TW202242010A - Substrate, optical filter, solid-state imaging device and camera module capable of being used in an optical filter which has excellent transmission characteristics of visible light rays and a part of near infrared rays and can suppress ghosting - Google Patents

Abstract

The invention provides a substrate capable of being used in an optical filter which has excellent transmission characteristics of visible light rays and a part of near infrared rays and can suppress ghosting. A substrate which is a substrate that has a resin layer containing a resin and a pigment, and the substrate satisfies the following requirements (a) and (b), wherein the resin layer contains a compound (S) having a maximum absorption wavelength at a wavelength of 620 nm to 760 nm, and a compound (Z) having a maximum absorption wavelength at a wavelength of 761 nm to 850 nm, and the substrate transmits at least one of the light in a visible region and the light in a near-infrared region. (a) In a wavelength region of 600 nm to 950 nm, the difference between the longest wavelength (Xa) at which the transmittance is 2% or less from more than 2% when measured from the vertical direction of the substrate and the shortest wavelength (Xb) at which the transmittance is 2% or more from less than 2% when measured from the vertical direction of the substrate is 80 nm or more. (b) In the wavelength region of 450nm to 570 nm, the average value of the transmittance when measured from the vertical direction of the substrate is 70% or more.

Description

Substrate, optical filter, solid-state imaging device and camera module

The invention relates to a substrate, an optical filter and a device using the optical filter. In detail, it relates to a substrate containing a compound having specific absorption and selectively transmitting visible rays and a part of near-infrared rays, an optical filter composed of the substrate, and a solid-state imaging device using the optical filter. and camera modules.

In solid-state imaging devices such as video cameras, digital still cameras, mobile phones with camera functions, and smart phones, Charge-coupled Devices (CCDs) or complementary metal-oxide-semiconductor ( Complementary Metal Oxide Semiconductor (CMOS) image sensor. These solid-state imaging devices use silicon light-emitting diodes that are sensitive to near-infrared rays that cannot be perceived by the human eye in their light-receiving parts. Most of these solid-state imaging devices use optical substrates (optical filters, such as near-infrared cutoff, etc. filter).

On the other hand, in recent years, attempts have been made to add sensing functions such as motion capture and distance recognition (spatial recognition) using near-infrared rays to camera modules. In such an application, it is necessary to selectively transmit visible rays and a part of near-infrared rays, and therefore it is not possible to use a conventional substrate that completely shields near-infrared rays.

Therefore, as a base material that selectively transmits visible rays and a part of near-infrared rays, for example, as in Patent Document 1 and Patent Document 2, an optical fiber that uses a near-infrared absorbing dye to reduce the incident angle dependence of the visible transmission band is reported. filter. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 5884953 [Patent Document 2] Japanese Patent No. 6642578

[Problem to be Solved by the Invention]

By using a substrate that selectively transmits the visible rays and a part of the near-infrared rays, for example, as an optical filter, the incidence angle dependence of the visible transmission band is small, compared with ordinary optical filters using only dielectric multilayer films , can reduce the color shading of the camera image, but on the other hand, there is a problem of image defects called "ghosting" around the light source. In mobile devices such as smartphones, the demand for high image quality of cameras is also very high, and a substrate that can suppress ghosting and selectively transmit visible light and some near-infrared rays is desired.

[Means to solve the problem]

The inventors of the present invention conducted diligent research to achieve the above-mentioned object, and found that by using two kinds of dyes having different absorption characteristics and having a wide The base material of the absorption band can obtain an optical filter that has excellent transmission characteristics of visible rays and some near-infrared rays, and can suppress ghosting, thereby completing the present invention. Embodiment examples of the present invention are shown below.

The aspect of this invention is as follows. [1] A base material having a resin layer comprising a resin and a pigment, The substrate satisfies the necessary conditions of (a) and (b) below, The resin layer includes a compound (S) having a maximum absorption wavelength at a wavelength of 620 nm to 760 nm, and a compound (Z) having a maximum absorption wavelength at a wavelength of 761 nm to 850 nm, The substrate transmits at least one of light in the visible region and light in the near-infrared region, (a) In the wavelength region of 600 nm to 950 nm, the transmittance when measured from the direction perpendicular to the substrate is the longest wavelength (Xa) at which the transmittance exceeds 2% and becomes 2% or less, and when measured in the direction perpendicular to the substrate The difference in the shortest wavelength (Xb) at which the transmittance becomes more than 2% from less than 2% is 80 nm or more; (b) The average value of the transmittance when measured from the direction perpendicular to the base material in the wavelength region of 450 nm to 570 nm is 70% or more. [2] The substrate according to [1], wherein the compound (Z) is selected from squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, cyanine-based compounds, and crotonium-based compounds. , and at least one compound in the group consisting of polymethine-based compounds. [3] The substrate according to [1], comprising two or more compounds (S) in the resin layer. [4] The substrate according to [1], wherein the resin is selected from the group consisting of cyclic (poly)olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene Polyester-based resins, polycarbonate-based resins, polyamide-based resins, polyarylate-based resins, polyamide-based resins, polyether-based resins, polyparaphenylene-based resins, polyamide-imide-based resins, polyamide-imide-based resins, Ethylene naphthalate-based resins, fluorinated aromatic polymer-based resins, (modified) acrylic resins, epoxy-based resins, allyl ester-based curable resins, silsesquioxane-based UV-curable resins , at least one of the group consisting of an acrylic ultraviolet curable resin and a vinyl ultraviolet curable resin. [5] The substrate according to [1], wherein the resin layer is provided on a resin substrate or a glass substrate as a support. [6] The substrate according to [1], further comprising a compound (N) having an absorption maximum wavelength in the wavelength region of Xb+50 nm to Xb+250 nm. [7] An optical filter having the substrate according to [1] and satisfying the following requirement (c), (c) It has a light blocking band Za, a light transmitting band Zb, and a light blocking band Zc in the region with a wavelength of 600 nm or more, and the central wavelength of each band is Za<Zb<Zc, and the value of Za in the vertical direction from the substrate is measured The minimum transmittance when measured in Zb is 1% or less, the maximum transmittance (Tb) when measured from the vertical direction of the substrate in Zb is 45% or more, and the minimum transmittance when measured in the vertical direction from the substrate in Zc is rates are below 15%. [8] The optical filter according to [7], wherein the optical filter further satisfies the following requirement (d), (d) On the long-wavelength side of the light transmission band Zb, the value (Ye) of the shortest wavelength at which the transmittance when measured from the vertical direction of the optical filter becomes half of the above-mentioned Tb, and the value (Ye) from the vertical direction to the optical filter On the other hand, when the transmittance is measured at an angle of 30°, the absolute value |Ye−Yf| of the difference of the shortest wavelength value (Yf) which is half of Tb is less than 35 nm. [9] The optical filter according to [7], which has a dielectric multilayer film on at least one side of the substrate. [10] The optical filter according to [9], wherein the dielectric multilayer film is formed by alternately stacking different material layers, and the difference in refractive index between the material layers is 0.8 or less. [11] A solid-state imaging device including the optical filter according to [7]. [12] A camera module comprising the optical filter according to [7]. [Effect of the invention]

According to the present invention, it is possible to provide a base material that can be used in an optical filter that has excellent transmission characteristics of visible rays and some near-infrared rays and can suppress ghosting.

