KR20200134161A - Optical filter and use thereof - Google Patents

Abstract

An objective of the present invention is an optical filter to provide excellent near-infrared shielding properties even with a thin thickness and uses thereof. According to the present invention, the optical filter satisfies the following conditions: (a) in the region of a wavelength of 700 to 900 nm, the minimum value (OD_a-0) of the optical density (OD value) for light incident from a direction perpendicular to the plane of the optical filter is 2.0 or more; (b) in the region of a wavelength 430 to 580 nm, the average value (T_a-0) of the transmittance of light incident from a direction perpendicular to the surface of the optical filter is 40% or more; (c) in the region of a wavelength of 420 to 900 nm, the average value (Rf_a-5) of the reflectance for light incident at an angle of 5 degrees with respect to the direction perpendicular to the plane of the optical filter is 20% or less; and (d) a layer containing at least three kinds of compounds (A) having an absorption maximum in a region of a wavelength of 650 nm or more and less than 950 nm is included.

Description

Optical filter and use thereof TECHNICAL FIELD [OPTICAL FILTER AND USE THEREOF}

The present invention relates to optical filters and uses thereof. Specifically, the present invention relates to an optical filter (for example, a near-infrared cut filter) containing a compound having absorption in a specific wavelength region and having specific optical properties, and an imaging device and a camera module using the optical filter.

In solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions, CCDs and CMOS image sensors, which are solid-state imaging elements for color images, are used. As for these solid-state imaging devices, a silicon photodiode having sensitivity to near-infrared rays that cannot be detected by the human eye is used in the light receiving portion thereof. In these solid-state imaging devices, it is necessary to perform luminous sensitivity correction to produce a natural color tone as seen by the human eye, and when an optical filter (for example, a near-infrared cut filter) that selectively transmits or cuts light in a specific wavelength range is used. There are many.

As such near-infrared cut filters, conventionally, those manufactured by various methods have been used. For example, an absorption glass type optical filter (for example, see Patent Document 1) using an absorption glass in which copper oxide is dispersed in a phosphate glass is known as a substrate.

In recent years, thinner solid-state imaging devices have been demanded, and thinner optical filters are also required. The absorption principle of the above absorption glass type optical filter is that absorption derived from the d orbital of copper ions is often used, but since the absorption strength is weak, sufficient near-infrared cutting performance may not be obtained when the thickness is reduced.

In such a thin absorption glass type optical filter, in order to supplement the near-infrared cutting performance, a dielectric multilayer film having near-infrared reflectivity is often provided on the surface of the base material (see, for example, Patent Document 2). By providing a dielectric multilayer film having near-infrared reflecting ability on the surface of the substrate, it is possible to achieve both thinning and near-infrared shielding properties.

As an optical filter having such a dielectric multilayer film having near-infrared reflectivity, not only an absorption glass type, but also a transparent resin is used as a substrate, and a dye having an absorption maximum in a region of 650 to 800 nm is contained in the transparent resin. , A resin-type optical filter using a dielectric multilayer film having near-infrared reflectivity on both sides of the substrate (Patent Document 3), a filter coated with copper phosphate or cesium tungsten oxide particles on a glass substrate (Patent Document 4), and absorption in the vicinity of 700 to 750 nm. Various types are known, such as a glass substrate-coated optical filter (Patent Document 5) coated with a resin layer containing a dye having a dye.

However, like the above-described absorption glass type, resin type, and glass substrate coated optical filter, the optical filter having near-infrared reflectivity on the surface of the substrate is a phenomenon in which the light reflected from the surface of the optical filter enters the sensor again, that is, ghost. Occurs, there was a case that an image defect of the obtained solid-state imaging device was caused.

In addition, in these optical filters, although the thickness of each layer of the dielectric multilayer film is thin, it is necessary to increase the number of layers in order to exhibit near-infrared reflectivity. Therefore, since a long time is required in manufacturing the dielectric multilayer film, the manufacturing throughput is poor and the manufacturing cost tends to increase.

By the way, it has been known from before that ghost is suppressed by providing an antireflection layer in an optical filter (patent document 6). However, since the antireflection layer in the conventional optical filter is an antireflection layer having a wavelength of 420 nm to 780 nm (visible light region), reflection by light having a wavelength of 781 nm to 900 nm cannot be prevented, resulting in ghosting. In addition, when the near-infrared reflectivity is not imparted to the thin substrate, the optical density (OD) at a wavelength of 700 nm or more and 900 nm or less is not sufficient, so that the thickness reduction and near-infrared shielding performance could not be compatible. That is, an optical filter having a thin, excellent near-infrared shielding property and low reflectance over a wavelength in the visible region to the near-infrared region was not obtained.

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

An object of the present invention is to provide an optical filter excellent in near-infrared shielding properties even if the thickness is thin, and an imaging device and a camera module using the optical filter.

Examples of aspects of the present invention are shown below.

[1] An optical filter characterized by satisfying the following requirements (a) to (d): (a) Optical density for light incident from a direction perpendicular to the surface of the optical filter in a region of 700 nm to 900 nm The minimum value (OD _a-0 ) of (OD value) is 2.0 or more; (b) in the region of wavelength 430 nm to 580 nm, the average value (T _a-0 ) of the transmittance of light incident from the direction perpendicular to the surface of the optical filter is 40% or more; (c) in the region of wavelength 420 nm to 900 nm, the average value of reflectance (Rf _a-5 ) for light incident at an angle of 5 degrees with respect to the direction perpendicular to the surface of the optical filter is 20% or less; (d) A layer containing at least three types of compounds (A) having an absorption maximum in a region having a wavelength of 650 nm or more and less than 950 nm is included.

[2] The optical filter according to item [1], further satisfying the following requirement (e): (e) a substrate including the layer according to the requirement (d), and a dielectric multilayer film on at least one side of the substrate And the product (N×TN) of the sum of the thicknesses of each layer having a thickness of 0.5 μm or less (N) and the thickness of each layer having a thickness of 0.5 μm or less (TN) (μm) among the layers constituting the dielectric multilayer film is 150 Below.

[3] The optical filter according to item [1] or [2], wherein the thickness is 160 µm or less.

[4] Any one of [1] to [3], characterized in that at least one of the compounds (A) is dissolved in dichloromethane and measured as absorption properties, which satisfy the following requirements (f) and (g). The optical filter according to one of the preceding claims: (f) the maximum absorption wavelength λmax in a region having a wavelength 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 ελ _max in the region of wavelength 650 nm or more and less than 950 nm is normalized to 1,

(g-1) the absorption coefficient ελ _{max-10 at the} wavelength (λmax-10) nm is 0.80 or more,

(g-2) the extinction coefficient ελ _{max+10 at the} wavelength (λmax+10) nm is 0.80 or more,

(g-3) The average value _ε430-580ave of the extinction coefficient in a region having a wavelength of 430 or more and 580 nm or less is 0.03 or less.

[5] The compound (A) is a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a chromonium compound, a cyanine compound, a dimonium compound, a metal dithiolate compound and a pyrrolopyrrole compound. The optical filter according to any one of items [1] to [4], comprising at least one compound selected from the group consisting of.

[6] The layer containing the compound (A) is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, and a polycarbonate. Resin, polyamide resin, aramid resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) Acrylic resin, epoxy resin, silsesquioxane UV curable resin, maleimide resin, alicyclic epoxy thermosetting resin, polyetheretherketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, Any one of items [1] to [5], characterized in that it is a resin layer comprising at least one resin selected from the group consisting of a vinyl-based UV-curable resin and a resin containing as a main component silica formed by a sol-gel method. The optical filter described in.

[7] The optical filter according to item [2], wherein the substrate includes a fluorophosphate-based glass layer containing a copper component or a substrate including a phosphate-based glass layer.

[8] An imaging device comprising the optical filter according to any one of [1] to [7].

[9] A camera module comprising the optical filter according to any one of [1] to [7].

Advantageous Effects of Invention According to the present invention, an optical filter having excellent near-infrared shielding properties even when the thickness is thin and having a good manufacturing throughput, and an imaging device and a camera module using the optical filter can be provided.

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

Hereinafter, embodiments 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 this invention may be comprised only with the base material mentioned later. That is, the optical filter of the present invention may or may not have a dielectric multilayer film.

(a) In a region of 700 nm to 900 nm in wavelength, the minimum value (OD _a-0 ) of the optical density (OD value) for light incident from a direction perpendicular to the surface of the optical filter is 2.0 or more.

(b) In a region having a wavelength of 430 nm to 580 nm, the average value (T _a-0 ) of the transmittance of light incident from the direction perpendicular to the surface of the optical filter is 40% or more.

(c) In a region having a wavelength of 300 nm to 1200 nm, the reflectance (R _a-0 ) for light incident from a direction perpendicular to the surface of the optical filter is 20% or less.

(d) A layer containing at least three types of compounds (A) having an absorption maximum in a region having a wavelength of 650 nm or more and less than 950 nm is included.

The optical filter of the present invention may further satisfy the following requirement (e).

(e) a substrate (hereinafter also referred to as ``substrate (i)'') comprising the layer described in the above requirement (d), and a layer comprising a dielectric multilayer film having a dielectric multilayer film on at least one side of the substrate (i), The product (N×TN) of the number of layers (N) of a layer having a thickness of 0.5 μm or less and the sum of the thicknesses of each layer having a thickness of 0.5 μm or less (TN) (µm) is 150 or less.

Details of the requirements (a) to (e) will be described later.

In other words, the optical filter of the present invention may satisfy the following requirement (X).

Requirement (X): In a region with a wavelength of 300 nm or more and 1200 nm or less, the maximum value Rfall _a-5 of the reflectance of light incident from a direction inclined by 5 degrees with respect to the vertical direction on one side of the optical filter, and on the other side The maximum value Rfall _b-5 of the reflectance of light incident from the direction inclined at 5 degrees with respect to the vertical direction is 50% or less, and more preferably 45% or less.

By satisfying the requirement (X), it is possible to reduce the reflectance of light with a wavelength of 300 nm or more and 1200 nm or less at which the silicon photodiode is sensitive, on any surface of the optical filter, and thus the optical filter of the present invention can be used for solid-state imaging devices or cameras. When used as a module, since multiple reflections between the optical filter and the lens and multiple reflections between the optical filter and the sensor are reduced, a good image with less ghost can be obtained.

As a method of satisfying the requirement (X), i.e., a method of adjusting the reflectance, for example, a method of preparing a plurality of conical structures having a size less than the wavelength of light, and forming a layer continuously changing the refractive index from the incident medium to the substrate And a method of forming an antireflection layer using a multilayer dielectric multilayer film.

As a method that satisfies the requirement (X), i.e., a design method of an optical filter having a low reflectance, for example, in a wavelength range of 580 to 800 nm, the shortest transmittance when measured from the vertical direction of the substrate is 50%. The absolute value |Xa-Xb| of the difference between the wavelength value (Xa) and the longest wavelength value (Xb) at which the transmittance is 50% when measured from the vertical direction of the substrate in a region with a wavelength of 700 to 1200 nm or more A method of using a substrate having a thickness of 300 nm or more is mentioned.

<Requirement (a)>

Requirement (a): The minimum value OD _a-0 in _a region with a wavelength of 700 nm or more and 900 nm or less is 2.0 or more, and preferably 2.1 or more and 8.0 or less.

Here, the OD value is a common logarithmic value of the transmittance, and can be calculated by the following equation.

Minimum value of optical density (OD value) in a certain wavelength region = -Log ₁₀ (maximum value (%)/100 of transmittance by wavelength in a certain wavelength region)

When the minimum value of the OD value for each wavelength in the specified wavelength range is high, the optical filter indicates that the light cut characteristic in the wavelength range is high.

It is preferable that the optical filter of this invention further meets the following requirement (aX).

Requirement (aX): In a region with a wavelength of 700 nm or more and 900 nm or less, the minimum value OD _a-0 of the optical density for light incident from a direction perpendicular to the surface of the optical filter, and incident from _a direction inclined at 30 degrees to the vertical direction. The minimum value OD _a-30 of the optical density for light and the minimum value OD _a-60 of the optical density for light incident from a direction inclined at 60 degrees with respect to the vertical direction are both 2.0 or more, preferably 2.0 or more and 8.0 or less, more Preferably it is 2.1 or more and 8.0 or less.

