbance value (OD2) at the absorption maximum of the second absorption peak may satisfy the condition of Equation 1 at 0.18 to 0.35.
  • the optical article according to the present invention may include a transparent substrate, and the transparent substrate may have a structure including one or more near-infrared absorbing pigments that absorb light in a wavelength range of 600 nm to 1,000 nm.
  • the optical article may include a transparent substrate 10, and the transparent substrate 10 may include a near-infrared absorbing pigment 11 and a base layer 12. It may include.
  • the near-infrared absorbing pigment 11 is applied to the near-infrared absorbing layers 13, 13a and / or 13b formed on one side and / or both sides of the base layer 12, as shown in FIGS. 1A and 1B. It may be included or may be included in a form uniformly dispersed in the base layer 12 as shown in (c) of FIG.
  • the transparent substrate 10 provided in the optical article according to the present invention will be described in more detail for each component.
  • the substrate layer 12 serves as a base substrate of the transparent substrate and the optical filter including the same, and is not particularly limited as long as it is transparent.
  • the base layer 12 may use a variety of materials known in the art, which may also be appropriately selected and used according to required functions and uses.
  • the base material layer 12 for example, one or more may be selected from glass, a polymer resin, and the like.
  • the polymer resin include polyester resins, polycarbonate resins, acrylic resins, polyolefin resins, cyclic olefin resins, polyimide resins, polyamide resins, and polyurethane resins.
  • the resin may be used in the form of a single sheet, laminated sheet or coextruded material.
  • the base layer 12 may be made of a polymer resin according to an exemplary form, and may include a polyester resin that is advantageous in heat resistance and the like as a base resin.
  • a polyester resin that is advantageous in heat resistance and the like as a base resin.
  • the polyester-based resin at least one selected from the group consisting of polyethylene terephthalate (PET: Polyethylene Naphthalate), polybutylene terephthalate (PBT: Polybutylene Terephthalate) But it is not limited thereto.
  • the base layer 12 may be selected from polyolefin resin, and the polyolefin resin may include, for example, polypropylene (PP).
  • the near-infrared absorbing dye 11 may be used without particular limitation as long as it is a dye, pigment and / or metal complex that absorbs light in the wavelength range of 600 nm to 1,000 nm.
  • the near-infrared absorbing pigment 11 may have an absorption maximum in the 650 nm to 750 nm wavelength range and the 830 nm to 980 nm wavelength range when the absorption spectrum is measured using a spectrophotometer in the wavelength range of 380 nm to 1,200 nm.
  • the first and The second pigment may be used in a uniformly mixed form (see FIGS. 1A and 1C).
  • each of the first and second dyes may be used alone in each of the absorbing layers 13a and 13b. Or uniformly mixed forms (see FIG. 1B).
  • the near-infrared absorbing dye (11) for example, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, benzoporphyrin compounds, squarylium compounds, anthraquinone compounds, and croconium compounds , Dimonium-based compounds, dithiol metal complex compounds and the like.
  • the near-infrared absorbing dye 11 may optionally include any one or more of the compounds represented by the following Chemical Formulas 1 and 2 as the first and second pigments:
  • A is an aminophenyl group; Indolyl methylene group; Or indolinyl, but two A's It has a structure that forms a conjugation (conjugation) with respect to each other, wherein any one or more of the hydrogen present in the aminophenyl group, indolyl methylene group or indolinyl group is independently of each other hydrogen, halogen, hydroxy group, cyano group, nitro Or a carboxyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a sulfonamide group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms An amide group unsubstituted or substituted with a haloalkyl group having 4 to 4 or an aralkyl group having 7 to
  • B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 7 , B 8 , B 9 , B 10 , B 11 , B 12 , B 13 , B 14 , B 15 and B 16 are independent of each other Hydrogen, halogen group, hydroxy group, cyano group, nitro group, carboxyl group, phenoxy group, phenylsulfanyl group, C1-C20 alkyl group, C3-C20 cycloalkyl group, C1-C10 alkoxy group, C1-C10 Alkylamine group or aralkyl group having 7 to 20 carbon atoms,
