JP7505259B2 - Optical filters and their uses - Google Patents

Description

The present invention relates to an optical filter and its uses. More specifically, the present invention relates to an optical filter (e.g., a near-infrared cut filter) that contains a compound that absorbs in a specific wavelength range and has specific optical properties, as well as an imaging device and a camera module that use the optical filter.

Solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions use CCD and CMOS image sensors, which are solid-state imaging elements for color images. These solid-state imaging elements use silicon photodiodes in their light receiving sections that are sensitive to near-infrared light, which cannot be detected by the human eye. These solid-state imaging elements require visibility correction to make the colors appear natural to the human eye, and often use optical filters (for example, near-infrared cut filters) that selectively transmit or cut light in a specific wavelength range.

Near-infrared cut filters manufactured by various methods have been used in the past. For example, an absorbing glass type optical filter (see, for example, Patent Document 1) is known, which uses an absorbing glass made of phosphate glass with copper oxide dispersed in it as a base material.

In recent years, there has been a demand for thinner solid-state imaging devices, and therefore thinner optical filters are also required. The absorption principle of the above-mentioned absorbing glass type optical filters often uses absorption derived from the d-orbital of copper ions, but because the absorption intensity is weak, there are cases where a sufficient near-infrared blocking performance cannot be obtained when the filter is made thinner.

In such thin absorbing glass type optical filters, a dielectric multilayer film with near-infrared reflectivity is often provided on the substrate surface to compensate for the near-infrared cut performance (see, for example, Patent Document 2). By providing a dielectric multilayer film with near-infrared reflectivity on the substrate surface, it is possible to achieve both thinness and near-infrared shielding properties.

As optical filters having a dielectric multilayer film with near-infrared reflectivity, in addition to the absorbing glass type, various types are known, such as a resin-type optical filter that uses a transparent resin as a substrate, contains a dye with an absorption maximum in the 650 to 800 nm region, and uses a dielectric multilayer film with near-infrared reflectivity on both sides of the substrate (Patent Document 3), a filter in which copper phosphate or cesium tungsten oxide particles are applied to a glass substrate (Patent Document 4), and a glass substrate-coated optical filter in which a resin layer containing a dye with absorption in the 700 to 750 nm region is applied (Patent Document 5).

However, optical filters that have near-infrared reflectivity on the substrate surface, such as the above-mentioned absorbing glass type, resin type, and glass substrate coating type optical filters, can cause a phenomenon in which light reflected from the surface of the optical filter is again incident on the sensor, i.e., ghosting, which can cause image defects in the resulting solid-state imaging device.

In addition, in these optical filters, although the thickness of each layer in the dielectric multilayer film is thin, the number of layers needs to be increased in order to achieve near-infrared reflectivity. This means that it takes a long time to manufacture the dielectric multilayer film, which results in poor manufacturing throughput and a tendency for manufacturing costs to rise.

It has long been known that providing an anti-reflection layer on an optical filter can suppress ghosting (Patent Document 6). However, the anti-reflection layer in conventional optical filters is an anti-reflection layer for wavelengths of 420 nm to 780 nm (visible light region), and therefore cannot prevent reflection of light with wavelengths of 781 nm to 900 nm, resulting in the generation of ghosting. Furthermore, if near-infrared reflectivity is not imparted to a thin substrate, the optical density (OD) at wavelengths of 700 nm to 900 nm is insufficient, making it impossible to achieve both thinning and near-infrared shielding performance. In other words, no optical filter has been obtained that is thin, has excellent near-infrared shielding properties, and has low reflectance over the wavelength range from the visible light region to the near-infrared region.

International Publication No. 2011/071157 International Publication No. 2011/158635 Japanese Patent Application Laid-Open No. 6-200113 JP 2014-052482 A JP 2014-063144 A International Publication No. 2016/174954

The object of the present invention is to provide an optical filter that has excellent near-infrared shielding properties even when it is thin, and an imaging device and a camera module that use the optical filter.

Examples of aspects of the present invention are given below.
[1] An optical filter characterized by satisfying the following requirements (a) to (d): (a) in the wavelength region of 700 nm to 900 nm, the minimum optical density (OD value) (OD _{a-0 ) for light incident perpendicularly to the surface of the optical filter is 2.0 or more; (b) in the wavelength region of 430 nm to 580 nm, the average transmittance (T a- 0} ) for light incident perpendicularly to the surface of the optical filter is 40% or more; (c) in the wavelength region of 420 nm to 900 nm, the average reflectance (Rf a- ₅ ) for light incident at an angle of 5 degrees from the perpendicular direction to the surface of the optical filter is 20% or less; (d) the optical filter comprises a layer containing at least three types of compounds (A) having an absorption maximum in the wavelength region of 650 nm or more and less than 950 nm.
[2] The optical filter according to item [1], further satisfying the following requirement (e): (e) the optical filter has a substrate including the layer according to requirement (d) and a dielectric multilayer film on at least one surface of the substrate, and the product (N×TN) of the number of layers (N) having a thickness of 0.5 μm or less among the layers constituting the dielectric multilayer film and the sum (TN) (μm) of the thicknesses of the layers having a thickness of 0.5 μm or less is 150 or less.
[3] The optical filter according to item [1] or [2], having a thickness of 160 μm or less.
[4] The optical filter according to any one of items [1] to [3], characterized in that at least one of the compounds (A) satisfies the following requirements (f) and (g) as absorption characteristics measured after dissolving in dichloromethane: (f) the maximum absorption wavelength λmax in the wavelength region of 650 nm or more and less than 950 nm is a wavelength of 850 nm or more and 935 nm or less; (g) when the maximum extinction coefficient _ελmax in the wavelength region of 650 nm or more and less than 950 nm is normalized by 1,
(g-1) the absorption coefficient ελmax _-10 at a wavelength of (λmax-10) nm is 0.80 or more;
(g-2) the absorption coefficient ελmax ₊₁₀ at a wavelength of (λmax+10) nm is 0.80 or more;
(g-3) The average value ε _430-580ave of the absorption coefficient in the wavelength region of 430 nm or more and 580 nm or less is 0.03 or less.
[5] The optical filter according to any one of items [1] to [4], wherein the compound (A) includes at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, cyanine compounds, diimonium compounds, metal dithiolate compounds, and pyrrolopyrrole compounds.
[6] The layer containing the compound (A) is a resin layer made of at least one resin selected from the group consisting of cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane UV-curable resins, maleimide resins, alicyclic epoxy thermosetting resins, polyether ether ketone resins, polyarylate resins, allyl ester curable resins, acrylic UV-curable resins, vinyl UV-curable resins, and resins formed by a sol-gel method, the main component of which is silica. The optical filter according to any one of [1] to [5].
[7] The optical filter according to item [2], wherein the base material includes a substrate made of a fluorine phosphate-based glass layer or a phosphate-based glass layer containing a copper component.
[8] An imaging device comprising the optical filter according to any one of items [1] to [7].
[9] A camera module comprising the optical filter according to any one of items [1] to [7].

The present invention provides an optical filter that has excellent near-infrared shielding properties even when thin and has good manufacturing throughput, as well as an imaging device and a camera module that use the optical filter.

FIG. 13 is a diagram showing a configuration for measuring a transmission spectrum in a direction perpendicular to the surface of an optical filter, a direction at an angle of 30 degrees, and a direction at an angle of 60 degrees. FIG. 1 is a schematic diagram showing an example of a method for measuring the reflectance of light incident on a surface of an optical filter at an angle of 5 degrees with respect to a direction perpendicular to the surface.

Hereinafter, an embodiment of the present invention will be described in detail.
[Optical filter]
The optical filter of the present invention is characterized by satisfying the following requirements (a) to (d). The optical filter of the present invention may be composed only of a substrate described below. In other words, the optical filter of the present invention may or may not have a dielectric multilayer film.
(a) In the wavelength region of 700 nm to 900 nm, the minimum optical density (OD value) for light incident perpendicularly to the surface of the optical filter (OD _a-0 ) is 2.0 or more.
(b) In the wavelength region of 430 nm to 580 nm, the average transmittance (T _a-0 ) of light incident perpendicularly to the surface of the optical filter is 40% or more.
(c) In the wavelength region of 420 nm to 900 nm, the average reflectance (Rf _a-5 ) for light incident at an angle of 5 degrees from the perpendicular direction to the surface of the optical filter is 20% or less.
(d) A layer containing at least three kinds of compounds (A) having an absorption maximum in the wavelength region of 650 nm or more and less than 950 nm.

The optical filter of the present invention may further satisfy the following requirement (e).
(e) A substrate (hereinafter also referred to as "substrate (i)") containing the layer described in requirement (d) and a dielectric multilayer film on at least one surface of the substrate (i), wherein the product (N x TN) of the number of layers (N) having a thickness of 0.5 μm or less among the layers constituting the dielectric multilayer film and the sum (TN) (μm) of the thicknesses of each layer having a thickness of 0.5 μm or less is 150 or less.
The above requirements (a) to (e) will be described in detail later.

The optical filter of the present invention may satisfy the following requirement (X).
Requirement (X): In the wavelength region of 300 nm or more and 1200 nm or less, the maximum value Rfall _a-5 of the reflectance of light incident on one surface of the optical filter from a direction oblique at 5 degrees with respect to the vertical direction, and the maximum value Rfall _b-5 of the reflectance of light incident on the other surface from a direction oblique at 5 degrees with respect to the vertical direction are both 50% or less, more preferably 45% or less.

By satisfying requirement (X), the reflectance of light with wavelengths of 300 nm or more and 1200 nm or less, to which the silicon photodiode is sensitive, can be reduced on both sides of the optical filter. When the optical filter of the present invention is used for a solid-state imaging device or as a camera module, multiple reflections between the optical filter and the lens and between the optical filter and the sensor are reduced, making it possible to obtain good images with fewer ghosts.

Methods that satisfy requirement (X), i.e., methods of adjusting the reflectance, include, for example, a method of forming a layer that changes the refractive index continuously from the incident medium to the substrate by providing numerous cone-shaped structures whose size is less than the wavelength of light, and a method of forming an anti-reflection layer using a dielectric multilayer film consisting of multiple layers.

As a method for satisfying requirement (X), i.e., a method for designing an optical filter with low reflectance, for example, there is a method using a substrate in which the absolute value |Xa-Xb| of the difference between the shortest wavelength value (Xa) at which the transmittance is 50% when measured perpendicular to the substrate in the wavelength range of 580 to 800 nm and the longest wavelength value (Xb) at which the transmittance is 50% when measured perpendicular to the substrate in the wavelength range of 700 to 1200 nm or more is 300 nm or more.

<Requirement (a)>
Requirement (a): The minimum value OD _a-0 in the wavelength region of 700 nm or more and 900 nm or less is 2.0 or more, preferably 2.1 or more and 8.0 or less.
Here, the OD value is the common logarithm of the transmittance and can be calculated by the following formula.
Minimum optical density (OD value) in a certain wavelength range=−Log ₁₀ (Maximum wavelength-specific transmittance in a certain wavelength range (%)/100)

If the minimum wavelength-specific OD value in a specified wavelength range is high, it indicates that the optical filter has high light-cutting characteristics in that wavelength range.

It is preferable that the optical filter of the present invention further satisfies the following requirement (aX).
Requirement (aX): In the wavelength region of 700 nm or more and 900 nm or less, the minimum optical density OD _a-0 for light incident perpendicularly to the surface of the optical filter, the minimum optical density OD _a-30 for light incident at an oblique angle of 30 degrees to the perpendicular direction, and the minimum optical density OD _a-60 for light incident at an oblique angle of 60 degrees to the perpendicular direction are all 2.0 or more, preferably 2.0 or more and 8.0 or less, and more preferably 2.1 or more and 8.0 or less.

As a method for satisfying requirement (a), preferably requirement (aX), i.e., a method for adjusting the minimum value of each optical density, there can be mentioned, for example, a method in which the concentration of a compound contained in the base material is adjusted so that the minimum value of the optical density in the wavelength region of 700 nm or more and 900 nm or less is 2.0 or more.
By satisfying the requirement (a), and preferably the requirement (aX), the optical filter can sufficiently cut not only the near-infrared light transmitted in the perpendicular direction, but also the near-infrared light transmitted at a high incidence angle.

<Requirement (b)>
Requirement (b): The average transmittance T _a-0 in the wavelength region of 430 nm or more and 580 nm or less is 40% or more, preferably 45% or more, more preferably 50% or more, and particularly preferably 55% or more.

It is preferable that the optical filter of the present invention further satisfies the following requirement (bX).
Requirement (bX): In the wavelength region of 430 nm or more and 580 nm or less, the average transmittance T _a-0 of light incident perpendicularly to the surface of the optical filter, the average transmittance T _a-30 of unpolarized light incident at an oblique angle of 30 degrees from the vertical direction, and the average transmittance T _a-60 of unpolarized light incident at an oblique angle of 60 degrees from the vertical direction are all 40% or more, preferably 43 to 99%, more preferably 46 to 98%, and particularly preferably 48 to 97%.

As a method for satisfying requirement (b), preferably requirement (bX), i.e., a method for adjusting the average value of each transmittance, for example, a method of adjusting the concentration of a compound added to the substrate so that the average absorbance in the wavelength range of 430 nm or more and 580 nm or less is preferably 0.35 or less, more preferably 0.26 or less, can be mentioned.

By satisfying requirement (b), and preferably requirement (bX), good images can be obtained when the optical filter of the present invention is used as a solid-state imaging device.

As a method for satisfying both requirements (a) and (b), and preferably both requirements (aX) and (bX), for example, a method in which the base material (i) contains a compound (A) having a maximum absorption in the wavelength region of 650 nm or more and less than 950 nm can be mentioned. More preferably, the base material (i) satisfies the requirement (d). It is preferable that the compound (A) has little absorption in the wavelength region of 430 nm or more and 580 nm or less.

<Requirement (c)>
Requirement (c): In the wavelength region of 420 nm to 900 nm, the average reflectance (Rf _a-5 ) of light incident at an angle of 5 degrees from the perpendicular direction to the surface of the optical filter is 20% or less, preferably 15% or less, more preferably 6% or less, even more preferably 0.1 to 4%, and particularly preferably 0.1 to 3%.

By satisfying requirement (c), the reflectance of light with wavelengths of 420 nm or more and 900 nm or less, to which silicon photodiodes have strong sensitivity, can be reduced on both sides of the optical filter, and good images can be obtained when the optical filter of the present invention is used for a solid-state imaging device or as a camera module.

