WO2025041770A1 - Optical filter - Google Patents

Abstract

The present invention pertains to an optical filter provided with: a phosphate glass; a dielectric multilayer film 1 and a dielectric multilayer film 2 which are provided on the opposing surfaces of the phosphate glass; a barrier film 1 provided between the phosphate glass and the dielectric multilayer film 1; a barrier film 2 provided between the phosphate glass and the dielectric multilayer film 2; and a light absorption layer provided on the dielectric multilayer film 2. The barrier film 1 and the barrier film 2 each independently contain at least one selected from TiO₂, Nb₂O₅, Ta₂O₅, and HfO₂. The optical filter satisfies all of specific spectral characteristics (i-1) to (i-5).

Description

Optical Filters

The present invention relates to an optical filter that transmits visible light and blocks near-infrared light.

In imaging devices that use solid-state imaging elements, optical filters are used that transmit light in the visible wavelength range (hereafter also referred to as "visible light") and block light in the near-infrared wavelength range (hereafter also referred to as "near-infrared light") in order to reproduce color tones well and obtain clear images.

Such optical filters include various types, such as reflective filters that use optical interference to reflect the light to be blocked by alternately laminating thin dielectric films with different refractive indices (dielectric multilayer film) on one or both sides of a transparent substrate, absorptive filters that absorb the light to be blocked by using glass or dyes that absorb light in a specific wavelength range, and filters that combine reflective and absorptive types.

Phosphate glass is known as a type of glass that absorbs light, but it is easily affected by moisture in the environment, and there is a risk that phosphoric acid will dissolve and decompose other constituent materials of the optical filter. Therefore, technology to prevent the dissolution of phosphoric acid is being studied.
Patent Document 1 describes phosphate glass whose surface is coated with alumina to form a protective film for improving moisture resistance.
Patent Document 2 describes an infrared cut filter in which infrared absorbing glass such as phosphate glass and a cover glass are bonded together with an adhesive in order to improve moisture resistance.

Japanese Patent Application Publication No. 4-139035 Japanese Patent Application Publication No. 2016-18092

However, in the technology described in Patent Document 1, the surface of the phosphate glass covered with an alumina protective film is less susceptible to the effects of moisture and moisture resistance is improved, but it is not possible to suppress the reaction between moisture and the glass end face that is not covered with the protective film. Furthermore, there is a risk that phosphoric acid eluted from the glass end face will react with the alumina protective film, resulting in reduced adhesion and causing the film to peel off.
In addition, in the technology described in Patent Document 2, since the adhesive is an organic material, moisture easily penetrates from the vicinity of the end face, and therefore there is a risk that the adhesive will deteriorate due to phosphoric acid eluted from the glass, resulting in a decrease in adhesion.

In addition, optical filters with dielectric multilayer film have a problem in that the optical film thickness of the dielectric multilayer film changes depending on the angle of incidence of light, and so the change in the spectral transmittance curve due to the angle of incidence is an issue. In particular, with the recent trend towards lower profile camera modules, it is expected that they will be used under high angle of incidence conditions, so there is a demand for optical filters that are less susceptible to the effects of the angle of incidence.

The present invention aims to provide an optical filter that has excellent moisture resistance, transmits visible light even at high angles of incidence, and blocks near-infrared light.

The present invention provides an optical filter etc. having the following configuration.
An optical filter comprising: phosphate glass; a dielectric multilayer film 1 and a dielectric multilayer film 2 provided on both sides of the phosphate glass; a barrier film 1 provided between the phosphate glass and the dielectric multilayer film 1; a barrier film 2 provided between the phosphate glass and the dielectric multilayer film 2; and a light absorbing layer provided on the dielectric multilayer film 2,
the light absorbing layer contains a near infrared absorbing dye,
The barrier film 1 and the barrier film 2 each independently contain one or more selected from TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and HfO ₂ ;
The optical filter satisfies all of the following spectral characteristics (i-1) to (i-5).
(i-1) The average transmittance of wavelengths from 440 to 500 nm is 80% or more at an incident angle of 0 degrees and 70% or more at an incident angle of 60 degrees. (i-2) The average transmittance of wavelengths from 750 to 1000 nm is 0.5% or less at an incident angle of 0 degrees and 0.5% or less at an incident angle of 60 degrees. (i-3) The wavelength IR10 _{(0 deg)} at which the transmittance is 10% in the spectral transmittance curve at an incident angle of 0 degrees is in the range of 600 to 700 nm. (i-4) The wavelength IR10 _{(0 deg)} at which the transmittance is 10% in the range of 600 to 700 nm in the spectral transmittance curve at an incident angle of 0 degrees and the wavelength IR10 (i-5) When the light absorbing layer side is the incident direction, the maximum reflectance at wavelengths of 450 to 950 nm is 24% or less at an incident angle of 5 degrees and 35% or less at an incident angle of ₆₀ degrees.

The present invention provides an optical filter that has excellent moisture resistance, transmits visible light even at high angles of incidence, and blocks near-infrared light.

FIG. 1 is a cross-sectional view illustrating an example of an optical filter according to an embodiment. FIG. 2 is a cross-sectional view illustrating a schematic configuration of another example of the optical filter according to the embodiment. FIG. 3 is a diagram showing the spectral transmittance curves of glasses 1 to 5. FIG. 4 is a diagram showing the spectral transmittance curve of the light absorbing layer. FIG. 5 is a graph showing the spectral reflectance curve of a laminated film 1 consisting of a dielectric multilayer film 1A and a barrier film 1. In FIG. FIG. 6 is a graph showing the spectral reflectance curve of the laminated film 1 consisting of the dielectric multilayer film 1C and the barrier film 1. In FIG. FIG. 7 is a diagram showing the spectral transmittance curve of the optical filter of Example 2-1. FIG. 8 is a diagram showing the spectral reflectance curve on the dielectric multilayer film 1 side of the optical filter of Example 2-1. FIG. 9 is a diagram showing a spectral reflectance curve on the light absorption layer side of the optical filter of Example 2-1. FIG. 10 is a diagram showing the spectral transmittance curve of the optical filter of Example 2-7. FIG. 11 is a diagram showing the spectral reflectance curve on the dielectric multilayer film 1 side of the optical filter of Example 2-7. FIG. 12 is a diagram showing a spectral reflectance curve on the light absorption layer side of the optical filter of Example 2-7.

Hereinafter, an embodiment of the present invention will be described.
In this specification, the near-infrared absorbing dye may be abbreviated as "NIR dye" and the ultraviolet absorbing dye may be abbreviated as "UV dye".
In this specification, the compound represented by formula (I) is referred to as compound (I). The same applies to compounds represented by other formulas. The dye consisting of compound (I) is also referred to as dye (I), and the same applies to other dyes. In addition, the group represented by formula (I) is also referred to as group (I), and the same applies to groups represented by other formulas.

In this specification, the transmittance of glass, the transmittance of a light absorbing layer including a case where a dye is contained in a resin, the transmittance measured by dissolving the dye in a solvent such as dichloromethane, the transmittance of a dielectric multilayer film, and the transmittance of an optical filter having a dielectric multilayer film are actually measured transmittances.

In this specification, for example, a transmittance of 90% or more in a specific wavelength range means that the transmittance is not below 90% in the entire wavelength range, i.e., the minimum transmittance is 90% or more in the wavelength range. Similarly, for example, a transmittance of 1% or less in a specific wavelength range means that the transmittance is not more than 1% in the entire wavelength range, i.e., the maximum transmittance is 1% or less in the wavelength range. The average transmittance in a specific wavelength range is the arithmetic mean of the transmittance per 1 nm in the wavelength range.
The spectral characteristics can be measured using a UV-Vis spectrophotometer.
In this specification, any numerical range expressed by "to" includes the upper and lower limits.

<Optical filter>
An optical filter according to one embodiment of the present invention (hereinafter also referred to as "the present filter") comprises phosphate glass, a dielectric multilayer film 1 and a dielectric multilayer film 2 provided on both sides of the phosphate glass, and a light absorbing layer provided on the dielectric multilayer film 2. The present filter further comprises a barrier film 1 between the phosphate glass and the dielectric multilayer film 1, and a barrier film 2 between the phosphate glass and the dielectric multilayer film 2. The barrier films 1 and 2 contain specific materials as described below. Such a barrier film prevents the phosphate glass from reacting with moisture in the environment, and an optical filter with excellent moisture resistance is obtained.

An example of the configuration of this filter will be explained using the drawings. Figures 1 and 2 are cross-sectional views that show an outline of an example of an optical filter according to one embodiment.