Hereinafter, the present invention will be specifically described.

[Substrate] The base material of the present invention includes a resin layer containing a resin, a compound (S) having a maximum absorption wavelength at a wavelength of 620 nm to 760 nm, and a compound having a maximum absorption wavelength at a wavelength of 761 nm to 850 nm (Z). Such a substrate has both high transmittance in the visible region and broad absorption in the wavelength range of 600 nm to 950 nm, and can function as an optical filter that selectively transmits visible light and some near-infrared rays.

Therefore, if the base material of the present invention is applied to an optical filter, unlike conventional filters that selectively transmit visible rays and a part of near-infrared rays, there is no need to use a dielectric multilayer film for the gap between the transmitted near-infrared rays and the visible region. Cut off light in the wavelength region. As a result, ghosting of a camera image due to reflected light from the dielectric multilayer film can be suppressed, and excellent image quality that has never been achieved before can be achieved. In this way, the base material of the present invention can be directly used as an optical filter, and it is not necessarily necessary to provide a dielectric multilayer film. Furthermore, if necessary, a dielectric multilayer film can be provided, and the substrate with the dielectric multilayer film can be used as an optical filter.

When the substrate of the present invention is used as an optical filter for a solid-state imaging device or the like, it is preferable that the visible light transmittance is high. When such a substrate is used for a solid-state imaging device, excellent imaging sensitivity can be achieved. If the substrate of the present invention has the following resin layer, it may be a single-layer substrate (i) or a multi-layer laminated substrate (ii), and the resin layer contains one or more kinds of A compound (S) having a maximum absorption wavelength in nm, and a compound (Z) having a maximum absorption wavelength at a wavelength of 761 nm to 850 nm.

In the case of the single-layer substrate (i), for example, a single-layer substrate composed of a resin layer containing the compound (S) and the compound (Z) is mentioned, and such a single-layer substrate is sometimes referred to as transparent resin. substrate.

When the base material is the laminated base material (ii), it is only necessary to laminate a resin layer containing the compound (S) and the compound (Z) on the surface of a support or the like, for example: A laminated base material (ii-1) in which a resin layer containing a compound (S) and a compound (Z) is laminated on a glass support; A laminated substrate (ii-2) in which a resin layer containing the compound (S) and the compound (Z) is laminated on a transparent resin support that does not contain the compound (S) and the compound (Z); A laminated base material (ii-3) in which a resin layer containing one of the compound (S) or the compound (Z) and a resin layer containing the other or both are laminated; A laminated base material (ii-4) etc. in which a resin layer comprising a compound (S) and a compound (Z) is laminated on a single-layer base material (i), Further examples include laminated substrates in which an overcoat layer and the like are further laminated on the above single-layer substrate (i) or the above-mentioned laminated substrates (ii-1) to laminated substrates (ii-4).

In a preferred aspect of the present invention, regardless of whether it is a single-layer base material or a laminated base material, the entire base material is made of a resin material. When the entire substrate is made of a resin material, a laminated substrate in which an overcoat layer and the like are laminated on the surface of the resin layer is more preferable from the viewpoint of improving scratch resistance. In addition, in the present invention, it is also preferable to have a glass substrate. In this case, it is more preferable to have a compound (S) and a compound ( Z) The base material of the resin layer.

The base material of the present invention satisfies the following requirement (a) and requirement (b).

(a) In the wavelength region of 600 nm to 950 nm, the transmittance when measured from the direction perpendicular to the substrate is the longest wavelength (Xa) at which the transmittance exceeds 2% and becomes 2% or less, and when measured in the direction perpendicular to the substrate The difference in the shortest wavelength (Xb) at which the transmittance becomes 2% or more from less than 2% is 80 nm or more.

The difference between Xb and Xa is preferably 90 nm or more, more preferably 100 nm or more, still more preferably 130 nm or more, particularly preferably 150 nm or more. If the difference between Xb and Xa is in the above range, light can be sufficiently cut between the visible wavelength region and the near-infrared transmission band only by the absorption of the substrate, and unlike conventional optical filters, it is not necessary to use a multilayer dielectric The film performs light cutoff in the wavelength region. Therefore, it is possible to reduce ghosts caused by reflection of the dielectric multilayer film inside the camera module, and to obtain extremely good camera images.

(b) The average value of the transmittance when measured from the direction perpendicular to the base material in the wavelength region of 450 nm to 570 nm is 70% or more.

The average transmittance of the substrate at a wavelength of 450 nm to 570 nm is preferably 72% or more, more preferably 74% or more, particularly preferably 76% or more. Using a substrate having such a transmission characteristic can achieve high light transmission characteristics in the near-infrared region aimed at the visible region, and can achieve both camera function and near-infrared sensing function at a good level. Furthermore, when the substrate is a laminated substrate, the average transmittance may be measured from the side of the resin layer containing the compound (S) and the compound (Z), or may be measured from the opposite side, and the transmittance will not vary. change.

The thickness of the resin layer containing the compound (S) and the compound (Z) can be appropriately selected according to the intended use, and is not particularly limited. It is preferably appropriately selected to reduce the incident angle dependence of the optical filter used, preferably It is 10 μm to 200 μm, more preferably 20 μm to 180 μm, particularly preferably 30 μm to 150 μm. When the base material has a plurality of resin layers, the total thickness is preferably within the above-mentioned range.

When the thickness of the resin layer is within the above range, the thickness and weight of the optical filter having the base material can be reduced, and it can be suitably used in various applications such as solid-state imaging devices. Especially, when it is used for the lens unit of a camera module etc., since the profile and weight of a lens unit can be made low, it is preferable.