  • phenoxy group phenylsulfanyl group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkylamine group having 1 to 10 carbon atoms, or aralkyl group having 7 to 20 carbon atoms
  • At least one of hydrogen is a halogen group, a hydroxyl group, a cyano group, an aminophenyl group, a phenoxy group, a phenylsulfanyl group, an indole group, an indolinyl group, a pyridinyl group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or Substituted or unsubstituted with an aralkyl group having 7 to 20 carbon atoms;
  • M is copper, zinc, nickel, titanium, vanadium, indium, gallium, platinum, silicon
  • Chemical Formula 1 may be any one of compounds represented by Chemical Formulas 1a to 1c:
  • a 1 , a 2, and a 3 are each independently hydrogen, a halogen group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon atoms.
  • the content of the near infrared absorbing dye (11) is 0.01 to 10.0 parts by weight based on 100 parts by weight of the resin constituting the matrix of the near infrared absorbing layer (13, 13 (a), 13 (b)); 0.01 to 8.0 parts by weight; Or 0.01 to 5.0 parts by weight.
  • the present invention provides an optical filter including the optical article.
  • the optical filter according to the present invention includes a transparent substrate containing at least one pigment for absorbing near infrared rays; Including a selective wavelength reflection layer formed on one or both surfaces of the transparent substrate, when measuring the transmission spectrum using a spectrophotometer in the wavelength range of 380nm to 1,200nm, the following conditions (A) and (B) may be satisfied:
  • the optical filter according to the present invention includes an optical article containing first and second pigments having an absorption maximum in the wavelength range of 650 nm to 750 nm and the wavelength range of 830 nm to 980 nm, respectively.
  • a light transmittance of about 90% or more can be exhibited in a wavelength range of about 430 nm to 565 nm, which is a visible light region, regardless of the viewing angle.
  • the optical filter transmits light having a wavelength of about 800 nm to 1,000 nm at a maximum transmittance of 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, or 0.6% or less regardless of the incident angle.
  • the optical filter may exhibit a maximum transmittance of 0.6% or less, 0.55% or less, or 0.5% or less for light incident at an angle of incidence of 30 °, and an average transmittance of 0.3% or less, 0.2% or less, or 0.1% or less.
  • the maximum transmittance may be suppressed to 0.1% or less and 0.5% or less, respectively, to satisfy the above conditions (A) and (B).
  • the optical filter according to the present invention has a high transmittance for light having a wavelength in the visible range by including the optical article, and at the same time suppresses the transmittance for light having a wavelength in the range of 800 nm to 1,000 nm to 0.6% or less. It means you can.
  • the optical filter according to the present invention includes a transparent substrate 10 including a near-infrared absorbing pigment 11 and a substrate layer 12, and selected wavelengths positioned on one side and / or both sides of the transparent substrate. It may have a structure including a reflective layer 20 and / or 30.
  • the transparent substrate 10 includes a base layer 12 to serve as a base substrate of the optical filter.
  • the transparent substrate 10, that is, the optical article may have two or more absorption peaks each having an absorption maximum in the wavelength range of 650 nm to 750 nm and the wavelength range of 830 nm to 980 nm, including one or more near infrared absorption pigments. It may include a first and a second absorption peak.
  • the absorbance value (OD1) at the absorption maximum of the first absorption peak to be 1
  • the absorbance value (OD2) at the absorption maximum of the second absorption peak may be greater than 0.03 and less than 0.36.
  • the formula 1 may be satisfied by 0.2 to 0.3.
  • the absorbance value (OD2) at the absorption maximum of the second absorption peak is 0.18 to 0.35 to satisfy the condition of Equation 1.
  • the selective wavelength reflecting layers 20 and 30 reflect the light having a wavelength of 700 nm or more, specifically, a wavelength in the range of 700 nm to 1,100 nm among the light incident on the optical filter. It serves to prevent the light in the range from being incident on the image sensor or to prevent the light in the visible light region in the 400 nm to 700 nm wavelength range from being reflected. That is, the selective wavelength reflecting layers 20 and 30 serve as an near infrared reflecting layer (IR layer) reflecting near infrared rays and / or an anti-reflection layer (AR layer) for preventing visible light from being reflected. Can be performed.