As a method that satisfies the requirement (a), preferably the requirement (aX), that is, as a method of adjusting the minimum value of each optical density, for example, by adjusting the concentration of the compound to be contained in the substrate, the wavelength is 700 nm or more and 900 nm or less. A method of making the minimum value of optical density in 2.0 or more is mentioned.

By satisfying the requirement (a), preferably the requirement (aX), the optical filter can sufficiently cut not only the near infrared rays transmitted in the vertical direction but also the near infrared rays transmitted at a high angle of incidence.

<Requirement (b)>

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

It is preferable that the optical filter of this invention further meets the following requirement (bX).

Requirement (bX): In a region with a wavelength of 430 nm or more and 580 nm or less, the average value T _a-0 of the transmittance of light incident from the direction perpendicular to the surface of the optical filter, and unpolarized light incident from the direction inclined at 30 degrees to the vertical direction The average value T _a-30 of the light transmittance of and the average value T _a-60 of the light transmittance of the unpolarized light incident from the oblique direction at 60 degrees with respect to the vertical direction are both 40% or more, preferably 43 to 99%, more It is preferably 46 to 98%, particularly preferably 48 to 97%.

As a method that satisfies the requirement (b), preferably the requirement (bX), that is, the method of adjusting the average value of each transmittance, for example, by adjusting the concentration of the compound added to the substrate, in a region of a wavelength of 430 nm to 580 nm The average absorbance of is preferably 0.35 or less, and more preferably 0.26 or less.

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

As a method of satisfying the requirements (a) and (b), preferably the requirements (aX) and (bX) together, for example, in the substrate (i), a compound having a maximum absorption in a region having a wavelength of 650 nm or more and less than 950 nm The method of containing (A) is mentioned. More preferably, it is preferable that the substrate (i) satisfies the requirement (d). In other words, it is preferable that the compound (A) has little absorption in a region having a wavelength of 430 nm or more and 580 nm or less.

<Requirement (c)>

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

By satisfying the requirement (c), the reflectance of light having a wavelength of 420 nm or more and 900 nm or less, at which the silicon photodiode is highly sensitive, can be reduced on any surface of the optical filter, so that the optical filter of the present invention can be used for solid-state imaging devices or When used as a camera module, good images can be obtained.

As a method that satisfies the requirement (c), that is, as a method of adjusting the average value of each reflectance, for example, a plurality of conical structures having a size less than the wavelength of light are provided, and a layer that continuously changes the refractive index from the incident medium to the substrate is provided. A method of forming and a method of forming an antireflection layer using a multilayer dielectric multilayer film are mentioned.

As a method that satisfies the requirement (c), i.e., a design method of an optical filter having a low reflectance, for example, in a region of 580 to 800 nm, the transmittance when measured from the vertical direction of the substrate is 50%. The absolute value |Xa-Xb| of the difference between the wavelength value (Xa) and the longest wavelength value (Xb) at which the transmittance is 50% when measured from the vertical direction of the substrate in a region with a wavelength of 700 to 1200 nm or more A method of using a substrate having a thickness of 300 nm or more is mentioned.

<Requirement (d)>

Requirement (d): A layer containing at least three types of compounds (A) having an absorption maximum in a region having a wavelength of 650 nm or more and less than 950 nm is included.

When the number of compounds (A) contained in the layer is three or more, it becomes possible to improve the solubility. When the number of compounds (A) contained in the layer is 2 or less, it is necessary to increase the content of the compound (A) in order to make OD _a-0 2.0 or more, and the compound (A) is precipitated from the layer. There is.

Further, when the number of compounds (A) contained in the layer is three or more, it becomes possible to absorb a wide range of near infrared rays. By absorbing a wide range of near-infrared rays, it is possible to obtain a filter with a reduced reflectance in a wide range of near-infrared rays. By using a filter having a reduced reflectance in such a wide near-infrared region, a good image with reduced ghost can be obtained.

<Requirement (e)>

Requirement (e): The number of layers (N) of layers having a dielectric multilayer film on at least one side of the substrate (i) and having a thickness of 0.5 μm or less among the layers constituting the dielectric multilayer film (N) and the thickness of each layer having a thickness of 0.5 μm or less. The product (N×TN) of the sum (TN) (µm) is 150 or less. The product (N×TN) is preferably 100 or less, and more preferably 50 or less.

Details will be described later, but if the product (N×TN) is within this range, the time required for manufacturing the dielectric multilayer film can be shortened and the manufacturing cost can be reduced, which is preferable.

In the optical filter of the present invention, from the viewpoint of color reproducibility in an image obtained by an imaging device or a camera module, the R transmittance, G transmittance, and B transmittance when incident from the vertical direction of the optical filter are all, preferably 30%. It is above, more preferably, it is 34% or more, and still more preferably, it is 38% or more. The R transmittance is an average transmittance at a wavelength of 580 to 650 nm, G transmittance is an average transmittance at a wavelength of 500 to 580 nm, and B transmittance is an average transmittance at a wavelength of 420 to 500 nm. When such an optical filter is used in an imaging device or a camera module, since it becomes easy to correct the brightness and color sense of an image, it becomes easy to correct the visibility of a natural color tone as seen by the human eye.

The optical filter of the present invention may be an embodiment comprising only the substrate (i), and may have antireflection layers on both surfaces of the substrate (i). By having antireflection layers on both sides of the base material (i), stray light reflected from various components such as cover glass, lens, microlens, sensor, housing, etc., built into the imaging device or camera module, reflects the optical filter to the sensor It is possible to reduce the phenomenon that is incident on the device and reduce 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 still 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. When the thickness is 10 µm or more, it is preferable to control the warpage easily.

<Note (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. Further, the substrate (i) may contain a compound (B) having an absorption maximum in a region of a wavelength of 950 nm to 1800 nm, and the compound (B) may be contained in the same layer as the compound (A) or a different layer It may be included in. 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 a "resin layer".

Examples of the substrate (i) in the case where the layer containing the compound (A) and the layer containing the compound (B) are the same include, for example, a substrate including a resin substrate containing the compound (A) and the compound (B), On a resin substrate containing a compound (A) and a compound (B), a resin layer such as an overcoat layer containing a curable resin is laminated on a substrate, a glass support, or a support such as a resin support as a base. A substrate on which a transparent resin layer such as an overcoat layer including a curable resin containing A) and a compound (B) is laminated may be mentioned.

As the substrate (i) when the layer containing the compound (A) and the layer containing the compound (B) are different, for example, curable containing the compound (A) on a resin substrate containing the compound (B) A resin layer such as an overcoat layer containing a curable resin containing a compound (B) or the like is laminated on a substrate on which a transparent resin layer such as an overcoat layer containing a resin is laminated, or a resin substrate containing a compound (A) A transparent resin layer such as an overcoat layer containing a curable resin containing the compound (A), etc., and a curable resin containing the compound (B) on a support such as a substrate, a glass support, or a resin support as a base. A substrate in which a resin layer such as an overcoat layer is laminated, and a substrate in which a transparent resin layer such as an overcoat layer containing a curable resin containing compound (A), etc. is laminated on a glass substrate containing compound (B). I can.

<Compound (A)>

The compound (A) is not particularly limited as long as there is an absorption maximum in the range of 650 nm or more and less than 950 nm in wavelength, but from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, chromonium compounds and cyanine compounds. It is preferable to contain at least one compound selected, more preferably containing at least one compound selected from squarylium-based compounds, phthalocyanine-based compounds and cyanine-based compounds, and squarylium-based compounds and phthalocyanine-based compounds And it is particularly preferable to contain at least three types selected from cyanine compounds. A compound having an absorption maximum at a wavelength of 649 nm or less tends to have a high mass extinction coefficient at 420 nm to 580 nm due to absorption due to the peak of the maximum absorption wavelength.

The maximum absorption wavelength of the 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 still more preferably 700 nm or more and less than 950 nm.

The substrate (i), as the compound (A), preferably contains at least one compound having an absorption maximum in a region having a wavelength of 650 nm or more and less than 800 nm, more preferably 700 nm or more and less than 800 nm. When the optical filter obtained by this is used for an imaging device or a camera module, red luminous intensity correction becomes good.

Moreover, it is preferable that the said base material (i) contains as compound (A) at least 1 type of compound which has an absorption maximum in the range of 800 nm or more and less than 950 nm. When the optical filter obtained thereby is used in an imaging device or a camera module, the sensitivity of the silicon photodiode is high, and the light in the region of 800 nm to 900 nm, which is low in sensitivity to the human eye, can be effectively shielded, thereby emitting strong near-infrared rays. The visibility correction of a flame, a halogen lamp, or a black body radiation light source is improved.

In addition, the substrate (i), as compound (A), contains at least one compound each having an absorption maximum in a region of 650 nm or more and less than 800 nm, and a compound having an absorption maximum in a region of 800 nm or more and less than 950 nm. It is preferable to do, and it is more preferable to contain two or more types each. When the optical filter obtained by this is used for an imaging device or a camera module, the red luminous sensitivity correction and the shielding performance of light in a region of 700 nm or more and 900 nm or less are both compatible, and the obtained image is improved.

In addition, the substrate (i), as compound (A), contains at least two compounds having an absorption maximum in a region of 650 nm or more and less than 800 nm, and at least one compound having an absorption maximum in a region of 800 nm or more and 950 nm. It is more preferable to contain. This makes it possible to obtain an optical filter that has absorbed widely from the red region to the near infrared region. When such an optical filter is used for an imaging device or a camera module, it is possible to obtain a better image in which both red visibility correction and ghost reduction are achieved.

Examples of compounds having an absorption maximum in a region of 650 nm or more and less than 800 nm in wavelength include squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, chromonium compounds, cyanine compounds, dimonium compounds, metal dithiolate compounds, and A pyrrolopyrrole compound is preferable, and a squarylium type compound, a phthalocyanine type compound, and a cyanine type compound are more preferable. By containing these compounds, it is possible to obtain an optical filter in which high visible light transmittance and good durability are compatible.

Examples of compounds having an absorption maximum in a region of 800 nm or more and less than 950 nm in wavelength include squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, chromonium compounds, cyanine compounds, dimonium compounds, metal dithiolate compounds, and A pyrrolopyrrole compound is preferable, and a squarylium type compound, a phthalocyanine type compound, and a cyanine type compound are more preferable. By containing these compounds, it is possible to obtain an optical filter in which high visible light transmittance and good durability are compatible.

In addition, in the above-described substrate (i), it is preferable that at least one of the compound (A) satisfies the following requirements (f) and (g) as absorption properties measured by dissolving in dichloromethane. (f) The maximum absorption wavelength λmax in a region having a wavelength 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 ελ _max in the region of wavelength 650 nm or more and less than 950 nm is normalized to 1,

(g-1) the absorption coefficient ελ _{max-10 at the} wavelength (λmax-10) nm is 0.80 or more,

(g-2) the extinction coefficient ελ _{max+10 at the} wavelength (λmax+10) nm is 0.80 or more,

(g-3) The average value _ε430-580ave of the extinction coefficient in a region having a wavelength of 430 or more and 580 nm or less is 0.03 or less. ελ _max-10 is more preferably 0.85 or more, and even more preferably 0.90 or more. In addition, ελ _max+10 is more preferably 0.85 or more, and even more preferably 0.90 or more. In addition, _ε430-580ave is more preferably 0.025 or less, and even more preferably 0.020 or less.

When the optical filter obtained by this is used for an imaging device or a camera module, a high visible light transmittance and a shielding performance of light in a region of 700 nm or more and 900 nm or less are both compatible, and the obtained image is improved.