＜Compound (S)＞ The compound (S) is not particularly limited as long as it is a compound having a maximum absorption wavelength at a wavelength of 620 nm to 760 nm, but it is preferably a solvent-soluble pigment compound, more preferably selected from squarylium-based compounds and phthalocyanine-based compounds. At least one of the group consisting of a naphthalocyanine compound, a polymethine compound, and a cyanine compound. In the present invention, among these, in terms of excellent visible light transmission characteristics, steep absorption characteristics, and high molar absorptivity, it is more preferred to be selected from squarylium-based compounds, phthalocyanine-based compounds, and polymeric compounds. At least one of the group consisting of methyl-based compounds, particularly preferably at least one of squarylium-based compounds and at least one selected from the group consisting of phthalocyanine-based compounds and polymethine-based compounds A combined form.

In addition, although squarylium-based compounds and cyanine-based compounds are included in polymethine-based compounds in a broad sense, in this specification, polymethine-based compounds other than squarylium-based compounds and cyanine-based compounds are included. The base compound is defined as "polymethine compound".

In the present invention, the maximum absorption wavelength of a compound may be measured, for example, by using a spectrophotometer after dissolving the compound in an appropriate solvent such as dichloromethane.

Regarding the compound (S), two or more kinds of compounds may be contained in the resin layer. In the case of multiple compounds, these compounds may be contained in the same resin layer or may be contained in different resin layers. When contained in the same layer, for example, two or more compounds (S) are in the same resin layer, that is, a single-layer base material; or two or more compounds are laminated on a support such as a glass support A lamination base material of the resin layer of the compound (S). In addition, when contained in a different resin layer, for example, a laminated substrate in which a resin layer containing another compound (S) is laminated on a single-layer substrate containing the compound (S); A laminated substrate or the like in which two or more resin layers each containing a different compound (S) are laminated on the body.

More preferably, two or more compounds (S) are contained in the same resin layer, and in this case, it is easier to control the content ratio than the case where they are contained in different resin layers.

The content of the compound (S) is preferably It is 0.01 mass part - 2.0 mass parts, More preferably, it is 0.02 mass part - 1.5 mass parts, Especially preferably, it is 0.03 mass part - 1.0 mass part.

In addition, in the case of a laminated base material in which a resin layer including a resin composition containing a compound (S) is laminated on a support such as a glass support or a resin support, the constituent resin layer 100 parts by mass of the resin, preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 4.0 parts by mass, particularly preferably 0.3 to 3.0 parts by mass. When the content of the compound (S) is within the above range, an optical filter having both good near-infrared absorption and transmission characteristics and high visible light transmittance can be obtained.

＜Compound (Z)＞ The compound (Z) is not particularly limited as long as it is a compound having a maximum absorption wavelength at a wavelength of 761 nm to 850 nm. It is preferably a solvent-soluble pigment compound, more preferably a squarylium-based compound and a phthalocyanine-based compound. Compounds, naphthalocyanine-based compounds, cyanine-based compounds, crotonium-based compounds, and polymethine-based compounds other than these are selected from the viewpoint of achieving excellent visible light transmission characteristics. For example, squarylium-based compounds, crotonium-based compounds, and polymethine-based compounds are particularly preferred.

The compound (Z) and the compound (S) may be included in the same layer or may be included in a different layer. When contained in the same layer, for example: a single-layer base material in which both the compound (Z) and the compound (S) are contained in the resin layer; In the case where Z) and the resin layer of the compound (S) are laminated substrates contained in different layers, for example, a resin layer containing the compound (S) and a resin layer containing the compound (Z) are laminated. Laminate substrates.

It is more preferable that the compound (Z) and the compound (S) are included in the same layer. In this case, it is easier to control the content ratio than when they are included in different layers. Regarding the compound (Z), two or more types may be contained in the resin layer. In the case of a plurality of compounds, these compounds may be contained in the same resin layer or may be contained in different resin layers, but ideally, they are preferably contained in the same resin layer.

Regarding the content of the compound (Z), when the base material is a single-layer base material or a laminated base material in which an overcoat layer is laminated on the surface thereof, relative to the resin constituting the resin layer containing the compound (Z) 100 The parts by mass are preferably 0.05 parts by mass to 2.5 parts by mass, more preferably 0.08 parts by mass to 1.8 parts by mass, particularly preferably 0.10 parts by mass to 1.5 parts by mass.

In the case of a laminated base material in which the following resin layer is laminated on a support such as a glass support or a resin support, that is, a resin layer containing a resin composition containing the compound (Z), relative to the composition containing the compound (Z) ) in the resin layer of 100 parts by mass, preferably 0.5 parts by mass to 25.0 parts by mass, more preferably 0.8 parts by mass to 18.0 parts by mass, particularly preferably 1.0 parts by mass to 15.0 parts by mass. When the content of the compound (Z) is within the above range, high visible light transmittance and good near-infrared absorption and transmission characteristics can be achieved, and the difference between Xb and Xa can be increased, which is preferable.

<Compound (N)> The base material may further contain a compound (N) having a maximum absorption wavelength in the wavelength region of Xb+50 nm to Xb+250 nm. The compound (N) is not particularly limited as long as it has an absorption maximum wavelength in the wavelength range, and is preferably a solvent-soluble pigment compound, more preferably selected from squarylium-based compounds, cyanine-based compounds, and crotonium compounds. At least one of the group consisting of compounds, metal dithioctene complexes, and polymethine compounds, particularly preferably squarylium compounds, metal dithioctene complexes Compounds, polymethine compounds.

The Xb does not substantially change whether the compound (N) is added or not, so the compound (N) can be selected based on the measurement results in a substrate not containing the compound (N).

The compound (N) may be included in the same layer as the compound (S) and the compound (Z), or may be included in a different layer. When contained in the same layer, for example: a single-layer base material in which the compound (N), the compound (S) and the compound (Z) are contained in the same resin layer; or on a support such as a glass support In the case of laminated substrates with resin layers comprising compound (N), compound (S) and compound (Z) laminated together in different layers, for example, compound (S) and compound (Z) can be listed. ) is laminated on the resin layer of the base material containing the resin layer of the compound (N).