The optical filter 1A shown in FIG. 1 is an example that includes phosphate glass 10, a dielectric multilayer film 21 provided on one main surface side of the phosphate glass 10, a dielectric multilayer film 22 provided on the other main surface side of the phosphate glass 10, a light absorbing layer 30 provided on the dielectric multilayer film 22, a barrier film 11 provided between the phosphate glass 10 and the dielectric multilayer film 21, and a barrier film 12 provided between the phosphate glass 10 and the dielectric multilayer film 22.

The optical filter 1B shown in FIG. 2 is an example that further includes a dielectric multilayer film 23 laminated on the light absorbing layer 30.

The optical filter according to the embodiment of the present invention satisfies all of the following spectral characteristics (i-1) to (i-5).
(i-1) The average transmittance of wavelengths from 440 to 500 nm is 80% or more at an incident angle of 0 degrees and 70% or more at an incident angle of 60 degrees. (i-2) The average transmittance of wavelengths from 750 to 1000 nm is 0.5% or less at an incident angle of 0 degrees and 0.5% or less at an incident angle of 60 degrees. (i-3) The wavelength IR10 _{(0 deg)} at which the transmittance is 10% in the spectral transmittance curve at an incident angle of 0 degrees is in the range of 600 to 700 nm. (i-4) The wavelength IR10 _{(0 deg)} at which the transmittance is 10% in the range of 600 to 700 nm in the spectral transmittance curve at an incident angle of 0 degrees and the wavelength IR10 (i-5) When the light absorbing layer side is the incident direction, the maximum reflectance at wavelengths of 450 to 950 nm is 24% or less at an incident angle of 5 degrees and 35% or less at an incident angle of ₆₀ degrees.

This filter, which satisfies all of the spectral characteristics (i-1) to (i-5), is an optical filter that has excellent visible light transmittance as shown in characteristic (i-1), excellent blocking of specific near-infrared light as shown in characteristic (i-2), is resistant to shifts in transmittance even at high angles of incidence as shown in characteristic (i-4), and has reduced reflectance at wavelengths of 450 to 950 nm as shown in characteristic (i-5).

Satisfying the spectral characteristic (i-1) means that the transmittance of the visible light region of 440 to 500 nm is excellent even at a high angle of incidence.
The average transmittance in the wavelength range of 440 to 500 nm is preferably 82% or more, more preferably 85% or more, at an incident angle of 0 degrees, and is preferably 72% or more, more preferably 75% or more, at an incident angle of 60 degrees.
In order to satisfy the spectral characteristic (i-1), for example, a dielectric multilayer film, phosphate glass, or a near-infrared absorbing dye having excellent transmittance in the visible light region may be used.

Satisfying the spectral characteristic (i-2) means that the film has excellent shielding properties for the near-infrared light region of 750 to 1000 nm even at a high angle of incidence.
The average transmittance in the wavelength range of 750 to 1000 nm is preferably 0.4% or less, more preferably 0.2% or less, at an incident angle of 0 degrees, and is preferably 0.4% or less, more preferably 0.2% or less, at an incident angle of 60 degrees.
In order to satisfy the spectral characteristic (i-2), for example, light can be blocked by the absorption ability of phosphate glass or a near-infrared absorbing dye.

Satisfying the spectral characteristic (i-3) means that the wavelength region of 600 to 700 nm is a region in which the spectral transmittance curve rises from the near-infrared shielding region to the visible light transmitting region.
The wavelength IR10 _{(0 deg)} is preferably in the range of 630 to 700 nm, and more preferably in the range of 650 to 700 nm.

Satisfying the spectral characteristic (i-4) means that the spectral transmittance curve is unlikely to shift in the wavelength region of 600 to 700 nm even at a high angle of incidence.
The absolute value of the difference between the wavelength IR10 _{(0 deg)} and the wavelength IR10 _{(60 deg)} is preferably 13 nm or less, and more preferably 12 nm or less.
In order to satisfy the spectral characteristic (i-4), for example, light in the wavelength region of 600 to 700 nm can be blocked by the absorption of phosphate glass or a near-infrared light absorbing dye, which is not affected by the angle of incidence.

Satisfying the spectral characteristic (i-5) means that the reflection characteristic at wavelengths of 450 to 950 nm is suppressed in the incident direction on the light absorbing layer side. This makes it possible to suppress reflection on the optical filter side when reflected light from the sensor side is incident on the optical filter, which is preferable because it can prevent unnecessary light from entering the sensor.
The maximum reflectance at wavelengths of 450 to 950 nm is preferably 20% or less, more preferably 10% or less, at an incident angle of 5 degrees, and is preferably 30% or less, more preferably 25% or less, at an incident angle of 60 degrees.
In order to satisfy the spectral characteristic (i-5), for example, an antireflection film may be laminated on the light absorbing layer side.

The optical filter according to this embodiment preferably satisfies the following spectral characteristic (i-6).
(i-6) When the dielectric multilayer film 1 side is the incident direction, the maximum reflectance of wavelengths from 750 to 950 nm is 20% or more at an incident angle of 5 degrees and 30% or more at an incident angle of 60 degrees. Satisfying the spectral characteristic (i-6) means that the reflectance of near-infrared light with wavelengths of 750 to 950 nm is high.
The maximum reflectance at wavelengths of 750 to 950 nm is more preferably 50% or more, more preferably 70% or more, at an incident angle of 5 degrees, and more preferably 50% or more, more preferably 70% or more, at an incident angle of 60 degrees.
In order to satisfy the spectral characteristic (i-6), for example, a dielectric multilayer film 1 having a high reflectance in the wavelength range of 750 to 950 nm may be used.

The optical filter according to this embodiment preferably satisfies the following spectral characteristic (i-7).
(i-7) The absolute value of the difference between the average transmittance at an incident angle of 0 degrees and the average transmittance at an incident angle of 60 degrees, for wavelengths of 440 to 500 nm, is 15% or less. Satisfying the spectral characteristic (i-7) means that the change in transmittance of visible light (ripple) is small even at high incident angles.
The above absolute value is more preferably 12% or less.
In order to satisfy the spectral characteristic (i-7), it is possible to use a dielectric multilayer film in which the change in transmittance (ripple) of visible light is small even at a high angle of incidence.

The optical filter according to this embodiment preferably satisfies the following spectral characteristic (i-8).
(i-8) Average transmittance for wavelengths of 900 to 1000 nm is 1% or less at an incident angle of 0 degrees. Satisfying the spectral characteristic (i-8) means excellent shielding properties for near-infrared light with wavelengths of 900 to 1000 nm.
The average transmittance for wavelengths from 900 to 1000 nm at an incident angle of 0 degree is more preferably 0.1% or less, and further preferably 0.01% or less.
In order to satisfy the spectral characteristic (i-8), for example, the absorption ability of phosphate glass and the reflection characteristic of a dielectric multilayer film can be combined to shade such an area.

<Phosphate glass>
The optical filter according to the present embodiment includes phosphate glass. In this specification, phosphate glass means glass _that contains 40% or more _P2O5 in mole percent based on oxide and does not substantially contain fluorine atoms. Here, "substantially does not contain fluorine atoms" means that when the content of component elements other than fluorine atoms contained in the glass is taken as 100 mass % and the content of fluorine atoms contained in the glass is expressed as an exclusive percentage, the content of fluorine atoms is less than 3 mass % in exclusive percentage.
Phosphate glass absorbs near-infrared light and also functions as a support for optical filters. In addition, because it blocks light by absorbing it, the light blocking ability is less susceptible to the effects of the angle of incidence, unlike dielectric multilayer films.

The phosphate glass preferably has an average transmittance of 70% or more at wavelengths of 440 to 500 nm, a transmittance of 20% or less at a wavelength of 1200 nm, a transmittance of 7% or less at a wavelength of 1000 nm, and a transmittance of 7% or less at a wavelength of 800 nm, calculated based on a plate thickness of 0.29 mm. Phosphate glass that satisfies such spectral characteristics is preferable because it has sufficient transmittance for visible light and excellent near-infrared light absorption ability.
The average transmittance in the wavelength range of 440 to 500 nm is more preferably 75% or more, and further preferably 80% or more.
The transmittance at a wavelength of 1200 nm is more preferably 17% or less, further preferably 15% or less, and even more preferably 10% or less.
The transmittance at a wavelength of 1000 nm is more preferably 6% or less, further preferably 5% or less, and even more preferably 3% or less.
The transmittance at a wavelength of 800 nm is more preferably 6% or less, and further preferably 4% or less.