The amount of compound (A) to be used is appropriately selected depending on desired properties. As the substrate (i), for example, a resin layer such as a substrate including a resin substrate containing the compound (A) or an overcoat layer containing a curable resin on a resin substrate containing the compound (A) In the case of using this laminated substrate, the content of the compound (A) is preferably 0.01 to 2.0 parts by mass, more preferably 0.03 to 1.5 parts by mass, even more preferably 0.05 to 1.0, based on 100 parts by mass of the resin. It is a mass part. In addition, when a substrate in which a transparent resin layer containing a compound (A) is laminated on a support such as a glass support or a resin support serving as the base is used as the substrate (i), the content of the compound (A) is, With respect to 100 parts by mass of the resin forming the transparent resin layer, it is preferably 0.4 to 20.0 parts by mass, more preferably 0.6 to 15.0 parts by mass, and still more preferably 0.8 to 12.5 parts by mass.

≪Squararylium compound≫

The squarylium-based compound is not particularly limited, but a squarylium-based compound represented by the following formula (I) (hereinafter also referred to as ``compound (I)''), a squarylium-based compound represented by the following formula (II) ( Hereinafter, also referred to as "Compound (II)"), and a squarylium compound represented by the following formulas (III-J), (III-K) and (III-L) (hereinafter, "Compound (III-J)" respectively , "Compound (III-K)" and (Compound (III-L)), also referred to collectively as "Compound (III)"). At least one compound selected from the group consisting of) is preferred.

ㆍEquation (I)

In formula (I), R ^a , R ^b and Ya satisfy the following condition (α) or (β).

Condition (α):

Each of ^a plurality of R ^a independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or -NR ^e R ^f group;

Each of a plurality of R ^b independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or -NR ^g R ^h group;

A plurality of Ya each independently represents a -NR ^j R ^k group; L ¹ represents L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h ;

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 are each independently a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or a -C(O)R ⁱ group (R ⁱ is -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;

L ^c 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 C3-C14 heterocyclic group 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 is 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 , At least one substituent selected from the group consisting of a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group and an amino group.

Condition (β):

At least one of two R ^a on one benzene ring is bonded to each other with Y on the same benzene ring to form a heterocycle having 5 or 6 constituent atoms including at least one nitrogen atom;

The heterocycle may have a substituent, and R ^b and R ^a not involved in the formation of the heterocycle are each independently the same as R ^b and R ^a in the above condition (α).

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

As R ^a in the above condition (α), 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, and tert-butyl Group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, nitro group, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and 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, and tert-butyl Group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t -Butanoylamino group, cyclohexinoylamino group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, hydroxyl group, dimethylamino group, nitro group, acetylamino group, propy They are an onylamino group, a trifluoromethanoylamino group, a pentafluoroethanoylamino group, a t-butanoylamino group, and a cyclohexinoylamino group.

As the Ya, preferably, an amino group, methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-t-butylamino group, N-ethyl-N -Methylamino group, N-cyclohexyl-N-methylamino group, more preferably dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-t-butyl It is an amino group.

The number of constituent atoms including at least one nitrogen atom formed by bonding of at least one of two R ^a on one benzene ring to Y on the same benzene ring in condition (β) of the above formula (I) Examples of the 5 or 6 heterocycle include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, and pyrazine. Among these heterocycles, a heterocycle constituting the heterocycle and in which one atom adjacent to the carbon atom constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.

ㆍEquation (II)

In formula (II), X independently represents O, S, Se, NR ^c or C(R ^d R ^d ); A plurality of R ^c each independently represents a hydrogen atom, L ^a , L ^b , L ^c , L ^d or L ^e ; A plurality of R ^d each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or -NR ^e R ^f group, and adjacent R ^d groups are connected to each other to form a substituent. You may form a ring which may have; L ^a to L ^e , L ¹ , R ^e and R ^f are synonymous with L ^a to L ^e , L ¹ , R ^e and R ^f defined in the above formula (I).

As R ^c in the above formula (II), 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, and n -Hexyl group, cyclohexyl group, phenyl group, trifluoromethyl group, pentafluoroethyl group, more preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, and isopropyl group.

As R ^d in the formula (II), 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, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, methoxy group, trifluoromethyl group, pentafluoroethyl group, 4-aminocyclohexyl group, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, They are methyl, ethyl, n-propyl, isopropyl, trifluoromethyl, and pentafluoroethyl.

The X is preferably O, S, Se, N-Me, N-Et, CH ₂ , C-Me ₂ , C-Et ₂ , more preferably S, C-Me ₂ , C-Et ₂ to be.

In the above formula (II), adjacent R ^{d may be} connected to each other to form a ring. Examples of such rings include benzoindolenine ring, α-naphthoimidazole ring, β-naphthoimidazole ring, α-naphthooxazole ring, β-naphthooxazole ring, α-naphthothiazole ring, β-naph Tothiadazole ring, α-naphthoselenazole ring, and β-naphthoselenazole ring are mentioned.

ㆍFormulas (III-J) to (III-L)

In formulas (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 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, -NR ^g R ^h group, -SO ₂ R ⁱ group, -OSO ₂ R ⁱ A group or any of the following L ^a to L ^h is represented, R ^g and R ^h each independently represent a hydrogen atom, a -C(O)R ⁱ group or any of the following L ^a to L ^e , and R ⁱ is the following It represents any of L ^a to L ^e .

(L ^a ) C 1 to C 12 aliphatic hydrocarbon group

(L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms

(L ^c ) C3-C14 alicyclic hydrocarbon group

(L ^d ) C6-C14 aromatic hydrocarbon group

(L ^e ) C3-C14 heterocyclic group

(L ^f ) C1-C12 alkoxy group

(L ^g ) an acyl group having 1 to 12 carbon atoms which may have a substituent L

(L ^h ) C1-C12 alkoxycarbonyl group which may have a substituent L

Substituent L is composed 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. It is at least 1 type selected from the group.

Compound (I), compound (II) and compound (III-J), in addition to the described methods such as the following formula (I-1), the following formula (II-1), the following formula (III-J-1) , The structure can also be represented by a description method that takes a resonance structure as in the following formula (I-2) and the following formula (II-2), and the following formula (III-J-2) (compounds (III-K) and ( The same is true for III-L)). That is, the difference between the following formula (I-1) and the following formula (I-2), the difference between the following formula (II-1) and the following formula (II-2), and the following formula (III-J-1) and ( The difference in III-J-2) is only the description method of the structure, and both represent the same compound. In the present invention, unless otherwise specified, the structure of the squarylium-based compound will be shown by the following formula (I-1), the following formula (II-1), and the following formula (III-J-1). .

In addition, for example, the compound represented by the following formula (I-3) and the compound represented by the following formula (I-4) can be regarded as the same compound.

The structures of the compounds (I), (II) and (III) are not particularly limited as long as the requirements of each of the formulas are satisfied. For example, when the structure is shown as in the formulas (I-1), (II-1) and (III-J-1), the left and right substituents bonded to the central 4-membered ring may be the same or different, The same one is preferable because it is easy to synthesize.

Specific examples of the compounds (I), (II) and (III) include the following formulas (IA) to (IF), the following formulas (II-G) to (II-H), and the following formulas (III-J) to ( The compounds (a-1) to (a-94) shown in Tables 1 to 7 below, which have a basic skeleton represented by III-L), can be mentioned.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

The compounds (I), (II) and (III) may be synthesized by a generally known method, for example, Japanese Patent Laid-Open No. 1-228960, Japanese Patent Laid-Open No. 2001-40234, Japanese Patent It can be synthesized by referring to a method described in Japanese Gazette No. 3196383 or the like.

≪Phthalocyanine compound≫

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

In formula (IV), M represents a substituted metal atom including two hydrogen atoms, two monovalent metal atoms, divalent metal atoms, or trivalent or tetravalent metal atoms, and a plurality of R _a , R _b , R _c and R _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ , or _a combination of at least one of R _a and R _b , R _b and R _c and R _c and R _d is bonded to the following formulas (A) to (H ) Represents at least one group selected from the group consisting of groups represented by ). However, 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 group, amide group, imide group and silyl group may have a substituent L defined in the formula (I),

L ¹ is synonymous with L ¹ defined in the above formula (I),

L ² represents a hydrogen atom or any of L ^a to L ^e defined in the formula (I),

L ³ represents a hydroxyl group or any of the above L ^a to L ^e ,

L ⁴ represents any of the above L ^a to L ^e .

In formulas (A) to (H), R _x and R _y represent a carbon atom, and a plurality of R _A to R _L are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amide group, and already Denotes, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ , and the amino group, amide group, imide group and silyl group It may have a substituent L defined in formula (I), and L ¹ to L ⁴ have the same meaning as L ¹ to L ⁴ defined in the formula (IV).

The method of synthesizing the phthalocyanine-based compound by a cyclization reaction of a phthalonitrile derivative such as the following formula (V) is generally known, but the phthalocyanine-based compound obtained is represented by the following formulas (VI-1) to (VI-4) It is a mixture of the same four isomers. In the present invention, unless otherwise specified, only one isomer is exemplified for one phthalocyanine-based compound, but the other three isomers can also be used in the same manner. Incidentally, although these isomers can be used separately as necessary, in the present invention, isomer mixtures are collectively handled.

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

[Table 8]

[Table 9]

[Table 10]

[Table 11]

Compound (IV) can be synthesized by a generally known method, and can be synthesized, for example, by referring to the method described in Japanese Patent No. 4081149 or ``phthalocyanine-chemistry and function -'' (IPC, 1997). have.

≪Cyanine compound≫

The cyanine-based compound is not particularly limited, but 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)'') It is preferable to be. (VII-4) to (VII-6) and (VII-9) to (VII-11) are preferred in that high visible light transmittance can be achieved, and (VII-4) and (VII-9) are particularly desirable.

In formulas (VII-1) to (VII-13), X _a ^- represents a monovalent anion, a plurality of D independently represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and a plurality of X is, Independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR _a -, and a plurality of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ³ , -SO _2- L ³ , -N=NL ⁴ , or a combination of at least one of 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 _i This bond represents at least one group selected from the group consisting of groups represented by the formulas (A) to (H), and the amino group, amide group, imide group and silyl group are the substituent L defined in the formula (I). You may have

L ¹ is synonymous with L ¹ defined in the above formula (I),

L ² represents a hydrogen atom or any of L ^a to L ^e defined in the formula (I),

L ³ represents a hydrogen atom or any of the above L ^a to L ^e ,

L ⁴ represents any of the above L ^a to L ^e ,

Z _a to Z _c and Y _a to Y _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ (L ¹ to L ⁴ are synonymous with L ¹ to L ⁴ in R _a to R _i ), or adjacent among them An aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding of Z or Y selected from two to each other; 5-6 membered alicyclic hydrocarbon group which may contain at least one nitrogen atom, oxygen atom, or sulfur atom; Or a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms containing at least one nitrogen atom, an oxygen atom or a sulfur atom, and these aromatic hydrocarbon groups, alicyclic hydrocarbon groups and heteroaromatic hydrocarbon groups are aliphatic hydrocarbon groups having 1 to 9 carbon atoms or You may have a halogen atom.

In terms of achieving both a high visible light transmittance and a high OD value in the region of 700 to 900 nm, the plurality of Xs are preferably oxygen atoms or sulfur atoms, and particularly preferably oxygen atoms. A plurality of 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 , L ^f .

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding of Z to each other or Y to each other in Z _a to Z _c and Y _a to Y _d include, for example, in the aromatic hydrocarbon group in the substituent L The exemplified compound is mentioned.

_A 5-6 membered alicyclic hydrocarbon group which may contain at least one nitrogen atom, an oxygen atom, or a sulfur atom formed by bonding of Z to each other or Y to each other in the Z _a to Z _c and Y _a to Y _d Examples of examples include the alicyclic hydrocarbon group in the substituent L and the compounds exemplified by the heterocycle (excluding the heteroaromatic hydrocarbon group).

Z _a to Z _c and Y _a to Y _d are each independently selected from a hydrogen atom, a halogen atom, an amino group having a substituent L, or adjacent two of them, in that the chemical stability of the compound and high visible light transmittance are compatible. Particularly preferred is an aromatic hydrocarbon group having 6 to 14 carbon atoms and an alicyclic hydrocarbon group having 5 to 6 membered rings which are formed by bonding of Z or Y to each other.