Methods for satisfying requirement (c), i.e., methods for adjusting the average value of each reflectance, include, for example, a method of forming a layer in which the refractive index changes continuously from the incident medium to the substrate by providing numerous cone-shaped structures whose size is less than the wavelength of light, and a method of forming an anti-reflection layer using a dielectric multilayer film consisting of multiple layers.

As a method for satisfying requirement (c), i.e., a method for designing an optical filter with low reflectance, for example, there is a method using a substrate in which the absolute value |Xa-Xb| of the difference between the shortest wavelength value (Xa) at which the transmittance is 50% when measured perpendicular to the substrate in the wavelength range of 580 to 800 nm and the longest wavelength value (Xb) at which the transmittance is 50% when measured perpendicular to the substrate in the wavelength range of 700 to 1200 nm or more is 300 nm or more.

<Requirement (d)>
Requirement (d): The optical element includes a layer containing at least three kinds of compounds (A) having an absorption maximum in the wavelength region of 650 nm or more and less than 950 nm.

The layer contains three or more kinds of compound (A), which makes it possible to improve the solubility. If the layer contains two or less kinds of compound (A), it becomes necessary to increase the content of compound (A) in order to make OD _a-0 2.0 or more, which may result in precipitation of compound (A) from the layer.

In addition, when the layer contains three or more types of compound (A), it becomes possible to absorb a wide range of the near-infrared region. By absorbing a wide range of the near-infrared region, a filter with reduced reflectance can be obtained in a wide range of the near-infrared region. By using such a filter with reduced reflectance in a wide range of the near-infrared region, it is possible to obtain a good image with reduced ghosting.

<Requirement (e)>
Requirement (e): The substrate (i) has a dielectric multilayer film on at least one surface thereof, and the product (N×TN) of the number (N) of layers constituting the dielectric multilayer film that have a thickness of 0.5 μm or less and the sum (TN) (μm) of the thicknesses of each layer that has a thickness of 0.5 μm or less is 150 or less. The product (N×TN) is preferably 100 or less, and more preferably 50 or less.

As will be described in detail later, it is preferable for the product (N x TN) to be within this range, since this reduces the time required to manufacture the dielectric multilayer film and reduces manufacturing costs.

In the optical filter of the present invention, from the viewpoint of color reproducibility in images obtained by an imaging device or camera module, the R transmittance, G transmittance, and B transmittance when light is incident perpendicularly to the optical filter are all preferably 30% or more, more preferably 34% or more, and even more preferably 38% or more. The R transmittance is the average transmittance at wavelengths of 580 to 650 nm, the G transmittance is the average transmittance at wavelengths of 500 to 580 nm, and the B transmittance is the average transmittance at wavelengths of 420 to 500 nm. When such an optical filter is used in an imaging device or camera module, it becomes easier to correct the brightness and color of the image, facilitating luminosity correction to make the color appear natural to the human eye.

The optical filter of the present invention may be an embodiment consisting of only the substrate (i), or may have an anti-reflection layer on both sides of the substrate (i). By having an anti-reflection layer on both sides of the substrate (i), it is possible to reduce the phenomenon in which stray light reflected by various components such as cover glass, lenses, microlenses, sensors, and housings incorporated in an imaging device or camera module is reflected by the optical filter and enters the sensor, thereby reducing the occurrence of ghosts.

The thickness of the optical filter of the present invention is not particularly limited, but is preferably 160 μm or less, more preferably 10 to 130 μm, and even more preferably 10 to 120 μm. When the thickness of the optical filter is within the above range, the optical filter can be made thinner, smaller, and lighter. A thickness of 10 μm or more is preferable because it makes it easier to control warping.

<Substrate (i)>
The substrate (i) is not particularly limited as long as it satisfies the requirement (d), and may be a single layer or a multilayer. The substrate (i) may also contain a compound (B) having an absorption maximum in the wavelength region of 950 nm to 1800 nm, and the compound (B) may be contained in the same layer as the compound (A) or in a different layer. Hereinafter, a layer containing at least one compound (A) and a resin is also referred to as a "transparent resin layer", and other resin layers are also simply referred to as "resin layers".

Examples of the substrate (i) when the layer containing compound (A) and the layer containing compound (B) are the same include a substrate made of a resin substrate containing compound (A) and compound (B), a substrate in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a resin substrate containing compound (A) and compound (B), and a substrate in which a transparent resin layer such as an overcoat layer made of a curable resin containing compound (A) and compound (B) is laminated on a support such as a glass support or a base resin support.

Examples of the substrate (i) in the case where the layer containing compound (A) and the layer containing compound (B) are different include a substrate in which a transparent resin layer such as an overcoat layer made of a curable resin containing compound (A) is laminated on a resin substrate containing compound (B), a substrate in which a resin layer such as an overcoat layer made of a curable resin containing compound (B) is laminated on a resin substrate containing compound (A), a substrate in which a transparent resin layer such as an overcoat layer made of a curable resin containing compound (A) and a resin layer such as an overcoat layer made of a curable resin containing compound (B) are laminated on a support such as a glass support or a base resin support, and a substrate in which a transparent resin layer such as an overcoat layer made of a curable resin containing compound (B) is laminated on a glass substrate containing compound (B).

<Compound (A)>
The compound (A) is not particularly limited as long as it has an absorption maximum in the wavelength region of 650 nm or more and less than 950 nm, but it preferably contains at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds, more preferably contains at least one compound selected from squarylium compounds, phthalocyanine compounds, and cyanine compounds, and particularly preferably contains at least three compounds selected from squarylium compounds, phthalocyanine compounds, and cyanine compounds. Compounds having an absorption maximum at a wavelength of 649 nm or less tend to have a high mass absorption coefficient at 420 nm to 580 nm due to absorption caused by the peak of the maximum absorption wavelength.

The absorption maximum wavelength of compound (A) is preferably 670 nm or more and less than 950 nm, more preferably 690 nm or more and less than 950 nm, and even more preferably 700 nm or more and less than 950 nm.

The substrate (i) preferably contains, as compound (A), one or more compounds having an absorption maximum in the wavelength region of 650 nm or more and less than 800 nm, more preferably in the wavelength region of 700 nm or more and less than 800 nm. When the optical filter obtained from this is used in an imaging device or camera module, the visibility correction of red light is good.

The substrate (i) preferably contains, as compound (A), one or more compounds having an absorption maximum in the wavelength region of 800 nm or more and less than 950 nm. When the optical filter obtained from this is used in an imaging device or camera module, it can efficiently block light in the region of 800 nm or more and 900 nm or less, where the sensitivity of silicon photodiodes is high and the sensitivity of the human eye is low, and the luminosity correction of flames, halogen lamps, and blackbody radiation sources that emit strong near-infrared rays can be improved.

Furthermore, the substrate (i) preferably contains, as compound (A), one or more of a compound having an absorption maximum in the wavelength region of 650 nm or more and less than 800 nm, and one or more of a compound having an absorption maximum in the wavelength region of 800 nm or more and less than 950 nm, and more preferably contains two or more of each. When the optical filter obtained by this is used in an imaging device or camera module, both red visibility correction and light shielding performance in the region of 700 nm or more and 900 nm or less are achieved, and the obtained image is good.

More preferably, the substrate (i) contains, as compound (A), two or more compounds having an absorption maximum in the wavelength region of 650 nm or more and less than 800 nm, and one or more compounds having an absorption maximum in the wavelength region of 800 nm or more and less than 950 nm. This makes it possible to obtain an optical filter that absorbs a wide range of light from the red region to the near-infrared region. When such an optical filter is used in an imaging device or camera module, it is possible to obtain a better image that achieves both red visibility correction and ghost reduction.

Preferred compounds having an absorption maximum in the wavelength region of 650 nm or more and less than 800 nm include squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, croconium-based compounds, cyanine-based compounds, diimonium-based compounds, metal dithiolate-based compounds, and pyrrolopyrrole-based compounds, with squarylium-based compounds, phthalocyanine-based compounds, and cyanine-based compounds being more preferable. By containing these compounds, an optical filter that combines high visible light transmittance and good durability can be obtained.

Preferred compounds having an absorption maximum in the wavelength region of 800 nm or more and less than 950 nm include squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, croconium-based compounds, cyanine-based compounds, diimonium-based compounds, metal dithiolate-based compounds, and pyrrolopyrrole-based compounds, with squarylium-based compounds, phthalocyanine-based compounds, and cyanine-based compounds being more preferable. By containing these compounds, an optical filter that combines high visible light transmittance and good durability can be obtained.

Furthermore, in the substrate (i), at least one of the compounds (A) preferably satisfies the following requirements (f) and (g) as absorption characteristics measured after dissolving in dichloromethane: (f) the maximum absorption wavelength λmax in the wavelength region of 650 nm or more and less than 950 nm is 850 nm or more and 935 nm or less; (g) when the maximum absorption coefficient _ελmax in the wavelength region of 650 nm or more and less than 950 nm is normalized by 1,
(g-1) the absorption coefficient ελmax _-10 at a wavelength of (λmax-10) nm is 0.80 or more;
(g-2) the absorption coefficient ελmax ₊₁₀ at a wavelength of (λmax+10) nm is 0.80 or more;
(g-3) The average value of the absorption coefficients in the wavelength region of 430 nm or more and 580 nm or less, ε _430-580ave , is 0.03 or less. ε λ _max-10 is more preferably 0.85 or more, and even more preferably 0.90 or more. Furthermore, ε λ _max+10 is more preferably 0.85 or more, and even more preferably 0.90 or more. Furthermore, ε _430-580ave is more preferably 0.025 or less, and even more preferably 0.020 or less.

When the optical filter obtained in this way is used in an imaging device or camera module, it achieves both high visible light transmittance and blocking performance for light in the range of 700 nm to 900 nm, resulting in good images.

The amount of compound (A) used is appropriately selected depending on the desired properties. For example, when a substrate made of a resin substrate containing compound (A) or a substrate in which a resin layer such as an overcoat layer made of a curable resin is laminated on a resin substrate containing compound (A) is used as the substrate (i), the content of compound (A) is preferably 0.01 to 2.0 parts by mass, more preferably 0.03 to 1.5 parts by mass, and even more preferably 0.05 to 1.0 parts by mass, relative to 100 parts by mass of resin. When a substrate in which a transparent resin layer containing compound (A) is laminated on a support such as a glass support or a base resin support is used as the substrate (i), the content of compound (A) is preferably 0.4 to 20.0 parts by mass, more preferably 0.6 to 15.0 parts by mass, and even more preferably 0.8 to 12.5 parts by mass, relative to 100 parts by mass of the resin forming the transparent resin layer.

Squarylium compounds
The squarylium compound is not particularly limited, but is preferably at least one compound selected from the group consisting of a squarylium compound represented by the following formula (I) (hereinafter also referred to as "compound (I)"), a squarylium compound represented by the following formula (II) (hereinafter also referred to as "compound (II)"), and squarylium compounds represented by the following formulas (III-J), (III-K) and (III-L) (hereinafter also referred to as "compound (III-J)", "compound (III-K)" and (compound (III-L)), respectively, and collectively referred to as "compound (III)").

Formula (I)

In formula (I), R ^a , R ^b and Ya satisfy the following condition (α) or (β).
Condition (α):
Each of the multiple R ^a 's independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -L ¹ or -NR ^e R ^f group;
Each of the multiple R ^b 's independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -L ¹ or a -NR ^g R ^h group;
Each of the multiple Ya's independently represents a ^{-NRjRk group} ; ^L1 represents ^La , ^Lb , ^Lc , ^Ld , ^Le , ^Lf , ^Lg , or ^Lh ;
R ^e and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ;
R ^g and R ^h each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e , or a -C(O)R ⁱ group (R ⁱ represents -L ^a , -L ^b , -L ^c , -L ^d , or -L ^e );
R ^j and R ^k each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ;
L ^a represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L;
L ^b represents a halogen-substituted alkyl group having 1 to 12 carbon atoms which may have a substituent L;
^Lc represents an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L;
L ^d represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent L;
L ^e represents a heterocyclic group having 3 to 14 carbon atoms which may have a substituent L;
L ^f represents an alkoxy group having 1 to 9 carbon atoms which may have a substituent L;
L ^g represents an acyl group having 1 to 9 carbon atoms which may have a substituent L;
L ^h represents an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L;
L represents at least one substituent selected from the group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, and an amino group.

Condition (β):
At least one of two R ^a on one benzene ring is mutually bonded to Y on the same benzene ring to form a heterocycle having 5 or 6 constituent atoms containing at least one nitrogen atom;
The heterocycle may have a substituent, and R ^b and R ^a which is not involved in the formation of the heterocycle each independently have the same meaning as R ^b and R ^a in the above proviso (α).

The total number of carbon atoms including the substituents in each of L ^a to L ^h is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. If the number of carbon atoms is greater than this range, synthesis of the compound may become difficult and the light absorption intensity per unit mass tends to decrease.

R ^a in the above condition (α) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, or a nitro group, and more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a hydroxyl group.

R ^b in the above condition (α) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a cyano group, a nitro group, an acetylamino group, a propionylamino group, an N-methylacetylamino group, a trifluoromethanoylamino group, a pentafluoroethanoylamino group, a t-butanoylamino group, or a cyclohexanoylamino group, and more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a hydroxyl group, a dimethylamino group, a nitro group, an acetylamino group, a propionylamino group, a trifluoromethanoylamino group, a pentafluoroethanoylamino group, a t-butanoylamino group, or a cyclohexanoylamino group.

The above-mentioned Ya is preferably an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-t-butylamino group, an N-ethyl-N-methylamino group, or an N-cyclohexyl-N-methylamino group, and more preferably a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, or a di-t-butylamino group.

In the condition (β) of the formula (I), examples of the heterocycle containing at least one nitrogen atom and having 5 or 6 constituent atoms, which is formed by at least one of the two ^R on one benzene ring being mutually bonded to Y on the same benzene ring, include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, pyrazine, etc. Among these heterocycles, a heterocycle which constitutes the heterocycle and in which one atom adjacent to a carbon atom constituting the benzene ring is a nitrogen atom is preferred, and pyrrolidine is more preferred.

Formula (II)

In formula (II), X independently represents O, S, Se, N- ^Rc , or C( ^{RdRd )} ; each of the multiple ^Rc 's independently represents a hydrogen atom, L ^a , L ^b , ^Lc , ^Ld , or L ^e ; each of the multiple Rd ^'s independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -L ¹ , or -NR ^e R ^f group, and adjacent ^Rd 's may be bonded to each other to form a ring which may have a substituent; L ^a to L ^e , L ¹ , R ^e , and R ^f are the same as L ^a to L ^e , L ¹ , R ^e , and R ^f defined in formula (I) above.

