WO2017146413A2 - Optical article and optical filter comprising same - Google Patents

Abstract

The present invention relates to an optical article and an optical filter comprising the same. The optical filter comprises an optical article containing one or more near-infrared absorbing dyes and having two or more absorption peaks comprising a first absorption peak and a second absorption peak in a wavelength range of 380 nm to 1,200 nm whereby the optical filter has advantages in that transmissivity is high with respect to light having the wavelength of a visible light region and transmissivity is suppressed to 0.6% or less with respect to light having a wavelength in the range of 800 nm to 1,000 nm so that ghost image problems can be prevented, and a yield and productivity can be improved through the reduction of poor assembly caused by the bending of the optical filter in an imaging device assembling process.

Description

Optical article and optical filter including the same

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. There is an essential need for an optical component that can transmit light in the range of nm to 600 nm to approximate correction to human visibility.

Examples of such 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.

However, in the case of the reflective near-infrared cut filter, which is conventionally used, an unintended image is not generated when the image is captured by the imaging device due to the internal reflection between the optical filter and the lens of the solid-state image sensor, specifically the optical filter and the microlens of the CIS. Since the phenomenon to be picked up (hereinafter, referred to as "ghost phenomenon" or "ghost image") occurs severely, there is a limit that cannot be applied to a high pixel camera module of 5 megapixels or more.

In addition, in the case of a conventional absorption near-infrared cut filter, the effect of blocking the wavelength in the range of 800 nm to 1,000 nm is good, but due to the characteristics of the material, the durability is weak, making it difficult to thin and to break.

Therefore, there is an urgent need for the development of an optical component that can block light having a wavelength in the range of 800 nm to 1,000 nm and can be made thin.

SUMMARY OF THE INVENTION 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.

In order to solve the object of the present invention, 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 (λmax2) 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.

In another embodiment, 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.

1 is a cross-sectional view showing the structure of an optical article according to an embodiment of the present invention.

2 is a cross-sectional view showing the structure of an optical filter according to another embodiment of the present invention.

3 is a cross-sectional view showing a bent state of the optical filter:

Here, A to C and (a) to (g) are as follows.

A and B: test specimen in the (-) direction, C: test specimen in the (+) direction,

(a): horizontal plane, (b): specimen,

(c): degree of warpage, (d): midplane,

(e): cotton comprising the ends of the specimen,

(f) and (g): The point where the degree of warpage is greatest on the inner surface of the specimen.

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.

7 to 10 show the spectral transmittances measured in the wavelength range of 300 nm to 1,200 nm for the optical filters prepared in Examples 5, 7, 7, and 4 according to the present invention. It is a graph shown.

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.

As the inventive concept allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description.

However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In the present invention, the terms "comprise", "having" or "comprise" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification. Or other features or numbers, steps, operations, components, parts or combinations thereof in any way should not be excluded in advance.

In addition, it is to be understood that the accompanying drawings in the present invention are shown to be enlarged or reduced for convenience of description.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings, and the same or corresponding components will be given the same reference numerals regardless of the reference numerals, and redundant description thereof will be omitted.

In the present invention, 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.

In addition, in the present invention, "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 μm. In the present invention, the degree of blocking of the "near-infrared" may be expressed as absorbance with respect to the near-infrared. In this case, the absorbance OD is defined as a value obtained by taking a commercial log with respect to Io / I when the intensity of incident light when the light passes through the absorbing medium is Io and the intensity of light passing through is I. That is, it means a value expressed as absorbance (OD) = log (Io / I). The absorbance can be calculated using a spectrophotometer.

In addition, in the present invention, the "absorption band" means a wavelength range in which light is absorbed, that is, a wavelength having maximum absorbance at the absorption band.

In addition, in the present invention, 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). In this case, 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).

In addition, in this invention, a "bending direction" means the direction to which an optical filter bends, and can represent it in a (+) direction or a (-) direction. Specifically, as shown in FIGS. 3A and 3B, 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. On the contrary, as shown in C of FIG. 3, the point (g) having the largest degree of warpage (c) 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 (g). If () does not exist between the horizontal plane (a) and the center plane (d), it can be said that the deflection of the specimen (b) has a (+) direction.