  • IR layer near infrared reflecting layer
  • AR layer anti-reflection layer
  • the selective wavelength reflection layers 20 and 30 may have a structure such as a dielectric multilayer film in which a high refractive index layer and a low refractive index layer are alternately stacked, and an aluminum deposition film; Precious metal thin film; Alternatively, the method may further include a resin film in which one or more fine particles of indium oxide and tin oxide are dispersed.
  • the selective wavelength reflecting layers 20 and 30 may have a structure in which a dielectric layer (not shown) having a first refractive index and a dielectric layer (not shown) having a second refractive index are alternately stacked, and having the first refractive index.
  • the refractive index deviation of the dielectric layer and the dielectric layer having the second refractive index is 0.2 or more; 0.3 or more; Or 0.2 to 1.0.
  • the high refractive index layer and the low refractive index layer of the selective wavelength reflecting layers 20 and 30 are not particularly limited as long as the refractive index deviations of the high refractive index layer and the low refractive index layer are included in the above-described range, but specifically, the high refractive index is high.
  • the layer comprises one or more selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide and indium oxide having a refractive index of 1.6 to 2.4.
  • the indium oxide may further include a small amount of titanium oxide, tin oxide, cerium oxide, and the like.
  • the low refractive index layer may include at least one member selected from the group consisting of silicon dioxide, lanthanum fluoride, magnesium fluoride, and sodium hexafluoride sodium (cryolite, Na 3 AlF 6 ) having a refractive index of 1.3 to 1.6.
  • the selective wavelength reflecting layers 20 and 30 may be formed on one surface of the transparent substrate 10; In some cases, the first and second selective wavelength reflecting layers 20 and 30 are formed on both surfaces of the transparent substrate 10 so that the first selective wavelength reflecting layer is positioned on the first main surface of the transparent substrate 10.
  • the second selective wavelength reflecting layer may be disposed on the second main surface of (10).
  • the thickness of each of the selective wavelength reflecting layers 20 and 30 may satisfy Equation 3 below:
  • D1 represents the thickness of the first selective wavelength reflecting layer
  • D2 represents the thickness of the second selective wavelength reflecting layer
  • the thickness ratio of the first and second selective wavelength reflecting layers 20 and 30 is 0.8 to 1.2; 0.8 to 1.0; 0.9 to 1.1; 1.0 to 1.2; 0.85 to 1.0; Alternatively, the condition of Equation 3 may be satisfied by 1.1 to 1.2.
  • each of the selective wavelength reflecting layers 20 and 30 may have a dielectric multilayer structure of 30 layers or less.
  • Equation 4 can be satisfied:
  • Equation 4 P1 represents the number of stacked multilayer dielectric films forming the first selective wavelength reflecting layer, and P2 represents the number of laminated multilayer dielectric films forming the second selective wavelength reflecting layer.
  • the first and second selective wavelength reflecting layers 20 and 30 are 30 layers or less; 29 layers or less; 28 layers or less; 27 layers or less; 26 layers or less; Or 25 or less dielectric layers, wherein the variation in the number of layers is less than 6 layers, 1 to 5 layers, and 2 to 5 layers; 3 to 5 layers; 1 to 3 layers; 0 to 3 layers; Alternatively, the conditions of Equation 4 may be satisfied with 2 to 4 layers.
  • the imaging apparatus since the warpage phenomenon generated during the manufacture of the optical filter can be improved by controlling the ratio of the variation and thickness of the number of stacked layers of the first and second selective wavelength reflecting layers 20 and 30 within the above range, the imaging apparatus including the same There is an advantage that can prevent the assembly failure due to the bending of the optical filter.
  • the conventional optical filter a near-infrared reflective layer having a dielectric multilayer structure is formed thick to block light having a wavelength of 700 nm or more.
  • the conventional optical filter is not sufficient to block light in the region of 800 nm to 1,000 nm, and due to the thick dielectric dielectric film, ghost phenomenon occurs or thinning is difficult. there was.