^Rc in the formula (II) is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, a trifluoromethyl group, or a pentafluoroethyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

^Rd in the formula (II) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, a methoxy group, a trifluoromethyl group, a pentafluoroethyl group, or a 4-aminocyclohexyl group, and more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a trifluoromethyl group, or a pentafluoroethyl group.

The aforementioned X is preferably O, S, Se, N-Me, N-Et, CH ₂ , C-Me ₂ or C-Et ₂ , and more preferably S, C-Me ₂ or C-Et ₂ .

In the formula (II), adjacent ^Rds may be bonded to each other to form a ring. Examples of such a ring include a benzoindolenine ring, an α-naphthoimidazole ring, a β-naphthoimidazole ring, an α-naphthoxazole ring, a β-naphthoxazole ring, an α-naphthothiazole ring, a β-naphthothiazole ring, an α-naphthoselenazole ring, and a β-naphthoselenazole ring.

式（ＩＩＩ－Ｊ）～（ＩＩＩ－Ｌ）中、Ｘは、独立に酸素原子、硫黄原子、セレン原子、テルル原子または－ＮＲ⁸－を表し、
Ｒ¹～Ｒ⁸は、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、－ＮＲ^gＲ^h基、－ＳＯ₂Ｒⁱ基、－ＯＳＯ₂Ｒⁱ基または下記Ｌ^a～Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、－Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a～Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a～Ｌ^eのいずれかを表す。
（Ｌ^a）炭素数１～１２の脂肪族炭化水素基
（Ｌ^b）炭素数１～１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３～１４の脂環式炭化水素基
（Ｌ^d）炭素数６～１４の芳香族炭化水素基
（Ｌ^e）炭素数３～１４の複素環基
（Ｌ^f）炭素数１～１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１～１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１～１２のアルコキシカルボニル基 置換基Ｌは、炭素数１～１２の脂肪族炭化水素基、炭素数１～１２のハロゲン置換アルキル基、炭素数３～１４の脂環式炭化水素基、炭素数６～１４の芳香族炭化水素基および炭素数３～１４の複素環基からなる群より選ばれる少なくとも１種である。 Formulae (III-J) to (III-L)

In formulae (III-J) to (III-L), X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ⁸ -;
R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, a -NR ^g R ^h group, a -SO ₂ R ⁱ group, a -OSO ₂ R ⁱ group, or any of L ^a to L ^h described below; R ^g and R ^h each independently represent a hydrogen atom, a -C(O)R ⁱ group, or any of L ^a to L ^e described below; and R ⁱ represents any of L ^a to L ^e described below.
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms; (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms; (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms; (L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms; (L ^e ) a heterocyclic group having 3 to 14 carbon atoms; (L ^f ) an alkoxy group having 1 to 12 carbon atoms; (L ^g ) an acyl group having 1 to 12 carbon atoms which may have a substituent L;
(L ^h ) An alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L. The substituent L is at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms.

Compounds (I), (II) and (III-J) can be represented by the following formulas (I-1), (II-1) and (III-J-1), as well as the following formulas (I-2), (II-2) and (III-J-2) that have resonance structures (similar to compounds (III-K) and (III-L)). In other words, the difference between formulas (I-1) and (I-2), between formulas (II-1) and (II-2) and between formulas (III-J-1) and (III-J-2) is only the method of describing the structure, and both represent the same compound. In the present invention, unless otherwise specified, the structure of squarylium-based compounds is represented by the following formulas (I-1), (II-1) and (III-J-1).

さらに、例えば、下記式（Ｉ－３）で表される化合物と下記式（Ｉ－４）で表される化合物とは、同一の化合物であると見なすことができる。

Furthermore, for example, a compound represented by the following formula (I-3) and a compound represented by the following formula (I-4) can be considered to be the same compound.

前記化合物（Ｉ）、（ＩＩ）および（ＩＩＩ）は、それぞれ前記各式の要件を満たせば特に構造は限定されない。例えば前記式（Ｉ－１）、（ＩＩ－１）および（ＩＩＩ－Ｊ－１）のように構造を表した場合、中央の四員環に結合している左右の置換基は同一であっても異なっていてもよいが、同一であった方が合成上容易であるため好ましい。

The structures of the compounds (I), (II) and (III) are not particularly limited as long as they satisfy the requirements of the respective formulas. For example, when the structures are represented as in the formulas (I-1), (II-1) and (III-J-1), the left and right substituents bonded to the central four-membered ring may be the same or different, but it is preferable that they are the same because synthesis is easier.

Specific examples of the compounds (I), (II) and (III) include compounds (a-1) to (a-94) in Tables 1 to 7 below, which have basic skeletons represented by the following formulas (I-A) to (I-F), (II-G) to (II-H) and (III-J) to (III-L).

The compounds (I), (II) and (III) may be synthesized by a generally known method, for example, by referring to the methods described in JP-A-1-228960, JP-A-2001-40234, JP-A-3196383, etc.

<Phthalocyanine compounds>
The phthalocyanine compound is not particularly limited, but is preferably a compound represented by the following formula (IV) (hereinafter also referred to as "compound (IV)").

式（ＩＶ）中、Ｍは、２個の水素原子、２個の１価の金属原子、２価の金属原子、または３価もしくは４価の金属原子を含む置換金属原子を表し、複数あるＲ_a、Ｒ_b、Ｒ_cおよびＲ_dは、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシ基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、－Ｌ¹、－Ｓ－Ｌ²、－ＳＳ－Ｌ²、－ＳＯ₂－Ｌ³、－Ｎ＝Ｎ－Ｌ⁴、または、Ｒ_aとＲ_b、Ｒ_bとＲ_cおよびＲ_cとＲ_dのうち少なくとも１つの組み合わせが結合した、下記式（Ａ）～（Ｈ）で表される基からなる群より選ばれる少なくとも１種の基を表す。但し、同じ芳香環に結合したＲ_a、Ｒ_b、Ｒ_cおよびＲ_dのうち少なくとも１つが水素原子ではない。

In formula (IV), M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing a trivalent or tetravalent metal atom, and the multiple R _a , R _b , R _c , and R _d each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amido group, an imido group, a cyano group, a silyl group, -L ¹ , -S-L ² , -SS-L ² , -SO ₂ -L ³ , -N═N-L ⁴ , or at least one group selected from the group consisting of groups represented by the following formulas (A ₎ to (H) in which at least one combination of R _a and R _b , R _b and R c , and R _c and R _d is bonded, provided that at least one of R _a , R _b , R _c , and R _d bonded to the same aromatic ring is not a hydrogen atom.

The amino, amido, imido and silyl groups may carry a substituent L as defined in formula (I) above,
L ¹ has the same meaning as L ¹ defined in formula (I).
^L2 represents a hydrogen atom or any one of L ^a to L ^e defined in formula (I);
^L3 represents a hydroxyl group or any one of L ^a to L ^e described above;
^L4 represents any one of L ^a to L ^e .

式（Ａ）～（Ｈ）中、Ｒ_xおよびＲ_yは炭素原子を表し、複数あるＲ_A～Ｒ_Lはそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、－Ｌ¹、－Ｓ－Ｌ²、－ＳＳ－Ｌ²、－ＳＯ₂－Ｌ³、－Ｎ＝Ｎ－Ｌ⁴を表し、前記アミノ基、アミド基、イミド基およびシリル基は、前記式（Ｉ）において定義した置換基Ｌを有してもよく、Ｌ¹～Ｌ⁴は前記式（ＩＶ）において定義したＬ¹～Ｌ⁴と同義である。

In formulas (A) to (H), R _x and R _y represent carbon atoms, and the multiple R _A to R _L each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amido group, an imido group, a cyano group, a silyl group, -L ¹ , -S-L ² , -SS-L ² , -SO ₂ -L ³ , or -N═N-L ⁴ , and the amino group, amido group, imido group and silyl group may have a substituent L defined in formula (I) above, and L ¹ to L ⁴ are synonymous with L ¹ to L ⁴ defined in formula (IV).

The phthalocyanine compound is generally synthesized by a cyclization reaction of a phthalonitrile derivative as shown in formula (V) below, and the resulting phthalocyanine compound is a mixture of four isomers as shown in formulas (VI-1) to (VI-4) below. In the present invention, unless otherwise specified, only one isomer is exemplified for one type of phthalocyanine compound, but the other three isomers can also be used in the same manner. These isomers can be used separately as necessary, but the present invention deals with the isomer mixture as a whole.

前記化合物（ＩＶ）の具体例としては、下記式（ＩＶ－Ａ）～（ＩＶ－Ｊ）で表わされる基本骨格を有する、下記表８～１１に記載の（ｂ－１）～（ｂ－６１）などを挙げることができる。

Specific examples of the compound (IV) include (b-1) to (b-61) in Tables 8 to 11 below, which have basic skeletons represented by the following formulas (IV-A) to (IV-J).

化合物（ＩＶ）は、一般的に知られている方法で合成すればよく、たとえば、特許第４０８１１４９号公報や「フタロシアニン －化学と機能―」（アイピーシー、１９９７年）に記載されている方法を参照して合成することができる。

Compound (IV) may be synthesized by a generally known method, for example, by referring to the methods described in Japanese Patent No. 4081149 or "Phthalocyanine - Chemistry and Functions -" (IPC, 1997).

<Cyanine compounds>
The cyanine compound is not particularly limited, but is preferably a compound represented by any one of the following formulas (VII-1) to (VII-13) (hereinafter also referred to as "compounds (VII-1) to (VII-13)"). Since high visible light transmittance can be achieved, (VII-4) to (VII-6) and (VII-9) to (VII-11) are preferred, and (VII-4) and (VII-9) are particularly preferred.

式（ＶＩＩ－１）～（ＶＩＩ－１３）中、Ｘ_a ^-は１価の陰イオンを表し、複数あるＤは独立に、炭素原子、窒素原子、酸素原子または硫黄原子を表し、複数あるＸは、独立に酸素原子、硫黄原子、セレン原子、テルル原子または－ＮＲ_a－を表し、複数あるＲ_a、Ｒ_b、Ｒ_c、Ｒ_d、Ｒ_e、Ｒ_f、Ｒ_g、Ｒ_hおよびＲ_iはそれぞれ独立に、水素原子、ハロゲン原子、水酸基、カルボキシ基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、－Ｌ¹、－Ｓ－Ｌ²、－ＳＳ－Ｌ³、－ＳＯ₂－Ｌ³、－Ｎ＝Ｎ－Ｌ⁴、または、Ｒ_bとＲ_c、Ｒ_dとＲ_e、Ｒ_eとＲ_f、Ｒ_fとＲ_g、Ｒ_gとＲ_hおよびＲ_hとＲ_iのうち少なくとも１つの組み合わせが結合した、前記式（Ａ）～（Ｈ）で表される基からなる群より選ばれる少なくとも１種の基を表し、前記アミノ基、アミド基、イミド基およびシリル基は、前記式（Ｉ）において定義した置換基Ｌを有してもよく、
Ｌ¹は、前記式（Ｉ）において定義したＬ¹と同義であり、
Ｌ²は、水素原子または前記式（Ｉ）において定義したＬ^a～Ｌ^eのいずれかを表し、
Ｌ³は、水素原子または前記Ｌ^a～Ｌ^eのいずれかを表し、
Ｌ⁴は、前記Ｌ^a～Ｌ^eのいずれかを表し、
Ｚ_a～Ｚ_cおよびＹ_a～Ｙ_dはそれぞれ独立に、水素原子、ハロゲン原子、水酸基、カルボキシ基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、－Ｌ¹、－Ｓ－Ｌ²、－ＳＳ－Ｌ²、－ＳＯ₂－Ｌ³、－Ｎ＝Ｎ－Ｌ⁴（Ｌ¹～Ｌ⁴は、前記Ｒ_a～Ｒ_iにおけるＬ¹～Ｌ⁴と同義である。）、または、これらのうち隣接した二つから選ばれるＺ同士もしくはＹ同士が相互に結合して形成される、炭素数６～１４の芳香族炭化水素基；窒素原子、酸素原子もしくは硫黄原子を少なくとも１つ含んでもよい５乃至６員環の脂環式炭化水素基；もしくは、窒素原子、酸素原子もしくは硫黄原子を少なくとも１つ含む、炭素数３～１４の複素芳香族炭化水素基を表し、これらの芳香族炭化水素基、脂環式炭化水素基および複素芳香族炭化水素基は、炭素数１～９の脂肪族炭化水素基またはハロゲン原子を有してもよい。

In formulas (VII-1) to (VII-13), X _a ^- represents a monovalent anion; each of D independently represents a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom; each of X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR _a -; each of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h , and R _i , independently, represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amido group, an imido group, a cyano group, a silyl group, -L ¹ , -S-L ² , -SS-L ³ , -SO ₂ -L ³ , -N═N-L ⁴ , or R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h , and R _h and R at least one group selected from the group consisting of groups represented by formulas (A) to (H) to which at least one combination of _i is bonded, and the amino group, amido group, imido group and silyl group may have a substituent L defined in formula (I),
L ¹ has the same meaning as L ¹ defined in formula (I).
^L2 represents a hydrogen atom or any one of L ^a to L ^e defined in formula (I);
^L3 represents a hydrogen atom or any one of L ^a to L ^e described above;
^L4 represents any one of L ^a to L ^e ;
Z _a to Z _c and Y _a to Y _d each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amido group, an imido group, a cyano group, a silyl group, -L ¹ , -S-L ² , -SS-L ² , -SO ₂ -L ³ , or -N═N-L ⁴ (L ¹ to L ⁴ represent L ¹ to L 4 in R _a to R _i above). 4.) or adjacent two Z's or Y's selected from among these are bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms; an alicyclic hydrocarbon group having a 5- or 6-membered ring which may contain at least ^one nitrogen atom, oxygen atom or sulfur atom; or a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, and these aromatic hydrocarbon groups, alicyclic hydrocarbon groups and heteroaromatic hydrocarbon groups may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

Since both a high visible light transmittance and a high OD value in the 700 to 900 nm region can be achieved, the multiple X's are preferably oxygen atoms or sulfur atoms, and more preferably oxygen atoms. The multiple R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i are each independently preferably a hydrogen atom, L ^a , L ^c , L ^d or L ^f .

In the above Z _a to Z _c and Y _a to Y _d , examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding together between Z or between Y include the compounds exemplified as the aromatic hydrocarbon group in the above substituent L.