At this time, 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.

In addition, 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.

Furthermore, in the present invention, "alkyl group" means a substituent derived from a saturated hydrocarbon in a linear or branched form.

At this time, as the "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), 1,1,2-trimethylpropyl group, 1-propylpropyl group, 1-methylbutyl group (1 -methylbutyl group), 2-methylbutyl group, 1,1-dimethylbutyl group (1,1-dimethylbutyl group), 1,2-dimethylbutyl group (1,2-dimethylbutyl group), 2 , 2-dimethylbutyl group (2,2-dimet hylbutyl group), 1,3-dimethylbutyl group (1,3-dimethylbutyl group), 2,3-dimethylbutyl group (2,3-dimethylbutyl group), 2-ethylbutyl group (2-ethylbutyl group), 2- Methyl pentyl group (2-methylpentyl group), 3-methylpentyl group, etc. are mentioned.

In addition, the "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.

In addition, in the present invention, "cycloalkyl group" means a substituent derived from a monocyclic saturated hydrocarbon.

As the "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.

In addition, the "cycloalkyl group" may have 3 to 20 carbon atoms, for example, 3 to 12 carbon atoms, or 3 to 6 carbon atoms.

Further, in the present invention, "aryl group" means a monovalent substituent derived from an aromatic hydrocarbon.

At this time, 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 group.

In addition, 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.

In addition, in the present invention, "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.

At this time, 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 group, phthalazinyl group, naphthyridinyl group ( naphthylidinyl group), quinoxalinyl group, quinazolinyl group, cinnolinyl (cinnolinyl group), pteridinyl group (pteridinyl group), imidazotriazinyl group, acridinyl group, acridinyl group, phenanthridinyl group, carbazolyl group, carbazolyl group Carbazolinyl group, pyrimidinyl group, phenanthrolinyl group, phenanthrolinyl group, phenazinyl group, imidazopyridinyl group, imidazopyrimidinyl group A nitrogen-containing heteroaryl group including a pyrazolopyridinyl group and the like; Sulfur-containing heteroaryl groups including thienyl group, benzothienyl group, dibenzothienyl group and the like; Furyl group, pyranyl group, cyclopentapyranyl group, cyclopentapyranyl group, benzofuranyl group, isobenzofuranyl group, dibenzofuranyl group, dibenzofuranyl group, benzo Oxygen-containing heteroaryl group containing a dioxole group, a benzotrioxole group, etc. are mentioned.

In addition, as a specific example of the "heteroaryl group", 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).

Furthermore, the "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. For example, when including a hetero atom, the heteroaryl group may have a ring member of 5 to 21.

In addition, in the present invention, "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.

Hereinafter, the present invention will be described in detail.

<Optical article>

The present invention includes a transparent base material containing at least one pigment for absorbing near infrared rays in one embodiment, 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. In the case where 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. Provides:

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. There is an indispensable need for an optical article that can transmit light in the range of 600 nm to approximate correction to human visibility. 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. There is a limit that can not be applied to high pixel camera module of more than 5 megapixels because it occurs badly. In addition, in the case of the absorption type near-infrared cut filter using a fluorophosphate-based glass containing divalent copper ions as a coloring component, the material is weak in durability due to the characteristics of the material, and thus it is difficult to be thinned and broken; In addition, there is a limit that is difficult to selectively suppress the transmittance of light having a wavelength in the range of 800 nm to 1,000 nm.

In order to overcome this problem, 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 λmax1 and λmax2. have. In addition, 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. Preferably, 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.

1 is a cross-sectional view showing the structure of an optical article according to the present invention. Referring to FIGS. 1A to 1C, 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. At this time, 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.

Hereinafter, the transparent substrate 10 provided in the optical article according to the present invention will be described in more detail for each component.

First, in the transparent substrate according to the present invention, 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. As the base material layer 12, for example, one or more may be selected from glass, a polymer resin, and the like. Examples of 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.