Phosphate glass is substantially free of fluorine atoms and has the following content, expressed as mole percent on an oxide basis:
P ₂ O ₅ 40% to 75%,
Al ₂ O ₃ 10% to 30%,
ΣR ₂ O 0.1% to 30% (wherein R ₂ O is one or more components selected from Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O, and ΣR ₂ O represents the total content of R ₂ O);
ΣR′O 0% to 30% (wherein R′O is one or more components selected from CaO, MgO, BaO, SrO, and ZnO, and ΣR′O represents the total content of R′O),
CuO 2-30%,
It is preferred that the compound contains

The components that may constitute phosphate glass and their suitable contents are described below. In this specification, unless otherwise specified, the content of each component and the total content are expressed as mole percent based on the oxide.

P ₂ O ₅ is a main component forming glass and is a component for enhancing near-infrared cutoff properties. If the content of _{P 2} O ₅ is 40% or more, the effect is sufficiently obtained, and if it is 75% or less, problems such as glass becoming unstable and weather resistance decreasing are unlikely to occur. Therefore, the content is preferably 40 to 75%, more preferably 45 to 73%, even more preferably 47 to 71%, even more preferably 50 to 69%, and most preferably 55 to 67%.

Al ₂ O ₃ is a main component that forms glass and is a component for increasing the strength of glass, etc. If the content of _{Al 2} O ₃ is 10% or more, the effect is sufficiently obtained, and if it is 30% or less, problems such as glass becoming unstable and near-infrared cutoff performance decreasing are unlikely to occur. Therefore, it is preferably 10 to 30%, more preferably 11 to 29%, even more preferably 12 to 28%, even more preferably 13 to 27%, and most preferably 14 to 26%. If the content of _{Al 2} O ₃ is 14% or more, the weather resistance of the glass can be increased.

R ₂ O (wherein R ₂ O is one or more components selected from Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O) is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, stabilizing glass, and the like. If the total amount of R ₂ O (ΣR ₂ O) is 0.1% or more, the effect is sufficiently obtained, and if it is 30% or less, the glass is less likely to become unstable, which is preferable. Therefore, it is preferably 0.1 to 30%, more preferably 0.4 to 27%, even more preferably 0.7 to 24%, even more preferably 1.0 to 21%, and most preferably 1.3 to 18%.

Li ₂ O is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, stabilizing glass, etc. The Li ₂ O content is preferably 0 to 20%. If the Li ₂ O content is 20% or less, problems such as glass instability and reduced near-infrared cutoff properties are unlikely to occur, which is preferable. The Li 2 O content is more preferably 0 to 15%, even more preferably 0 to 10%, even more preferably 0 to 5%, and most preferably substantially free of Li ₂ O.
In the present invention, "substantially free of a specific component" means that the component is not intentionally added, and does not exclude the component being unavoidably mixed in from raw materials, etc., to the extent that it does not affect the desired properties.

Na ₂ O is a component for lowering the melting temperature of glass, lowering the liquidus temperature of glass, stabilizing glass, etc. The Na ₂ O content is preferably 0 to 20%. If the Na ₂ O content is 20% or less, the glass is less likely to become unstable, which is preferable. The Na 2 O content is more preferably 0.5 to 17%, even more preferably 1 to 14%, and even more preferably 1.5 to 11%.

K ₂ O is a component that has the effects of lowering the melting temperature of glass, lowering the liquidus temperature of glass, etc. The K ₂ O content is preferably 0 to 20%. If the K ₂ O content is 20% or less, the glass is less likely to become unstable, which is preferable. The K 2 O content is more preferably 1 to 18%, even more preferably 2 to 15%, and even more preferably 3 to 13%.

Rb ₂ O is a component that has the effects of lowering the melting temperature of glass, lowering the liquidus temperature of glass, etc. The content of Rb ₂ O is preferably 0 to 20%. If the content of Rb ₂ O is 20% or less, the glass is less likely to become unstable, which is preferable. The content is more preferably 0.5 to 18%, further preferably 1 to 16%, and even more preferably 2 to 14%.

Cs ₂ O is a component that has the effects of lowering the melting temperature of glass, lowering the liquidus temperature of glass, etc. The content of Cs ₂ O is preferably 0 to 20%. If the content of Cs ₂ O is 20% or less, it is preferable because the glass is less likely to become unstable. It is more preferably 0.5 to 18%, further preferably 1 to 16%, and even more preferably 2 to 14%.

In addition, when two or more types of alkali metal components represented by R ₂ O are added simultaneously, a mixed alkali effect occurs in the glass, and the mobility of R ⁺ ions decreases. As a result, when the glass comes into contact with water, the hydration reaction caused by ion exchange between H ⁺ ions in water molecules and R ⁺ ions in the glass is inhibited, and the weather resistance of the glass is improved. Therefore, the glass of this embodiment preferably contains two or more components selected from Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O. In this case, the total amount (ΣR ₂ O) of R ₂ O (wherein R ₂ O is two or more components selected from Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O) is preferably 12 to 25%. If the total amount of R ₂ O is 12% or more, the effect can be sufficiently obtained, and if it is 25% or less, problems such as glass instability, reduced near-infrared cutoff property, reduced glass strength, etc. are unlikely to occur, so this is preferable. Therefore, ΣR ₂ O is preferably 12 to 25%, more preferably 13 to 24%, even more preferably 14 to 25%, still more preferably 15% to 26%, and most preferably 16 to 24%.

R'O (where R'O is one or more components selected from CaO, MgO, BaO, SrO, and ZnO) is a component that lowers the melting temperature of glass, lowers the liquidus temperature of glass, stabilizes glass, and increases the strength of glass. The total amount of R'O (ΣR'O) is preferably 0-30%. If the total amount of R'O is 30% or less, problems such as glass instability, reduced near-infrared cutoff properties, reduced short-wavelength infrared transmittance, and reduced glass strength are unlikely to occur, which is preferable. It is more preferably 0-25%, and even more preferably 0-20%. Even more preferably 0-15%, and even more preferably 0-10%.

The glass of the present embodiment preferably contains substantially no divalent cations other than Cu, for the reasons described below.
When the glass of the present embodiment contains CuO, light in the near infrared region is cut by the light absorption of Cu ²⁺ ions. The light absorption occurs due to electronic transition between d orbitals of Cu ²⁺ ions split by the electric field of O ^2- ions. The splitting of d orbitals is promoted when the symmetry of O ^2- ions around Cu ²⁺ ions decreases. For example, when a cation exists around an O ^2- ion, the O ^2- ion is attracted by the electric field of the cation, and the symmetry of the O ^2- ion decreases. As a result, the splitting of d orbitals is promoted, and light absorption occurs due to electronic transition between the split d orbitals, so that the light absorption ability in the near infrared region is weakened and the light absorption ability in the short wavelength infrared region is strengthened. Since the strength of the electric field of the cations is stronger when the valence of the ions is large, the addition of an oxide containing a divalent cation other than Cu to the glass may reduce the near infrared cutoff property and reduce the transmittance of short wavelength infrared rays.

CaO is a component that lowers the melting temperature of glass, lowers the liquidus temperature of glass, stabilizes glass, and increases the strength of glass. The CaO content is preferably 0-20%. If the CaO content is 20% or less, problems such as glass instability, reduced near-infrared blocking properties, and reduced short-wavelength infrared transmittance are unlikely to occur, which is preferable. It is more preferably 0-15%, even more preferably 0-10%, and even more preferably 0-5%. Most preferably, it contains substantially no CaO.

MgO is a component that lowers the melting temperature of glass, lowers the liquidus temperature of glass, stabilizes glass, and increases the strength of glass. The MgO content is preferably 0-20%. If the MgO content is 20% or less, problems such as glass instability, reduced near-infrared cutoff properties, and reduced short-wavelength infrared transmittance are unlikely to occur, which is preferable. It is more preferably 0-15%, even more preferably 0-10%, and even more preferably 0-5%. Most preferably, it contains substantially no MgO.

BaO is a component that lowers the melting temperature of glass, lowers the liquidus temperature of glass, stabilizes glass, etc. The BaO content is preferably 0-20%. If the BaO content is 20% or less, problems such as glass instability, reduced near-infrared cutoff properties, and reduced short-wavelength infrared transmittance are unlikely to occur, which is preferable. The BaO content is more preferably 0-15%, even more preferably 0-10%, and even more preferably 0-5%. The BaO content may be 0.1% or more. Most preferably, BaO is substantially free of content.

SrO is a component that lowers the melting temperature of glass, lowers the liquidus temperature of glass, stabilizes glass, etc. The SrO content is preferably 0-20%. If the SrO content is 20% or less, problems such as glass instability, reduced near-infrared cutoff properties, and reduced short-wavelength infrared transmittance are unlikely to occur, which is preferable. It is more preferably 0-15%, and even more preferably 0-10%. Most preferably, it contains substantially no SrO.