In Z _a to Z _c and Y _a to Y _d , examples of the 5- or 6-membered alicyclic hydrocarbon group which may contain at least one nitrogen atom, oxygen atom or sulfur atom and which is formed by bonding between Zs or between Ys include the compounds exemplified as the alicyclic hydrocarbon group and heterocycle in the substituent L (excluding heteroaromatic hydrocarbon groups).

In order to achieve both chemical stability and high visible light transmittance of the compound, it is particularly preferable that Z _a to Z _c and Y _a to Y _d each independently represent a hydrogen atom, a halogen atom, an amino group having a substituent L, or an aromatic hydrocarbon group having 6 to 14 carbon atoms or an alicyclic hydrocarbon group having a 5- or 6-membered ring formed by bonding together adjacent Z or Y selected from two of these.

In Z _a to Z _c and Y _a to Y _d , examples of the heteroaromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding together between Z or between Y include the compounds exemplified as the heterocyclic group in the substituent L (excluding alicyclic hydrocarbon groups containing at least one nitrogen atom, oxygen atom or sulfur atom).

In the formulas (VII-1) to (VII-13), -S- ^L , -SS- ^L , -SO- _L ^, -N=N-L ^, and the amino group, amido group, imido group and silyl group which may have a substituent L include the same groups as exemplified in the formula (IV).

X _a ^- is not particularly limited as long as it is a monovalent anion, and examples thereof include Cl ^- , I ^- , Br ^- , PF ₆ ^- , N(SO ₂ CF ₃ ) ₂ ^- , B(C ₆ F ₅ ) ₄ ^- , nickel dithiolate complexes, copper dithiolate complexes, etc. From the viewpoint of chemical stability of the compound, B(C ₆ F ₅ ) ₄ ^- is preferred.

Specific examples of the compounds (VII-1) to (VII-13) include compounds (c-1) to (c-116) shown in Tables 12-1 to 12-5 below.

前記化合物（ＶＩＩ－１）～（ＶＩＩ－６）は、一般的に知られている方法で合成すればよく、たとえば特開２００９－１０８２６７号公報に記載されている方法で合成することができる。

The compounds (VII-1) to (VII-6) may be synthesized by a generally known method, for example, the method described in JP-A-2009-108267.

<Compound (B)>
The compound (B) is not particularly limited as long as it has an absorption maximum in the wavelength region of 950 nm to 1800 nm, but is preferably at least one compound selected from the group consisting of near infrared absorbing fine particles, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, cyanine compounds, diimonium compounds, metal dithiolate compounds and pyrrolopyrrole compounds.The compound (B) may be used alone or in combination of two or more.By using such a compound (B), it is possible to achieve absorption characteristics and excellent visible light transmittance in a wide near infrared wavelength region.

The maximum absorption wavelength of the compound (B) is preferably 1020 nm or more and 1750 nm or less, more preferably 1020 nm or more and 1720 nm or less. When the maximum absorption wavelength of the compound (B) is in such a range, it is possible to efficiently cut off unnecessary near-infrared rays and to reduce the incidence angle dependency of the incident light.

The mass extinction coefficient at the absorption maximum wavelength of compound (B) is preferably 8×10 L·cm ⁻¹ ·g ⁻¹ or more, more preferably 9.5×10 L·cm ⁻¹ ·g ⁻¹ or more. If it is 8×10 L·cm ⁻¹ ·g ⁻¹ or more, it becomes possible to efficiently shield near-infrared rays even in a thin optical filter provided with an antireflection layer, and it becomes possible to achieve both a thin structure, high near-infrared shielding properties, and low reflection characteristics.

The amount of the compound (B) (excluding near-infrared absorbing fine particles) used is appropriately selected according to the desired properties. For example, when a substrate made of a resin substrate containing the compound (A) and the compound (B) is used as the substrate (i), the content of the compound (B) is preferably 0.01 to 5.0 parts by mass, more preferably 0.02 to 3.0 parts by mass, and particularly preferably 0.03 to 2.0 parts by mass, relative to 100 parts by mass of the resin. In addition, when a substrate in which a resin layer containing the compound (A) and the compound (B) is laminated on a support such as a glass support or a base resin support, or a substrate in which a resin layer containing the compound (B) is laminated on a resin substrate containing the compound (A), the content of the compound (B) is preferably 0.1 to 40.0 parts by mass, more preferably 0.2 to 30.0 parts by mass, and particularly preferably 0.3 to 25.0 parts by mass, relative to 100 parts by mass of the resin forming the resin layer containing the compound (A). When the content of compound (B) is within the above range, an optical filter that combines good near-infrared absorbing properties with high visible light transmittance can be obtained. Note that the amount of near-infrared absorbing particles used as compound (B) will be described later.

The compound (B) may be synthesized by a generally known method, for example, by referring to the methods described in Japanese Patent No. 4168031, Japanese Patent No. 4252961, Japanese Translation of PCT International Publication No. 2010-516823, and Japanese Patent Laid-Open Publication No. 63-165392.

<Diimmonium compounds>
The diimonium compound is not particularly limited, but is preferably, for example, a compound represented by the following formula (s1).

式（ｓ１）中、Ｒ¹は、独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、カルボキシ基、リン酸基、－ＳＲⁱ基、－ＳＯ₂Ｒⁱ基、－ＯＳＯ₂Ｒⁱ基または下記Ｌ^a～Ｌ^hのいずれかを表し、Ｒ²は、独立にハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、－ＮＲ^gＲ^h基、－ＳＲⁱ基、－ＳＯ₂Ｒⁱ基、－ＯＳＯ₂Ｒⁱ基または下記Ｌ^a～Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、－Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a～Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a～Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１～１２の脂肪族炭化水素基
（Ｌ^b）炭素数１～１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３～１４の脂環式炭化水素基（Ｌ^d）炭素数６～１４の芳香族炭化水素基
（Ｌ^e）炭素数３～１４の複素環基
（Ｌ^f）炭素数１～１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１～１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１～１２のアルコキシカルボニル基
置換基Ｌは、炭素数１～１２の脂肪族炭化水素基、炭素数１～１２のハロゲン置換アルキル基、炭素数３～１４の脂環式炭化水素基、炭素数６～１４の芳香族炭化水素基および炭素数３～１４の複素環基からなる群より選ばれる少なくとも１種であり、ｎは０～４の整数、Ｘは電荷を中和させるのに必要なアニオンを表す。

In formula (s1), R ¹ independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a carboxy group, a phosphate group, a -SR ⁱ group, a -SO ₂ R ⁱ group, a -OSO ₂ R ⁱ group, or any of L ^a to L ^h described below; R ² independently represents a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, a -NR ^g R ^h group, a -SR ⁱ group, a -SO ₂ R ⁱ group, a -OSO ₂ R ⁱ group, or any of L ^a to L ^h described below; R ^g and R ^h each independently represent a hydrogen atom, a -C(O)R ⁱ group, or any of L ^a to L ^e described below; and R ⁱ represents any of L ^a to L ^e described below;
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms, (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms, (L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms, (L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms, (L ^e ) a heterocyclic group having 3 to 14 carbon atoms, (L ^f ) an alkoxy group having 1 to 12 carbon atoms, (L ^g ) an acyl group having 1 to 12 carbon atoms which may have a substituent L,
(L ^h ) An alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L. The substituent L is at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms, n is an integer of 0 to 4, and X is an anion necessary for neutralizing the charge.

The above X is an anion required to neutralize the charge. If the anion is divalent, one molecule is required, and if the anion is monovalent, two molecules are required. In the latter case, the two anions may be the same or different, but from a synthesis standpoint, it is preferable that they are the same. X is not particularly limited as long as it is such an anion, but examples include those listed in Table 13 below.

Ｘは、酸とした際の酸性度が高いものであればジイモニウム系化合物のアニオンとした際にジイモニウム系化合物の耐熱性を向上できる傾向にあり、上記表１０中の（Ｘ－１０）、（Ｘ－１６）、（Ｘ－１７）、（Ｘ－２１）、（Ｘ－２２）、（Ｘ－２４）、（Ｘ－２８）が特に好ましい。

X has a tendency to improve the heat resistance of a diimonium-based compound when it is converted into an anion of the diimonium-based compound, so that (X-10), (X-16), (X-17), (X-21), (X-22), (X-24), and (X-28) in Table 10 above are particularly preferred.

<Metal dithiolate compounds>
The metal dithiolate compound is not particularly limited, but is preferably, for example, a compound represented by the following formula (s2).

式（ｓ２）中、Ｒ³は、上記式（ｓ１）中のＲ¹およびＲ²と同義であり、隣り合うＲ³同士は置換基Ｌを有してもよい環を形成してもよい。ＺはＤ（Ｒⁱ）₄を表し、Ｄは窒素原子、リン原子またはビスマス原子を表し、ｙは０もしくは１を表す。

In formula (s2), ^R3 has the same meaning as ^R1 and ^R2 in formula (s1), and adjacent ^R3 may form a ring which may have a substituent L. Z represents D( ^Ri ) ₄ , D represents a nitrogen atom, a phosphorus atom or a bismuth atom, and y represents 0 or 1.

The R ³ is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, a phenyl group, a methylthio group, an ethylthio group, an n-propylthio group, an n-butylthio group, a phenylthio group, or a benzylthio group. When adjacent R ³ groups form a ring, it is preferable that the ring is a heterocycle containing at least one sulfur atom or nitrogen atom.

The above M is preferably a transition metal, and more preferably Ni, Pd, or Pt.
The D is preferably a nitrogen atom or a phosphorus atom, and the R ⁱ is preferably an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, or a phenyl group.

<Near infrared absorbing particles>
The near-infrared absorbing fine particles are not particularly limited as long as they have absorption in a wavelength region of 950 nm or more and 1800 nm or less. For example, the near-infrared absorbing fine particles described in paragraphs [0047] to [0075] of WO 2017/018419 can be mentioned.

<Commercially available products of compounds (A) and (B)>
Examples of commercially available products of the compound (A) include T090821, T091021, T089021, T090721, and T090122 (manufactured by Tosco Co., Ltd.), B4360, D4773, and D5013 (manufactured by Tokyo Chemical Industry Co., Ltd.), S4253 and S1426 (manufactured by Spectrum Info Co., Ltd.), ExcolorIR12, ExcolorIR14, ExcolorIR10A, ExcolorIR28, ExcolorTX-EX720, ExcolorTX-EX820, and ExcolorTX-EX906 (manufactured by Nippon Shokubai Co., Ltd.).

Commercially available products of the compound (B) (excluding near-infrared absorbing particles) include CIR-108x, CIR-96x, CIR-RL, CIR-1080 (manufactured by Nippon Carlit), S1445 (manufactured by Spectrum Info), ExcolorIR915, ExcolorIR906 (manufactured by Nippon Shokubai), S2058, S2007 (manufactured by FEW Chemicals), etc.

<Resin>
The resin used for the (transparent) resin layer, resin substrate or resin support constituting the base material is not particularly limited as long as it does not impair the effects of the present invention, but examples thereof include resins having a glass transition temperature (Tg) of preferably 110 to 380° C., more preferably 110 to 370° C., and even more preferably 120 to 360° C., in order to ensure thermal stability and formability into a film and to obtain a film capable of forming a dielectric multilayer film by high-temperature deposition at a deposition temperature of 100° C. or higher. In addition, when the glass transition temperature of the resin is 150° C. or higher, a film having a glass transition temperature capable of forming a dielectric multilayer film by deposition at a high temperature can be obtained, which is particularly preferred, even when a compound is added to the resin in a high concentration and the glass transition temperature is lowered.

The resin that can be used is one that, when a 0.05 mm-thick resin plate is formed from the resin, has a total light transmittance (JIS K7105) of preferably 75 to 95%, more preferably 78 to 95%, and particularly preferably 80 to 95%. If a resin with a total light transmittance in this range is used, the resulting substrate will exhibit good transparency as an optical film.

The polystyrene-equivalent mass average molecular weight (Mw) of the resin measured by gel permeation chromatography (GPC) is usually 15,000 to 350,000, preferably 30,000 to 250,000, and the number average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.

Examples of the resins include cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane UV-curable resins, maleimide resins, alicyclic epoxy thermosetting resins, polyetheretherketone resins, polyarylate resins, allyl ester curable resins, acrylic UV-curable resins, vinyl UV-curable resins, and resins containing silica as a main component formed by the sol-gel method. Among these, it is preferable to use cyclic polyolefin resins, aromatic polyether resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, and polyarylate resins, since they provide optical filters with an excellent balance of transparency (optical properties), heat resistance, reflow resistance, etc.

<Cyclic polyolefin resin>
As the cyclic polyolefin resin, a resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ), and a resin obtained by hydrogenating such a resin are preferred.

式（Ｘ₀）中、Ｒ^x1～Ｒ^x4はそれぞれ独立に、下記（i'）～（ix'）より選ばれる原子または基を表し、ｋ^x、ｍ^xおよびｐ^xはそれぞれ独立に、０～４の整数を表す。
（i'）水素原子
（ii'）ハロゲン原子
（iii'）トリアルキルシリル基
（iv'）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数１～３０の炭化水素基
（v'）置換または非置換の炭素数１～３０の炭化水素基
（vi'）極性基（但し、（ii'）および（iv'）を除く。）
（vii'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成されたアルキリデン基（但し、前記結合に関与しないＲ^x1～Ｒ^x4は、それぞれ独立に前記（ｉ'）～（vi'）より選ばれる原子または基を表す。）
（viii'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1～Ｒ^x4は、それぞれ独立に前記（i'）～（vi'）より選ばれる原子または基を表す。）
（ix'）Ｒ^x2とＲ^x3とが、相互に結合して形成された単環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1とＲ^x4は、それぞれ独立に前記（i'）～（vi'）より選ばれる原子または基を表す。）

In formula (X ₀ ), R ^x1 to R ^x4 each independently represent an atom or group selected from the following (i′) to (ix′); k ^x , m ^x and p ^x each independently represent an integer of 0 to 4:
(i') a hydrogen atom, (ii') a halogen atom, (iii') a trialkylsilyl group, (iv') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms and having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, (v') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and (vi') a polar group (excluding (ii') and (iv')).
(vii') an alkylidene group formed by mutual bonding of R ^x1 and R ^x2 or R ^x3 and R ^x4 (wherein R ^x1 to R ^x4 not involved in the bond each independently represent an atom or group selected from (i') to (vi') above);
(viii') R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring (wherein R ^x1 to R ^x4 that are not involved in the bond each independently represent an atom or group selected from (i') to (vi').
(ix') R ^x2 and R ^x3 are bonded to each other to form a monocyclic hydrocarbon ring or heterocycle (wherein R ^x1 and R ^x4 that are not involved in the bond each independently represent an atom or group selected from (i') to (vi').