In addition, 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. And as an example of 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. As another example, the base layer 12 may be selected from polyolefin resin, and the polyolefin resin may include, for example, polypropylene (PP).

Next, in the transparent substrate according to the present invention, 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.

As an example, 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. Pigments having, specifically, the first and second pigments having an absorption maximum (λ max1 and λ max2) in the wavelength range of 650nm to 750nm and 830nm to 980nm, respectively.

Here, when the near infrared absorbing dye 11 is included in the near infrared absorbing layer 13 formed on one surface of the base layer 12 or dispersed in the base layer 12 as described above, the first and The second pigment may be used in a uniformly mixed form (see FIGS. 1A and 1C). In addition, when the near-infrared absorbing dye 11 is included in the near-infrared absorbing layers 13a and 13b formed on both sides of the base layer 12, 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).

In addition, as 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. As one example, 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:

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, 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 20 carbon atoms;

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,

Existing in the 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, oxotitanium or oxovanadium.

Specifically, Chemical Formula 1 may be any one of compounds represented by Chemical Formulas 1a to 1c:

[Formula 1a]

[Formula 1b]

[Formula 1c]

In 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. An amide unsubstituted or substituted with an alkoxy group having 1 to 6, an aralkyl group having 7 to 20 carbon atoms, a sulfonamide group, or an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms It is.

Further, 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.

<Optical filter>

In another embodiment, the present invention provides an optical filter including the optical article.

As one example, 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:

(A) a maximum transmittance of 0.3% or less for light incident in a direction perpendicular to the optical filter in the wavelength range of 800 nm to 1,000 nm,

(B) In the 800 nm to 1,000 nm wavelength region, the maximum transmittance with respect to light incident in a direction perpendicular to the optical filter at an angle of 30 degrees is 0.6% or less.

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. (An angle formed with the vertical direction of the optical filter), that is, 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. In addition, 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. It can be suppressed. In particular, 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. Can be represented. As an example, when measuring a transmission spectrum for light having an incident angle of 0 ° and 30 ° using a spectrophotometer in the wavelength range of 300 nm to 1,200 nm for the optical filter, 800 nm to 1,000 nm In the wavelength region, 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).

This shows that 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.

2 is a cross-sectional view showing the structure of an optical filter according to an embodiment of the present invention. Referring to FIG. 2, 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.

Hereinafter, each component of the optical filter according to the present invention will be described in more detail with reference to FIG. 2.

First, in the optical filter according to the present invention, 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. In addition, 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. As from 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 0.3. Preferably, 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. Under the above conditions, it is possible to selectively and / or effectively absorb light having a wavelength of 700 nm or more, specifically, a wavelength in the range of 800 nm to 1,000 nm, of the incident light, and also provide high transmittance for light in the visible region.

Next, in the optical filter according to the present invention, 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.

In this case, 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. For example, 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.

Further, 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. In addition, 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.

Furthermore, 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).

In addition, in one embodiment, when the selective wavelength reflecting layer includes the first and second selective wavelength reflecting layers 20 and 30, the thickness of each of the selective wavelength reflecting layers 20 and 30 may satisfy Equation 3 below:

0.8 <D1 / D2 <1.2

In Equation 3, D1 represents the thickness of the first selective wavelength reflecting layer, and D2 represents the thickness of the second selective wavelength reflecting layer.

Specifically, 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.

As another example, when the selective wavelength reflecting layer includes the first and second selective wavelength reflecting layers 20 and 30, each of the selective wavelength reflecting layers 20 and 30 may have a dielectric multilayer structure of 30 layers or less, The condition of Equation 4 can be satisfied:

[Equation 4] 0 ≤ | P1-P2 | <6

In 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.

Specifically, 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.

According to the present invention, 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.

In 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. However, 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. However, 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. Since the light having the above wavelength can be effectively blocked, the number and thickness of the selective wavelength reflecting layers 20 and 30 can be lowered to the above range, so that the ghost phenomenon is improved and the optical filter 10 can be easily thinned. In addition, 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.