ZnO has the effect of lowering the melting temperature of glass, lowering the liquidus temperature of glass, etc. The ZnO content is preferably 0-20%. If the ZnO content is 20% or less, problems such as deterioration of the glass's solubility, deterioration of the near-infrared cutoff property, and deterioration of the short-wavelength infrared transmittance are unlikely to occur, which is preferable. It is more preferably 0-15%, even more preferably 0-10%, and even more preferably 0-5%. Most preferably, it contains substantially no ZnO.

CuO is a component for blocking near-infrared rays. The CuO content is preferably 2-30%. If the CuO content is 2% or more, the effect is sufficiently obtained, and if it is 30% or less, problems such as a decrease in the transmittance of visible light and a decrease in the transmittance of short-wavelength infrared rays are unlikely to occur, so this is preferable. It is more preferable that it is 4-25%, even more preferable that it is 5-19%, and even more preferable that it is 6-20%. Furthermore, even more preferable that it is 8% or more. In particular, when the glass does not substantially contain divalent cations other than Cu, a CuO content of 8% or more can further increase the blocking properties of near-infrared rays and the transmittance of short-wavelength infrared rays. It is more preferable that it is 10-18%, and most preferable that it is 11-18%.

Fe ₂ O ₃ is a component for cutting near-infrared rays. The content of Fe ₂ O ₃ is preferably 0.1% or more and 35% or less. If the content of Fe ₂ O ₃ is 0.1% or more, the near-infrared cutting effect is sufficiently obtained, and if the content of Fe ₂ O ₃ is 35% or less, the transmittance of light in the visible region is less likely to decrease, which is preferable. The content of Fe ₂ O ₃ is more preferably 1 to 35%, even more preferably 2% to 35%, even more preferably 3% to 35%, particularly preferably 4% to 35%, particularly more preferably 5% to 35%, and most preferably 6% to 35%.

B ₂ O ₃ may be contained in the range of 15% or less in order to stabilize the glass. If the content of _{B 2} O ₃ is 15% or less, problems such as deterioration of the weather resistance of the glass, deterioration of the near infrared cutoff property, and deterioration of the transmittance of short-wavelength infrared rays are unlikely to occur, so this is preferable. It is more preferably 13% or less, even more preferably 11% or less, even more preferably 9% or less, particularly preferably 7% or less, and most preferably substantially free of B ₂ O ₃ .

In the glass of this embodiment, F (fluorine atoms) is an effective component for improving weather resistance, but since it is an environmentally hazardous substance and there is a risk of reducing near-infrared cutoff properties, F is not substantially contained. Here, "substantially not contained" means that when the content of component elements other than F contained in the glass is taken as 100 mass % and the content of F contained in the glass is expressed as an exclusive percentage, the content of F is less than 3 mass % exclusive.

_{In the} glass of this embodiment, _SiO2 , _GeO2 , ZrO2, _SnO2 , _TiO2 , _CeO2 , _WO3 , _Y2O3 , _La2O3 , _Gd2O3 , _Yb2O3 , and _Nb2O5 may be contained in a range of 5% or less in order to increase the weather resistance of _{the glass} . If the content _{of these} components is 5% or less, problems such as a decrease in near-infrared cutoff property and a decrease in short-wavelength infrared transmittance are unlikely to occur, which is preferable. It is preferably 4% or less, more preferably 3% or less, even more preferably 2% or less, and even more preferably 1% or less.

The thickness of the phosphate glass is preferably 3 mm or less, more preferably 2 mm or less, and even more preferably 1 mm or less, from the viewpoint of ease of optical design when incorporating it into a camera module, and is preferably 0.1 mm or more from the viewpoint of element strength and the need to obtain the desired optical characteristics.

<Barrier film>
The optical filter according to this embodiment includes barrier films 1 and 2 on both main surfaces of the phosphate glass. Each of these barrier films independently contains one or more selected from TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and HfO _2. TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and HfO ₂ are all highly resistant to moisture, and the barrier film having such a configuration between the phosphate glass and the dielectric multilayer film can suppress dissolution of the phosphate glass due to the influence of moisture. Also, from the viewpoint of excellent adhesion to the phosphate glass, it is preferable that the barrier film has such a configuration.

For example, resin materials are not preferred as materials for the first barrier layer 120 and the second barrier layer 130 because they have a lower ability to inhibit moisture penetration than inorganic materials.

The barrier film preferably contains one or more selected from TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and HfO ₂ in a total content of 80 mol % or more, more preferably 90 mol % or more, even more preferably 95 mol % or more, and particularly preferably 100 mol %.
Here, the barrier film may contain 80 mol % or more of one or more materials selected from TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and HfO ₂ alone, or may contain 80 mol % or more of two or more materials in total.
In addition, the barrier film may contain materials other than TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and HfO ₂ , as long as the resistance to moisture is not impaired. For example, from the viewpoint of adjusting the refractive index of the barrier film, SiO ₂ or Al ₂ O ₃ may be contained. When materials other than TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and HfO ₂ are contained, the total content is preferably 20 mol % or less. On the other hand, materials containing Si may reduce the adhesion to the glass substrate, so from this viewpoint, it is preferable not to contain them. In addition, from the viewpoint of increasing the water resistance of the optical filter, it is preferable not to contain materials other than the oxides of metals such as aluminum (Al), titanium (Ti), niobium (Nb), tantalum (Ta), and hafnium (Hf).

Furthermore, the physical thickness of the barrier film 2 and the dielectric multilayer film 2 positioned in the direction of incidence of external light satisfies a specific condition. That is, when a film consisting of the barrier film 2 and the dielectric multilayer film 2 is defined as a laminated film 2, it is preferable that X defined by the following formula is 35% or more.
It is preferable that the film (laminate film 2) consisting of the dielectric multilayer film 2 and the barrier film 2 present between the phosphate glass and the light absorbing layer satisfies a specific physical film thickness condition, since this further enhances the moisture resistance of the optical filter and avoids the effects of interface reflection caused by the provision of the barrier film 2.

Here, QWOT (Quarter Wave Optical Thickness) is the optical thickness at λ/4 of the wavelength and is calculated by the following formula.
QWOT = (physical film thickness nm/550 nm) x 4 x (refractive index at 550 nm)

By controlling X, it is possible to suppress the reflection behavior caused by the provision of a barrier film, and it is possible to obtain an optical filter having better spectral characteristics.
If X is 35% or more, for example, the maximum reflectance of wavelengths of 450 to 950 nm when the light absorbing layer side is the incident direction, as shown in the spectral characteristics (i-5) of the optical filter, tends to be within the desired range, which is preferable. As described above, by suppressing the maximum reflectance when the light absorbing layer side is the incident direction, it is possible to suppress the intrusion of unnecessary light into the sensor. In other words, by providing the barrier film 2 and the dielectric multilayer film 2 in which X satisfies 35% or more, it is possible to control the reflectance on the light absorbing layer side.
X is more preferably 50% or more, and further preferably 70% or more.

The total physical thickness of the laminated film 2 is determined by adding up the physical thickness of the barrier film 2 and the physical thickness of the dielectric multilayer film 2 .
The total physical thickness of the multilayer film 2 having a thickness of QWOT2 or more is determined by adding up the physical thicknesses of the barrier film 2 and the films having a thickness of QWOT2 or more contained in the dielectric multilayer film 2 .
The total physical thickness of the laminated film 2 having a refractive index of 1.9 or less and a thickness of less than QWOT2 is determined by adding up the physical thicknesses of the barrier film 2 and the films contained in the dielectric multilayer film 2 having a refractive index of 1.9 or less and a thickness of less than QWOT2.

Furthermore, when the laminate film 2 has a layer made of _SiO2 , in the laminate film 2, X' defined by the following formula is preferably 35% or more, more preferably 50% or more, and even more preferably 70% or more, from the viewpoint of suppressing the reflectance on the light absorbing layer side.
X' (%) = {total thickness of SiO ₂ layers having a thickness of 180 nm or less in the laminated film 2 / (total physical film thickness of the laminated film 2 - total thickness of SiO ₂ layers having a thickness of more than 180 nm in the laminated film 2)} x 100

The thickness of the barrier film 1 is preferably 10 nm or more, and more preferably 20 nm or more, from the viewpoint of improving the moisture resistance and reliability of the optical filter.
The thickness of the barrier film 2 is preferably 10 nm or more, and more preferably 20 nm or more, from the viewpoint of improving the moisture resistance and reliability of the optical filter.

The total physical thickness of the barrier film 1 and the dielectric multilayer film 1 is preferably 1.5 μm or more, more preferably 2.0 μm or more, in view of improving the water resistance of the optical filter and preventing deformation of the film when the glass surface is altered.
The total physical thickness of the barrier film 2 and the dielectric multilayer film 2 is preferably 1.5 μm or more, more preferably 2.0 μm or more, in view of improving the water resistance of the optical filter and preventing deformation of the film when the glass surface is altered.