式（Ｙ₀）中、Ｒ^y1およびＲ^y2はそれぞれ独立に、前記（i'）～（vi'）より選ばれる原子または基を表すか、Ｒ^y1とＲ^y2とが、相互に結合して形成された単環もしくは多環の脂環式炭化水素、芳香族炭化水素または複素環を表し、ｋ^yおよびｐ^yはそれぞれ独立に、０～４の整数を表す。

In formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from (i') to (vi') above, or R ^y1 and R ^y2 are bonded together to form a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon, or heterocycle, and k ^y and p ^y each independently represent an integer of 0 to 4.

<Aromatic polyether resin>
The aromatic polyether resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

式（１）中、Ｒ¹～Ｒ⁴はそれぞれ独立に、炭素数１～１２の１価の有機基を示し、ａ～ｄはそれぞれ独立に、０～４の整数を示す。

In formula (1), R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and a to d each independently represent an integer of 0 to 4.

式（２）中、Ｒ¹～Ｒ⁴およびａ～ｄはそれぞれ独立に、前記式（１）中のＲ¹～Ｒ⁴およびａ～ｄと同義であり、Ｙは、単結合、－ＳＯ₂－または－ＣＯ－を示し、Ｒ⁷およびＲ⁸はそれぞれ独立に、ハロゲン原子、炭素数１～１２の１価の有機基またはニトロ基を示し、ｇおよびｈはそれぞれ独立に、０～４の整数を示し、ｍは０または１を示す。但し、ｍが０のとき、Ｒ⁷はシアノ基ではない。

In formula (2), R ¹ to R ⁴ and a to d each independently have the same meaning as R ¹ to R ⁴ and a to d in formula (1), Y represents a single bond, -SO ₂ - or -CO-, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, g and h each independently represent an integer of 0 to 4, and m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

In addition, it is preferable that the aromatic polyether resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

式（３）中、Ｒ⁵およびＲ⁶はそれぞれ独立に、炭素数１～１２の１価の有機基を示し、Ｚは、単結合、－Ｏ－、－Ｓ－、－ＳＯ₂－、－ＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－または炭素数１～１２の２価の有機基を示し、ｅおよびｆはそれぞれ独立に、０～４の整数を示し、ｎは０または１を示す。

In formula (3), ^R5 and ^R6 each independently represent a monovalent organic group having 1 to 12 carbon atoms; Z represents a single bond, -O-, -S-, _-SO2- , -CO-, -CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms; e and f each independently represent an integer of 0 to 4; and n represents 0 or 1.

式（４）中、Ｒ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈはそれぞれ独立に、前記式（２）中のＲ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈと同義であり、Ｒ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆはそれぞれ独立に、前記式（３）中のＲ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆと同義である。

In formula (4), ^R7 , ^R8 , Y, m, g and h are each independently defined as ^R7 , ^R8 , Y, m, g and h in formula (2), and ^R5 , ^R6 , Z, n, e and f are each independently defined as ^R5 , ^R6 , Z, n, e and f in formula (3).

<Polyimide resin>
The polyimide resin is not particularly limited as long as it is a polymer compound containing an imide bond in the repeating unit, and can be synthesized by the method described in, for example, JP-A-2006-199945 or JP-A-2008-163107.

<Fluorene polycarbonate resin>
The fluorene polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized, for example, by the method described in JP-A-2008-163194.

<Fluorene polyester resin>
The fluorene polyester resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety, and can be synthesized by the method described in, for example, JP-A-2010-285505 or JP-A-2011-197450.

<Fluorinated aromatic polymer resin>
The fluorinated aromatic polymer resin is not particularly limited, but is preferably a polymer containing an aromatic ring having at least one fluorine atom and a repeating unit containing at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond, and can be synthesized by the method described in, for example, JP-A-2008-181121.

<Acrylic UV-curable resin>
The acrylic ultraviolet curing resin is not particularly limited, but can be synthesized from a resin composition containing a compound having one or more acrylic or methacrylic groups in the molecule and a compound that decomposes by ultraviolet light to generate active radicals.The acrylic ultraviolet curing resin can be particularly suitably used as the curing resin when the substrate (i) is a substrate in which a transparent resin layer containing compound (A) and a curing resin is laminated on a glass support or a base resin support, or a substrate in which a resin layer such as an overcoat layer made of a curing resin or the like is laminated on a transparent resin substrate containing compound (A).

<Resin mainly composed of silica formed by the sol-gel method>
As a resin containing silica as a main component by the sol-gel method, a compound obtained by a sol-gel reaction through hydrolysis of one or more silanes selected from tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, and methoxytriethoxysilane, and phenylalkoxysilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane can be used as the resin.

<Commercially available products>
Examples of commercially available transparent resins include the following commercially available products. Examples of commercially available cyclic polyolefin resins include Arton manufactured by JSR Corporation, Zeonor manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Co., Ltd. Examples of commercially available polyethersulfone resins include Sumikaexcel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available polycarbonate resins include Pure Ace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. An example of a commercially available acrylic resin is Acriviewer manufactured by Nippon Shokubai Co., Ltd. An example of a commercially available silsesquioxane ultraviolet curable resin is Silplus manufactured by Nippon Steel Chemical Co., Ltd.

<Other ingredients>
The base material (i) may further contain additives such as an antioxidant, a near ultraviolet absorbing agent, and a fluorescence quencher, within the range not impairing the effects of the present invention. These other components may be used alone or in combination of two or more.

<Near-ultraviolet light absorber>
The near-ultraviolet absorbent is not particularly limited as long as it is a compound having at least one absorption maximum in a wavelength region of 250 to 420 nm, and examples thereof include azomethine-based compounds, indole-based compounds, benzotriazole-based compounds, triazine-based compounds, and anthracene-based compounds.

(UA) Azomethine Compound The azomethine compound is not particularly limited, but can be represented, for example, by the following formula (U-1).

式（Ｕ－１）中、Ｒ^a1～Ｒ^a5は、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシル基、炭素数１～１５のアルキル基、炭素数１～９のアルコキシ基または炭素数１～９のアルコキシカルボニル基を表す。

In formula (U-1), R ^a1 to R ^a5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an alkoxycarbonyl group having 1 to 9 carbon atoms.

(UB) Indole Compound The indole compound is not particularly limited, but can be represented, for example, by the following formula (U-2).

式（Ｕ－２）中、Ｒ^b1～Ｒ^b5は、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシル基、シアノ基、フェニル基、アラルキル基、炭素数１～９のアルキル基、炭素数１～９のアルコキシ基または炭素数１～９のアルコキシカルボニル基を表す。

In formula (U-2), R ^b1 to R ^b5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a phenyl group, an aralkyl group, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an alkoxycarbonyl group having 1 to 9 carbon atoms.

(U-C) Benzotriazole Compound The benzotriazole compound is not particularly limited, but can be represented, for example, by the following formula (U-3).

式（Ｕ－３）中、Ｒ^c1～Ｒ^c3は、それぞれ独立に水素原子、ハロゲン原子、水酸基、アラルキル基、炭素数１～９のアルキル基、炭素数１～９のアルコキシ基、または置換基として炭素数１～９のアルコキシカルボニル基を有する炭素数１～９のアルキル基を表す。

In formula (U-3), R ^c1 to R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an aralkyl group, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an alkyl group having 1 to 9 carbon atoms and an alkoxycarbonyl group having 1 to 9 carbon atoms as a substituent.

(UD) Triazine-Based Compound The triazine-based compound is not particularly limited, but can be represented, for example, by the following formula (U-4), (U-5) or (U-6).

式（Ｕ－４）～（Ｕ－６）中、Ｒ^d1は、独立に水素原子、炭素原子数１～１５のアルキル基、炭素原子数３～８のシクロアルキル基、炭素原子数３～８のアルケニル基、炭素原子数６～１８のアリール基、炭素原子数７～１８のアルキルアリール基またはアリールアルキル基を表す。ただし、これらアルキル基、シクロアルキル基、アルケニル基、アリール基、アルキルアリール基およびアリールアルキル基は、ヒドロキシ基、ハロゲン原子、炭素原子数１～１２のアルキル基またはアルコキシ基で置換されてもよく、酸素原子、硫黄原子、カルボニル基、エステル基、アミド基またはイミノ基で中断されてもよい。また、前記置換及び中断は組み合わされてもよい。Ｒ^d2～Ｒ^d9は、それぞれ独立に水素原子、ハロゲン原子、水酸基、炭素原子数１～１５のアルキル基、炭素原子数３～８のシクロアルキル基、炭素原子数３～８のアルケニル基、炭素原子数６～１８のアリール基、炭素原子数７～１８のアルキルアリール基またはアリールアルキル基を表す。

In formulas (U-4) to (U-6), R ^d1 independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group. However, these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups, and arylalkyl groups may be substituted with a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, or may be interrupted with an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, or an imino group. The above substitutions and interruptions may be combined. R ^d2 to R ^d9 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group or an arylalkyl group having 7 to 18 carbon atoms.

<Antioxidants>
Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, and tris(2,4-di-t-butylphenyl)phosphite.

The additives may be mixed with the resin when producing the transparent resin, or may be added when synthesizing the resin. The amount of additives added is selected appropriately depending on the desired properties, but is usually 0.01 to 5.0 parts by mass, and preferably 0.05 to 2.0 parts by mass, per 100 parts by mass of the transparent resin.

<Support>
<Resin support>
The resin used for the resin substrate or resin support is as described above.

<Glass support>
The glass support is not particularly limited, and examples thereof include borosilicate glass, silicate glass, soda-lime glass, near-infrared absorbing glass, etc. The near-infrared absorbing glass is preferred in that it can improve the near-infrared cut property and reduce the incidence angle dependency, and specific examples thereof include fluorine phosphate glass and phosphate glass containing a copper component.

<Method for producing substrate (i)>
When the substrate (i) is a substrate including a resin substrate containing the compound (A), the resin substrate can be formed, for example, by melt molding or cast molding. If necessary, after molding, the substrate can be coated with a coating agent such as an antireflection agent, a hard coat agent, and/or an antistatic agent to produce a substrate having an overcoat layer laminated thereon.

When the substrate (i) is a substrate in which a transparent resin layer such as an overcoat layer made of a curable resin containing compound (A) is laminated on a glass substrate or a base resin substrate, a substrate in which a transparent resin layer is formed on a glass substrate or a base resin substrate can be produced, for example, by melt-molding or casting a resin solution containing compound (A) on the glass substrate or base resin substrate, preferably by coating the substrate by a method such as spin coating, slit coating, or inkjet, followed by drying and removing the solvent, and further irradiating the substrate with light or heating as necessary.

<Melt molding>
Specific examples of the melt molding include a method of melt molding pellets obtained by melt kneading a resin and a compound (A), a method of melt molding a resin composition containing a resin and a compound (A), or a method of melt molding pellets obtained by removing a solvent from a resin composition containing a compound (A), a resin, and a solvent, etc. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding, etc.

<Cast molding>
The cast molding can be produced by a method of casting a resin composition containing the compound (A), a resin, and a solvent onto a suitable support and removing the solvent; or a method of casting a curable composition containing the compound (A) and a photocurable resin and/or a thermosetting resin onto a suitable support and removing the solvent, and then curing the composition by an appropriate method such as ultraviolet irradiation or heating.

When the substrate (i) is a substrate made of a resin substrate containing compound (A), the substrate (i) can be obtained by peeling off the coating film from the support after cast molding. When the substrate (i) is a substrate in which a transparent resin layer such as an overcoat layer made of a curable resin containing compound (A) is laminated on a support such as a glass support or a base resin support, the substrate (i) can be obtained by not peeling off the coating film after cast molding.

Examples of the support include glass plates, steel belts, steel drums, and supports made of transparent resins (e.g., polyester films, cyclic olefin resin films).

In addition, a transparent resin layer can be formed on an optical component such as a glass plate, quartz, or transparent plastic by coating the resin composition on the optical component and then drying the solvent, or by coating the curable composition on the optical component and then curing and drying the composition.

The amount of residual solvent in the transparent resin layer (resin substrate) obtained by the above method should be as small as possible. Specifically, the amount of residual solvent is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on the weight of the transparent resin layer (resin substrate). When the amount of residual solvent is within the above range, a transparent resin layer (resin substrate) that is resistant to deformation and changes in properties and can easily perform the desired function can be obtained.

<Anti-reflection layer>
The optical filter of the present invention may have an antireflection layer on at least one surface of the substrate (i). The antireflection layer in the present invention is a layer having an effect of making the average reflectance after forming the antireflection layer on at least one surface of the substrate (i) equal to or smaller than the average reflectance of the substrate (i) alone in a wavelength region of 420 nm or more and 1000 nm or less.

The anti-reflection layer preferably has anti-reflection properties over the entire wavelength range of 420 to 1050 nm, more preferably 420 to 1100 nm, and even more preferably 420 to 1150 nm.

Examples of anti-reflection layers include a layer with numerous cone-shaped structures smaller than the wavelength of light, with the refractive index changing continuously from the incident medium to the substrate, a dielectric multilayer film in which high-refractive index material layers and low-refractive index material layers are alternately stacked, and a thin film made of a low-refractive index material layer.

As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and usually a material having a refractive index of 1.8 to 3.6 is selected. Such materials include, for example, materials mainly composed of titanium oxide, zirconium oxide, tantalum oxide, niobium oxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, barium titanate, silicon, etc., containing small amounts (for example, 0 to 10% by mass of the main component) of hydrogen, titanium oxide, niobium oxide, tin oxide, and/or cerium oxide, etc.; cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polysulphide resins, etc. Examples of the main components include polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane UV-curable resins, maleimide resins, alicyclic epoxy thermosetting resins, polyetheretherketone resins, polyarylate resins, allyl ester curable resins, acrylic UV-curable resins, vinyl UV-curable resins, and resins formed by the sol-gel method that contain silica as the main component, and other transparent resins in which the main component is dispersed.

The material that constitutes the low refractive index material layer can be a material with a refractive index of 1.7 or less, and typically a material with a refractive index of 1.2 to 1.7 is selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride; transparent resins such as cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane UV-curable resins, maleimide resins, alicyclic epoxy thermosetting resins, polyether ether ketone resins, polyarylate resins, allyl ester curable resins, acrylic UV-curable resins, vinyl UV-curable resins, and resins containing silica as the main component formed by the sol-gel method; or transparent resins in which silica, alumina, lanthanum fluoride, magnesium fluoride, or sodium aluminum hexafluoride is dispersed.