  • the optical filter according to the present invention is 800 nm by providing the transparent base material 10, that is, the optical article according to the present invention, comprising the base material layer 12 and at least one near infrared absorbing dye 11 absorbing near infrared rays.
  • the optical filter has an advantage of improving the bending phenomenon of the optical filter, which may occur in manufacturing the optical filter, by controlling the number and thickness of laminated layers of the selective wavelength reflecting layer.
  • the present invention provides an imaging device including the optical filter.
  • An imaging device comprises an optical article containing an optical article containing a first dye having an absorption maximum in the wavelength range of 650 nm to 750 nm and a second dye having an absorption maximum in the wavelength range of 830 nm to 980 nm. It is possible to suppress the ghost phenomenon when taking an image by displaying a high transmittance with respect to light having a wavelength in the visible ray region including a filter and a transmittance of 0.6% or less with respect to light having a wavelength in the range of 800 nm to 1,000 nm.
  • the thickness of the selective wavelength reflecting layer provided in the optical filter can be lowered, the optical filter can be thinned and the image pickup device can be downsized.
  • the warpage phenomenon generated during the manufacture of the optical filter is improved to lower the assembly failure rate in the assembly process has the advantage of improving the yield and productivity.
  • the solid-state imaging device is an electronic device to which the solid-state imaging device is applied, for example, a digital still camera, a mobile phone camera, a digital video camera, a PC camera, a surveillance camera, a car camera, a portable information terminal, a personal computer, It can be usefully used for video games, medical devices, USB memory devices, portable game machines, fingerprint authentication systems, and digital music players.
  • an optical article having first and second absorption peaks was prepared as follows.
  • polymethyl methacrylate (PMMA) resin was used as the resin, and cyclohexanone was used as the organic solvent. After stirring for more than 24 hours to prepare a near-infrared absorbing solution.
  • the prepared near-infrared absorbing solution was applied to both sides of a polyethylene terephthalate film (PET film, purchased by Toyo Spun Yarn, trade name A4100) having a thickness of 0.1 mm, and cured at 120 for 50 minutes to form a near-infrared absorbing layer on both sides as shown in FIG.
  • the formed optical article was prepared.
  • the near infrared absorber A and the near infrared absorber B having an absorption maximum in the wavelength range of 702 ⁇ 5 nm and 905 ⁇ 5 nm the near infrared absorbing dyes represented by Formula 1 and Formula 2 were used, respectively.
  • the absorption spectrum according to the wavelength was measured in the wavelength range of 380 nm to 1,200 nm using a spectrophotometer. .
  • the absorbance at the absorption maximum of the peak (first absorption peak) in the wavelength range of 650 nm to 750 nm (the first absorption peak) and the absorption peak at the wavelength range of the 830 nm to 980 nm (second absorption peak) The absorbance value at the absorption maximum of the second absorption peak (OD2) when the absorbance curve was normalized to derive the absorbance at the absorption maximum of 1 and the absorbance value (OD1) at the absorption maximum of the first absorption peak is 1. ) was calculated.
  • Table 1 the absorbance curve for each of the optical article according to the preparation example disclosed in Table 1 is shown in FIG. Referring to Table 1 and Figure 4, it can be seen that the absorbance value OD2 represents a value in the range of 0.04 to 0.35.
  • E-beam evaporator By using an electron beam evaporator (E-beam evaporator) to alternately deposit SiO 2 and Ti 3 O 5 on the first main surface of the optical article prepared in Preparation Examples 1 to 4 at 110 ⁇ 5 °C temperature of the dielectric multilayer film structure A selective wavelength reflection layer was formed. Subsequently, SiO 2 and Ti 3 O 5 are alternately deposited on the second main surface of the optical article using an E-beam evaporator at 110 ⁇ 5 ° C. to form a second selective wavelength reflecting layer having a dielectric multilayer structure. An optical filter having the same structure as in (c) was prepared. In this case, the number of laminated layers and the thickness of the stacked first and second selective wavelength reflecting layers are shown in Table 2 below. Here, the thickness means the total thickness of each of the first and second selective wavelength reflecting layers, and the unit is micrometer ( ⁇ m).