Examples of the heteroaromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding of Z to each other or Y to each other in Z _a to Z _c and Y _a to Y _d are, for example, as a heterocyclic group in the substituent L The exemplified compounds (excluding alicyclic hydrocarbon groups containing at least one nitrogen atom, oxygen atom, or sulfur atom) are mentioned.

In the formulas (VII-1) to (VII-13), -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=NL ⁴ , an amino group which may have a substituent L, an amide group, Examples of the imide group and the silyl group include groups similar to the groups illustrated in the above formula (IV).

X _a ^- is when a monovalent anion is not particularly ^{limited, Cl -, I -, Br} -, PF 6 -, N (SO 2 CF 3) 2 -, B (C 6 F 5) 4 -, a nickel dithiol-rate And a copper dithiolate-based complex. From the viewpoint of the chemical stability of the compound, B(C ₆ F ₅ ) ₄ ^- is preferred.

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

[Table 12-1]

[Table 12-2]

[Table 12-3]

[Table 12-4]

[Table 12-5]

The compounds (VII-1) to (VII-6) may be synthesized by a generally known method, and can be synthesized, for example, by the method described in Japanese Patent Laid-Open No. 2009-108267.

<Compound (B)>

The compound (B) is not particularly limited as long as it has an absorption maximum in a region of 950 nm to 1800 nm in wavelength, but near-infrared absorbing fine particles, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, chromonium compounds, and cyanine compounds , A dimonium compound, a metal dithiolate compound, and a pyrrolopyrrole compound. In other words, compound (B) may be used singly or in combination of two or more. By using such a compound (B), absorption characteristics and excellent visible light transmittance in a wide near-infrared wavelength range can be achieved.

The maximum absorption wavelength of the compound (B) is preferably 1020 nm or more and 1750 nm or less, and more preferably 1020 nm or more and 1720 nm or less. When the absorption maximum wavelength of the compound (B) is in such a range, unnecessary near-infrared rays can be efficiently cut, and the dependence of the incident angle of incident light can be reduced.

The mass extinction coefficient at the absorption maximum wavelength of the compound (B) is preferably 8×10 L·cm ^-1 ㆍg ^-1 or more, more preferably 9.5×10 L·cm ^-1 ㆍg ^-1 or more. If it is 8×10Lㆍcm ^-1 ㆍg ^-1 or more, it becomes possible to effectively shield near-infrared rays even in a thin optical filter with an anti-reflection layer, and it is possible to achieve both thinning and high shielding of near-infrared rays and low reflection characteristics. do.

The amount of the compound (B) (excluding the near-infrared absorbing fine particles) is appropriately selected according to desired properties. As the substrate (i), for example, when using a substrate including a resin substrate containing a compound (A) and a compound (B), the content of the compound (B) is based on 100 parts by mass of the resin, It 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. In addition, as the substrate (i), a substrate in which a resin layer containing a compound (A) and a compound (B) is laminated on a support such as a glass support or a resin support used as the base, or containing the compound (A). When using a base material in which a resin layer containing compound (B) is laminated on a resin substrate, the content of compound (B) is based on 100 parts by mass of the resin forming the resin layer containing compound (A). , 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. When the content of the compound (B) is within the above range, an optical filter in which satisfactory near-infrared absorption properties and high visible light transmittance are compatible can be obtained. In other words, when the near-infrared absorbing fine particles are used as the compound (B), the amount of the fine particles will be described later.

The compound (B) may be synthesized by a generally known method, and for example, Japanese Patent No. 4168031, Japanese Patent No. 4252961, Japanese Patent Publication No. 2010-516823, Japanese Patent Laid-Open No. 63- It can be synthesized by referring to a method described in Japanese Gazette No. 165392 or the like.

≪Dimonium compound≫

The dimonium-based compound is not particularly limited, but a compound represented by the following formula (s1) is preferable, for example.

In formula (s ₁ ), R ¹ is independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a carboxyl group, a phosphoric acid group, a -SR ⁱ group, a -SO ₂ R ⁱ group, a -OSO ₂ R ⁱ group or ^Represents any of the following L ^a to L ^h , and R ² is independently a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group or any of the following L ^a to L ^h is represented, and R ^g and R ^h are each independently a hydrogen atom, a -C(O)R ⁱ group or the following L ^a to L ^e Represents any of, R ⁱ represents any of the following L ^a to L ^e ,

(L ^a ) C 1 to C 12 aliphatic hydrocarbon group

(L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms

(L ^c ) C3-C14 alicyclic hydrocarbon group

(L ^d ) C6-C14 aromatic hydrocarbon group

(L ^e ) C3-C14 heterocyclic group

(L ^f ) C1-C12 alkoxy group

(L ^g ) an acyl group having 1 to 12 carbon atoms which may have a substituent L,

(L ^h ) C1-C12 alkoxycarbonyl group which may have a substituent L

Substituent L is composed 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. It is at least 1 type selected from the group, n is an integer of 0 to 4, and X represents an anion required to neutralize the charge.

X is an anion required to neutralize the charge, and when the anion is divalent, 1 molecule is required, and when the anion is monovalent, 2 molecules are required. In the latter case, the two anions may be the same or different, but the same is preferable from the viewpoint of synthesis. X is not particularly limited as long as it is such an anion, and examples thereof include those described in Table 13 below.

[Table 13]

X has a tendency to improve the heat resistance of the dimonium compound when the anion of the dimonium compound is used as long as the acidity is high, and (X-10) and (X-16 in Table 10 above) ), (X-17), (X-21), (X-22), (X-24) and (X-28) are particularly preferred.

≪Metal dithiolate compound≫

Although the said metal dithiolate type compound is not specifically limited, For example, a compound represented by the following formula (s2) is preferable.

In formula (s2), R ³ has the same definition as R ¹ and R ² in the formula (s1), and adjacent R ³ may form a ring which may have a substituent L. Z represents D(R ⁱ ) ₄ , D represents a nitrogen atom, a phosphorus atom or a bismuth atom, and y represents 0 or 1.

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

The M is preferably a transition metal, and more preferably Ni, Pd, and Pt.

D is preferably a nitrogen atom or a phosphorus atom, and R ⁱ is preferably an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- They are a pentyl group, an n-hexyl group, an n-heptyl group, and a phenyl group.

≪Near-infrared absorption fine particles≫

The near-infrared absorbing fine particles are not particularly limited as long as they have absorption in the wavelength range of 950 nm to 1800 nm, for example, the near-infrared absorbing fine particles described in paragraphs [0047] to [0075] of International Publication No. 2017/018419 I can.

≪Commercial products of compounds (A) and (B)≫

Commercially available products of the compound (A) include T090821, T091021, T089021, T090721, T090122 (manufactured by Tosco), B4360, D4773, D5013 (manufactured by Tokyo Kasei Kogyo), S4253, S1426 (manufactured by Spectrum Info.), Excolor IR12, Excolor IR14. , Excolor IR10A, Excolor IR28, Excolor TX-EX720, Excolor TX-EX820, Excolor TX-EX906 (made by Nippon Shokubai), and the like.

As commercially available products of the compound (B) (except for the near-infrared absorbing fine particles), CIR-108x, CIR-96x, CIR-RL, CIR-1080 (manufactured by Nihon Calit), S1445 (manufactured by Spectrum Info.), Excolor IR915, Excolor IR906 (made by Nippon Shokubai), S2058, S2007 (made by FEW Chemicals), etc. are mentioned.

<resin>

The resin used for the (transparent) resin layer, the resin substrate, or the resin support constituting the substrate is not particularly limited as long as it does not impair the effects of the present invention, but, for example, thermal stability and molding for a film The glass transition temperature (Tg) is preferably 110 to 380°C, more preferably 110 to ensure the property and to form a film capable of forming a dielectric multilayer film by high-temperature vapor deposition performed at a deposition temperature of 100°C or higher. To 370°C, more preferably 120 to 360°C. In addition, if the glass transition temperature of the resin is 150°C or higher, even when the glass transition temperature is lowered by adding a compound to the resin at a high concentration, a film having a glass transition temperature capable of depositing and forming a dielectric multilayer film at high temperature is obtained. Because it loses, it is particularly preferable.

As the resin, when a resin plate having a thickness of 0.05 mm containing the resin is formed, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95%. In particular, 80 to 95% of resin can be used. When a resin having a total light transmittance in such a range is used, the resulting substrate exhibits good transparency as an optical film.

The mass average molecular weight (Mw) in terms of polystyrene, measured by the gel permeation chromatography (GPC) method of the resin, 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 resin include cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin , Aramid resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, Silsesquioxane-based UV-curable resin, maleimide-based resin, alicyclic epoxy thermosetting resin, polyetheretherketone-based resin, polyarylate-based resin, allyl ester-based curable resin, acrylic UV-curable resin, vinyl-based UV-curable resin and sol Resins containing as a main component silica formed by a gel method are mentioned. Among these, the use of cyclic polyolefin resins, aromatic polyether resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, and polyarylate resins has transparency (optical properties), It is preferable in that an optical filter excellent in balance such as heat resistance and reflow resistance can be obtained.

≪Cycle 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 the resin Resin is preferred.

In formula (X ₀ ), R ^x1 to R ^x4 each independently represent an atom or group selected from the following (i') to (ix'), and k ^x , m ^x and p ^x are each independently 0 to 4 Represents the integer of.

(i') hydrogen atom

(ii') halogen atom

(iii') trialkylsilyl group

(iv') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms 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

(vi') polar group (except (ii') and (iv'))

(vii') an alkylidene group formed by bonding of R ^x1 and R ^x2 or R ^x3 and R ^x4 to each other (however, R ^x1 to R ^x4 not involved in the bonding are each independently the above (i') to ( vi') represents an atom or group selected from)

(viii') R ^x1 and R ^x2 or R ^x3 and R ^x4 are a monocyclic or polycyclic hydrocarbon ring or heterocycle formed by bonding to each other (however, R ^x1 to R ^x4 not involved in the bond are each independently the above (i') to (vi') represents an atom or group selected from)

(ix') R ^x2 and R ^x3 are bonded to each other to form a monocyclic hydrocarbon ring or heterocycle (however, R ^x1 and R ^x4 not involved in the bond are each independently the above (i') to (vi' ) Represents an atom or group selected from)

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

≪Aromatic polyether resin≫

It is preferable that the aromatic polyether resin 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).

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.

Equation (2), and R ¹ to R ⁴ and a to d are R ¹ to R ⁴ and a to d and in agreement, each independently, the formula (1), Y is a single bond, -SO ₂ - or Represents -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, 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).

In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z is a single bond, -O-, -S-, -SO ₂ -, -CO-, -CONH-, -COO- or a C1-C12 divalent organic group is represented, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1.

Equation (4) and of, R ^7, R ^8, Y, m, g, and h is R ^7, R ^8, Y, m, g, and h with consent of each independently, the formula (2), R ^5, R ⁶ , Z, n, e and f are each independently the same as R ⁵ , R ⁶ , Z, n, e and f in the above formula (3).

≪Polyimide resin≫

The polyimide resin is not particularly limited, and any polymer compound containing an imide bond in the repeating unit may be used. For example, it is described in Japanese Patent Laid-Open No. 2006-199945 or Japanese Patent Laid-Open No. 2008-163107. It can be synthesized in any way.

≪Fluorene polycarbonate resin≫

The fluorene polycarbonate resin is not particularly limited, and any polycarbonate resin containing a fluorene moiety may be used. For example, it can be synthesized by the method described in Japanese Patent Laid-Open No. 2008-163194. have.

≪Fluorene polyester resin≫

The fluorene polyester resin is not particularly limited, and may be a polyester resin containing a fluorene moiety, for example, as described in Japanese Patent Laid-Open No. 2010-285505 or Japanese Patent Laid-Open No. 2011-197450 It can be synthesized in any way.

≪Fluorinated aromatic polymer resin≫

The fluorinated aromatic polymer resin is not particularly limited, but at least one bond selected from the group consisting of an aromatic ring having at least one fluorine atom, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. It is preferably a polymer containing a repeating unit to be included, and can be synthesized, for example, by the method described in Japanese Patent Application Laid-Open No. 2008-181121.