Regarding the content of the compound (N), for example, in the case of using a single-layer base material containing the compound (N), or a laminated base material in which an overcoat layer is laminated on a single-layer base material, relative to the constituent resin layer 100 parts by mass of the resin, preferably 0.010 to 1.5 parts by mass, more preferably 0.015 to 1.0 parts by mass, particularly preferably 0.020 to 0.8 parts by mass.

In the case of a laminated base material in which a resin layer containing the compound (N) is laminated on a glass support or a resin support, it is preferably 0.10 parts by mass relative to 100 parts by mass of the resin forming the resin layer containing the compound (N). Parts by mass to 10.0 parts by mass, more preferably 0.15 parts by mass to 8.0 parts by mass, particularly preferably 0.20 parts by mass to 5.0 parts by mass.

When the content of the compound (N) is within the above range, it is possible to efficiently absorb unnecessary near-infrared rays while maintaining a high visible light transmittance, especially for applications such as camera modules with sensing functions. In this case, since the incident angle dependence on the long-wavelength side of the near-infrared transmission band can be reduced, it is preferable. Thereby, the number of layers of the dielectric multilayer film can be greatly reduced, and it can be used as a visible region-near infrared selective transmission filter even without a dielectric multilayer film according to the required characteristics.

＜Resin＞ The resin constituting the resin layer includes a transparent resin. As the transparent resin, one type may be used alone, or two or more types may be used.

The transparent resin is not particularly limited as long as it does not impair the effect of the present invention. Examples of substrates on which the dielectric multilayer film is formed by vapor deposition include resins having a glass transition temperature (Tg) of preferably 110°C to 380°C, more preferably 110°C to 370°C, and still more preferably 120°C to 360°C. Moreover, when the glass transition temperature of the said resin is 140 degreeC or more, since the film which can vapor-deposit and form a dielectric multilayer film at a higher temperature is obtained, it is especially preferable. Specifically, Tg can be measured by the method described in the following examples.

As the transparent resin, in the case of forming a resin support with a thickness of 0.1 mm including the resin, the total light transmittance (Japanese Industrial Standards (JIS) K7375) of the resin support can be preferably used. 75% or more, more preferably 78% or more, particularly preferably 80% or more of resin. When the resin whose total light transmittance is in such a range is used, the obtained base material (i) will show the favorable transparency as an optical film.

When a solvent-soluble resin is used as the transparent resin, the mass average molecular weight (Mw) of the transparent resin in terms of polystyrene measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) is usually 15,000 to 350,000, It is 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. Specifically, Mw and Mn can be measured by the methods described in the following examples.

Examples of transparent resins include cyclic olefin resins, cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, and polycarbonate resins. Ester resins, polyamide resins, polyarylate resins, polyethylene resins, polyether resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate Resins, fluorinated aromatic polymer resins, acrylic resins, modified acrylic resins, epoxy resins, allyl ester curable resins, silsesquioxane UV curable resins, acrylic UV curable resins Type resins and vinyl-based UV-curable resins.

Specific examples of these resins include resins described in International Publication No. 2019/168090, and the like.

In addition, the overcoat etc. in a base material refer to the resin layer which does not contain compound (S), compound (Z), and compound (N). The resin layer not containing the compound is not particularly limited as long as it contains a resin, and examples of the resin include the above-mentioned transparent resin and the like. In addition, a functional film containing other components may also be used.

＜Support＞ Examples of the transparent resin support that does not contain the compound (Z) used in the laminate base material (i-2) include polyester films, polycarbonate films, polyimide films, and cyclic olefin-based resin films. Wait. As a support body used for laminated base material (i-3), a glass plate, a steel belt, a steel cylinder, etc. are mentioned, for example.

As a support body, the support body made of a glass plate, a steel belt, a steel cylinder, and a transparent resin (for example, a polyester film, a cyclic olefin resin film) is mentioned, for example.

＜Other ingredients＞ The substrate may further contain additives such as antioxidants, near-ultraviolet absorbers, and fluorescent matting agents within a range that does not impair the effects of the present invention. Moreover, when manufacturing a base material by casting molding mentioned later, a base material can be manufactured easily by adding a leveling agent or an antifoaming agent. These other components may be used alone or in combination of two or more. These may be included in the resin layer, and may also be included in the overcoat layer.

Examples of the near ultraviolet absorber include azoformide-based compounds, indole-based compounds, benzotriazole-based compounds, triazine-based compounds, and the like.

Examples of the antioxidant include: 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5' -Dimethyldiphenylmethane, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, and the like.

In addition, these additives may be mixed together with resin etc. at the time of manufacturing a base material, and may be added at the time of synthesizing a resin. Moreover, although the addition amount is suitably selected according to the desired characteristic, it is 0.01-5.0 mass parts normally with respect to 100 mass parts of resins, Preferably it is 0.05-2.0 mass parts.

<Manufacturing method of base material> When the base material is a single-layer base material containing the compound (S) and the compound (Z), it can be formed by, for example, fusion molding or casting molding, and further, if necessary, it can also be laminated by fusion molding or casting molding. outer coating.

In the case where the substrate is laminated on a glass support or a resin support, or a resin layer containing the compound (S), the compound (Z), and optionally the compound (N) on the single-layer substrate, for example Melt molding or casting of a resin solution containing compound (S), compound (Z), and optionally compound (N) on a glass support, resin support, or single-layer substrate, or by spin coating, After coating by a method such as slit coating or inkjet, the solvent is dried and removed, and then irradiated with light or heated if necessary, to manufacture a laminated base material on which a resin layer is formed.

"Molten Forming" Specific examples of the melt molding include: a method of melt molding pellets obtained by melting and kneading a resin, a compound (S), a compound (Z), and the like; A method of melt-molding a resin composition; or a method of melt-molding pellets obtained by removing a solvent from a resin composition containing a compound (S), a compound (Z), a resin, and a solvent, and the like. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding, and the like.

"Casting and Forming" As the casting molding, the following methods can also be used: a method of casting a resin composition containing compound (S), compound (Z), resin and solvent on a suitable support and removing the solvent; or The resin composition of compound (S), compound (Z) and transparent resin is casted on a suitable support and the solvent is removed, and when the transparent resin is a curable resin, it is cured by an appropriate method such as ultraviolet irradiation or heating method etc.