The barrier film can be formed using vacuum deposition processes such as CVD, sputtering, and vacuum deposition, or wet deposition processes such as spraying and dipping.

<Dielectric multilayer film>
The optical filter according to this embodiment has a dielectric multilayer film 1 on the barrier film 1 side, and a dielectric multilayer film 2 on the barrier film 2 side. Although details will be described later, when a film consisting of the barrier film 1 and the dielectric multilayer film 1 is formed as a laminated film 1, the laminated film 1 is preferably designed as a reflective film that reflects a part of near-infrared light (hereinafter also referred to as an "NIR reflective film").

The NIR reflective film preferably has wavelength selectivity that transmits visible light and mainly reflects near-infrared light. Specifically, it is preferably configured to have a wavelength band with a width of 100 nm or more in which the reflectance at an incident angle of 5 degrees is 80% or more for light with wavelengths between 750 nm and 1200 nm. The NIR reflective film may also be appropriately designed to reflect light in wavelength ranges other than near-infrared light, for example, near-ultraviolet light.

A dielectric multilayer film is a laminate of dielectric films with different refractive indices. More specifically, examples include a low refractive index dielectric film (low refractive index film), a medium refractive index dielectric film (medium refractive index film), and a high refractive index dielectric film (high refractive index film), and the dielectric multilayer film is composed of two or more of these laminated together. By combining several types of dielectric films with different spectral characteristics when transmitting and selecting the desired wavelength band, the reflection characteristics can be adjusted.

The high refractive index material has a refractive index at a wavelength of 500 nm of preferably 1.9 or more and 3.0 or less, more preferably 1.9 or more and 2.8 or less, and even more preferably 1.9 or more and _2.6 or _less . Examples of high refractive index materials include _Ta2O5 , _TiO2 , TiO, and _Nb2O5 . Other commercially available products include OS50 ( _Ti3O5 ), OS10 ( _Ti4O7 ), OA500 (a _{mixture of Ta2O5 and ZrO2} ), and OA600 (a mixture of _Ta2O5 and _TiO2 ) manufactured by Canon Optron Co., Ltd. Among these, _TiO2 is preferred from the viewpoints of film forming properties, reproducibility in refractive index, _stability , and the like.

The medium refractive index material is a material with a relatively lower refractive index than the high refractive index material, and the refractive index at a wavelength of 500 nm is preferably 1.5 to 2.0, more preferably 1.5 to 1.95, and even more preferably 1.5 to 1.9. Examples of the medium refractive index material include ZrO ₂ , Nb ₂ O ₅ , Al ₂ O ₃ , HfO ₂ , OM-4, OM-6 (a mixture of Al ₂ O ₃ and ZrO ₂ ), OA-100 sold by Canon Optron, and H4 and M2 (alumina lanthania) sold by Merck. Among these, Al ₂ O ₃ -based compounds and mixtures of Al ₂ O ₃ and ZrO ₂ are preferred from the standpoint of film-forming properties, reproducibility in refractive index, stability, and the like.

The low refractive index material is a material with a relatively lower refractive index than the medium refractive index material, and the refractive index at a wavelength of 500 nm is preferably 1.3 to 1.7, more preferably 1.3 to 1.65, and even more preferably 1.3 to 1.6. Examples of low refractive index materials include SiO ₂ , SiO _x N _{y, and} MgF _2. Other commercially available products include S4F and S5F (a mixture of SiO ₂ and AlO ₂ ) manufactured by Canon Optron Co., Ltd. Among these, SiO ₂ is preferred from the viewpoints of reproducibility, stability, and economy in film formation.

When the dielectric multilayer film 1 is made into a laminate film 1 consisting of a barrier film 1 and a dielectric multilayer film 1, it is preferable that the laminate film 1 be designed as a reflective film that reflects a portion of near-infrared light, and it is more preferable that the laminate film 1 be designed as a reflective film that gently blocks the near-infrared region.
If the dielectric multilayer film is designed to enhance the reflectivity in the near-infrared region, ripples are likely to occur in the visible light region when light with a high incidence angle is incident, and the visible light transmittance decreases. By designing the laminated film 1 so that it does not strongly block light in the near-infrared region, an optical filter that is less susceptible to the influence of the incidence angle can be obtained. The light blocking properties in the near-infrared region that cannot be completely blocked by the reflectivity of the laminated film 1 are complemented by the absorption properties of the above-mentioned phosphate glass and the near-infrared absorbing dye described below, and the present invention provides excellent near-infrared light blocking properties as an entire optical filter.
Specifically, it is preferable that the average reflectance at an incident angle of 5° for wavelengths of 800 nm to 1200 nm is 50% or more and 90% or less.

The thickness (physical thickness) of the dielectric multilayer film 1 is preferably 1 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more, from the viewpoint of suppressing deterioration of the material. Also, from the viewpoint of productivity, it is preferably 10 μm or less.

The total number of layers in the dielectric multilayer film 1 is preferably 20 or more, more preferably 30 or more, and even more preferably 35 or more. However, as the total number of layers increases, warping and other problems may occur and the film thickness may increase, so the total number of layers is preferably 100 or less, more preferably 75 or less, and even more preferably 60 or less.

The thickness (physical thickness) of the dielectric multilayer film 2 is preferably 100 nm or more, more preferably 300 nm or more, from the viewpoint of improving the water resistance of the optical filter, and is preferably 10 μm or less, from the viewpoint of productivity.

The total number of layers in the dielectric multilayer film 2 is preferably 60 layers or less, more preferably 30 layers or less, and even more preferably 6 layers or less.

The filter may have a dielectric multilayer film 3 on at least one of the outermost surfaces, preferably on the light absorbing layer. From the viewpoint of reducing the occurrence of ripples in the visible light region, it is preferable that the dielectric multilayer film 3 is designed as, for example, a near-infrared anti-reflection film (NIR anti-reflection film).

The total number of layers in the dielectric multilayer film 3 is preferably 60 or less, more preferably 30 or less, further preferably 15 or less, and is preferably at least 8. In order to suppress reflection in the visible wavelength range even when the angle of incidence changes, a film having low reflectance over the entire wavelength range is preferred, rather than a film that reflects a specific wavelength.
The overall thickness (physical thickness) of the dielectric multilayer film 3 is preferably 200 to 1000 nm.

The dielectric multilayer film can be formed using, for example, vacuum deposition processes such as CVD, sputtering, and vacuum deposition, or wet deposition processes such as spraying and dipping.

<Light absorbing layer>
The optical filter according to this embodiment includes a light absorbing layer provided on the dielectric multilayer film 2. The light absorbing layer contains a near-infrared absorbing dye, and can compensate for the wavelength region that is not blocked by the reflection characteristics of the dielectric multilayer film by absorbing light. The near-infrared absorbing dye preferably has a maximum absorption wavelength in the range of 680 to 800 nm.
From the viewpoint of being able to absorb a wide range of the near-infrared region and being able to suppress a decrease in visible light transmittance, it is preferable to combine two or more near-infrared absorbing dyes having different maximum absorption wavelengths in the region of 680 to 800 nm, and it is more preferable to combine one or more near-infrared absorbing dyes having a maximum absorption wavelength of 700 nm or more and less than 740 nm with one or more near-infrared absorbing dyes having a maximum absorption wavelength of 740 to 800 nm.

As the near infrared absorbing dye, at least one selected from the group consisting of squarylium dyes, cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, dithiol metal complex dyes, azo dyes, polymethine dyes, phthalide dyes, naphthoquinone dyes, anthraquinone dyes, indophenol dyes, pyrylium dyes, thiopyrylium dyes, croconium dyes, tetradehydrocoline dyes, triphenylmethane dyes, aminium dyes, and diimmonium dyes is preferred.

The near-infrared absorbing dye preferably contains at least one dye selected from squarylium dyes, phthalocyanine dyes, and cyanine dyes. Among these dyes, squarylium dyes and cyanine dyes are preferred from the viewpoint of spectroscopy, and phthalocyanine dyes are preferred from the viewpoint of durability.

The light absorbing layer is also preferably a resin film containing the dye and a resin.
The content of the near infrared absorbing dye in the light absorbing layer is preferably 0.1 to 25 parts by mass, more preferably 0.3 to 15 parts by mass, based on 100 parts by mass of the resin. When two or more types of compounds are combined, the above content is the total content of each compound.

The light absorbing layer may contain other dyes in addition to the near infrared absorbing dyes. As the other dyes, dyes (UV dyes) that have a maximum absorption wavelength in the resin at 370 to 440 nm are preferred. This allows for efficient blocking of the near ultraviolet light region.