≪Acrylic UV-curable resin≫

The acrylic ultraviolet-curable resin is not particularly limited, and includes a resin composition containing a compound having one or more acrylic groups or methacrylic groups in a molecule and a compound that is decomposed by ultraviolet rays to generate active radicals. The acrylic ultraviolet-curable resin includes, as the substrate (i), a substrate in which a transparent resin layer including a compound (A) and a curable resin is laminated on a glass support or on a resin support as a base, or a compound (A). In the case of using a substrate in which a resin layer such as an overcoat layer containing a curable resin or the like is laminated on a transparent resin substrate, it can be particularly suitably used as the curable resin.

≪Resin mainly composed of silica formed by the sol-gel method≫

Examples of resins containing silica as a main component by the sol-gel method include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, and methoxytriethoxysilane, phenyltrimethoxysilane, and phenyltrie. A compound obtained by a sol-gel reaction by hydrolysis of one or more silanes selected from phenylalkoxysilanes such as oxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane can be used as the resin.

≪Commercial product≫

As a commercial item of a transparent resin, the following commercial item etc. are mentioned. Commercially available products of the cyclic polyolefin resin include JSR Corporation Aton, Nippon Xeon Corporation Zeonoa, Mitsui Chemical Corporation APEL, Polyplastics Corporation TOPAS, and the like. As a commercial item of a polyether sulfone resin, Sumika Excel PES etc. manufactured by Sumitomo Chemical Co., Ltd. are mentioned. As a commercial item of a polyimide resin, Mitsubishi Gas Chemical Co., Ltd. Neoprem L etc. are mentioned. As a commercial item of a polycarbonate-type resin, Teijin Co., Ltd. pure Ace etc. are mentioned. As a commercial item of a fluorene polycarbonate-type resin, Mitsubishi Gas Chemical Co., Ltd. Upzeta EP-5000 etc. are mentioned. As a commercial item of a fluorene polyester-type resin, Osaka Gas Chemical Co., Ltd. OKP4HT etc. are mentioned. As a commercial item of an acrylic resin, Nippon Shokubai Co., Ltd. Ark Reviewer etc. are mentioned. As a commercial item of a silsesquioxane type ultraviolet-curable resin, Shinnittetsu Chemical Co., Ltd. Silplus etc. are mentioned.

<Other ingredients>

The substrate (i) may further contain additives such as an antioxidant, a near-ultraviolet absorber, and a fluorescent quencher as long as the effect of the present invention is not impaired. These other components may be used individually by 1 type, and may use 2 or more types together.

≪Near ultraviolet absorber≫

The near-ultraviolet absorber is not particularly limited as long as it is a compound having at least one absorption maximum in the wavelength range of 250 to 420 nm, but for example, an azomethine compound, an indole compound, a benzotriazole compound, a triazine compound, an anthracene compound Compounds, etc. are mentioned.

(U-A) azomethine compound

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

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. Represents.

(U-B) indole compounds

The indole-based compound is not particularly limited, but may be, for example, represented by the following formula (U-2).

In formula (U-2), R ^b1 to R ^b5 are each independently 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-based compound

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

In formula (U-3), R ^c1 to R ^c3 are each independently 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 a substituent having 1 to carbon atoms It represents a C1-C9 alkyl group which has a 9 alkoxycarbonyl group.

(U-D) triazine compound

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

In formulas (U-4) to (U-6), R ^d1 is independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an alke having 3 to 8 carbon atoms. It represents a nil group, a C6-C18 aryl group, a C7-C18 alkylaryl group, or an arylalkyl group. However, these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups and arylalkyl groups may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, and an oxygen atom, a sulfur atom, a carbonyl group, It may be interrupted by an ester group, an amide group or an imino group. Further, the above substitution and interruption may be combined. R ^d2 to R ^d9 are each independently 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, and It represents a 6-18 aryl group, a C7-18 alkylaryl group, or an arylalkyl group.

≪Antioxidant≫

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenyl Methane, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane and tris(2,4-di-t-butylphenyl)phosphite, and the like. I can.

The additive may be mixed with a resin or the like when producing the transparent resin, or may be added when synthesizing the resin. In addition, although the addition amount is appropriately selected according to the desired properties, it is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass based on 100 parts by mass of the transparent resin.

<Support>

≪Resin support body≫

The resin used for the resin substrate or resin support is as described above.

≪Glass support≫

Although it does not specifically limit as said glass support, For example, borosilicate-type glass, silicate-type glass, soda-lime glass, near-infrared absorption glass, etc. are mentioned. The near-infrared absorbing glass is preferable in that it can improve the near-infrared cut property and can reduce the angle of incidence dependence, and specific examples thereof include fluorine phosphate-based glass and phosphate-based glass containing a copper component.

<Method of manufacturing base (i)>

When the substrate (i) is a substrate containing a resin substrate containing the compound (A), the resin substrate can be formed by, for example, melt molding or cast molding, and if necessary , After molding, by coating a coating agent such as an antireflection agent, a hard coat agent, and/or an antistatic agent, a substrate on which an overcoat layer is laminated can be produced.

When the substrate (i) is a glass support or a substrate in which a transparent resin layer such as an overcoat layer including a curable resin containing the compound (A) is laminated on a resin support as a base, for example, a glass support Alternatively, by melt molding or cast molding a resin solution containing the compound (A) on a resin support as a base, preferably after coating by a method such as spin coat, slit coat, ink jet, the solvent is dried and removed, if necessary. Accordingly, by further performing light irradiation or heating, a substrate having a transparent resin layer formed on a glass support or a resin support serving as a base can be manufactured.

≪Melt molding≫

As the melt molding, specifically, a method of melt-molding a pellet 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); Alternatively, a method of melt-molding a pellet obtained by removing a solvent from a resin composition containing a compound (A), a resin and a solvent may be mentioned. Examples of the melt-molding method include injection molding, melt extrusion molding, or blow molding.

≪Cast molding≫

As the cast molding, a method of removing a solvent by casting a resin composition containing a compound (A), a resin, and a solvent on a suitable support; Alternatively, a curable composition containing the compound (A) and a photocurable resin and/or a thermosetting resin may be cast on a suitable support to remove the solvent, and then cured by an appropriate method such as ultraviolet irradiation or heating. have.

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

Examples of the support include a glass plate, a steel belt, a steel drum, and a support made of a transparent resin (for example, a polyester film, a cyclic olefin resin film).

In addition, a transparent resin layer is formed on the optical component by coating the resin composition on an optical component such as a glass plate, quartz or transparent plastic to dry the solvent, or coating the curable composition to cure and dry it. It can also be formed.

The amount of residual solvent in the transparent resin layer (resin substrate) obtained by the above method is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less based on the weight of the transparent resin layer (resin substrate). When the residual solvent amount is in the above range, a transparent resin layer (resin substrate) capable of easily exerting a desired function in which deformation and characteristics are difficult to change is 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 means that the average reflectance after forming the antireflection layer on at least one surface of the substrate (i) in a region having a wavelength of 420 nm to 1000 nm is equal to the average reflectance of only the substrate (i), or It is a layer having a smaller effect.

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

As the antireflection layer, a layer having a structure in which a number of cone-shaped structures having a size less than the wavelength of light are provided, and the refractive index is continuously changed from the incident medium to the substrate, and a dielectric material in which a high refractive index material layer and a low refractive index material layer are alternately stacked And a thin film including a multilayer film and 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 higher can be used, and a material having a refractive index of 1.8 to 3.6 is usually selected. As such a material, for example, titanium oxide, zirconium oxide, tantalum oxide, niobium oxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, barium titanate, silicon, etc., as main components, hydrogen, titanium oxide, Niobium oxide, tin oxide, and/or cerium oxide, etc. contained in a small amount (for example, 0 to 10% by mass based on the main component); Cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, aramid resin, polysulfur Pone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioxane UV curable type Resin, maleimide resin, alicyclic epoxy thermosetting resin, polyetheretherketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin, and silica formed by the sol gel method What made the said main component disperse|distributed in transparent resin, such as a resin made into it, is mentioned.

As the material constituting the low refractive index material layer, a material having a refractive index of 1.7 or less can be used, and a material having a refractive index of 1.2 to 1.7 is usually selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride; Cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, aramid resin, polysulfur Pone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioxane UV curable type Resin, maleimide resin, alicyclic epoxy thermosetting resin, polyetheretherketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin, and silica formed by the sol gel method Transparent resins such as resins used; Alternatively, silica, alumina, lanthanum fluoride, magnesium fluoride, or sodium aluminum hexafluoride are dispersed in the transparent resin.

The dielectric multilayer film may have a metal layer and/or a semiconductor layer of about 1 to 100 nm. As the material constituting the metal layer, a material having a refractive index of 0.1 or more to 5.0 or less can be used. Examples of such materials include gold, silver, copper, zinc, aluminum, tungsten, titanium, magnesium, nickel, silicon, and germanium. These metal layers and semiconductor layers tend to have a high extinction coefficient of the wavelength in the visible region, and are preferably thin layers of about 1 to 20 nm.

The method of laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, on the substrate (i), a dielectric multilayer film is formed by alternately stacking high refractive index material layers and low refractive index material layers by direct, CVD method, sputtering method, vacuum vapor deposition method, ion assist vapor deposition method, ion plating method, etc. can do. In the case of laminating a layer containing a transparent resin, it is preferably formed by spin coat, dip coat, slit coat, gravure coat, etc. by melt molding, cast molding, or coating formation in the same manner as in the molding method of the above-described substrate (i). I can.

As described above, the optical filter of the present invention preferably satisfies the requirement (e). That is, the sum of the number of layers (N) of the layers having a thickness of 0.5 μm or less among the layers constituting the dielectric multilayer film (N) and the thickness of each layer having a thickness of 0.5 μm or less (TN) The product (N×TN) of (µm) is 150 or less, preferably 100 or less, and more preferably 50 or less. If the product (N×TN) is within the above range, the time required for forming the multilayer film, the labor and time loss related to the conversion of the constituent material of each layer can be reduced, so that the time required for the production of the dielectric multilayer film can be shortened. There is, and manufacturing cost can be reduced.

The total number of layers of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film (antireflection layer) is preferably 2 to 30 layers, and more preferably 2 to 22 layers as the whole optical filter. When the thickness of each layer, the thickness of the dielectric multilayer film as the whole optical filter, or the total number of stacked layers is within the above range, a sufficient manufacturing margin can be ensured, and warpage of the optical filter and cracks in the dielectric multilayer film can be reduced.

<Other functional films>

The optical filter of the present invention is provided between the substrate (i) and the antireflection layer (dielectric multilayer film), the surface opposite to the surface on which the antireflection layer of the substrate (i) is provided, or reflective within the range not impairing the effects of the present invention. On the side opposite to the surface on which the base material (i) of the prevention layer is provided, for the purpose of improving the surface hardness of the base material (i) or the antireflection layer, improving chemical resistance, preventing static electricity, and removing scratches, a hard coat film or an antistatic film, etc. The functional film of can be properly provided.

The optical filter of the present invention may contain one layer or two or more layers containing the functional film. When the optical filter of the present invention contains two or more layers containing the functional film, two or more layers of the same layer may be included, or two or more different layers may be included.

Although it does not specifically limit as a method of laminating|stacking a functional film, A method of melt-molding or cast-molding like the above with a coating agent, such as a hard coat agent and/or an antistatic agent, to the base material (i) or an antireflection layer, etc. are mentioned.

Further, it can also be prepared by applying a curable composition containing the above coating agent or the like on the substrate (i) or the antireflection layer with a bar coater or the like and then curing by irradiation with ultraviolet rays or the like.

Examples of the coating agent include ultraviolet (UV)/electron beam (EB) curable resins or thermosetting resins, and specifically, vinyl compounds, urethane, urethane acrylate, acrylate, epoxy and epoxy acrylates Resin, etc. are mentioned. Examples of the curable composition containing these coating agents include vinyl, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate curable compositions.