In the case where the base material is a single-layer base material containing the compound (S) and the compound (Z), the base material can peel off the coating film from the support after casting, thereby obtaining the coating film itself as a single-layer base material. material. In addition, when the substrate is a laminated substrate in which a resin layer containing the compound (S) and the compound (Z) is laminated on a support such as a glass support or a resin support, or a single-layer substrate, The substrate can be obtained without peeling off the coating film after casting. When the compound (S) and the compound (Z), and optionally the compound (N) are contained in different resin layers, it is only necessary to repeat the above molding method to bond the resin layers to each other.

Examples of the support include transparent resin supports such as polyester films, polycarbonate films, polyimide films, and cyclic olefin-based resin films, glass supports such as glass plates, steel belts, and steel cylinders. .

Furthermore, the following method can also be used to form the resin layer on the optical parts: using an optical part such as a glass plate, quartz or transparent plastic as a support, applying the resin composition and drying the solvent; In the case of a permanent resin, it is a suitable method of hardening.

The amount of residual solvent in the resin layer obtained by the method should be as small as possible. Specifically, the residual solvent amount is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less with respect to the weight of the resin layer. When the amount of the residual solvent is within the above range, a resin layer that is less likely to be deformed or changed in characteristics and can easily exhibit a desired function will be obtained.

＜Optical Filter＞

The optical filter of the present invention has the substrate and satisfies the following requirement (c). (c) It has a light blocking band Za, a light transmitting band Zb, and a light blocking band Zc in the region with a wavelength of 600 nm or more, and the central wavelength of each band is Za<Zb<Zc, and the value of Za in the vertical direction from the substrate is measured The minimum transmittance when measured in Zb is 1% or less, the maximum transmittance (Tb) when measured from the vertical direction of the substrate in Zb is 45% or more, and the minimum transmittance when measured in the vertical direction from the substrate in Zc is rates are below 15%.

Zb refers to the shortest wavelength Zb1 at which the transmittance of the optical filter is measured from 30% or less to 30% or less at a wavelength of 750 nm or more and 1050 nm or less, to the longest wavelength from 30% or less to 30% or less The wavelength band up to Zb2. Zc refers to the shortest wavelength Zc1 from exceeding 20% to less than 20% of the transmittance when measured from the vertical direction of the optical filter at a wavelength of 850 nm to less than 1200 nm, to the longest wavelength from less than 20% to 20% or more Wavelength band up to Zc2.

When the optical filter of the present invention is used in a solid-state imaging device having a near-infrared sensing function, etc., the maximum transmittance of light (near-infrared rays) in the transmission band Zb when measured in the vertical direction from the optical filter is preferably high. , the minimum transmittance of the light blocking band Za and the light blocking band Zc is preferably low. In this case, an excellent near-infrared sensing function can be achieved, and light rays of unnecessary wavelengths can be efficiently cut off, thereby improving the color reproducibility of camera images.

The minimum transmittance measured from the vertical direction of the optical filter in the light blocking band Za is 1% or less, preferably 0.8% or less, more preferably 0.7% or less, particularly preferably 0.6% or less. The minimum transmittance measured from the vertical direction of the optical filter in the light blocking band Zc is 15% or less, preferably 12% or less, more preferably 10% or less, particularly preferably 8% or less. The maximum transmittance measured from the vertical direction of the optical filter in the light transmission band Zb is 45% or more, preferably 48% or more, more preferably 50% or more, particularly preferably 53% or more. When the maximum transmittance in Zb or the minimum transmittance in Za and Zc is in the above range, a camera image with less noise and excellent color reproducibility can be obtained while achieving a high near-infrared sensing function.

Since the optical filter of the present invention has a base material including a resin layer containing a compound (S) having an absorption maximum wavelength at a wavelength of 620 nm to 760 nm, and a compound (S) having an absorption maximum wavelength at a wavelength of A compound (Z) having a maximum absorption wavelength between 761 nm and 850 nm.

The optical filter preferably further satisfies the following requirement (d). (d) On the long-wavelength side of the light transmission band Zb, the value (Ye) of the shortest wavelength at which the transmittance when measured from the vertical direction of the optical filter becomes half of the above-mentioned Tb, and the value (Ye) from the vertical direction to the optical filter On the other hand, when the transmittance is measured at an angle of 30°, the absolute value |Ye−Yf| of the difference of the shortest wavelength value (Yf) which is half of Tb is less than 35 nm.

In the optical filter of the present invention, it is further preferable that the incident angle dependence is reduced also on the long-wavelength side of the light transmission band Zb. Specifically, the value (Ye) of the shortest wavelength at which the transmittance is half of Tb when measured from the vertical direction of the optical filter, and the value (Ye) when measured from an angle of 30° relative to the vertical direction of the optical filter The absolute value |Ye-Yf| of the difference of the shortest wavelength value (Yf) whose transmittance becomes half of the Tb is preferably small, preferably less than 35 nm, more preferably less than 30 nm, still more preferably less than 25 nm, Particular preference is given to less than 20 nm. If |Ye-Yf| is within the range, especially in the case of applications such as camera modules with sensing functions, the near-infrared signal-to-noise ratio (signal-noise ratio, S/N ratio) difference becomes smaller, which can further reduce the noise during sensing.

In the optical filter of the present invention, in the wavelength range of 580 nm or more, the transmittance when measured from the vertical direction of the optical filter becomes the value (Ya) of the shortest wavelength of 20%, and the value (Ya) of the shortest wavelength from the vertical direction relative to the optical filter The absolute value |Ya-Yb| of the difference of the shortest wavelength value (Yb) at which the transmittance is 20% when measured at an angle of 30° is preferably small, preferably less than 10 nm, more preferably less than 8 nm, particularly preferably is less than 5 nm.

In the optical filter of the present invention, in the light transmission band Zb, the value (Yc) of the shortest wavelength at which the transmittance when measured from the vertical direction of the optical filter becomes half of the above-mentioned Tb, and the value (Yc) from the vertical direction relative to the optical filter The absolute value |Yc-Yd| of the difference of the shortest wavelength value (Yd) whose transmittance is half of Tb when measured at an angle of 30° is preferably small, preferably less than 15 nm, more preferably less than 12 nm, particularly preferably less than 10 nm.

If |Ya-Yb| or |Yc-Yd| is in the above range, an optical filter with a wide viewing angle can be obtained, especially in the case of a camera module with a sensor function, ghosting can be achieved. Less camera quality or color reproducibility at the edge of the image (less color shading), and a good sensing function with less noise can be obtained.

The thickness of the optical filter of the present invention may be appropriately selected according to the desired application, and it is preferable that the thickness of the optical filter of the present invention is also thin in accordance with recent trends such as thinning and weight reduction of solid-state imaging devices. Since the optical filter of the present invention includes the substrate, it can be thinned.