<Solid Imaging Device>

Furthermore, in an embodiment, the present invention provides an imaging device including the optical filter.

An imaging device according to the present invention 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. In addition, since 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. In addition, 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.

Therefore, 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.

Hereinafter, the present invention will be described in more detail by Examples, Examples and Experimental Examples.

However, the following Preparation Examples, Examples and Experimental Examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following Preparation Examples, Examples and Experimental Examples.

Preparation Examples 1 to 4.

As a preparation example according to the present invention, an optical article having first and second absorption peaks was prepared as follows.

Near-infrared absorber A and near-infrared absorber B having absorption maxima in the wavelength range of 702 ± 5 nm and 905 ± 5 nm, respectively, were mixed in the amounts shown in Table 1 below based on 100 parts by weight of the resin. At this time, 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. At this time, as 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.

	First absorption peak			Second absorption peak
	Absorbent Name	content	OD1	Absorbent Name	content	OD2
Preparation Example 1	A	1.0 parts by weight	1.00	B	3.6 parts by weight	0.35
Preparation Example 2	A	1.0 parts by weight	1.00	B	1.9 parts by weight	0.21
Preparation Example 3	A	1.0 parts by weight	1.00	B	1.0 parts by weight	0.10
Preparation Example 4	A	1.0 parts by weight	1.00	B	0.4 parts by weight	0.04

In order to evaluate the absorbance (OD) of the optical article for each of the optical article manufactured according to Preparation Examples 1 to 4 according to the present invention, the absorption spectrum according to the wavelength was measured in the wavelength range of 380 nm to 1,200 nm using a spectrophotometer. . From the measured absorbance results, 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. The results are shown in Table 1 above. In addition, 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.

Example  1 to Example  7.

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 ℃ 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 (μm).

Example No.	Used Optical Goods	First Selective Wave Reflective Layer		Second Selective Wave Reflective Layer		[Equation 3]	[Equation 4]
		Floor Level [P1]	Thickness [D1]	Floor Level [P2]	Thickness [D2]	| D1 / D2 |	| P1-P2 |
Example 1	Preparation Example 1	23	2.8	28	3.4	0.82	5
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 4	Preparation Example 1	31	3.9	28	3.4	1.15	3
Example 5	Preparation Example 2	23	2.8	26	3.1	0.90	3
Example 6	Preparation Example 3	23	2.8	26	3.1	0.90	3
Example 7	Preparation Example 4	23	2.8	26	3.1	0.90	3

Referring to Table 2, Examples 1 to 7, according to Formula 3 of the present specification | D1 / D2 | It can be seen that the numerical value is in the range of 0.8 to 1.2, specifically, 0.82 to 1.15. In addition, Examples 1 to 7, according to the formula [4] of the present specification | P1-P2 | It can be seen that the numerical value falls within the range of 0-6, specifically 0-5.

For example, 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 μm, 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 μm. As an example of the first selective wavelength reflecting layer and the second selective wavelength reflecting layer of the optical filter, 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.

Stacking order	material	Optical Thickness (QWOT)	Thickness (nm)
One	SiO 2	1.34	105.6
2	Ti 3 O 5	0.18	8.6
3	SiO 2	0.48	38.2
4	Ti 3 O 5	2.17	104.6
5	SiO 2	2.10	165.3
6	Ti 3 O 5	2.16	104.1
7	SiO 2	2.16	170.2
8	Ti 3 O 5	2.20	106.1
9	SiO 2	2.17	170.8
10	Ti 3 O 5	2.19	106.0
11	SiO 2	2.18	171.7
12	Ti 3 O 5	2.20	106.5
13	SiO 2	2.17	171.1
14	Ti 3 O 5	2.20	106.3
15	SiO 2	2.18	171.5
16	Ti 3 O 5	2.19	106.0
17	SiO 2	2.16	170.1
18	Ti 3 O 5	2.18	105.2
19	SiO 2	2.14	168.6
20	Ti 3 O 5	2.12	102.2
21	SiO 2	2.05	161.2
22	Ti 3 O 5	2.00	96.4
23	SiO 2	0.98	77.2