Examples of UV dyes include oxazole dyes, merocyanine dyes, cyanine dyes, naphthalimide dyes, oxadiazole dyes, oxazine dyes, oxazolidine dyes, naphthalic acid dyes, styryl dyes, anthracene dyes, cyclic carbonyl dyes, and triazole dyes. Among these, merocyanine dyes are particularly preferred. Furthermore, one type may be used alone, or two or more types may be used in combination.

The resin in the light absorbing layer is not limited as long as it is a transparent resin, and one or more transparent resins selected from polyester resin, acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyarylene ether phosphine oxide resin, polyamide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyurethane resin, polystyrene resin, etc. may be used. One of these resins may be used alone, or two or more may be used in combination.
From the viewpoints of the spectral characteristics, glass transition point (Tg) and adhesion of the light absorbing layer, one or more resins selected from polyimide resins, polycarbonate resins, polyester resins and acrylic resins are preferred.

When multiple compounds are used as near-infrared absorbing dyes or other dyes, they may be contained in the same light absorbing layer, or each may be contained in a separate light absorbing layer.

The light absorbing layer can be formed by dissolving or dispersing the dye, resin or raw material components of the resin, and each component that is mixed as necessary in a solvent to prepare a coating liquid, which is then applied to the surface of the dielectric multilayer film 2, dried, and further cured as necessary. Alternatively, the coating liquid can be applied to a peelable support that is used only when forming the light absorbing layer, and the light absorbing layer can be laminated on the dielectric multilayer film 2 afterwards. The solvent may be a dispersion medium that allows stable dispersion or a solvent that allows dissolution.

The coating liquid may also contain a surfactant to improve voids caused by tiny bubbles, depressions caused by the adhesion of foreign matter, and repellency during the drying process. For example, the dip coating method, cast coating method, or spin coating method can be used to apply the coating liquid. If the coating liquid contains raw materials for a transparent resin, a curing process such as heat curing or light curing is further performed.

The light absorbing layer can also be manufactured in the form of a film by extrusion molding. The resulting film-like absorbing layer can be laminated to the dielectric multilayer film 2 and integrated by thermocompression bonding or the like to produce the filter.

The optical filter may have one light absorbing layer or two or more layers. When there are two or more layers, each layer may have the same or different configuration, and may be formed on the surface of each dielectric multilayer film, or two or more layers may be stacked on the surface of one of the dielectric multilayer films.

The thickness of the light absorbing layer is 10 μm or less, preferably 5 μm or less, from the viewpoint of the in-plane film thickness distribution in the substrate after coating and the appearance quality, and is preferably 0.5 μm or more, from the viewpoint of expressing the desired spectral characteristics at an appropriate dye concentration. Note that, when the optical filter has two or more light absorbing layers, it is preferable that the total thickness of each light absorbing layer is within the above range.

The optical filter according to this embodiment may also include other components, such as components (layers) that absorb light using inorganic fine particles that control the transmission and absorption of light in a specific wavelength range. Specific examples of inorganic fine particles include ITO (indium tin oxide), ATO (antimony-doped tin oxide), cesium tungstate, lanthanum boride, and the like. ITO fine particles and cesium tungstate fine particles have high visible light transmittance and light absorption over a wide range of infrared wavelengths exceeding 1200 nm, and therefore can be used when blocking such infrared light is required.

<Imaging device>
The imaging device according to the embodiment of the present invention preferably includes the optical filter according to the embodiment of the present invention. The imaging device preferably further includes a solid-state imaging element and an imaging lens. The optical filter according to the present embodiment can be used, for example, by being disposed between the imaging lens and the solid-state imaging element, or by being directly attached to the solid-state imaging element, imaging lens, etc. of the imaging device via an adhesive layer. By including this filter, which has excellent visible light transmittance, specific near-infrared light shielding properties, and a spectral curve that is unlikely to shift even at a high incidence angle, an imaging device with excellent color reproducibility even for light at a high incidence angle can be obtained.

When mounting an optical filter on an imaging device, it is usually preferable to place dielectric multilayer film 1 on the lens side (external light incident side) and dielectric multilayer film 2 on the sensor side.

As described above, this specification discloses the following optical filters, etc.
[1] An optical filter comprising: a phosphate glass; a dielectric multilayer film 1 and a dielectric multilayer film 2 provided on both sides of the phosphate glass; a barrier film 1 provided between the phosphate glass and the dielectric multilayer film 1; a barrier film 2 provided between the phosphate glass and the dielectric multilayer film 2; and a light absorbing layer provided on the dielectric multilayer film 2,
the light absorbing layer contains a near infrared absorbing dye,
The barrier film 1 and the barrier film 2 each independently contain one or more selected from TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and HfO ₂ ;
The optical filter satisfies all of the following spectral characteristics (i-1) to (i-5).
(i-1) The average transmittance of wavelengths from 440 to 500 nm is 80% or more at an incident angle of 0 degrees and 70% or more at an incident angle of 60 degrees. (i-2) The average transmittance of wavelengths from 750 to 1000 nm is 0.5% or less at an incident angle of 0 degrees and 0.5% or less at an incident angle of 60 degrees. (i-3) The wavelength IR10 _{(0 deg)} at which the transmittance is 10% in the spectral transmittance curve at an incident angle of 0 degrees is in the range of 600 to 700 nm. (i-4) The wavelength IR10 _{(0 deg)} at which the transmittance is 10% in the range of 600 to 700 nm in the spectral transmittance curve at an incident angle of 0 degrees and the wavelength IR10 (i-5) When the light absorbing layer side is the incident direction, the maximum reflectance of a wavelength of 450 to 950 nm is 24% or less at an incident angle of 5 degrees and 35% or less at an incident angle of ₆₀ degrees. [2] When a film consisting of the barrier film 2 and the dielectric multilayer film 2 is a laminate film 2,
The optical filter according to [1], wherein X defined by the following formula is 35% or more.

(QWOT = (physical film thickness nm/550 nm) x 4 x refractive index at 550 nm)
[3] The optical filter according to [1] or [2], wherein the optical filter satisfies the following spectral characteristic (i-6):
(i-6) When the dielectric multilayer film 1 side is the incident direction, the maximum reflectance at wavelengths of 750 to 950 nm is 20% or more at an incident angle of 5 degrees and 30% or more at an incident angle of 60 degrees. [4] The optical filter according to any one of [1] to [3], wherein the optical filter satisfies the following spectral characteristic (i-7):
(i-7) The absolute value of the difference between the average transmittance at an incident angle of 0 degrees and the average transmittance at an incident angle of 60 degrees, at a wavelength of 440 to 500 nm, is 15% or less. [5] The optical filter according to any one of [1] to [4], wherein the optical filter satisfies the following spectral characteristic (i-8):
(i-8) The optical filter according to any one of [1] to [5], wherein the average transmittance at wavelengths of 900 to 1000 nm is 1% or less at an incident angle of 0 degrees. [6] The barrier film 1 and the barrier film 2 contain _TiO2 .
[7] The optical filter according to any one of [1] to [6], wherein the total thickness of the barrier film 2 and the dielectric multilayer film 2 is 1.5 μm or more.
[8] The optical filter according to any one of [1] to [7], wherein the total thickness of the barrier film 1 and the dielectric multilayer film 2 is 1.5 μm or more.
[9] The phosphate glass is substantially free of fluorine atoms,
In terms of oxide mole percentage, _{P2O5 is} 40% to 75%.
Al ₂ O ₃ 10% to 30%,
ΣR ₂ O 0.1% to 30% (wherein R ₂ O is one or more components selected from Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O, and ΣR ₂ O represents the total content of R ₂ O);
ΣR′O 0% to 30% (wherein R′O is one or more components selected from CaO, MgO, BaO, SrO, and ZnO, and ΣR′O represents the total content of R′O),
CuO 2-30%,
The optical filter according to any one of [1] to [8], comprising:
[10] The phosphate glass has a plate thickness of 0.29 mm,
The average transmittance for wavelengths between 440 and 500 nm is 70% or more.
The transmittance at a wavelength of 1200 nm is 20% or less.
The transmittance at a wavelength of 1000 nm is 7% or less.
The optical filter according to any one of [1] to [9], which has a transmittance of 7% or less at a wavelength of 800 nm.
[11] The optical filter according to any one of [1] to [10], wherein the light absorbing layer contains one or more near-infrared absorbing dyes having a maximum absorption wavelength in the range of 700 nm or more and less than 740 nm, and one or more near-infrared absorbing dyes having a maximum absorption wavelength in the range of 740 to 800 nm.
[12] An imaging device comprising the optical filter according to any one of [1] to [11].