Further, the curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or a thermal polymerization initiator may be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

In the curable composition, when the total amount of the curable composition is 100% by mass, the blending ratio of the polymerization initiator is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, further preferably 1 to 5 It is mass%. When the blending ratio of the polymerization initiator is within the above range, it is possible to obtain a functional film such as an antireflection layer hard coat film or an antistatic film, which is excellent in curing properties and handling properties of the curable composition and has a desired hardness.

Further, an organic solvent may be added as a solvent to the curable composition, and a known organic solvent may be used. As specific examples of the organic solvent, 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; Amides, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, are mentioned.

These solvents may be used individually by 1 type, and may use 2 or more types together. 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. In the case of 0.9 µm or less, similarly to the above, the influence of optical interference becomes strong, and the effect of the antireflection layer tends to be impaired.

In addition, for the purpose of enhancing the adhesion between the substrate (i) and the functional film and/or the antireflection layer, or between the functional film and the antireflection layer, the surface of the substrate (i), the functional film or the antireflection layer may be treated with corona treatment or plasma treatment. Surface treatment may be performed.

[Use of optical filter]

The optical filter of the present invention has a wide viewing angle, high red sensitivity, and improved ghosting. Therefore, it is useful for correcting the visibility of a solid-state imaging device such as a CCD or CMOS of a camera module. In particular, digital still cameras, mobile phone cameras, smartphone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, televisions, car navigation systems, portable information terminals, personal computers, video games, portable game machines, fingerprint authentication systems , Environmental light sensor, distance measuring sensor, iris authentication system, face authentication system, distance measuring camera, digital music player, etc.

<Solid 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 device such as a CCD or CMOS. As a member constituting the solid-state imaging device, a photoelectric conversion device that converts light of a specific wavelength into electric charges, such as a silicon photodiode or an organic semiconductor, is used.

<Camera module>

The 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, and the like, and outputs an image or distance information as an electric signal.

<Example>

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples at all. In other words, "part" means "part by mass" unless otherwise noted. In addition, the measuring method of each physical property value and the evaluation method of physical properties are as follows.

<molecular weight>

The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in the solvent.

(a) Using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS, the mass average molecular weight in terms of standard polystyrene ( Mw) and the number average molecular weight (Mn) were measured.

(b) Using the Tosoh Corporation GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF), the mass average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured.

<Glass transition temperature (Tg)>

Using a differential scanning calorimeter (DSC6200) manufactured by SII Technologies Co., Ltd., the temperature increase rate was measured at 20°C per minute under a nitrogen stream.

<Spectral transmittance>

The transmittance of the optical filter in each wavelength region was measured using a spectrophotometer (U-4100) manufactured by Hitachi High Technologies.

Here, in the transmittance when measured in the vertical direction of the optical filter, the light (1) transmitted perpendicularly to the optical filter (2) as shown in Fig. 1 (A) is measured with a spectrophotometer (3), and the optical filter In the transmittance when measured at an angle of 30 degrees with respect to the vertical direction of, as shown in Fig. 1(B), the light 1'transmitted at an angle of 30 degrees with respect to the vertical direction of the optical filter 2 is measured with a spectrophotometer 3 ) And measured at an angle of 60 degrees with respect to the vertical direction of the optical filter, as shown in Fig. 1C, the light transmitted at an angle of 60 degrees with respect to the vertical direction of the optical filter 2 (1 ") was measured with a spectrophotometer (3).

<Spectral reflectance>

The reflectance in each wavelength region of the optical filter was measured using a spectrophotometer (U-4100) manufactured by Hitachi High Technologies. Here, in the reflectance when measured at an angle of 5 degrees with respect to the vertical direction of the optical filter, the light 11 reflected at an angle of 5 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG. It was measured as.

The near-infrared absorbing dye used in the following examples was synthesized by a generally known method. As a general synthesis method, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent Laid-Open Publication No. 1-146846, Japanese Patent Laid-Open No. 1-228960, Japanese Patent No. 4081149, Japanese Patent Laid-Open No. 63-124054, ``Phthalocyanine-Chemistry and Function-'' (IPC, 1997), Japanese Patent Publication 2007-169315, Japanese Patent Publication No. 2009-108267, Japanese Patent Publication No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631, and the like. .

<Evaluation of compound (A)>

Absorption characteristics of dyes in dichloromethane Compounds (c-35), (a-63), (a-74) and (c) having a maximum absorption wavelength λmax in a range of 650 nm or more and less than 950 nm with a wavelength of 850 nm or more and 935 nm or less -27) was dissolved in dichloromethane, and the transmittance by wavelength was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-3100), and the maximum absorption wavelength in the range of 850 or more and less than 935 nm λmax, a wavelength of 650 or more (normalized to a = 1), maximum extinction coefficient ελ _max in the region of less than 950nm, absorption coefficient at the wavelength (λmax-10nm) at the time when the maximum normalized extinction coefficient ελ ελ 1 _max to _{max- 10nm,} in the region of wavelength 430 more than 580nm or less when normalized to the extinction coefficient ελ _{max + 10nm,} the maximum extinction coefficient ελ _max at a wavelength (λmax + 10nm) at the time when normalized to a maximum absorption coefficient ελ _max to 1 to 1, The average value _ε430-580ave of the extinction coefficient for each wavelength was calculated. Table 20 shows these results.

<Resin Synthesis Example 1>

In a 3L 4-neck flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, and 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. Next, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean Stark tube, and a cooling tube were installed in the four-neck flask. Subsequently, after nitrogen substitution in the flask, the obtained solution was reacted at 140° C. for 3 hours, and the produced water was removed from the Dean Stark tube from time to time. At the time when water was no longer produced, the temperature was gradually raised to 160°C, and the reaction was carried out for 6 hours at the same temperature. After cooling to room temperature (25°C), the resulting salt was removed with a filter paper, and the filtrate was put in methanol to reprecipitate, and the filtrate (residue) was isolated by filtration separation. The obtained filtrate was vacuum-dried at 60° C. overnight 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[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene (hereinafter also referred to as "DNM") represented by the following formula (8); 18 parts of 1-hexene (molecular weight modifier) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were put into a nitrogen-substituted reaction vessel, and the solution was heated to 80°C. Subsequently, as a polymerization catalyst, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol/liter) and 0.9 parts of a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol/liter) were added to the solution in the reaction vessel. The solution was heated and stirred at 80° C. for 3 hours to perform ring-opening polymerization to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution thus obtained was put into an autoclave, and 0.12 parts of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution, and the hydrogen gas pressure was 100 kg/cm 2, and the reaction temperature. Under the conditions of 165 degreeC, it heated and stirred for 3 hours, and performed hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released from pressure. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, and this was dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin B"). The obtained 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 substrate including a resin substrate was produced in the following procedures and conditions.

<Production 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 a light absorber "UA-3912" (hereinafter referred to as "Compound (u-1)") manufactured by Orient Chemical Industries as a near-ultraviolet absorber, and a compound ( As A), the compound (a-17) 0.03 parts, the compound (b-39) 0.07 parts, the compound (a-47) 0.04 parts, the compound (a-89) 0.15 parts, the compound (a-63) ) 0.05 parts, 0.05 parts of the compound (a-74), 0.03 parts of the compound (c-27), and N,N-dimethylacetamide were added to prepare a solution having a resin concentration of 20% by mass. The resulting solution was cast on a smooth glass plate, dried at 60° C. for 8 hours, dried at 60° C. for 8 hours, further dried at 140° C. for 8 hours under reduced pressure, and then peeled from the glass plate. The peeled coating film was further dried at 100° C. for 8 hours under reduced pressure to obtain an optical filter including a resin substrate having a thickness of 0.100 mm, a length of 200 mm, and a width of 200 mm.

Spectral transmittance from angles of 30 degrees and 60 degrees to the vertical and vertical directions of the obtained optical filter, spectral reflectance from an angle of 5 degrees to the vertical direction of the optical filter, and 5 to the vertical direction on the other side. The spectral reflectance from the angle of the degree was measured, and the optical properties in each wavelength region were evaluated. In addition, for the obtained optical filter, the number of layers (N) of the layer with a film thickness of 0.5 μm or less laminated on the substrate is 0, and the sum of the thicknesses of the layers with a film thickness of 0.5 μm or less (TN) (µm) is The product of 0.0, (N) and (TN) (µm) was 0. Table 14 shows these results.

[Example A2]

In Example A2, an optical filter having a substrate including a resin substrate having a resin layer on both sides was produced in the following procedures and conditions.

<Production of resin substrate>

In a container, 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 as a near-ultraviolet absorber, and compound (A ), by adding 0.03 parts of the compound (a-17), 0.10 parts of the compound (c-93), 0.10 parts of the compound (a-89) and 0.30 parts of the compound (c-35), and dichloromethane A solution having a concentration of 20% by mass was prepared. Except having used the obtained solution, it carried out similarly to Example 1, and obtained the resin board|substrate of 0.100mm in thickness, 200mm in length, and 200mm in width.

<Manufacture of base material and optical filter>

On one side of the obtained resin substrate, the resin composition (3) of the following composition was applied with a bar coater, and heated in an oven at 70° C. for 2 minutes to volatilize off the solvent. At this time, the application conditions of the bar coater were adjusted so that the thickness after drying was 4 μm. Subsequently, exposure (exposure amount 500 mJ/cm 2, 200 mW) was performed using a conveyor type exposure machine, the resin composition 3 was cured, and a resin layer was formed on the resin substrate. Similarly, a resin layer containing the resin composition (3) was formed on the other side of the resin substrate, and an optical filter including a substrate having a resin layer on both surfaces of the resin substrate containing the compound (A) was obtained. About the obtained optical filter, evaluation similar to Example A1 was performed. Table 14 shows the results.

Resin composition (3): tricyclodecane dimethanol diacrylate 60 parts by mass, dipentaerythritol hexaacrylate 40 parts by mass, 1-hydroxycyclohexylphenyl ketone 5 parts by mass, methyl ethyl ketone (solvent, solid content concentration ( TSC): 30%)

[Example A3]

In Example A3, an optical filter having a substrate including a resin substrate having a resin layer on both sides was produced in the following procedures and conditions.

<Production of resin substrate>

In a container, 100 parts by mass of the resin B obtained in Resin Synthesis Example 2, 0.30 parts of the compound (u-2) as a near-ultraviolet absorber, 0.04 parts of the compound (a-17) as the compound (A), and the compound (b-) 39) 0.04 parts, 0.14 parts of the compound (c-93), 0.27 parts of the compound (c-35), 0.11 parts of the compound (c-27), and dichloromethane were added to obtain a solution having a resin concentration of 20% by mass. Prepared. Except having used the obtained solution, it carried out similarly to Example A1, and obtained the resin board|substrate of 0.100mm in thickness, 200mm in length and 200mm in width.

<Manufacture of base material and optical filter>

On one side of the obtained resin substrate, the resin composition (3) was applied with a bar coater and heated in an oven at 70° C. for 2 minutes to volatilize off the solvent. At this time, in the same manner as in Example A2, except that the application conditions of the bar coater were adjusted so that the thickness after drying became 2 μm, optical containing a substrate having a resin layer on both sides of a resin substrate containing the compound (A) I got a filter. About the obtained optical filter, evaluation similar to Example A1 was performed. Table 14 shows the results.

[Example A4]

In Example A4, an optical filter having a base material including a resin substrate having a resin layer on both sides was produced by the following procedures and conditions.

<Production of resin substrate>

In a container, 100 parts by mass of the resin B obtained in Resin Synthesis Example 2, 0.30 parts of the compound (u-2) as a near-ultraviolet absorber, 0.06 parts of the compound (a-17) and the compound (b-) as a compound (A). 39) 0.07 parts, 0.20 parts of the compound (c-93) and 0.20 parts of the compound (c-35), 0.33 parts of the compound (B-1) as compound (B), and dichloromethane were added to obtain a resin concentration of 20 A solution of mass% was prepared. Except having used the obtained solution, it carried out similarly to Example A1, and obtained the resin board|substrate of 0.100mm in thickness, 200mm in length and 200mm in width.