The thickness of the optical filter of the present invention is, for example, preferably 200 μm or less, more preferably 180 μm or less, still more preferably 150 μm or less, particularly preferably 120 μm or less. The lower limit is not particularly limited, for example, it is ideally 20 μm. The optical filter of the present invention may consist only of the base material, or may have other functional films, for example, may have a dielectric multilayer film shown below on at least one side of the base material.

[Dielectric Multilayer Film] The dielectric multilayer film may or may not be in direct contact with the substrate. The dielectric multilayer film is a film having the ability to block unnecessary near-infrared rays by reflection and transmit necessary near-infrared rays, or a film having an anti-reflection function in the visible region and a part of the near-infrared wavelength region. In the present invention, the dielectric multilayer film may be provided on one or both surfaces of the substrate. When provided on one side, the manufacturing cost and ease of manufacture are excellent, and when provided on both sides, an optical filter having high strength and hardly warping can be obtained.

When the optical filter of the present invention is applied to applications such as solid-state imaging devices, it is preferable that the warpage of the optical filter is small, so it is preferable to provide a dielectric multilayer film on both surfaces of the base material, and to provide a dielectric multilayer film on both surfaces. The spectral characteristics can be the same or different. When the spectral characteristics of the dielectric multilayer films provided on both sides are the same, the transmittances of the light blocking band Za and the light blocking band Zc can be efficiently reduced in the near-infrared wavelength region, and the dielectric multilayer films provided on both sides When the spectral characteristics are different, it tends to expand the light blocking band Zc to the longer wavelength side easily.

The dielectric multilayer film is stacked with two or more material layers. Examples of materials constituting the multilayer film include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as the main component, and a small amount (for example, Materials such as titanium oxide, tin oxide, and/or cerium oxide (0% to 10% by mass relative to the main component), silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride, etc. .

Two or more materials are selected from these materials so as to obtain a predetermined difference in refractive index. In addition, if a predetermined refractive index difference is formed, when the two material layers are alternately three or more layers, they are not limited to regular stacking, as long as the same material layers are not stacked. Layers of other materials may be laminated as appropriate. The refractive index of the material constituting the multilayer film is not particularly limited as long as it is about 1.2 to 2.5.

The smaller the difference in refractive index between the material layers constituting the multilayer film, the smaller the absolute value |Ye-Yf|, which is preferable. The refractive index difference is preferably 0.8 or less, more preferably 0.5 or less. Furthermore, when it consists of three or more materials, it is preferable that the refractive index difference of adjacent material layers exists in the said range.

The method of laminating material layers having a predetermined difference in refractive index is not particularly limited as long as a dielectric multilayer film is formed. For example, chemical vapor deposition (chemical vapor deposition, CVD) method, sputtering method, vacuum evaporation method, ion-assisted evaporation method or ion plating method can be used on the substrate to directly form A dielectric multilayer film in which layers of materials are stacked alternately.

The physical film thickness of each layer of the material layer constituting the multilayer film also depends on the refractive index of each layer, and is usually preferably 5 nm to 500 nm. The total value of the physical film thickness of the dielectric multilayer film is preferably 1.0 μm to 8.0 μm for the entire optical filter. μm.

The total number of stacked dielectric multilayer films is preferably 2 to 60 layers, more preferably 4 to 56 layers, and particularly preferably 6 to 50 layers, based on the entire optical filter. When the thickness of each layer, the thickness of the dielectric multilayer film based on the optical filter as a whole, or the total number of laminations are within the above-mentioned range, a sufficient manufacturing margin can be ensured, and warping of the optical filter or dielectric multilayer can be reduced. By cracking the film, an optical filter having a wide light blocking frequency band or a light transmitting frequency band can be obtained.

[other functional films] For purposes such as improving the surface hardness of the substrate or the dielectric multilayer film, improving chemical resistance, antistatic, and eliminating damage, the optical filter of the present invention can be used on the substrate and the Between the dielectric multilayer films, on the side of the substrate opposite to the side on which the dielectric multilayer film is provided, or on the side of the dielectric multilayer film opposite to the side on which the substrate is provided, an antireflection film or a hard coat film is preferably provided. Or functional films such as antistatic films.

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

The method of laminating the functional film is not particularly limited, and examples thereof include melt molding on a substrate or a coating agent such as an antireflective agent, a hard coat agent, and/or an antistatic agent on a base material or a dielectric multilayer film in the same manner as described above. Or casting methods, etc.

In addition, it can also be produced by applying a curable composition containing the coating agent or the like to a substrate or a dielectric multilayer film using a bar coater or the like, and then curing it by ultraviolet irradiation or the like.

Examples of the coating agent include ultraviolet (Ultraviolet, UV)/electron beam (electron beam, EB) curable resins, thermosetting resins, etc., specifically vinyl compounds, urethanes, acrylic amino Formate, acrylate, epoxy and epoxy acrylate resins, etc. Examples of the curable composition containing these coating agents include vinyl-based, urethane-based, acrylic-urethane-based, acrylate-based, epoxy-based, and epoxy-acrylate-based curable compositions. Wait.

In addition, the curable composition may also 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 mixing ratio of the polymerization initiator is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 10% by mass. % by mass, and more preferably 1% by mass to 5% by mass. When the blending ratio of the polymerization initiator is within the above range, a curable composition having excellent curability and handleability and a desired hardness of a functional film such as an antireflection film, hard coat film, or antistatic film can be obtained.

Furthermore, an organic solvent may be added as a solvent to the curable composition. Known solvents may be used as the organic solvent, and one type may be used alone or two or more types may be used in combination.

The thickness of the functional film is preferably 0.1 μm to 20 μm, more preferably 0.5 μm to 10 μm, particularly preferably 0.7 μm to 5 μm.

In addition, for the purpose of improving the adhesion between the substrate and the functional film and/or the dielectric multilayer film, or the adhesion between the functional film and the dielectric multilayer film, corona may be applied to the surface of the substrate, the functional film, or the dielectric multilayer film. Surface treatment such as treatment or plasma treatment.