  • Example 2 Preparation Example 1 23 2.8 26 3.1 0.90 3
  • Example 3 Preparation Example 1 28 3.5 28 3.4 1.03 0
  • Example 7 Preparation Example 4 23 2.8 26 3.1 0.90 3
  • the numerical value is in the range of 0.8 to 1.2, specifically, 0.82 to 1.15.
  • the first and second selective wavelength reflecting layers may have a structure in which SiO 2 and Ti 3 O 5 are alternately stacked.
  • the first selective wavelength reflecting layer has a 23-31 layer structure, the thickness thereof is in the range of 2.8 to 3.9 ⁇ m
  • the second selective wavelength reflecting layer has a 26-28 layer structure, and the thickness thereof may be in the range of 3.1 to 3.4 ⁇ m.
  • stacked structures and thicknesses of the first selective reflecting reflective layer and the second selective wavelength reflecting layer applied to Example 1 are shown in Tables 3 and 4, respectively. Respectively.
  • the spectral transmittance of the first selective wavelength reflective layer disclosed in Table 3 is shown in FIG. 5
  • the spectral transmittance of the second selective wavelength reflective layer disclosed in Table 4 is shown in FIG. 6.
  • Absorbance values of the optical articles according to Comparative Preparation Examples 1 to 3 were calculated in substantially the same manner as those for measuring the absorbance of the optical articles according to Preparation Examples 1 to 4 described above. The results are shown in Table 5 above. In addition, absorbance curves of the optical articles according to Comparative Preparation Examples 1 to 3 disclosed in Table 5 are shown in FIG. 4. Referring to Table 5 and Figure 5, it can be seen that the absorbance value OD2 is out of the range of 0.04 to 0.35.
  • E-beam evaporator By using an electron beam evaporator (E-beam evaporator) at 110 ⁇ 5 °C to alternately deposit SiO 2 and Ti 3 O 5 on the first main surface of the optical article prepared in Comparative Preparation Examples 1 to 3 first of the dielectric multilayer film structure A selective wavelength reflection layer was formed. Subsequently, SiO 2 and Ti 3 O 5 are alternately deposited on the second main surface of the optical article at 110 ⁇ 5 ° C. using an E-beam evaporator to form a second selective wavelength reflective layer having a dielectric multilayer structure. An optical filter having the same structure as in (c) was prepared. At this time, the number and thickness of laminated layers of the first and second selective wavelength reflecting layers formed on the optical filter are shown in Table 6 below. Here, the thickness means the total thickness of each of the first and second selective wavelength reflecting layers, and the unit is micrometer ( ⁇ m).
  • the transmission spectra of the optical filters prepared in Examples 2, 5 to 7 and Comparative Examples 4 to 6 were measured using a spectrophotometer in the wavelength range of 380 nm to 1,200 nm.
  • the transmittance of light incident on the optical filter in the vertical direction (incidence angle: 0 °) and light incident on the optical filter incident in the direction perpendicular to the optical filter (incidence angle: 30 °) is measured, and the visible angle is determined according to the incident angle.
  • the transmittances of light and near infrared were derived. The results are shown in Table 7 and FIGS. 7 to 10.
  • the average visible light transmittance means an arithmetic mean value of the transmittance of each wavelength in the wavelength range of 430 nm to 565 nm
  • the near infrared mean transmittance means an arithmetic mean value of the transmittance of each wavelength in the wavelength range of 800 nm to 1,000 nm.
  • Maximum transmittance means the maximum value of the transmittance in the 800 nm to 1,000 nm wavelength range.
  • Table 7 shows the absorbance values OD2 for each of the optical articles used in Examples 2, 5 to 7, and Comparative Examples 4 to 6.
  • the optical filter according to the present invention is excellent in transmittance to light in the visible light region, and can effectively block light having a wavelength of 800 nm or more.
  • examples of the optical filters manufactured in Examples 2 and 5 to 7 each include light having a wavelength range of 800 nm to 1,000 nm when incident angle is incident at 0 ° and incident angle is 30 °.
  • the near infrared maximum transmittance was 0.1% or less and 0.6% or less, respectively, and both cases showed very low transmittance of 0.6% or less.