Next, the present invention will be described more specifically with reference to examples.
The spectral characteristics were measured using an ultraviolet-visible spectrophotometer (UH-4150, manufactured by Hitachi High-Technologies Corporation).
In addition, unless the angle of incidence is specifically stated, the spectral characteristics are values measured at an angle of incidence of 0 degrees (perpendicular to the principal surface of the optical filter).

The dyes used in each example are as follows:
Compound 1 (cyanine compound): Synthesized based on Dyes and pigments 73 (2007) 344-352.
Compound 2 (merocyanine compound): Synthesized according to the specification of German Patent Publication No. 10109243.
Compound 3 (squarylium compound): Synthesized based on WO 2017/135359.
Compound 4 (squarylium compound): Synthesized based on WO 2014/088063 and WO 2016/133099.
Compound 5 (merocyanine compound): synthesized based on the specification of German Patent Publication No. 10109243.

Compounds 1, 3, and 4 are near-infrared absorbing dyes (NIR dyes), and compounds 2 and 5 are near-ultraviolet absorbing dyes (UV dyes). The maximum absorption wavelengths of each dye are shown in Table 5 below.

<Spectral properties of glass>
The following glasses were prepared:
The raw materials were weighed and mixed so as to obtain the contents shown in Table 1 as phosphate glass or fluorophosphate glass, expressed in mol% on an oxide basis, and placed in a crucible with an internal volume of about 400 mL and melted for 2 hours in a reducing atmosphere. The mixture was then clarified, stirred, and poured into a rectangular mold with dimensions of 100 mm length x 80 mm width x 20 mm height that had been preheated to about 300°C to 500°C, and then slowly cooled at a rate of about 1°C/min to obtain a plate-shaped glass sample with both sides optically polished.

The spectral characteristics of each glass are shown in Table 1 below.
The spectral transmittance curves of each glass are shown in FIG.

<Glass reliability test 1>
A test piece of Glass 1 manufactured above, 5 mm long and 5 mm wide, was prepared, and the materials shown in Table 2 below were laminated by vapor deposition on both main surfaces to form barrier films.
The glass substrate with the barrier film was subjected to a high temperature and high humidity test under the following conditions.
After leaving the glass substrate with the barrier film in an environment of 85°C and 85% relative humidity for the time shown in Table 2, the end face was observed from the main surface side with a metallurgical microscope at 200x magnification to evaluate the degree of deterioration. The distance from the end face to the most deteriorated point was measured and evaluated based on the following criteria. C or higher is considered to be pass.
A: End face deterioration is less than 50 μm. B: End face deterioration is 50 μm or more but less than 100 μm. C: End face deterioration is 100 μm or more but less than 200 μm. D: End face deterioration is 200 μm or more. The evaluation results are shown in Table 2 below.
Examples 1-1 and 1-2 are reference examples, and Examples 1-3 to 1-5 are reference comparative examples.

The above results show that barrier films made from titania or tantalum have excellent durability. On the other hand, end face degradation was observed in barrier films made from alumina, silica, and zirconia, and durability was not achieved.

<Glass reliability test 2>
A test piece of glass 1 manufactured above, 5 mm long and 5 mm wide, was prepared, and barrier films were formed on both main surfaces by depositing the materials shown in Table 4 below. _SiO2 and _TiO2 were alternately deposited on the surface of each barrier film by deposition to form a dielectric multilayer film having the structure shown in Table 3. Film number 1 is the layer in contact with the barrier film.
The degree of deterioration of the end face of the obtained test piece was evaluated by the same method and criteria as in Glass Reliability Test 1.
The evaluation results are shown in Table 4 below.
Examples 1-6 to 1-7 are reference examples.

 

 

 

 

The above results confirmed that the barrier film had durability in both cases where dielectric multilayer film A or B was laminated. Furthermore, durability was further improved in Example 1-6, where the total thickness of the dielectric multilayer film and barrier film was 1.5 μm or more.

<Spectral characteristics of light absorbing layer>
The dyes of Compounds 1 to 5 were dissolved in polyimide resin C-3G30G manufactured by Mitsubishi Gas Chemical Company, Inc., mixed at the concentrations shown in Table 5 below, and stirred and dissolved for 2 hours at 50° C. to obtain coating solutions. The obtained coating solutions were applied to alkaline glass (D263 glass manufactured by SCHOTT, thickness 0.2 mm) by spin coating to form light absorbing layers 1 and 2 with a thickness of 1 μm.
The resulting light absorbing layer was measured for its spectral transmittance curve and spectral reflectance curve in the wavelength range of 350 to 1200 nm using an ultraviolet-visible spectrophotometer.
The results are shown in Table 5 below.
The spectral transmittance curve of the light absorbing layer is shown in FIG.

 

 

<Example 2-1: Spectral characteristics of optical filters>
Barrier film 1 and barrier film 2 were formed by depositing TiO ₂ on both main surfaces of glass 1 (phosphate glass).
A dielectric multilayer film 1A having the configuration shown in Table 6 was formed by alternately laminating _SiO2 and _TiO2 on the surface of the barrier film 1 by vapor deposition.
SiO ₂ and TiO ₂ were alternately laminated on the surface of the barrier film 2 by vapor deposition to form a dielectric multilayer film 2A having the configuration shown in Table 7.
A resin solution having the same composition as the light absorbing layer 1 was applied to the surface of the barrier film 2 and heated sufficiently to remove the organic solvent, thereby forming a light absorbing layer having a thickness of 1 μm.
A dielectric multilayer film 3A (anti-reflection film) having the configuration shown in Table 8 was formed by alternately laminating _SiO2 and _TiO2 on the surface of the light absorbing layer by vapor deposition.
In this manner, the optical filter 2-1 was manufactured.

<Example 2-2>
Optical filter 2-2 was manufactured in the same manner as in Example 2-1, except that a dielectric multilayer film 2B having the configuration shown in Table 7 was formed instead of dielectric multilayer film 2A, and the thickness of barrier film 2 was changed to the value shown in Table 9.

<Example 2-3>
Optical filter 2-3 was manufactured in the same manner as in Example 2-1, except that a dielectric multilayer film 1B having the configuration shown in Table 6 was formed instead of dielectric multilayer film 1A, and the thickness of barrier film 1 was changed to the value shown in Table 9.

<Example 2-4>
An optical filter 2-4 was manufactured in the same manner as in Example 2-1, except that a dielectric multilayer film 2C having the configuration shown in Table 7 was formed instead of the dielectric multilayer film 2A, and the thickness of the barrier film 2 was changed to the value shown in Table 9.

<Example 2-5>
Optical filter 2-5 was manufactured in the same manner as in Example 2-1, except that a dielectric multilayer film 2D having the configuration shown in Table 7 was formed instead of dielectric multilayer film 2A, and the thickness of barrier film 2 was changed to the value shown in Table 9.

<Example 2-6>
An optical filter 2-6 was manufactured in the same manner as in Example 2-1, except that a dielectric multilayer film 2E having the configuration shown in Table 7 was formed instead of the dielectric multilayer film 2A, and the thickness of the barrier film 2 was changed to the value shown in Table 9.

<Example 2-7>
An optical filter 2-7 was manufactured in the same manner as in Example 2-1, except that a 2000 nm silica film was formed instead of the dielectric multilayer film 2A and the thickness of the barrier film 2 was changed to the value shown in Table 9.

<Example 2-8>
Optical filter 2-8 was manufactured in the same manner as in Example 2-1, except that a dielectric multilayer film 1C having the configuration shown in Table 6 was formed instead of dielectric multilayer film 1A, and the thickness of barrier film 1 was changed to the value shown in Table 9.

<Example 2-9>
An optical filter 2-9 was produced in the same manner as in Example 2-1, except that glass 2 (phosphate glass) was used instead of glass 1 (phosphate glass).

<Example 2-10>
An optical filter 2-10 was produced in the same manner as in Example 2-1, except that Glass 3 (phosphate glass) was used instead of Glass 1 (phosphate glass).

<Example 2-11>
An optical filter 2-11 was produced in the same manner as in Example 2-1, except that Glass 4 (fluorophosphate glass) was used instead of Glass 1 (phosphate glass).

<Example 2-12>
Barrier film 1 and barrier film 2 were formed by depositing TiO ₂ on both main surfaces of glass 5 (phosphate glass).
A dielectric multilayer film 1D having the configuration shown in Table 6 was formed on the surface of the barrier film 1 by alternately laminating _SiO2 and _TiO2 by vapor deposition.
SiO ₂ and TiO ₂ were alternately laminated on the surface of the barrier film 2 by vapor deposition to form a dielectric multilayer film 2B having the configuration shown in Table 7.
A resin solution having the same composition as the light absorbing layer 2 was applied to the surface of the barrier film 2 and heated sufficiently to remove the organic solvent, thereby forming a light absorbing layer having a thickness of 1 μm.
A dielectric multilayer film 3B (anti-reflection film) having the configuration shown in Table 8 was formed by alternately laminating _SiO2 and _TiO2 on the surface of the light absorbing layer by vapor deposition.
In this manner, the optical filter 2-12 was manufactured.