<Manufacture of base material and optical filter>

On one side of the obtained resin substrate, the resin composition (3) was applied with a bar coater and heated in an oven at 70° C. for 2 minutes to volatilize off the solvent. At this time, in the same manner as in Example A2, except that the application conditions of the bar coater were adjusted so that the thickness after drying became 2 μm, optical containing a substrate having a resin layer on both sides of a resin substrate containing the compound (A) I got a filter. About the obtained optical filter, evaluation similar to Example A1 was performed. Table 14 shows the results.

[Example A5]

In Example A5, an optical filter having a substrate including a glass substrate was produced in the following procedures and conditions.

<Preparation of resin solution (D-1)>

In a container, 100 parts by mass of the 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 the compound (A), and the compound (a- 20) 2.50 parts 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 are added Thus, a solution having a resin concentration of 10% by mass was prepared. Thereafter, it was filtered through a Millipore filter having a pore diameter of 5 µm to obtain a resin solution (D-1).

<Preparation of resin composition (2)>

Isocyanurate ethylene oxide-modified triacrylate (brand name: Aronics M-315, Toa Kosei Chemical Co., Ltd. product) 30 parts by mass, 1,9-nonanediol diacrylate 20 parts by mass, methacrylic acid 20 parts Parts, glycidyl methacrylate 30 parts by mass, 3-glycidoxypropyltrimethoxysilane 5 parts by mass, 1-hydroxycyclohexylbenzophenone (brand name: IRGACURE184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 Mixing parts by mass and 1 part by mass of Sunade SI-110 (manufactured by Sanshin Chemical Industry Co., Ltd.), dissolving in propylene glycol monomethyl ether acetate so that the solid content concentration is 50 wt%, and using a Millipore filter having a pore diameter of 0.2 µm It filtered to prepare a resin composition (2).

<Manufacture of base material and optical filter>

The resin composition (2) was coated on one side of a near-infrared absorption glass substrate "BS-11" (thickness 80 µm) cut into dimensions of 200 mm in length and 200 mm in width by a spin coat manufactured by Matsunami Glass Kogyo Co., Ltd. Thereafter, it was heated on a hot plate at 80° C. for 2 minutes to volatilize off the solvent, and a resin layer functioning as an adhesive layer with a transparent resin layer described later was formed. At this time, the application conditions of the spin coater were adjusted so that the film thickness of the resin layer was about 0.8 µm.

Then, on the resin layer, the resin solution (D-1) was applied using a spin coater under the condition that the thickness after drying became 2 μm, heated on a hot plate at 80° C. for 5 minutes, and the solvent was volatilized off. A transparent resin layer was formed. Subsequently, after exposure (exposure amount 1 J/cm 2, illuminance 200 mW) using a conveyor type exposure machine from the side of the glass surface, it was fired in an oven at 230° C. for 20 minutes to obtain an optical filter including a substrate having a length of 200 mm and a width of 200 mm. About the obtained optical filter, evaluation similar to Example A1 was performed. Table 14 shows the results.

[Example A6]

In Example A6, an optical filter having a substrate containing a glass substrate was produced in the following procedures and conditions.

<Preparation of resin solution (D-2)>

In a container, 100 parts by mass of the 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 the compound (A), and the compound (b-) 39) 0.88 parts, 3.50 parts of the compound (c-93), 6.75 parts of the compound (c-35), 2.75 parts of the compound (c-27), and dichloromethane were added to obtain a solution having a resin concentration of 10% by mass. Prepared. Thereafter, it was filtered through a Millipore filter having a pore diameter of 5 µm to obtain a resin solution (D-2).

<Manufacture of base material and optical filter>

The resin composition (2) was coated on one side of an ultra-thin glass film "OA-10G" (trade name, thickness 100 µm) made by Nippon Denki Glass Co., Ltd. cut into dimensions of 200 mm in length and 200 mm in width. Thereafter, it was heated on a hot plate at 80° C. for 2 minutes to volatilize off the solvent, and a resin layer functioning as an adhesive layer with a transparent resin layer described later was formed. At this time, the application conditions of the spin coater were adjusted so that the film thickness of the resin layer was about 0.8 µm. Subsequently, on the resin layer, a substrate having a length of 200 mm and a width of 200 mm was prepared in the same manner as in Example A5 except that the resin solution (D-2) was applied on the resin layer under the condition that the film thickness after drying was 4 μm. The included optical filter was obtained. About the obtained optical filter, evaluation similar to Example A1 was performed. Table 14 shows the results.

[Example A7]

In Example A7, an optical filter having a base material including a resin substrate having a resin layer on both sides was produced by the following procedures and conditions.

<Production of resin substrate>

In a container, 100 parts by mass of resin B obtained in Resin Synthesis Example 2, as compound (A), 0.05 parts of the compound (a-17), 0.05 parts of the compound (b-39), and 0.10 parts of the compound (a-89) , 0.10 parts of the compound (a-63), 0.05 parts of the compound (a-74), and as the compound (B), 0.30 parts of the compound (B-1), and dichloromethane were added to have a resin concentration of 20% by mass. A solution was prepared. Other than that, an optical filter including a substrate having a resin layer on both surfaces of a resin substrate containing the compound (A) was obtained in the same procedure as in Example A2. About the obtained optical filter, evaluation similar to Example A1 was performed. Table 14 shows the results.

[Example A8]

In Example A8, an optical filter having a substrate including a resin substrate having a resin layer on both sides was produced in the following procedures and conditions.

<Production of resin substrate>

In a container, 100 parts by mass of the resin B obtained in Resin Synthesis Example 2, as compound (A), 0.21 parts of the compound (a-47), 0.05 parts of the compound (a-89), and 0.05 parts of the compound (a-63) And 0.06 parts of the compound (a-74) and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass. Other than that, an optical filter including a substrate having a resin layer on both surfaces of a resin substrate containing the compound (A) was obtained in the same procedure as in Example A2. About the obtained optical filter, evaluation similar to Example A1 was performed. Table 14 shows the results.

[Example A9]

In Example A9, an optical filter having a substrate including a resin substrate having a resin layer on both sides was produced in the following procedures and conditions.

<Production of resin substrate>

In a container, 100 parts by mass of the resin B obtained in Resin Synthesis Example 2, as the compound (A), 0.06 parts of the compound (a-17), 0.08 parts of the compound (b-39), 0.22 parts of the compound (a-63) And 0.10 part of the compound (a-74) and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass. Other than that, an optical filter including a substrate having a resin layer on both surfaces of a resin substrate containing the compound (A) was obtained in the same procedure as in Example A2. About the obtained optical filter, evaluation similar to Example A1 was performed. Table 14 shows the results.

[Comparative Example A1]

In Comparative Example A1, an optical filter having a substrate including a glass substrate was produced in the following procedures and conditions.

<Production of optical filter>

In accordance with the procedure of Examples [0075] to [0079] and [0102] of Japanese Patent No. 6267823, an optical filter containing a glass substrate (thickness of 380 μm), corresponding to Example 22 of Japanese Patent No. 6267823 ) Was written. About the obtained optical filter, evaluation similar to Example A1 was performed. Table 14 shows the results.

[Comparative Example A2]

In Comparative Example A2, an optical filter having a substrate including a resin substrate having a resin layer on both sides was produced in the following procedures and conditions.

<Production of resin substrate>

In a container, 100 parts by mass of the resin B obtained in Resin Synthesis Example 2, 0.07 parts of the compound (u-1) as a near-ultraviolet absorber, 0.03 parts of the compound (a-17) as a compound (A), and the compound (b-) 39) 0.07 parts and 0.04 parts of the compound (a-47), 0.10 parts of the compound (a-89) and 0.05 parts of the compound (a-63), and dichloromethane were added to obtain a solution having a resin concentration of 20% by mass. Prepared. Except having used the obtained solution, it carried out similarly to Example A1, and obtained the resin board|substrate of 0.100mm in thickness, 200mm in length, and 200mm in width.

<Manufacture of base material and optical filter>

On one side of the obtained resin substrate, the resin composition (3) was applied with a bar coater and heated in an oven at 70° C. for 2 minutes to volatilize and remove the solvent. At this time, in the same manner as in Example A2, except that the application conditions of the bar coater were adjusted so that the thickness after drying became 2 μm, optical containing a substrate having a resin layer on both sides of a resin substrate containing the compound (A) I got a filter. About the obtained optical filter, evaluation similar to Example A1 was performed. Table 14 shows the results.

[Comparative Example A3]

In Comparative Example A3, an optical filter having a substrate including a resin substrate was produced in the following procedures and conditions.

<Production of resin substrate (optical filter)>

A solution having a resin concentration of 20% by mass was prepared in the same manner as in Example A1. The resulting solution was cast on a smooth glass plate, dried at 60°C for 8 hours, 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 for 8 hours under reduced pressure to obtain an optical filter including a resin substrate having a thickness of 0.200 mm, a length of 200 mm, and a width of 200 mm. The obtained optical filter was whitened because there were many residual solvents, and evaluation of the spectral transmittance was impossible.

[Table 14]

[Example B1]

In Example B1, an optical filter having an antireflection layer on both surfaces of a substrate including a resin substrate was produced in the following procedures and conditions.

<Production of optical filter>

A substrate including 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 by the following procedure. First, on one side of the substrate, a resin composition (4) ("Opster TU2360" manufactured by Arakawa Chemical Co., Ltd.; 590 nm refractive index: 1.39) was applied with a bar coater, and the solvent was volatilized by heating in an oven at 70° C. for 2 minutes. I did. At this time, the application 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, the resin composition 4 was cured, and an antireflection layer was formed on the resin substrate. Similarly, an optical filter was obtained by forming an antireflection layer containing the resin composition (4) also on the other side of the resin substrate.

[Table 15]

Spectral transmittance from angles of 30 degrees and 60 degrees to the vertical and vertical directions of the obtained optical filter, spectral reflectance from an angle of 5 degrees to the vertical direction of the optical filter, and 5 to the vertical direction on the other side. The spectral reflectance from the angle of the degree was measured, and the optical properties in each wavelength region were evaluated. In addition, for the obtained optical filter, the number of layers (N) of layers with a film thickness of 0.5 µm or less laminated on the substrate is 2, and the sum of the thicknesses of each of the layers with a film thickness of 0.5 µm or less (TN) (µm) is The product of 0.2, (N) and (TN) (µm) was 0.4. Table 19 shows these results.

[Example B2]

In Example B2, an optical filter having an antireflection layer on both surfaces of a substrate including a resin substrate was produced in the following procedures and conditions.

<Production of optical filter>

A substrate having a resin layer on both surfaces of a resin substrate was obtained in the same procedure as in Example A2. On both surfaces of the obtained substrate, using an ion-assisted vacuum evaporation apparatus, the antireflection layer (silica (SiO ₂ : refractive index 1.46 of 550 nm) and titania (TiO ₂ : 550 nm refractive index 2.48) of the design (IV) shown in Table 16 below. An optical filter was obtained by forming a dielectric multilayer film in which layers are alternately stacked] at a deposition temperature of 120°C.

[Table 16]

About the obtained optical filter, evaluation similar to Example B1 was performed. In addition, for the obtained optical filter, the number of layers (N) of layers with a film thickness of 0.5 µm or less laminated on the substrate is 12, and the sum of the thicknesses of each of the layers with a film thickness of 0.5 µm or less (TN) (µm) is The product of 0.5, (N) and (TN) (µm) was 6.0. Table 19 shows these results.

[Example B3]

In Example B3, an optical filter having an antireflection layer on both surfaces of a substrate including a resin substrate was produced in the following procedures and conditions.

<Production of optical filter>

A substrate having a resin layer on both surfaces of a resin substrate was obtained in the same procedure as in Example A3. On both sides of the obtained substrate, using an ion-assisted vacuum evaporation apparatus, the antireflection layer (silica (SiO ₂ : refractive index 1.46 of 550 nm) layer and titania (TiO ₂ : 550 nm refractive index 2.48) layer of the design (IV) are alternately An optical filter was obtained by forming a laminated dielectric multilayer film] at a deposition temperature of 120°C. About the obtained optical filter, evaluation similar to Example B1 was performed. Table 19 shows the results.