  • the optical filter of Comparative Example 4 using an optical article having an absorbance value of OD2 of 0.00 and an optical filter of Comparative Example 6 using an optical article having an absorbance value of OD2 of 0.02 had a maximum transmittance of 0.6% for light having an incident angle of 30 °. It was found to exceed. If it exceeds 0.6%, there is a high possibility of ghosting when the image is taken under outdoor natural or indoor illumination light.
  • the optical filters manufactured in Examples 2 and 5 to 7 have an average transmittance when light having a wavelength range of 430 nm to 565 nm, which is a visible light region, is incident at an incident angle of 0 °. More than 80%. In particular, in the case of light incident at an angle of incidence of 30 °, the average transmittance was found to be 70% or more. On the other hand, the optical filter of Comparative Example 5 using the optical article having an absorbance value OD2 of 0.60 showed that the average transmittance of light incident at an incident angle of 30 ° was less than 70%. If the transmittance is lowered to 70% or less in the visible light region, there is a high possibility of ghosting when the image is taken.
  • the optical filter according to the present invention has excellent transmittance with respect to light in the visible light region and can effectively block light having a wavelength of 800 nm or more.
  • the optical filter using the optical article according to the present invention having an absorbance value OD2 of 0.03 to 0.36 provides excellent blocking performance with respect to light having a wavelength of 800 nm or more with high visible light transmittance.
  • the degree of warpage and direction indicated were measured.
  • the first selective wavelength reflecting layer of the optical filter is fixed so as to contact the horizontal plane of the roughness system and the heights of the points present on the fixed optical filter surface based on the horizontal plane were measured.
  • the temperature of the chamber to which the optical filter is fixed is 23 °C
  • the relative humidity was 60%
  • the vibration acceleration was 0.5 cm / s 2
  • the measured results are shown in Table 8 below.
  • the optical filter according to the present invention can improve the warpage by adjusting the number and thickness of laminated layers of the selective wavelength reflecting layer.
  • ) of the number of laminated layers of the first and second selective wavelength reflecting layers formed on the surface of the optical article is less than six layers;
  • the optical filters of Examples 1 to 4 having a thickness ratio (D1 / D2) of more than 0.8 and less than 1.2 were found to have a warping degree of about 7.0 ⁇ m or less regardless of the direction.
  • ) of the number of laminated layers of the first and second selective wavelength reflecting layers exceeds 6 layers; It was confirmed that the optical filters of Comparative Examples 1 to 3 in which the ratio of thickness (D1 / D2) was less than 0.8 or more than 1.2 had a large warpage phenomenon exceeding 7.0 ⁇ m.
  • Table 8 shows the assembly failure rate in the assembling process when assembling the optical filter (width 5.7 mm ⁇ length 4.6 mm) manufactured in Examples 1 to 4 and Comparative Examples 1 to 3 to the imaging device.
  • Table 8 shows the assembly failure rate in the assembling process when assembling the optical filter (width 5.7 mm ⁇ length 4.6 mm) manufactured in Examples 1 to 4 and Comparative Examples 1 to 3 to the imaging device.
  • FIG. 11B illustrates an image captured by the image pickup device equipped with the optical filter according to Comparative Example 6, and a strong ghost phenomenon can be seen in the lower region of the image center.
  • FIG. 11A a ghost phenomenon does not appear in the image photographed by the image pickup device equipped with the optical filter according to the seventh embodiment.
  • the optical filter according to the present invention exhibits high transmittance with respect to light having a wavelength in the visible light region and suppresses ghosting by suppressing transmittance with respect to light having a wavelength in the range of 800 nm to 1,000 nm to 0.6% or less. Can be.
  • the warpage phenomenon of the optical filter is improved by controlling the number and thickness of the selective wavelength reflecting layer to be laminated, there is an advantage that the assembly failure rate due to the warpage of the optical filter in the imaging device assembly process can be significantly lowered.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optical Filters (AREA)