Stacking order	material	Optical Thickness (QWOT)	Thickness (nm)
One	SiO 2	0.63	88.7
2	Ti 3 O 5	1.20	107.0
3	SiO 2	1.38	194.8
4	Ti 3 O 5	1.37	122.9
5	SiO 2	1.48	208.9
6	Ti 3 O 5	0.17	15.2
7	SiO 2	0.10	14.3
8	Ti 3 O 5	1.31	116.3
9	SiO 2	1.39	197.2
10	Ti 3 O 5	1.21	108.7
11	SiO 2	1.23	173.9
12	Ti 3 O 5	1.14	102.3
13	SiO 2	1.21	170.9
14	Ti 3 O 5	1.12	100.5
15	SiO 2	1.21	170.8
16	Ti 3 O 5	1.11	99.2
17	SiO 2	1.21	171.0
18	Ti 3 O 5	1.11	99.3
19	SiO 2	1.21	170.8
20	Ti 3 O 5	1.11	99.8
21	SiO 2	1.21	171.1
22	Ti 3 O 5	1.13	101.1
23	SiO 2	1.22	172.9
24	Ti 3 O 5	1.16	103.8
25	SiO 2	1.30	183.4
26	Ti 3 O 5	1.28	114.5
27	SiO 2	0.28	39.9
28	Ti 3 O 5	0.11	9.8

In addition, the spectral transmittance of the first selective wavelength reflective layer disclosed in Table 3 is shown in FIG. 5, and the spectral transmittance of the second selective wavelength reflective layer disclosed in Table 4 is shown in FIG. 6.

compare Production Example  1 to 3.

Comparison was made in substantially the same manner as in Production Examples 1 to 4 above except for the contents of the near infrared absorbent A having an absorption maximum in the wavelength range of 702 ± 5 nm and the near infrared absorbent B having an absorption maximum in the wavelength range of 905 ± 5 nm. An optical article according to Preparation Examples 1 to 3 was prepared. In this case, the contents of the near infrared absorbent A and the near infrared absorbent B are shown in Table 5 below.

	First absorption peak			Second absorption peak
	Absorbent Name	content	OD1	Absorbent Name	content	OD2
Comparative Production Example 1	A	1.0 parts by weight	1.00	B	0.0 parts by weight	0.00
Comparative Production Example 2	A	1.0 parts by weight	1.00	B	5.4 parts by weight	0.60
Comparative Production Example 3	A	1.0 parts by weight	1.00	B	0.2 parts by weight	0.02

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.

Comparative example  1 to 6.

By using an electron beam evaporator (E-beam evaporator) at 110 ± 5 ℃ 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 (μm).

Comparative Example No.	Optics used	First Selective Wave Reflective Layer		Second Selective Wave Reflective Layer		[Equation 3]	[Equation 4]
		Floor Level [P1]	Thickness [D1]	Floor Level [P2]	Thickness [D2]	| D1 / D2 |	| P1-P2 |
Comparative Example 1	Comparative Production Example 1	23	2.8	30	3.6	0.78	7
Comparative Example 2	Comparative Production Example 1	23	2.8	32	3.8	0.74	9
Comparative Example 3	Comparative Production Example 1	31	3.9	26	3.1	1.26	5
Comparative Example 4	Comparative Production Example 1	23	2.8	26	3.1	0.90	3
Comparative Example 5	Comparative Production Example 2	23	2.8	26	3.1	0.90	3
Comparative Example 6	Comparative Production Example 3	23	2.8	26	3.1	0.90	3

Referring to Table 6, Comparative Examples 1 to 3 according to [Formula 3] of the present specification | D1 / D2 | It can be seen that the values deviate from 0.8 to 1.2. In addition, Comparative Examples 1 and 2, according to [Formula 4] of the present specification | P1-P2 | It can be seen that the values deviate from 0 to 6.

Experimental Example  One.

In order to evaluate the transmittance according to the incident angle of the optical filter according to the present invention, the following experiment was performed.

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. Here, 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, and 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.

In addition, 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.