The dielectric multilayer film may have a metal layer and/or a semiconductor layer of about 1 to 100 nm. The material constituting the metal layer may have a refractive index of 0.1 or more and 5.0 or less. Such materials include gold, silver, copper, zinc, aluminum, tungsten, titanium, magnesium, nickel, silicon, and germanium. These metal layers and semiconductor layers tend to have high extinction coefficients for wavelengths in the visible light region, and are preferably thin layers of about 1 to 20 nm.

There are no particular limitations on the method of laminating the high refractive index material layer and the low refractive index material layer, so long as a dielectric multilayer film is formed by laminating these material layers. For example, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated can be formed directly on the substrate (i) by a CVD method, a sputtering method, a vacuum deposition method, an ion-assisted deposition method, an ion plating method, or the like. When laminating a layer containing a transparent resin, it can be formed by melt molding, cast molding, or coating formation in the same manner as the molding method of the substrate (i) described above, preferably by spin coating, dip coating, slit coating, gravure coating, or the like.

As described above, the optical filter of the present invention preferably satisfies requirement (e). That is, the substrate (i) has a dielectric multilayer film on one side thereof, and the product (N x TN) of the number of layers (N) that are 0.5 μm or less in the layers constituting the dielectric multilayer film and the sum (TN) (μm) of the thicknesses of each layer that is 0.5 μm or less is 150 or less, preferably 100 or less, and more preferably 50 or less. When the product (N x TN) is within the above range, the time required for forming the multilayer film and the effort and time loss associated with switching the constituent materials of each layer can be reduced, so that the time required for manufacturing the dielectric multilayer film can be shortened and manufacturing costs can be reduced.

The total number of layers of high refractive index material layers and low refractive index material layers in the dielectric multilayer film (anti-reflection layer) is preferably 2 to 30 layers, more preferably 2 to 22 layers, for the entire optical filter. If the thickness of each layer, the thickness of the dielectric multilayer film as the entire optical filter, and the total number of layers are within the above ranges, sufficient manufacturing margins can be ensured, and warping of the optical filter and cracks in the dielectric multilayer film can be reduced.

<Other functional films>
In the optical filter of the present invention, a functional film such as a hard coat film or an antistatic film may be appropriately provided between the substrate (i) and the antireflection layer (dielectric multilayer film), on the surface of the substrate (i) opposite to the surface on which the antireflection layer is provided, or on the surface of the antireflection layer opposite to the surface on which the substrate (i) is provided, for the purposes of improving the surface hardness of the substrate (i) or the antireflection layer, improving chemical resistance, preventing static electricity, and removing scratches, within a range that does not impair the effects of the present invention.

The optical filter of the present invention may include one layer of the functional film, or may include two or more layers. When the optical filter of the present invention includes two or more layers of the functional film, the optical filter may include two or more similar layers, or may include two or more different layers.

The method for laminating the functional film is not particularly limited, but examples include a method in which a coating agent such as a hard coat agent and/or an antistatic agent is melt-molded or cast-molded onto the substrate (i) or the antireflection layer in the same manner as described above.

It can also be produced by applying a curable composition containing the coating agent or the like to the substrate (i) or the anti-reflection layer with a bar coater or the like, and then curing the composition by exposure to ultraviolet light or the like.

Examples of the coating agent include ultraviolet (UV)/electron beam (EB) curable resins and thermosetting resins, and more specifically, examples of the coating agent include vinyl compounds, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based, and epoxy acrylate-based resins. Examples of the curable compositions that contain these coating agents include vinyl-based, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based, and epoxy acrylate-based curable compositions.

The curable composition may also contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or thermal polymerization initiator may be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. The polymerization initiator may be used alone or in combination of two or more types.

The blending ratio of the polymerization initiator in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass, when the total amount of the curable composition is taken as 100% by mass. When the blending ratio of the polymerization initiator is within the above range, the curable composition has excellent curing characteristics and handleability, and a functional film such as an antireflection layer hard coat film or an antistatic film having the desired hardness can be obtained.

Furthermore, an organic solvent may be added to the curable composition as a solvent, and known organic solvents can be used. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; and amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more. The thickness of the functional film is preferably 0.9 to 30 μm, more preferably 0.9 to 20 μm, and particularly preferably 0.9 to 5 μm. If the thickness is 0.9 μm or less, as described above, the effect of optical interference becomes strong, which tends to hinder the effect of the anti-reflection layer.

In addition, in order to increase the adhesion between the substrate (i) and the functional film and/or the antireflective layer, or between the functional film and the antireflective layer, the surface of the substrate (i), the functional film, or the antireflective layer may be subjected to a surface treatment such as a corona treatment or a plasma treatment.

[Optical filter applications]
The optical filter of the present invention has a wide viewing angle, high red sensitivity, and improved ghosting characteristics. Therefore, it is useful for correcting the visibility of solid-state imaging elements such as CCD and CMOS in camera modules. It is particularly useful for digital still cameras, mobile phone cameras, smartphone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, televisions, car navigation systems, personal digital assistants, personal computers, video games, portable game consoles, fingerprint authentication systems, environmental light sensors, distance measuring sensors, iris authentication systems, face authentication systems, distance measuring cameras, digital music players, etc.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the solid-state imaging device is an image sensor equipped with a solid-state imaging element such as a CCD or a CMOS. The solid-state imaging element is made of a photoelectric conversion element such as a silicon photodiode or an organic semiconductor that converts light of a specific wavelength into an electric charge.

<Camera module>
A camera module of the present invention includes the optical filter of the present invention. Here, the camera module is a device that includes an image sensor, a focus adjustment mechanism, a phase detection mechanism, a distance measurement mechanism, etc., and outputs image and distance information as electrical signals.

The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples. Note that "parts" means "parts by mass" unless otherwise specified. The methods for measuring each physical property value and evaluating the physical properties are as follows.

<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b), taking into consideration the solubility of each resin in a solvent, etc.
(a) The mass average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a gel permeation chromatography (GPC) apparatus manufactured by WATERS (150C type, column: Tosoh H-type column, developing solvent: o-dichlorobenzene).
(b) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a Tosoh GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF).

<Glass transition temperature (Tg)>
The measurement was performed using a differential scanning calorimeter (DSC6200) manufactured by SII Nanotechnologies Inc., at a temperature increase rate of 20° C. per minute under a nitrogen gas flow.

<Spectral transmittance>
The transmittance of the optical filter in each wavelength range was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.
Here, for the transmittance measured from the perpendicular direction of the optical filter, light 1 transmitted perpendicularly through optical filter 2 was measured by spectrophotometer 3 as in FIG. 1(A). For the transmittance measured from an angle of 30 degrees with respect to the perpendicular direction of the optical filter, light 1' transmitted at an angle of 30 degrees with respect to the perpendicular direction of the optical filter 2 was measured by spectrophotometer 3 as in FIG. 1(B). For the transmittance measured from an angle of 60 degrees with respect to the perpendicular direction of the optical filter, light 1'' transmitted at an angle of 60 degrees with respect to the perpendicular direction of the optical filter was measured by spectrophotometer 3 as in FIG. 1(C).

<Spectral reflectance>
The reflectance in each wavelength range of the optical filter was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corp. Here, for the reflectance measured at an angle of 5 degrees with respect to the perpendicular direction of the optical filter, light 11 reflected at an angle of 5 degrees with respect to the perpendicular direction of the optical filter 2 as shown in FIG.

The near-infrared absorbing dyes used in the examples below were synthesized by commonly known methods. Examples of general synthesis methods include those described in Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Publication No. 60-228448, Japanese Patent Publication No. 1-146846, Japanese Patent Publication No. 1-228960, Japanese Patent No. 4081149, Japanese Patent Publication No. 63-124054, "Phthalocyanine - Chemistry and Function -" (IPC, 1997), Japanese Patent Publication No. 2007-169315, Japanese Patent Publication No. 2009-108267, Japanese Patent Publication No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631, etc.

<Evaluation of Compound (A)>
Absorption Characteristics of Dye in Dichloromethane Compounds (c-35), (a-63), (a-74) and (c-27), each having a maximum absorption wavelength λmax in the wavelength range of 650 nm or more and less than 950 nm, of 850 nm or more and 935 nm or less, were dissolved in dichloromethane, and the wavelength-specific transmittance was measured using an ultraviolet-visible spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). The maximum absorption wavelength λmax in the wavelength range of 850 nm or more and less than 935 nm, the maximum absorption coefficient _ελmax (normalized at 1) in the wavelength range of 650 nm or more and less than 950 nm, the absorption coefficient ελmax _-10nm at a wavelength (λmax-10 nm) when the maximum absorption coefficient _ελmax is normalized by 1, the absorption coefficient _{ελmax +10nm} at a wavelength (λmax+10 nm) when the maximum absorption coefficient ελmax is normalized by 1 and the maximum absorption coefficient ελ The average value ε _430-580ave of the extinction coefficients by wavelength in the wavelength range of 430 nm or more and 580 nm or less was calculated when _max was normalized to 1. The results are shown in Table 20.

<Resin synthesis example 1>
35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis(4-hydroxyphenyl)fluorene, 41.46 g (0.300 mol) of potassium carbonate, 443 g of N,N-dimethylacetamide (hereinafter also referred to as "DMAc") and 111 g of toluene were added to a 3 L four-neck flask. Then, a thermometer, a stirrer, a three-way cock with a nitrogen inlet tube, a Dean-Stark tube and a cooling tube were attached to the four-neck flask. Next, after replacing the inside of the flask with nitrogen, the obtained solution was reacted at 140 ° C for 3 hours, and the generated water was removed from the Dean-Stark tube as needed. When the generation of water was no longer observed, the temperature was gradually increased to 160 ° C, and the reaction was continued at that temperature for 6 hours. After cooling to room temperature (25°C), the salt formed was removed with filter paper, the filtrate was poured into methanol to cause reprecipitation, and the residue was isolated by filtration. The residue was vacuum dried overnight at 60°C to obtain a white powder (hereinafter also referred to as "Resin A") (yield 95%). The obtained Resin A had a number average molecular weight (Mn) of 75,000, a mass average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285°C.

<Resin synthesis example 2>
100 parts of 8-methyl-8-methoxycarbonyltetracyclo[ ^{4.4.0.12,5.17,10} ]dodec-3-ene (hereinafter also ^referred to as "DNM") represented by the following formula (8), 18 parts of 1-hexene (molecular weight regulator), and 300 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a reaction vessel substituted with nitrogen, and the solution was heated to 80°C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol/L) and 0.9 parts of a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol/L) were added as polymerization catalysts to the solution in the reaction vessel, and the solution was heated and stirred at 80°C for 3 hours to carry out ring-opening polymerization reaction, thereby obtaining a ring-opened polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

このようにして得られた開環重合体溶液１，０００部をオートクレーブに仕込み、この開環重合体溶液に、ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃を０．１２部添加し、水素ガス圧１００ｋｇ／ｃｍ²、反応温度１６５℃の条件下で、３時間加熱撹拌して水素添加反応を行った。得られた反応溶液（水素添加重合体溶液）を冷却した後、水素ガスを放圧した。この反応溶液を大量のメタノール中に注いで凝固物を分離回収し、これを乾燥して、水素添加重合体（以下「樹脂Ｂ」ともいう。）を得た。得られた樹脂Ｂは、数平均分子量（Ｍｎ）が３２，０００、質量平均分子量（Ｍｗ）が１３７，０００であり、ガラス転移温度（Ｔｇ）が１６５℃であった。

_1,000 parts of the ring-opened polymer solution thus obtained was charged into an autoclave, 0.12 parts of RuHCl(CO)[P( _C6H5 ) ₃ ] ₃ was added to the ring-opened polymer solution, and the solution was heated and stirred for 3 hours under conditions of a hydrogen gas pressure of 100 kg/ ^cm2 and a reaction temperature of 165°C to carry out a hydrogenation reaction. After cooling the reaction solution (hydrogenated polymer solution), the hydrogen gas was released. The reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was then dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin B"). The resulting resin B had a number average molecular weight (Mn) of 32,000, a mass average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165°C.

[Example A1]
In Example A1, an optical filter having a base material made of a resin substrate was produced according to the following procedure and conditions.

<Preparation of Resin Substrate (Optical Filter)>
In a container, 100 parts by mass of resin A obtained in Resin Synthesis Example 1, 0.07 parts of light absorber "UA-3912" (hereinafter referred to as "compound (u-1)") manufactured by Orient Chemical Industry Co., Ltd. as a near ultraviolet absorber, 0.03 parts of the above compound (a-17) as compound (A), 0.07 parts of the above compound (b-39), 0.04 parts of the above compound (a-47), 0.15 parts of the above compound (a-89), 0.05 parts of the above compound (a-63), 0.05 parts of the above compound (a-74) and 0.03 parts of the above compound (c-27), and N,N-dimethylacetamide were added to prepare a solution with a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, then dried at 60 ° C. for 8 hours, and further dried at 140 ° C. under reduced pressure for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100° C. under reduced pressure for 8 hours to obtain an optical filter consisting of a resin substrate having a thickness of 0.100 mm, a length of 200 mm and a width of 200 mm.

The spectral transmittance of the obtained optical filter was measured in the vertical direction and at angles of 30 degrees and 60 degrees from the vertical direction, the spectral reflectance of the optical filter at an angle of 5 degrees from the vertical direction, and the spectral reflectance of the other side at an angle of 5 degrees from the vertical direction, to evaluate the optical characteristics in each wavelength region. In addition, for the obtained optical filter, the number of layers (N) with a thickness of 0.5 μm or less laminated on the substrate was 0, the sum (TN) (μm) of the thicknesses of the layers with a thickness of 0.5 μm or less laminated on the substrate was 0.0, and the product of (N) and (TN) (μm) was 0. These results are shown in Table 14.

[Example A2]
In Example A2, an optical filter having a base material made of a resin substrate having resin layers on both sides was produced according to the following procedure and conditions.

<Preparation of Resin Substrate>
A container was charged with 100 parts by mass of resin B obtained in Resin Synthesis Example 2, 0.2 parts of a light absorber "UVS-581" (hereinafter referred to as "compound (u-2)") manufactured by Kawasaki Kasei Chemical Industries, Ltd. as a near-ultraviolet absorber, 0.03 parts of the above compound (a-17) as compound (A), 0.10 parts of the above compound (c-93), 0.10 parts of the above compound (a-89), and 0.30 parts of the above compound (c-35), as well as dichloromethane to prepare a solution with a resin concentration of 20% by mass. A resin substrate having a thickness of 0.100 mm, a length of 200 mm, and a width of 200 mm was obtained in the same manner as in Example 1, except that the obtained solution was used.