Abstract

La présente invention concerne un article optique et un filtre optique le comprenant. Le filtre optique comprend un article optique contenant un ou plusieurs colorants absorbant le proche infrarouge et ayant deux pics d'absorption ou plus comprenant un premier pic d'absorption et un second pic d'absorption dans une plage de longueurs d'onde de 380 nm à 1 200 nm, le filtre optique présentant alors des avantages en ce que la transmissivité est élevée par rapport à la lumière ayant la longueur d'onde d'une région de lumière visible et en ce que la transmissivité est supprimée jusqu'à 0,6 % ou moins par rapport à la lumière ayant une longueur d'onde dans la plage de 800 nm à 1 000 nm, si bien que les problèmes d'image parasite peuvent être empêchés, et que le rendement et la productivité peuvent être améliorés en réduisant la médiocrité de l'assemblage provoquée par la flexion du filtre optique lors d'un procédé d'assemblage d'un dispositif d'imagerie.
PCT/KR2017/001688 2016-02-24 2017-02-16 Article optique et filtre optique le comprenant WO2017146413A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US16/078,728 US10767030B2 (en) 2016-02-24 2017-02-16 Optical article and optical filter comprising same
CN201780022221.0A CN109416420B (zh) 2016-02-24 2017-02-16 光学制品及其光学滤波器

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160021622 2016-02-24
KR10-2016-0021622 2016-02-24
KR1020170007027A KR101904500B1 (ko) 2016-02-24 2017-01-16 광학물품 및 이를 포함하는 광학필터
KR10-2017-0007027 2017-01-16

Publications (2)

Publication Number Publication Date
WO2017146413A2 true WO2017146413A2 (fr) 2017-08-31
WO2017146413A3 WO2017146413A3 (fr) 2018-08-02

Family

ID=59685397

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/001688 WO2017146413A2 (fr) 2016-02-24 2017-02-16 Article optique et filtre optique le comprenant

Country Status (1)

Country Link
WO (1) WO2017146413A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109932773A (zh) * 2017-12-19 2019-06-25 张家港康得新光电材料有限公司 一种可见光截止膜、其制备方法和应用
CN111108414A (zh) * 2017-09-28 2020-05-05 株式会社Lms 光学物品以及包括该光学物品的光学滤波器
CN112368612A (zh) * 2018-07-03 2021-02-12 株式会社Lms 指纹识别传感器用光学基板以及包括其的光学滤波器
CN114120832A (zh) * 2021-11-23 2022-03-01 武汉华星光电技术有限公司 显示面板
CN114637066A (zh) * 2018-02-05 2022-06-17 Ａｇｃ株式会社 滤光片以及成像装置

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103608705B (zh) * 2011-06-06 2016-10-12 旭硝子株式会社 滤光片、固体摄像元件、摄像装置用透镜和摄像装置
CN105754367A (zh) * 2011-10-14 2016-07-13 Jsr株式会社 固体摄影装置用滤光器及使用该滤光器的固体摄影装置及照相机模块
CN108761612B (zh) * 2012-08-23 2021-04-06 Ａｇｃ株式会社 近红外线截止滤波器和固体摄像装置
KR101527822B1 (ko) * 2013-09-06 2015-06-10 주식회사 엘엠에스 광학 필터 및 이를 포함하는 촬상 장치
KR101453469B1 (ko) * 2014-02-12 2014-10-22 나우주 광학 필터 및 이를 포함하는 촬상 장치