Optical filter	Used Optical Goods	OD2				Incident angle 0 °			Angle of incidence 30 °
			Visible ray average transmittance [%]	Near Infrared Maximum Transmittance [%]	Near infrared ray average transmittance [%]	Visible ray average transmittance [%]	Near Infrared Maximum Transmittance [%]	Near infrared ray average transmittance [%]
Example 2	Preparation Example 1	0.35	80.38	0.07	0.01	71.28	0.09	0.03
Example 5	Preparation Example 2	0.21	87.67	0.08	0.02	81.70	0.23	0.06
Example 6	Preparation Example 3	0.10	90.76	0.09	0.02	86.41	0.38	0.09
Example 7	Preparation Example 4	0.04	92.87	0.09	0.03	89.67	0.54	0.12
Comparative Example 4	Comparative Production Example 1	0.00	94.59	0.09	0.03	92.37	0.71	0.15
Comparative Example 5	Comparative Production Example 2	0.60	74.19	0.06	0.01	62.65	0.04	0.01
Comparative Example 6	Comparative Production Example 3	0.02	93.75	0.09	0.03	91.04	0.62	0.13

As shown in Table 7 and Figures 7 to 10 it can be seen that 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.

Specifically, referring to Table 7, 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. In contrast, 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.

In addition, referring to Table 7 and FIGS. 7 to 10, 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.

From these results, it can be seen that 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.

In addition, it can be seen that 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.

Experimental Example  2.

In order to evaluate the degree of warpage of the optical filter according to the present invention, the following experiment was performed.

The warpage of the optical filters (3 mm × 3 mm in length) prepared in Examples 1 to 4 and Comparative Examples 1 to 3 using an ultra-precision 3-D roughness gauge (Ultra accuracy 3-D profilometer, UA3P-300, Panasonic Corporation) The degree of warpage and direction indicated were measured. Specifically, 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. At this time, the temperature of the chamber to which the optical filter is fixed is 23 ℃, the relative humidity was 60%, the vibration acceleration was 0.5 cm / s ² , the measured results are shown in Table 8 below.

Optical filter	D1 / D2	│P1-P2│	Deflection Accuracy (㎛)	Assembly defect rate (%)
Example 1	0.82	5	7.0	0
Example 2	0.90	3	4.2	0
Example 3	1.03	0	0.0	0
Example 4	1.15	3	-4.9	0
Comparative Example 1	0.78	7	10.4	4
Comparative Example 2	0.74	9	13.9	7
Comparative Example 3	1.26	5	-7.2	One

Looking at Table 8, it can be seen that 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.

Specifically, the variation (| P1-P2 |) 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 μm or less regardless of the direction.

In contrast, the deviation (| P1-P2 |) 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 μm.

In addition, 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. As a result of measuring the bending degree of Table 8, it can be seen that the defect rate increases in the assembling process when the bending degree exceeds 7.0 μm. These results can improve the warpage of the optical filter by adjusting the ratio of the variation and the thickness of the laminated layers of the first and second selective wavelength reflecting layers formed on the surface of the optical article, and by reducing the assembly defect rate in the image pickup device assembly process This means that the yield and productivity can be improved.

Experimental Example 3.

In order to evaluate the image quality of the optical filter according to the present invention, the following experiment was performed.

An image was captured using an imaging device manufactured with a camera module equipped with an optical filter according to Embodiment 7 of the present invention. In addition, in order to compare and evaluate the image quality, the camera module photographed an image of the same subject using an image pickup device replaced with an optical filter according to Comparative Example 6 while the lens and the image sensor were left as they are. An image of the room lamp is shown in FIG. 10. 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. On the contrary, referring to 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.

Therefore, 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. In addition, since 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.

Claims (14)

A transparent base material containing at least one pigment for absorbing near infrared rays,

The absorption spectrum measured using a spectrophotometer in the wavelength range of 380 nm to 1,200 nm 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,

The second absorption peak has an absorption maximum lambda max2 in the wavelength range of 830 nm to 980 nm,

When 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 the following Equation 1:

[Equation 1]

0.03 <OD2 <0.36.