[Applications of Optical Filters] The optical filter of the present invention has a wide viewing angle and can selectively transmit visible light and a part of near-infrared rays. Therefore, it is effectively used for the correction of the sensitivity of a solid-state imaging device such as a CCD or a CMOS image sensor that has both a camera function and a near-infrared sensor function. Especially effective for: Digital still cameras, cameras for smart phones, cameras for mobile phones, digital video cameras, cameras for wearable devices, cameras for personal computers (PC), surveillance cameras, cameras for cars, night Video cameras, motion capture, laser distance meters, virtual try-ons, number plate recognition devices, televisions, car navigation, personal digital assistants, video game consoles, portable game consoles, Fingerprint authentication system, digital music player, etc.

[Solid-state imaging device] The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the so-called solid-state imaging device is an image sensor including a solid-state imaging element such as a CCD or a CMOS image sensor that has both a camera function and a near-infrared sensing function. Specifically, it can be used in digital still cameras, smartphone cameras, Cameras for mobile phones, cameras for wearable devices, digital video cameras, etc. For example, the camera module of the present invention includes the optical filter of the present invention. [Example]

Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. In addition, "part" means "quality part" unless otherwise indicated. In addition, the measurement method of each physical property value and the evaluation method of a physical property are as follows.

＜Molecular Weight＞ The molecular weight of the resin is measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent and the like.

(a) Gel Permeation Chromatography (GPC) device (Model 150C) manufactured by Waters (WATERS), column: H-type column manufactured by Tosoh Co., Ltd., developing solvent: o-dichlorobenzene ), and measure the mass average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene.

(b) Using a GPC device manufactured by Tosoh Co., Ltd. (HLC-8220 type, column: TSKgel α-M, developing solvent: tetrahydrofuran), the mass average molecular weight (Mw) and Number average molecular weight (Mn).

In addition, about the resin synthesize|combined in the resin synthesis example 3 mentioned later, it is not the measurement of the molecular weight by the said method, but the measurement of the logarithmic viscosity by the following method (c). (c) Part of the polyimide resin solution was poured into anhydrous methanol to precipitate the polyimide resin, and the unreacted monomer was separated by filtration. Dissolve 0.1 g of polyimide obtained by vacuum drying at 80°C for 12 hours in 20 mL of N-methyl-2-pyrrolidone, and use a Cannon-Fenske viscometer using the following Calculate the logarithmic viscosity (μ) at 30°C using the formula.

μ={ln(t _s /t ₀ )}/C t ₀ : flow down time of solvent t _s : flow down time of dilute polymer solution C: 0.5 g/dL

＜Glass transition temperature (Tg)＞ Using a differential scanning calorimeter (DSC6200) manufactured by SII Nanotechnologies Co., Ltd., measurement was performed at a heating rate: 20° C. per minute and nitrogen flow.

＜Spectral transmittance＞ The transmittance in each wavelength region of the base material and the optical filter was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Co., Ltd.

Here, the transmittance when measured from the direction perpendicular to the substrate and the optical filter is measured for light transmitted perpendicularly to the filter as shown in FIG. 1( a ). In addition, the transmittance when measured from an angle of 30° with respect to the vertical direction of the optical filter is measured for light transmitted at an angle of 30° with respect to the vertical direction of the filter as shown in (b) of Fig. 1 .

Furthermore, in the transmittance, except for the case of measuring Yb, Yd, and Yf of the optical filter, the spectrophotometer is used under the condition that the light is perpendicularly incident on the substrate and the optical filter. To measure. In the case of measuring Yb, Yd, and Yf, the above-mentioned spectrophotometer was used for measurement under the condition that light is incident at an angle of 30° with respect to the vertical direction of the optical filter.

＜Color shade evaluation＞ The evaluation of color shading when an optical filter is incorporated into a camera module is performed by the following method. Using the same method as Japanese Patent Laid-Open No. 2016-110067 to make a camera module, use the made camera module in the D65 light source (the standard light source device "Macbeth A" manufactured by X-Rite Company) and (Macbeth Judge) II"), a 300 mm x 400 mm size white board was photographed, and the color tone difference between the central part and the edge part of the white board in the camera image was evaluated according to the following criteria.

A level that can be tolerated without any problems is judged as "○", and a level that is acceptable as a high-quality camera module without any problem in practical use is judged as "△", and there is a difference in color tone In addition, the level that cannot be tolerated as a high-definition camera module application is judged as "×".

Furthermore, as shown in (c) of FIG. 1 , the positional relationship between the white board 112 and the camera module is adjusted so that the white board 112 occupies 90% or more of the area of the camera image 111 when shooting.

＜Ghost review＞ The evaluation of ghosting when an optical filter is incorporated in a camera module is performed by the following method. A camera module was produced by the same method as in Japanese Patent Application Laid-Open No. 2016-110067, and a halogen light source ("Luminar Ace" manufactured by Hayashi Shoji Kogyo Co., Ltd. LA-150TX"), and evaluated the occurrence of ghosting around the light source in the camera image according to the following criteria.

A level that can be tolerated without any problems is judged as "○", and a level that is acceptable as a high-quality camera module without any problems in practice is judged as "△", and ghosting occurs In addition, the level that cannot be tolerated as a high-definition camera module application is judged as "×".

[synthesis example] Compound (S), compound (Z) and compound (N) used in the following examples can be synthesized by commonly known methods, for example, refer to Japanese Patent No. 3366697, Japanese Patent No. 2846091, and Japanese Patent No. 2864475 , Japanese Patent No. 3094037, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent Laid-Open 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 Laid-Open No. 2007-169315, Japanese Patent Laid-Open No. 2009-108267, Japanese Patent Laid-Open Synthesis was carried out by the method described in KOKAI Publication No. 2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631, and the like.

<Resin Synthesis Example 1> 100 parts of 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene represented by the following formula (a) , 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 container, and the solution was heated to 80°C. Then, in the solution in the reaction vessel, add 0.2 parts of a toluene solution (concentration 0.6 mol/liter) of triethylaluminum as a polymerization catalyst, and a toluene solution (concentration 0.025 mol/liter) of methanol-modified tungsten hexachloride ) 0.9 parts, and the obtained solution was heated and stirred at 80° C. for 3 hours to perform ring-opening polymerization reaction, thereby obtaining a ring-opened polymer solution. The polymerization conversion rate in the polymerization reaction was 97%.