<Preparation of substrate and optical filter>
Resin composition (3) having the following composition was applied to one side of the obtained resin substrate using a bar coater, and the solvent was removed by volatilization by heating in an oven at 70°C for 2 minutes. At this time, the application conditions of the bar coater were adjusted so that the thickness after drying was 4 μm. Next, exposure (exposure amount 500 mJ/cm ² , 200 mW) was performed using a conveyor-type exposure machine to harden the resin composition (3) and form a resin layer on the resin substrate. Similarly, a resin layer made of the resin composition (3) was formed on the other side of the resin substrate, and an optical filter made of a substrate having a resin layer on both sides of the resin substrate containing the compound (A) was obtained. The obtained optical filter was evaluated in the same manner as in Example A1. The results are shown in Table 14.

Resin composition (3): 60 parts by weight of tricyclodecane dimethanol diacrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solids concentration (TSC): 30%)

[Example A3]
In Example A3, an optical filter having a base material made of a resin substrate having resin layers on both sides was produced according to the following procedure and conditions.

<Preparation of Resin Substrate>
In a container, 100 parts by mass of resin B obtained in Resin Synthesis Example 2, 0.30 parts of the above compound (u-2) as a near-ultraviolet absorber, 0.04 parts of the above compound (a-17) as compound (A), 0.04 parts of the above compound (b-39), 0.14 parts of the above compound (c-93), 0.27 parts of the above compound (c-35) and 0.11 parts of the above compound (c-27), and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass. A resin substrate having a thickness of 0.100 mm, a length of 200 mm, and a width of 200 mm was obtained in the same manner as in Example A1, except that the obtained solution was used.

<Preparation of substrate and optical filter>
The resin composition (3) was applied to one side of the obtained resin substrate by a bar coater, and the solvent was removed by volatilization by heating in an oven at 70°C for 2 minutes. In this case, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm, and the same procedure was followed as in Example A2 to obtain an optical filter made of a base material having a resin layer on both sides of a resin substrate containing compound (A). The obtained optical filter was evaluated in the same manner as in Example A1. The results are shown in Table 14.

[Example A4]
In Example A4, an optical filter having a base material made of a resin substrate having resin layers on both sides was produced according to the following procedure and conditions.

<Preparation of Resin Substrate>
In a container, 100 parts by mass of resin B obtained in Resin Synthesis Example 2, 0.30 parts of the above compound (u-2) as a near-ultraviolet absorber, 0.06 parts of the above compound (a-17) and 0.07 parts of the above compound (b-39) as compound (A), 0.20 parts of the above compound (c-93) and 0.20 parts of the above compound (c-35), 0.33 parts of the above compound (B-1) as compound (B), and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass. A resin substrate having a thickness of 0.100 mm, a length of 200 mm, and a width of 200 mm was obtained in the same manner as in Example A1 except that the obtained solution was used.

<Preparation of substrate and optical filter>
The resin composition (3) was applied to one side of the obtained resin substrate by a bar coater, and the solvent was removed by volatilization by heating in an oven at 70°C for 2 minutes. In this case, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm, and the same procedure was followed as in Example A2 to obtain an optical filter made of a base material having a resin layer on both sides of a resin substrate containing compound (A). The obtained optical filter was evaluated in the same manner as in Example A1. The results are shown in Table 14.

[Example A5]
In Example A5, an optical filter having a base material including a glass substrate was produced according to the following procedure and conditions.

<Preparation of resin solution (D-1)>
In a container, 100 parts by mass of resin B obtained in Resin Synthesis Example 2, 5.00 parts of the compound (u-1) as a near-ultraviolet absorber, 2.50 parts of the compound (b-39) as compound (A), 2.50 parts of the compound (a-20) and 2.50 parts of the compound (a-47), 5.00 parts of the compound (c-35), 5.00 parts of the compound (a-63), 2.50 parts of the compound (c-27), and dichloromethane were added to prepare a solution with a resin concentration of 10% by mass. Thereafter, the solution was filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (D-1).

<Preparation of resin composition (2)>
Isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toa Gosei Chemical Co., Ltd.) 30 parts by mass, 1,9-nonanediol diacrylate 20 parts by mass, methacrylic acid 20 parts by mass, glycidyl methacrylate 30 parts by mass, 3-glycidoxypropyltrimethoxysilane 5 parts by mass, 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by Ciba Specialty Chemical Co., Ltd.) 5 parts by mass and San-Aid SI-110 base agent (manufactured by Sanshin Chemical Industry Co., Ltd.) 1 part by mass were mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 50 wt%, and then filtered with a Millipore filter having a pore size of 0.2 μm to prepare a resin composition (2).

<Preparation of substrate and optical filter>
The resin composition (2) was applied by spin coating to one side of a near-infrared absorbing glass substrate "BS-11" (thickness 80 μm) manufactured by Matsunami Glass Industry Co., Ltd., which was cut to a size of 200 mm long and 200 mm wide, and then heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent, thereby forming a resin layer that functions as an adhesive layer with a transparent resin layer described later. At this time, the coating conditions of the spin coater were adjusted so that the film thickness of the resin layer was about 0.8 μm.

Next, the resin solution (D-1) was applied onto the resin layer using a spin coater under conditions such that the thickness after drying was 2 μm, and the layer was heated on a hot plate at 80° C. for 5 minutes to volatilize and remove the solvent to form a transparent resin layer. Next, the layer was exposed from the glass side using a conveyor-type exposure machine (exposure amount 1 J/cm ² , illuminance 200 mW), and then baked in an oven at 230° C. for 20 minutes to obtain an optical filter consisting of a substrate having a length of 200 mm and a width of 200 mm. The obtained optical filter was evaluated in the same manner as in Example A1. The results are shown in Table 14.

[Example A6]
In Example A6, an optical filter having a base material including a glass substrate was produced according to the following procedure and conditions.

<Preparation of resin solution (D-2)>
In a container, 100 parts by mass of resin B obtained in Resin Synthesis Example 2, 7.50 parts of the compound (u-2) as a near-ultraviolet absorber, 1.00 parts of the compound (a-17) as compound (A), 0.88 parts of the compound (b-39), 3.50 parts of the compound (c-93), 6.75 parts of the compound (c-35) and 2.75 parts of the compound (c-27), and dichloromethane were added to prepare a solution with a resin concentration of 10% by mass. Thereafter, the solution was filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (D-2).

<Preparation of substrate and optical filter>
The resin composition (2) was applied by spin coating to one side of an ultra-thin glass film "OA-10G" (trade name, thickness 100 μm) manufactured by Nippon Electric Glass Co., Ltd., cut to a size of 200 mm in length and 200 mm in width, and then heated on a hot plate at 80 ° C. for 2 minutes to volatilize and remove the solvent, and a resin layer that functions as an adhesive layer with a transparent resin layer described later was formed. At this time, the coating conditions of the spin coater were adjusted so that the film thickness of the resin layer was about 0.8 μm. Next, an optical filter consisting of a substrate having a length of 200 mm and a width of 200 mm was obtained in the same manner as in Example A5, except that the resin solution (D-2) was applied onto the resin layer using a spin coater under conditions such that the film thickness after drying was 4 μm. The obtained optical filter was evaluated in the same manner as in Example A1. The results are shown in Table 14.

[Example A7]
In Example A7, an optical filter having a base material made of a resin substrate having resin layers on both sides was produced according to the following procedure and conditions.

<Preparation of Resin Substrate>
In a container, 100 parts by mass of resin B obtained in Resin Synthesis Example 2, 0.05 parts of the above compound (a-17) as compound (A), 0.05 parts of the above compound (b-39), 0.10 parts of the above compound (a-89), 0.10 parts of the above compound (a-63), 0.05 parts of the above compound (a-74), and 0.30 parts of the above compound (B-1) as compound (B) and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass. An optical filter consisting of a base material having a resin layer on both sides of a resin substrate containing compound (A) was obtained in the same manner as in Example A2. The obtained optical filter was evaluated in the same manner as in Example A1. The results are shown in Table 14.

[Example A8]
In Example A8, an optical filter having a base material made of a resin substrate having resin layers on both sides was produced according to the following procedure and conditions.

<Preparation of Resin Substrate>
In a container, 100 parts by mass of resin B obtained in Resin Synthesis Example 2, 0.21 parts of the above compound (a-47), 0.05 parts of the above compound (a-89), 0.05 parts of the above compound (a-63), and 0.06 parts of the above compound (a-74) as compound (A), and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass. An optical filter consisting of a base material having a resin layer on both sides of a resin substrate containing compound (A) was obtained in the same manner as in Example A2. The obtained optical filter was evaluated in the same manner as in Example A1. The results are shown in Table 14.

[Example A9]
In Example A9, an optical filter having a base material made of a resin substrate having resin layers on both sides was produced according to the following procedure and conditions.

<Preparation of Resin Substrate>
In a container, 100 parts by mass of resin B obtained in Resin Synthesis Example 2, 0.06 parts of the above compound (a-17), 0.08 parts of the above compound (b-39), 0.22 parts of the above compound (a-63), and 0.10 parts of the above compound (a-74) as compound (A), and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass. An optical filter consisting of a base material having a resin layer on both sides of a resin substrate containing compound (A) was obtained in the same manner as in Example A2. The obtained optical filter was evaluated in the same manner as in Example A1. The results are shown in Table 14.

[Comparative Example A1]
In Comparative Example A1, an optical filter having a base material including a glass substrate was produced according to the following procedure and conditions.

<Preparation of Optical Filter>
According to the procedure of the examples of [0075] to [0079] and [0102] of Japanese Patent No. 6267823, an optical filter (thickness 380 μm) including a glass substrate corresponding to Example 22 of Japanese Patent No. 6267823 was prepared. The obtained optical filter was evaluated in the same manner as in Example A1. The results are shown in Table 14.

[Comparative Example A2]
In Comparative Example A2, an optical filter having a base material made of a resin substrate having resin layers on both sides was produced according to the following procedure and conditions.

<Preparation of Resin Substrate>
In a container, 100 parts by mass of resin B obtained in Resin Synthesis Example 2, 0.07 parts of the above compound (u-1) as a near-ultraviolet absorber, 0.03 parts of the above compound (a-17) as compound (A), 0.07 parts of the above compound (b-39) and 0.04 parts of the above compound (a-47), 0.10 parts of the above compound (a-89) and 0.05 parts of the above compound (a-63), and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass. A resin substrate having a thickness of 0.100 mm, a length of 200 mm, and a width of 200 mm was obtained in the same manner as in Example A1, except that the obtained solution was used.

<Preparation of substrate and optical filter>
The resin composition (3) was applied to one side of the obtained resin substrate by a bar coater, and heated in an oven at 70°C for 2 minutes to volatilize and remove the solvent. In this case, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm, and the same procedure was followed as in Example A2 to obtain an optical filter made of a base material having a resin layer on both sides of a resin substrate containing compound (A). The obtained optical filter was evaluated in the same manner as in Example A1. The results are shown in Table 14.

[Comparative Example A3]
In Comparative Example A3, an optical filter having a base material made of a resin substrate was produced according to the following procedure and conditions.

<Preparation of Resin Substrate (Optical Filter)>
A solution with a resin concentration of 20% by mass was prepared in the same manner as in Example A1. The obtained solution was cast on a smooth glass plate, dried at 60°C for 8 hours, then dried at 60°C for 8 hours, and further dried at 140°C under reduced pressure for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100°C under reduced pressure for 8 hours to obtain an optical filter consisting of a resin substrate with a thickness of 0.200 mm, a length of 200 mm, and a width of 200 mm. The obtained optical filter was whitened due to a large amount of residual solvent, and the spectral transmittance could not be evaluated.

[Example B1]
In Example B1, an optical filter having antireflection layers on both sides of a base material made of a resin substrate was produced according to the following procedure and conditions.

<Preparation of Optical Filter>
A substrate made of a resin substrate was obtained in the same procedure as in Example A1. An antireflection layer of design (III) shown in Table 15 below was formed on both sides of the obtained substrate in the following procedure. First, resin composition (4) (Arakawa Chemical's "Opstar TU2360"; refractive index at 590 nm: 1.39) was applied to one side of the substrate with a bar coater, and heated in an oven at 70°C for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 106.3 nm. Next, exposure (exposure amount 500 mJ/cm ² , 200 mW) was performed using a conveyor-type exposure machine to harden the resin composition (4) and form an antireflection layer on the resin substrate. Similarly, an antireflection layer made of resin composition (4) was formed on the other side of the resin substrate to obtain an optical filter.

The spectral transmittance of the obtained optical filter was measured in the vertical direction and at angles of 30 degrees and 60 degrees from the vertical direction, the spectral reflectance of the optical filter at an angle of 5 degrees from the vertical direction, and the spectral reflectance of the other side at an angle of 5 degrees from the vertical direction, to evaluate the optical characteristics in each wavelength region. In addition, for the obtained optical filter, the number of layers (N) with a thickness of 0.5 μm or less laminated on the substrate was 2, the sum (TN) (μm) of the thicknesses of the layers with a thickness of 0.5 μm or less laminated on the substrate was 0.2, and the product of (N) and (TN) (μm) was 0.4. These results are shown in Table 19.

[Example B2]
In Example B2, an optical filter having antireflection layers on both sides of a base material including a resin substrate was produced according to the following procedure and conditions.

<Preparation of Optical Filter>
A substrate having a resin layer on both sides of a resin substrate was obtained by the same procedure as in Example A2. An anti-reflection layer [a dielectric multilayer film consisting of a silica (SiO ₂ : refractive index 1.46 at 550 nm) layer and a titania (TiO ₂ : refractive index 2.48 at 550 nm) layer alternately stacked] of design (IV) shown in Table 16 below was formed on both sides of the obtained substrate at a deposition temperature of 120°C using an ion-assisted vacuum deposition device, thereby obtaining an optical filter.

The obtained optical filter was evaluated in the same manner as in Example B1. Furthermore, for the obtained optical filter, the number of layers (N) of layers with a thickness of 0.5 μm or less laminated on the substrate was 12, the sum of the thicknesses of the layers with a thickness of 0.5 μm or less laminated on the substrate (TN) (μm) was 0.5, and the product of (N) and (TN) (μm) was 6.0. These results are shown in Table 19.

[Example B3]
In Example B3, an optical filter having antireflection layers on both sides of a base material including a resin substrate was produced according to the following procedure and conditions.