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111108414A (zh) * 2017-09-28 2020-05-05 株式会社Lms 光学物品以及包括该光学物品的光学滤波器
US11698480B2 (en) 2017-09-28 2023-07-11 Lms Co., Ltd. Optical product and optical filter including same
CN109932773A (zh) * 2017-12-19 2019-06-25 张家港康得新光电材料有限公司 一种可见光截止膜、其制备方法和应用
CN114637066A (zh) * 2018-02-05 2022-06-17 Ａｇｃ株式会社 滤光片以及成像装置
CN112368612A (zh) * 2018-07-03 2021-02-12 株式会社Lms 指纹识别传感器用光学基板以及包括其的光学滤波器
CN112368612B (zh) * 2018-07-03 2022-10-21 株式会社Lms 指纹识别传感器用光学基板以及包括其的光学滤波器
CN114120832A (zh) * 2021-11-23 2022-03-01 武汉华星光电技术有限公司 显示面板
CN114120832B (zh) * 2021-11-23 2023-03-21 武汉华星光电技术有限公司 显示面板

Also Published As

Publication number Publication date
WO2017146413A3 (fr) 2018-08-02

Similar Documents

Publication Publication Date Title
WO2017146413A2 (fr) Article optique et filtre optique le comprenant
WO2015122595A1 (fr) Filtre optique et dispositif d'imagerie le comprenant
KR101852804B1 (ko) 적외선 센서, 근적외선 흡수 조성물, 감광성 수지 조성물, 화합물, 근적외선 흡수 필터 및 촬상 장치
JP6183041B2 (ja) 近赤外線カットフィルタ
KR101903884B1 (ko) 근적외선 차단 필터 및 근적외선 차단 필터를 포함하는 장치
WO2019066398A2 (fr) Article optique et filtre optique le comprenant
JPWO2017164024A1 (ja) 光学フィルターおよび光学フィルターを用いた装置
KR101904500B1 (ko) 광학물품 및 이를 포함하는 광학필터
WO2015034217A1 (fr) Filtre optique et dispositif d'imagerie le comprenant
WO2018190560A1 (fr) Article optique et filtre optique le comprenant
WO2023008291A1 (fr) Filtre optique
TW202113424A (zh) 光學構件及相機模組
KR20180062380A (ko) 광학 필터, 카메라 모듈 및 전자 장치
WO2016148518A1 (fr) Filtre optique et dispositif d'imagerie le comprenant
US11686892B2 (en) Combination structures and optical filters and image sensors and camera modules and electronic devices
US20230170364A1 (en) Combination structures and optical filters and image sensors and camera modules and electronic devices
TWI754100B (zh) 濾光器及攝像裝置
WO2018124756A1 (fr) Produit optique pour filtre de coupure proche infrarouge inclus dans un module de caméra, et filtre de coupure proche infrarouge pour module de caméra, comprenant celui-ci
US20210072439A1 (en) Combination structures and optical filters and image sensors and camera modules and electronic devices
TWI813759B (zh) 光學濾波器
WO2020009384A1 (fr) Disque optique pour capteur de reconnaissance d'empreinte digitale et filtre optique le comprenant
KR20180091208A (ko) 적외선 투과 필터 및 이를 포함하는 홍채 인식 및 일반 영상촬영용 촬상 장치
WO2018043955A1 (fr) Article optique pour filtre de coupure dans le proche infrarouge inclus dans un module d'appareil photographique et filtre de coupure dans le proche infrarouge de module d'appareil photographique comprenant celui-ci
JP7342958B2 (ja) 光学フィルタおよび撮像装置
WO2022255791A1 (fr) Module de lentille et dispositif d'affichage le comprenant

Legal Events

Date Code Title Description
NENP Non-entry into the national phase in:

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17756751

Country of ref document: EP

Kind code of ref document: A2

122 Ep: pct application non-entry in european phase

Ref document number: 17756751

Country of ref document: EP

Kind code of ref document: A2