The method of claim 1,

The absorbance value (OD2) at the absorption maximum of the second absorption peak satisfies the following Equation 2:

[Equation 2]

0.18 ≦ OD2 ≦ 0.35.

The method of claim 1,

The transparent substrate is an optical article comprising at least one of glass and polymer resin.

The method of claim 3,

The polymer resin includes at least one member selected from the group consisting of polyester resins, polycarbonate resins, acrylic resins, polyolefin resins, cyclic olefin resins, polyimide resins, polyamide resins and polyurethane resins. Optical article to say.

The method of claim 1,

The near-infrared absorption pigment,

A first pigment having an absorption maximum in the range of 650 nm to 750 nm; And

Optical article comprising a second pigment having an absorption maximum in the range of 830nm to 980nm.

The method of claim 1,

The near-infrared absorption pigment | dye is an optical article containing any one or more of the compounds represented by following formula (1) and (2):

[Formula 1]

[Formula 2]

In Chemical Formula 1 and Chemical Formula 2,

A is an aminophenyl group; Indolyl methylene group; Or indolinyl,

Two A's

It has a structure that forms a conjugation (conjugation) with each other,

At least one of hydrogen present in the aminophenyl group, indolyl methylene group or indolinyl group is independently of each other hydrogen, halogen group, hydroxy group, cyano group, nitro group, carboxyl group, alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms A cycloalkyl group, a C1-C10 alkoxy group, a C7-20 aralkyl group, a sulfonamide group, or a C1-C4 alkyl group, a C1-C4 haloalkyl group, or a C7-20 aralkyl group Or an unsubstituted amide group;

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,

Existing in the 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, oxotitanium or oxovanadium.

The method of claim 1,

The transparent substrate,

Base layer; And

An optical article comprising a near infrared absorbing layer formed on one surface or both surfaces of the substrate layer and containing a near infrared absorbing dye.

The method of claim 1,

The transparent substrate,

Base layer; And

An optical article comprising a pigment for absorbing near infrared rays dispersed in the base layer.

An optical filter comprising the optical article according to any one of claims 1 to 8.

Transparent base material containing at least 1 type of near-infrared absorption pigment | dye;

It includes a selective wavelength reflection layer formed on one side or both sides of the transparent substrate,

An optical filter satisfying the following conditions (A) and (B) when measuring a transmission spectrum using a spectrophotometer in the wavelength range of 380 nm to 1,200 nm:

(A) in the wavelength range of 800 nm to 1,000 nm, the maximum transmittance for light incident in the direction perpendicular to the optical filter is 0.3% or less,

(B) In the wavelength range of 800 nm to 1,000 nm, the maximum transmittance with respect to light incident in a direction perpendicular to the optical filter at an angle of 30 ° is 0.6% or less.

The method of claim 10,

The transparent substrate,

The absorption spectrum measured using a spectrophotometer in the wavelength range of 380 nm to 1,200 nm 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,

The second absorption peak has an absorption maximum lambda max2 in the wavelength range of 830 nm to 980 nm,

When 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.

The method of claim 10,

The optical filter,

A first selective wavelength reflecting layer formed on the first main surface of the transparent substrate; And

A second selective wavelength reflecting layer formed on the second main surface of the transparent substrate,

An optical filter that satisfies Equation 3 below:

[Equation 3]

0.8 <D1 / D2 <1.2

In equation 3,

D1 represents the thickness of the first selective wavelength reflecting layer,

D2 represents the thickness of the second selective wavelength reflecting layer.

The method of claim 11,

The first and second selective wavelength reflecting layers are each independently formed of a dielectric multilayer film,

An optical filter satisfying the following formula 4:

[Equation 4]

0 ≤ | P1-P2 | <6

In equation 4,

P1 represents the number of laminated multilayer dielectric films forming the first selective wavelength reflecting layer,

P2 represents the number of laminated multilayer dielectric films forming the second selective wavelength reflecting layer.

A solid-state imaging device comprising the optical filter according to any one of claims 10 to 13.

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