<Preparation of Optical Filter>
A substrate having a resin layer on both sides of a resin substrate was obtained in the same manner as in Example A3. An anti-reflection layer of the design (IV) [a dielectric multilayer film consisting of a silica (SiO ₂ : refractive index 1.46 at 550 nm) layer and a titania (TiO ₂ : refractive index 2.48 at 550 nm) layer alternately stacked] was formed on both sides of the obtained substrate using an ion-assisted vacuum deposition apparatus at a deposition temperature of 120° C. to obtain an optical filter. The obtained optical filter was evaluated in the same manner as in Example B1. The results are shown in Table 19.

[Example B4]
In Example B4, an optical filter having antireflection layers on both sides of a base material including a resin substrate was produced according to the following procedure and conditions.

<Preparation of Optical Filter>
A substrate having a resin layer on both sides of a resin substrate was obtained in the same manner as in Example A4.An anti-reflection layer of the design (III) was formed on both sides of the obtained substrate in the same manner as in Example B1 to obtain an optical filter.The obtained optical filter was evaluated in the same manner as in Example B1.The results are shown in Table 19.

[Example B5]
In Example B5, an optical filter having antireflection layers on both sides of a base material including a glass substrate was produced according to the following procedure and conditions.

<Preparation of Optical Filter>
A substrate having a transparent resin layer on one side of a glass substrate was obtained in the same manner as in Example A5. An anti-reflection layer [a dielectric multilayer film consisting of a silica ( _SiO2 : refractive index 1.46 at 550 nm) layer and a titania ( _TiO2 : refractive index 2.48 at 550 nm) layer alternately stacked] of design (V) shown in Table 17 below was formed on both sides of the obtained substrate at a deposition temperature of 120°C using an ion-assisted vacuum deposition device, thereby obtaining an optical filter.

The obtained optical filter was evaluated in the same manner as in Example B1. Furthermore, for the obtained optical filter, the number of layers (N) of layers with a thickness of 0.5 μm or less laminated on the substrate was 8, the sum of the thicknesses of the layers with a thickness of 0.5 μm or less laminated on the substrate (TN) (μm) was 0.5, and the product of (N) and (TN) (μm) was 4.0. These results are shown in Table 19.

[Example B6]
In Example B6, an optical filter having a base material including a glass substrate was produced according to the following procedure and conditions.

<Preparation of Optical Filter>
A substrate having a transparent resin layer on one side of a glass substrate was obtained in the same manner as in Example A6. An anti-reflection layer of the design (V) [a dielectric multilayer film consisting of a silica (SiO ₂ : refractive index 1.46 at 550 nm) layer and a titania (TiO ₂ : refractive index 2.48 at 550 nm) layer alternately stacked] was formed on both sides of the obtained substrate using an ion-assisted vacuum deposition apparatus at a deposition temperature of 120° C. to obtain an optical filter. The obtained optical filter was evaluated in the same manner as in Example B1. The results are shown in Table 19.

[Example B7]
In Example B7, an optical filter having antireflection layers on both sides of a base material including a resin substrate was produced according to the following procedure and conditions.

<Preparation of Optical Filter>
A substrate having a resin layer on both sides of a resin substrate was obtained in the same manner as in Example A7. An optical filter was obtained on both sides of the obtained substrate in the same manner as in Example B5. The obtained optical filter was evaluated in the same manner as in Example B1. The results are shown in Table 19.

[Example B8]
In Example B8, an optical filter having antireflection layers on both sides of a base material including a resin substrate was produced according to the following procedure and conditions.

<Preparation of Optical Filter>
A substrate having a resin layer on both sides of a resin substrate was obtained in the same manner as in Example A8. An optical filter was obtained on both sides of the obtained substrate in the same manner as in Example B5. The obtained optical filter was evaluated in the same manner as in Example B1. The results are shown in Table 19.

[Example B9]
In Example B9, an optical filter having antireflection layers on both sides of a base material including a resin substrate was produced according to the following procedure and conditions.

<Preparation of Optical Filter>
A substrate having a resin layer on both sides of a resin substrate was obtained in the same manner as in Example A9. An optical filter was obtained on both sides of the obtained substrate in the same manner as in Example B5. The obtained optical filter was evaluated in the same manner as in Example B1. The results are shown in Table 19.

[Comparative Example B1]
In Comparative Example B1, an optical filter having near-infrared reflective layers on both sides of a substrate was produced according to the following procedure and conditions.

<Preparation of Resin Substrate>
A solution with a resin concentration of 20% by mass was prepared by adding 100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 0.08 parts of Compound (a-17) and 0.11 parts of Compound (b-39) as Compound (A), and N,N-dimethylacetamide to a container. A resin substrate having a thickness of 0.070 mm, length of 200 mm, and width of 200 mm was obtained in the same manner as in Example A1, except that the obtained solution was used.

<Preparation of substrate and optical filter>
The resin composition (3) was applied to one side of the obtained resin substrate using a bar coater, and the solvent was removed by volatilization by heating in an oven at 70° C. for 2 minutes. In this case, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm, and a substrate having a resin layer on both sides of the resin substrate containing the compound (A) was obtained in the same manner as in Example A2.

Using an ion-assisted vacuum deposition apparatus, near-infrared cut layers of designs (I) and (II) shown in Table 18 below [dielectric multilayer films consisting of alternating layers of silica ( _SiO2 : refractive index 1.46 at 550 nm) and titania ( _TiO2 : refractive index 2.48 at 550 nm) layers] were formed on both sides of the obtained substrate at a deposition temperature of 120°C, obtaining an optical filter with a thickness of 0.079 mm.

The obtained optical filter was evaluated in the same manner as in Example B1. Furthermore, for the obtained optical filter, the number of layers (N) of layers with a thickness of 0.5 μm or less laminated on the substrate was 46, the sum of the thicknesses of the layers with a thickness of 0.5 μm or less laminated on the substrate (TN) (μm) was 5.3, and the product of (N) and (TN) (μm) was 243.8. These results are shown in Table 19.

The symbols for the base material configurations and various compounds in Tables 14 and 19 are as follows.
<Glass substrate>
Glass substrate (1): Near infrared absorbing glass substrate "BS-11" (manufactured by Matsunami Glass Industry Co., Ltd.)
Glass substrate (4): Ultra-thin glass film "OA-10G" (manufactured by Nippon Electric Glass Co., Ltd.)
Glass substrate (X): transparent glass substrate (see Japanese Patent No. 6267823, [0075] to [0078])

<Resin Composition>
Resin composition (2): 30 parts by weight of isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toa Gosei Chemical Co., Ltd.), 20 parts by weight of 1,9-nonanediol diacrylate, 20 parts by weight of methacrylic acid, 30 parts by weight of glycidyl methacrylate, 5 parts by weight of 3-glycidoxypropyltrimethoxysilane, 5 parts by weight of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemical Co., Ltd.), and 1 part by weight of San-Aid SI-110 base agent (manufactured by Sanshin Chemical Industry Co., Ltd.), propylene glycol monomethyl ether acetate (solvent, solid content concentration (TSC) 50%)
Resin composition (3): 60 parts by mass of tricyclodecane dimethanol diacrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solids concentration (TSC): 30%)
Resin composition (4): Opstar TU2360 (manufactured by Arakawa Chemical Industries, Ltd.)
Resin composition (X): Copper phosphate-containing resin composition (see Japanese Patent No. 6267823, [0075] to [0078])

<Light absorber>
<Near-ultraviolet light absorber>
Compound (u-1): Light absorber "UA-3912" manufactured by Orient Chemical Industries Co., Ltd. (maximum absorption wavelength in dichloromethane: 389 nm) Compound (u-2): Light absorber "UVS-581" manufactured by Kawasaki Kasei Chemical Industries, Ltd. (maximum absorption wavelength in dichloromethane: 367 nm)

<Compound (A)>
Compound (a-17): (maximum absorption wavelength in dichloromethane: 713 nm)
Compound (b-39): (maximum absorption wavelength in dichloromethane: 736 nm)
Compound (a-20): (maximum absorption wavelength in dichloromethane: 704 nm)
Compound (a-47): (maximum absorption wavelength in dichloromethane: 776 nm)
Compound (c-93): (maximum absorption wavelength in dichloromethane: 770 nm)
Compound (a-63): (maximum absorption wavelength in dichloromethane: 868 nm)
Compound (a-89): (maximum absorption wavelength in dichloromethane: 822 nm)
Compound (c-35): (maximum absorption wavelength in dichloromethane: 870 nm)
Compound (a-74): (maximum absorption wavelength in dichloromethane: 933 nm)
Compound (c-27): (maximum absorption wavelength in dichloromethane: 933 nm)

<Compound (B)>
Compound (B-1): Light absorber "CIR-RL" manufactured by Nippon Carlit Co., Ltd. (maximum absorption wavelength in dichloromethane: 1095 nm)

1', 1''...light 2...optical filter 3...spectrophotometer 11...reflected light

Claims (10)

An optical filter characterized by satisfying the following requirements (a) to (d):
(a) in the wavelength region of 700 nm to 900 nm, the minimum optical density (OD value) for light incident perpendicularly to the surface of the optical filter (OD _a-0 ) is 2.0 or more;
(b) the average transmittance (T _a-0 ) of light incident perpendicularly to the surface of the optical filter in the wavelength region of 430 nm to 580 nm is 40% or more;
(c) the average reflectance (Rf _a-5 ) for light incident at an angle of 5 degrees from the perpendicular direction to the surface of the optical filter in the wavelength region of 420 nm to 900 nm is 20% or less;
(d) A layer containing at least three kinds of compounds (A) having an absorption maximum in a wavelength region of 650 nm or more and less than 950 nm, at least one of the compounds (A) being a cyanine compound represented by the following formula (VII-4) or (VII- 9) :

[In formula (VII-4) or (VII- 9 ), X _a ^- represents a monovalent anion;
A plurality of X's each represent an oxygen atom .
A plurality of R _b , R _c , R _d , R _e , R _f and R _g each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group _, a nitro group, an amino group, an amido group, an imido group, a cyano _group , a silyl group, -L ¹ , -S-L ² , -SS-L ³ , _{-SO 2} -L ³ _{, -N═N} -L ⁴ or groups represented by the following formulae (A) to (H) in which at least one combination of R _b and R _c , R d and R e , R e and R f , and R f and R _g is bonded, and the amino group, amido group, imido group and silyl group may have a substituent L,
L represents at least one substituent selected from the group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, and an amino group;
^L1 represents L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h ;
L ^a represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L;
L ^b represents a halogen-substituted alkyl group having 1 to 12 carbon atoms which may have a substituent L;
^Lc represents an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L;
L ^d represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent L;
L ^e represents a heterocyclic group having 3 to 14 carbon atoms which may have a substituent L;
^Lf represents an alkoxy group having 1 to 9 carbon atoms which may have a substituent L;
L ^g represents an acyl group having 1 to 9 carbon atoms which may have a substituent L;
^Lh represents an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L;
^L2 represents a hydrogen atom or any one of L ^a to L ^e described above;
^L3 represents a hydrogen atom or any one of L ^a to L ^e described above;
^L4 represents any one of L ^a to L ^e ;
Z _a to Z _c and Y _a to Y _d each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amido group, an imido group, a cyano group, a silyl group, -L ¹ , -S-L ² , -SS-L ² , -SO ₂ -L ³ , or -N═N-L ⁴ (L ¹ to L ⁴ represent L ¹ to L in R _b to R _g above). 4.) or adjacent two Z's or Y's selected from among these are bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms; an alicyclic hydrocarbon group having a 5- or 6-membered ring which may contain at least ^one nitrogen atom, oxygen atom or sulfur atom; or a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, and these aromatic hydrocarbon groups, alicyclic hydrocarbon groups and heteroaromatic hydrocarbon groups may contain an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.]

[In formulae (A) to (H), R _x and R _y represent carbon atoms, and the multiple R _A to R _L each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amido group, an imido group, a cyano group, a silyl group, -L ¹ , -S-L ² , -SS-L ² , -SO ₂ -L ³ , or -N═N-L ⁴ , and the amino group, amido group, imido group and silyl group may have the substituent L, and L ¹ to L ⁴ are the same as L ¹ to L ⁴ defined in formula (VII-4) or (VII- 9 ).] 2. The optical filter according to claim 1, characterized in that the minimum optical density (OD value) (OD _a-0 ) in the requirement (a) is 2.1 or more, and the average transmittance (T _a-0 ) in the requirement (b) is 55% or more. 3. The optical filter according to claim 1, further satisfying the following requirement (e):
(e) A substrate including the layer described in requirement (d) and a dielectric multilayer film on at least one surface of the substrate, wherein the product (N x TN) of the number of layers (N) having a thickness of 0.5 μm or less among the layers constituting the dielectric multilayer film and the sum (TN) (μm) of the thicknesses of each layer having a thickness of 0.5 μm or less is 150 or less. The optical filter according to any one of claims 1 to 3, characterized in that it has a thickness of 160 μm or less. The optical filter according to any one of claims 1 to 4, characterized in that at least one of the compounds (A) satisfies the following requirements (f) and (g) as absorption characteristics measured after dissolving in dichloromethane:
(f) the maximum absorption wavelength λmax in the wavelength region of 650 nm or more and less than 950 nm is 850 nm or more and 935 nm or less;
(g) When the maximum absorption coefficient ελ _max in the wavelength region of 650 nm or more and less than 950 nm is normalized to 1,
(g-1) the absorption coefficient ελmax _-10 at a wavelength of (λmax-10) nm is 0.80 or more;
(g-2) the absorption coefficient ελmax ₊₁₀ at a wavelength of (λmax+10) nm is 0.80 or more;
(g-3) The average value ε _430-580ave of the absorption coefficient in the wavelength region of 430 nm or more and 580 nm or less is 0.03 or less. The optical filter according to any one of claims 1 to 5, characterized in that the compound (A) contains at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, cyanine compounds (excluding the cyanine compounds represented by formulas (VII-4) and (VII- 9 )), diimonium compounds, metal dithiolate compounds, and pyrrolopyrrole compounds. The optical filter according to any one of claims 1 to 6, characterized in that the layer containing the compound (A) is a resin layer made of at least one resin selected from the group consisting of cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane UV-curable resins, maleimide resins, alicyclic epoxy thermosetting resins, polyetheretherketone resins, polyarylate resins, allyl ester curable resins, acrylic UV-curable resins, vinyl UV-curable resins, and resins formed by a sol-gel method and containing silica as a main component. The optical filter according to claim 3, characterized in that the base material includes a substrate made of a fluorine phosphate-based glass layer or a phosphate-based glass layer containing a copper component. An imaging device comprising an optical filter according to any one of claims 1 to 8. A camera module comprising an optical filter according to any one of claims 1 to 8.

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