For each of the optical filters obtained above, the spectral transmittance curves at incident angles of 0 degrees and 60 degrees and the spectral reflectance curves at incident angles of 5 degrees and 60 degrees in the wavelength range of 350 to 1200 nm were measured using an ultraviolet-visible spectrophotometer.
In addition, the degree of deterioration of the end faces was evaluated using the same method and criteria as in Glass Reliability Test 1.
From the obtained data of spectral characteristics, the various characteristics shown in Tables 9 and 10 below were calculated.
The method of calculating X in the laminated film 2 will be specifically shown by taking as an example a laminated film 2 consisting of a dielectric multilayer film 2A and a barrier film 2. Here, the refractive index of _SiO2 is 1.9 or less, and the refractive index of _TiO2 exceeds 1.9.
The total physical thickness of the laminated film 2 having a QWOT of less than 2 and a refractive index of 1.9 or less can be calculated from the sum of the physical thickness of the SiO ₂ film of film number 3 constituting the dielectric multilayer film 2A shown in Table 7 and the physical thickness of the SiO ₂ film of film number 5.
The total physical thickness of the laminated film 2 can be calculated from the sum of the physical thickness of the entire dielectric multilayer film 2 A and the physical thickness of the barrier film 2 .
The total physical thickness of the laminated film 2 having a QWOT of 2 or more corresponds to the physical thickness of the SiO ₂ film having film number 1 constituting the dielectric multilayer film 2A shown in Table 7.
From the above, X was calculated.

5 shows the spectral reflectance curve of the laminated film 1 consisting of the dielectric multilayer film 1A and the barrier film 1. FIG. 6 shows the spectral reflectance curve of the laminated film 1 consisting of the dielectric multilayer film 1C and the barrier film 1.
The spectral transmittance curve of the optical filter of Example 2-1 is shown in FIG. 7, the spectral reflectance curve on the dielectric multilayer film 1 side is shown in FIG. 8, and the spectral reflectance curve on the light absorption layer side is shown in FIG.
The spectral transmittance curve of the optical filter of Example 2-7 is shown in FIG. 10, the spectral reflectance curve on the dielectric multilayer film 1 side is shown in FIG. 11, and the spectral reflectance curve on the light absorption layer side is shown in FIG.

Note that Examples 2-1 to 2-4, 2-9 to 2-10, and 2-12 are working examples, and Examples 2-5 to 2-8 and 2-11 are comparative examples.

From the above results, it can be seen that the optical filters of Examples 2-1 to 2-4, 2-9 to 2-10, and 2-12 are optical filters that have excellent visible light transmittance even at a high incidence angle, excellent near-infrared light shielding properties of 750 to 1000 nm, small reflection characteristics of light with wavelengths of 450 to 950 nm, and small shift in the spectral curve even at a high incidence angle.
The optical filters of Examples 2-5 to 2-7 had high reflectance characteristics in the wavelength range of 450 to 950 nm. Furthermore, X calculated from the laminated film 2 consisting of the barrier film 2 and the dielectric multilayer film 2C was less than 35%.
The optical filter of Example 2-8 had low visible light transmittance and low near-infrared light blocking ability of 750 to 1000 nm at high incidence angles. In addition, the shift in the spectral curve was large at high incidence angles. This is believed to be due to the fact that the multilayer film 1C used as the dielectric multilayer film 1 has high reflection characteristics.
The optical filter of Example 2-11 had a low near-infrared light shielding ability of 750 to 1000 nm at a high incidence angle. This is believed to be because the use of fluorophosphate glass results in low absorption characteristics in this region.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-135693) filed on August 23, 2023, the contents of which are incorporated herein by reference.

The optical filter of the present invention has excellent visible light transmittance and near-infrared light blocking properties. It is useful for applications in information acquisition devices, such as cameras and sensors for transport aircraft, which have become increasingly high-performance in recent years.

1A, 1B Optical filter 10 Phosphate glass 11, 12 Barrier film 21, 22, 23 Dielectric multilayer film 30 Light absorption layer

Claims (12)

An optical filter comprising: phosphate glass; a dielectric multilayer film 1 and a dielectric multilayer film 2 provided on both sides of the phosphate glass; a barrier film 1 provided between the phosphate glass and the dielectric multilayer film 1; a barrier film 2 provided between the phosphate glass and the dielectric multilayer film 2; and a light absorbing layer provided on the dielectric multilayer film 2,
the light absorbing layer contains a near infrared absorbing dye,
The barrier film 1 and the barrier film 2 each independently contain one or more selected from TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and HfO ₂ ;
The optical filter satisfies all of the following spectral characteristics (i-1) to (i-5).
(i-1) The average transmittance of wavelengths from 440 to 500 nm is 80% or more at an incident angle of 0 degrees and 70% or more at an incident angle of 60 degrees. (i-2) The average transmittance of wavelengths from 750 to 1000 nm is 0.5% or less at an incident angle of 0 degrees and 0.5% or less at an incident angle of 60 degrees. (i-3) The wavelength IR10 _{(0 deg)} at which the transmittance is 10% in the spectral transmittance curve at an incident angle of 0 degrees is in the range of 600 to 700 nm. (i-4) The wavelength IR10 _{(0 deg)} at which the transmittance is 10% in the range of 600 to 700 nm in the spectral transmittance curve at an incident angle of 0 degrees and the wavelength IR10 (i-5) When the light absorbing layer side is the incident direction, the maximum reflectance at wavelengths of 450 to 950 nm is 24% or less at an incident angle of 5 degrees and 35% or less at an incident angle of ₆₀ degrees. When a film consisting of the barrier film 2 and the dielectric multilayer film 2 is defined as a laminate film 2,
2. The optical filter according to claim 1, wherein X defined by the following formula is 35% or more.

(QWOT = (physical film thickness nm/550 nm) x 4 x refractive index at 550 nm) 2. The optical filter according to claim 1, wherein the optical filter satisfies the following spectral characteristic (i-6).
(i-6) When the dielectric multilayer film 1 side is the incident direction, the maximum reflectance of a wavelength of 750 to 950 nm is 20% or more at an incident angle of 5 degrees and 30% or more at an incident angle of 60 degrees. 2. The optical filter according to claim 1, wherein the optical filter satisfies the following spectral characteristic (i-7):
(i-7) The absolute value of the difference between the average transmittance at an incident angle of 0 degrees and the average transmittance at an incident angle of 60 degrees in the wavelength range of 440 to 500 nm is 15% or less. 2. The optical filter according to claim 1, wherein the optical filter satisfies the following spectral characteristic (i-8).
(i-8) The average transmittance of the wavelength of 900 to 1000 nm is 1% or less at an incident angle of 0 degrees. The optical filter of claim 1 , wherein said barrier film 1 and said barrier film 2 comprise TiO ₂ . The optical filter according to claim 1, wherein the combined thickness of the barrier film 2 and the dielectric multilayer film 2 is 1.5 μm or more. The optical filter according to claim 1, wherein the combined thickness of the barrier film 1 and the dielectric multilayer film 1 is 1.5 μm or more. The phosphate glass is substantially free of fluorine atoms,
In terms of oxide mole percentage, _{P2O5 is} 40% to 75%.
Al ₂ O ₃ 10% to 30%,
ΣR ₂ O 0.1% to 30% (wherein R ₂ O is one or more components selected from Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O, and ΣR ₂ O represents the total content of R ₂ O);
ΣR′O 0% to 30% (wherein R′O is one or more components selected from CaO, MgO, BaO, SrO, and ZnO, and ΣR′O represents the total content of R′O),
CuO 2-30%,
The optical filter of claim 1 , comprising: The phosphate glass has a plate thickness of 0.29 mm.
The average transmittance for wavelengths between 440 and 500 nm is 70% or more.
The transmittance at a wavelength of 1200 nm is 20% or less.
The transmittance at a wavelength of 1000 nm is 7% or less.
2. The optical filter according to claim 1, which has a transmittance of 7% or less at a wavelength of 800 nm. The optical filter of claim 1, wherein the light absorbing layer contains one or more near-infrared absorbing dyes having a maximum absorption wavelength in the range of 700 nm to less than 740 nm, and one or more near-infrared absorbing dyes having a maximum absorption wavelength in the range of 740 to 800 nm. An imaging device equipped with an optical filter according to any one of claims 1 to 11.

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