[Example B4]

In Example B4, an optical filter having an antireflection layer on both surfaces of a substrate including a resin substrate was produced in the following procedures and conditions.

<Production of optical filter>

A substrate having a resin layer on both surfaces of a resin substrate was obtained in the same procedure as in Example A4. An optical filter was obtained by forming antireflection layers of the design (III) on both surfaces of the obtained substrate in the same manner as in Example B1. About the obtained optical filter, evaluation similar to Example B1 was performed. Table 19 shows the results.

[Example B5]

In Example B5, an optical filter having an antireflection layer on both surfaces of a substrate including a glass substrate was produced in the following procedures and conditions.

<Production of optical filter>

A substrate having a transparent resin layer on one side of the glass substrate was obtained by the same procedure as in Example A5. On both sides of the obtained substrate, using an ion-assisted vacuum evaporation apparatus, an antireflection layer (silica (SiO ₂ : refractive index of 1.46 of 550 nm) of design (V) shown in Table 17 below and titania (TiO ₂ : refractive index of 550 nm of 2.48) An optical filter was obtained by forming a dielectric multilayer film in which layers are alternately stacked] at a deposition temperature of 120°C.

[Table 17]

About the obtained optical filter, evaluation similar to Example B1 was performed. In addition, for the obtained optical filter, the number of layers (N) of the layer with a film thickness of 0.5 μm or less laminated on the substrate is 8, and the sum of the thicknesses of the layers with a film thickness of 0.5 μm or less (TN) (µm) stacked on the substrate is The product of 0.5, (N) and (TN) (µm) was 4.0. Table 19 shows these results.

[Example B6]

In Example B6, an optical filter having a base material including a glass substrate was produced under the following procedures and conditions.

<Production of optical filter>

A substrate having a transparent resin layer on one side of the glass substrate was obtained by the same procedure as in Example A6. On both sides of the obtained substrate, using an ion-assisted vacuum evaporation apparatus, the antireflection layer (silica (SiO ₂ : refractive index 1.46 of 550 nm) layer and titania (TiO ₂ : 550 nm refractive index 2.48) layer of the design (V) are alternately An optical filter was obtained by forming a laminated dielectric multilayer film] at a deposition temperature of 120°C. About the obtained optical filter, evaluation similar to Example B1 was performed. Table 19 shows the results.

[Example B7]

In Example B7, an optical filter having an antireflection layer on both surfaces of a substrate including a resin substrate was produced in the following procedures and conditions.

<Production of optical filter>

A substrate having a resin layer on both surfaces of a resin substrate was obtained in the same procedure as in Example A7. On both sides of the obtained substrate, an optical filter was obtained in the same procedure as in Example B5. About the obtained optical filter, evaluation similar to Example B1 was performed. Table 19 shows the results.

[Example B8]

In Example B8, an optical filter having an antireflection layer on both surfaces of a substrate including a resin substrate was produced in the following procedures and conditions.

<Production of optical filter>

A substrate having a resin layer on both surfaces of a resin substrate was obtained in the same procedure as in Example A8. On both sides of the obtained substrate, an optical filter was obtained in the same procedure as in Example B5. About the obtained optical filter, evaluation similar to Example B1 was performed. Table 19 shows the results.

[Example B9]

In Example B9, an optical filter having an antireflection layer on both surfaces of a substrate including a resin substrate was produced in the following procedures and conditions.

<Production of optical filter>

A substrate having a resin layer on both surfaces of a resin substrate was obtained in the same procedure as in Example A9. On both sides of the obtained substrate, an optical filter was obtained in the same procedure as in Example B5. About the obtained optical filter, evaluation similar to Example B1 was performed. Table 19 shows the results.

[Comparative Example B1]

In Comparative Example B1, an optical filter having a near-infrared reflective layer on both sides of the substrate was produced in the following procedures and conditions.

<Production of resin substrate>

In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, as the compound (A), 0.08 parts of the compound (a-17) and 0.11 part of the compound (b-39), and N,N-dimethylacetamide were added. It was added to prepare a solution having a resin concentration of 20% by mass. Except having used the obtained solution, it carried out similarly to Example A1, and the thickness of 0.070 mm, the length of 200 mm, and the width of 200 mm of resin board were obtained.

<Manufacture of base material and optical filter>

On one side of the obtained resin substrate, the resin composition (3) was applied with a bar coater and heated in an oven at 70° C. for 2 minutes to volatilize off the solvent. At this time, it carried out similarly to Example A2 except having adjusted the application|coating conditions of a bar coater so that the thickness after drying might become 2 micrometers, and the base material which has a resin layer on both surfaces of the resin board|substrate containing compound (A) was obtained.

On both sides of the obtained substrate, using an ion-assisted vacuum evaporation apparatus, a near-infrared cut layer (silica (SiO ₂ : refractive index of 550 nm 1.46) of Design (I) and Design (II) shown in Table 18) and titania (TiO ₂₎ : A dielectric multilayer film obtained by alternately stacking 550 nm refractive index 2.48) layers at a deposition temperature of 120°C to obtain an optical filter having a thickness of 0.079 mm.

[Table 18]

The obtained optical filter was evaluated in the same manner as in Example B1. In addition, for the obtained optical filter, the number of layers (N) of the layer with a film thickness of 0.5 μm or less laminated on the substrate is 46, and the sum of the thicknesses of each layer with a film thickness of 0.5 μm or less (TN) (µm) is The product of 5.3, (N) and (TN) (µm) was 243.8. Table 19 shows these results.

[Table 19]

The constitution of the description in Table 14 and Table 19, symbols of various compounds, etc. are as follows.

<Glass substrate>

Glass substrate (1): Near-infrared absorption glass substrate "BS-11" (manufactured by Matsunami Glass High School Co., Ltd.)

Glass substrate (4): Ultrathin glass film "OA-10G" (made by Nippon Denki Glass Co., Ltd.)

Glass substrate (X): a transparent glass substrate (refer to Japanese Patent No. 6267823 [0075] to [0078])

<Resin composition>

Resin composition (2): Isocyanurate ethylene oxide-modified triacrylate (trade name: Aronics M-315, Toa Kosei Chemical Co., Ltd. product) 30 parts by mass, 1,9-nonanediol diacrylate 20 parts by mass , 20 parts by mass of methacrylic acid, 30 parts by mass of glycidyl methacrylate, 5 parts by mass of 3-glycidoxypropyltrimethoxysilane, 1-hydroxycyclohexylbenzophenone (brand name: IRGACURE184, Ciba Specialty Chemicals Co., Ltd.) 5 parts by mass and Sun-Aid SI-110 main body (Sanshin Chemical Co., Ltd.) 1 part by mass, propylene glycol monomethyl ether acetate (solvent, solid content concentration (TSC) 50%)

Resin composition (3): tricyclodecane dimethanol diacrylate 60 parts by mass, dipentaerythritol hexaacrylate 40 parts by mass, 1-hydroxycyclohexylphenyl ketone 5 parts by mass, methyl ethyl ketone (solvent, solid content concentration ( TSC): 30%)

Resin composition (4): Obster TU2360 (manufactured by Arakawa Chemical Corporation)

Resin composition (X): copper phosphate-containing resin composition (refer to Japanese Patent Nos. 6267823 [0075] to [0078])

<Light absorber>

≪Near ultraviolet absorber≫

Compound (u-1): Light absorber "UA-3912" manufactured by Orient Chemical Industries, Ltd. (maximum absorption wavelength 389 nm in dichloromethane)

Compound (u-2): Kawasaki Kasei Co., Ltd. light absorber "UVS-581" (maximum absorption wavelength 367 nm in dichloromethane)

≪Compound (A)≫

Compound (a-17): (maximum absorption wavelength 713 nm in dichloromethane)

Compound (b-39): (maximum absorption wavelength 736 nm in dichloromethane)

Compound (a-20): (maximum absorption wavelength 704 nm in dichloromethane)

Compound (a-47): (maximum absorption wavelength 776 nm in dichloromethane)

Compound (c-93): (maximum absorption wavelength 770 nm in dichloromethane)

Compound (a-63): (maximum absorption wavelength 868 nm in dichloromethane)

Compound (a-89): (maximum absorption wavelength 822 nm in dichloromethane)

Compound (c-35): (maximum absorption wavelength 870 nm in dichloromethane)

Compound (a-74): (maximum absorption wavelength 933 nm in dichloromethane)

Compound (c-27): (maximum absorption wavelength 933 nm in dichloromethane)

[Table 20]

≪Compound (B)≫

Compound (B-1): a light absorbing agent "CIR-RL" manufactured by Nippon Kalito (maximum absorption wavelength in dichloromethane: 1095 nm)

1', 1": optical
2: optical filter
3: spectrophotometer
11: reflected light

Claims (9)

An optical filter characterized by satisfying the following requirements (a) to (d):
(a) the minimum value (OD _a-0 ) of the optical density (OD value) for light incident from a direction perpendicular to the surface of the optical filter in a region of 700 nm to 900 nm in wavelength is 2.0 or more;
(b) in the region of wavelength 430 nm to 580 nm, the average value (T _a-0 ) of the transmittance of light incident from the direction perpendicular to the surface of the optical filter is 40% or more;
(c) in the region of wavelength 420 nm to 900 nm, the average value of reflectance (Rf _a-5 ) for light incident at an angle of 5 degrees with respect to the direction perpendicular to the surface of the optical filter is 20% or less;
(d) A layer containing at least three types of compounds (A) having an absorption maximum in a region having a wavelength of 650 nm or more and less than 950 nm is included. The optical filter according to claim 1, characterized in that it further meets the following requirement (e):
(e) the number of layers (N) of a layer having a thickness of 0.5 µm or less among the base material including the layer described in the above requirement (d), and having a dielectric multilayer film on at least one side of the base material and constituting the dielectric multilayer film, and the thickness The product (N×TN) of the sum of the thicknesses (TN) (µm) of each layer of 0.5µm or less is 150 or less. The optical filter according to claim 1, wherein the thickness is 160 µm or less. The optical filter according to claim 1, wherein at least one of the compounds (A) satisfies the following requirements (f) and (g) as absorption properties measured by dissolving in dichloromethane:
(f) the maximum absorption wavelength λmax in the region of the wavelength 650 nm or more and less than 950 nm is the wavelength 850 nm or more and 935 nm or less;
(g) When the maximum extinction coefficient ελ _max in the region of wavelength 650 nm or more and less than 950 nm is normalized to 1,
(g-1) the absorption coefficient ελ _{max-10 at the} wavelength (λmax-10) nm is 0.80 or more,
(g-2) the extinction coefficient ελ _{max+10 at the} wavelength (λmax+10) nm is 0.80 or more,
(g-3) The average value _ε430-580ave of the extinction coefficient in a region having a wavelength of 430 or more and 580 nm or less is 0.03 or less. The compound according to claim 1, wherein the compound (A) is a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a chromonium compound, a cyanine compound, a dimonium compound, a metal dithiolate compound, and a pyrrolo. An optical filter comprising at least one compound selected from the group consisting of pyrrole compounds. The method according to claim 1, wherein the layer containing the compound (A) is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, and poly Carbonate resin, polyamide resin, aramid resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (Modified) Acrylic resin, epoxy resin, silsesquioxane-based UV-curable resin, maleimide-based resin, alicyclic epoxy thermosetting resin, polyetheretherketone-based resin, polyarylate-based resin, allyl ester-based curable resin, acrylic ultraviolet An optical filter comprising a resin layer comprising at least one resin selected from the group consisting of a curable resin, a vinyl-based ultraviolet curable resin, and a resin mainly containing silica formed by a sol-gel method. The optical filter according to claim 2, wherein the substrate includes a fluorophosphate-based glass layer containing a copper component or a substrate containing a phosphate-based glass layer. An imaging device comprising the optical filter according to any one of claims 1 to 7. A camera module comprising the optical filter according to any one of claims 1 to 7.

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