[chemical 1]

1,000 parts of the thus-obtained ring-opened polymer solution was charged 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 under hydrogen Under the condition of air pressure of 100 kg/cm ² and reaction temperature of 165°C, hydrogenation reaction was carried out by heating and stirring for 3 hours. After the obtained reaction solution (hydrogenated polymer solution) was cooled, the hydrogen gas was decompressed. The reaction solution was poured into a large amount of methanol, the coagulated matter was separated and recovered, and dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The number average molecular weight (Mn) of the obtained resin A was 32,000, the mass average molecular weight (Mw) was 137,000, and the glass transition temperature (Tg) was 165 degreeC.

＜Resin Synthesis Example 2＞ Add 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 of potassium carbonate ( 0.300 mol), N,N-dimethylacetamide (hereinafter also referred to as "DMAc") 443 g and toluene 111 g. Next, a thermometer, a stirrer, a three-way cock with a nitrogen inlet tube, a Dean-Stark tube, and a cooling tube were installed in the four-necked flask. Next, after replacing the inside of the flask with nitrogen, the obtained solution was reacted at 140° C. for 3 hours, and the generated water was removed from the Dean-Stark tube as needed. When the production of water was not confirmed, the temperature was gradually raised to 160° C., and the reaction was carried out at the temperature for 6 hours. After cooling to room temperature (25° C.), generated salts were removed with filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was separated by filtration. The obtained filtrate was vacuum-dried overnight at 60° C. to obtain a white powder (hereinafter also referred to as “resin B”) (95% yield). The obtained resin B 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 3> Under nitrogen flow, put Add 27.66 g (0.08 moles) of 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene and 7.38 g (0.02 moles) of 4,4'-bis(4-aminophenoxy)biphenyl ), and dissolved in 68.65 g of γ-butyrolactone and 17.16 g of N,N-dimethylacetamide. The obtained solution was cooled to 5°C using an ice-water bath, and 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added together while maintaining the same temperature, and as imidization Catalyst triethylamine 0.50 g (0.005 mol). After completion of the addition, the temperature was raised to 180° C., and the distillate was distilled off as needed, while reflux was performed for 6 hours. After completion of the reaction, air cooling was performed until the internal temperature reached 100°C, then 143.6 g of N,N-dimethylacetamide was added for dilution, and cooling was performed while stirring to obtain a polyimide having a solid content concentration of 20% by mass. Resin solution 264.16 g. A part of the polyimide resin solution was poured into 1 L of methanol to precipitate polyimide. The polyimide separated by filtration was washed with methanol, and then dried in a vacuum dryer at 100° C. for 24 hours to obtain a white powder (hereinafter also referred to as “resin C”). As a result of measuring the infrared (IR) spectrum of the obtained resin C, absorptions at 1704 cm ^-1 and 1770 cm ^-1 peculiar to imide groups were observed. Resin C had a glass transition temperature (Tg) of 310° C. and a logarithmic viscosity of 0.87.

[Example 1] In Example 1, an optical filter was fabricated using a single-layer base material including a transparent resin-made substrate. 100 parts of the resin A obtained in Synthesis Example 1, and a compound (s-1) represented by the following formula (s-1) as a compound (S) (absorption maximum wavelength in dichloromethane 711 nm) 0.04 parts by mass and 0.08 parts by mass of the compound (s-2) represented by the following formula (s-2) (absorption maximum wavelength in dichloromethane is 736 nm), as the following compound (Z) 0.14 parts by mass of the compound (z-1) represented by the above formula (z-1) (absorption maximum wavelength in methylene chloride is 770 nm), and methylene chloride, to obtain a resin concentration of 20 mass % The solution. Next, the obtained solution was cast on a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. Furthermore, the peeled coating film was dried at 100 degreeC under reduced pressure for 8 hours, and the single-layer base material containing the transparent resin-made substrate of 0.1 mm in thickness, 60 mm in length, and 60 mm in width was obtained.

[Chem 2]

The spectral transmittance of the base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in FIG. 2 and Table 1.

Then, a dielectric multilayer film (I) was formed on one side of the obtained single-layer substrate, and a dielectric multilayer film (II) was further formed on the other side of the substrate to obtain an optical filter with a thickness of about 0.105 mm.

The dielectric multilayer film (I) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (18 layers in total). The dielectric multilayer film (II) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (18 layers in total). In any of the dielectric multilayer film (I) and the dielectric multilayer film (II), the silicon dioxide layer and the titanium dioxide layer are formed from the base material side by a titanium dioxide layer, a silicon dioxide layer, a titanium dioxide layer, ... silicon dioxide Layers, titanium dioxide layers, and silicon dioxide layers are stacked alternately in sequence, and the outermost layer of the optical filter is set as the silicon dioxide layer.

The dielectric multilayer film (I) and the dielectric multilayer film (II) are designed as follows. Regarding the thickness and number of layers of each layer, the wavelength dependence of the refractive index of the substrate or the compound (S) or The absorption characteristics of the compound (Z) were optimized using an optical film design software (Essential Macleod, manufactured by Thin Film Center, Inc.). When performing optimization, in the first embodiment, the input parameters (target (Target) values) to the software were set as shown in Table 1 below.

[Table 1] Dielectric Multilayer Film wavelength (nm) Input parameters to the software angle of incidence Required value target tolerance Types of (I), (II) 400～700 0 100 1 Transmittance 800～870 0 100 0.5 Transmittance 950～1200 0 0 0.8 Transmittance

The result of film structure optimization is that in Example 1, both the dielectric multilayer film (I) and the dielectric multilayer film (II) have a silicon dioxide layer with a film thickness of 40 nm to 196 nm and a titanium dioxide film with a film thickness of 12 nm to 120 nm. A multilayer vapor-deposited film in which layers are alternately laminated with a stack number of 18. An example of the optimized membrane structure is shown in Table 2.

[Table 2] Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (I) 1 SiO ₂ 88.8 0.233 λ 2 TiO ₂ 110.0 0.480λ 3 SiO ₂ 191.6 0.503 λ 4 TiO ₂ 112.1 0.489 λ 5 SiO ₂ 189.2 0.497λ 6 TiO ₂ 115.9 0.506 λ 7 SiO ₂ 183.5 0.482 λ 8 TiO ₂ 106.2 0.463 λ 9 SiO ₂ 177.7 0.467λ 10 TiO ₂ 109.3 0.477λ 11 SiO ₂ 184.7 0.485λ 12 TiO ₂ 113.8 0.497λ 13 SiO ₂ 195.7 0.514 λ 14 TiO ₂ 114.0 0.497λ 15 SiO ₂ 184.6 0.485λ 16 TiO ₂ 120.2 0.525 λ 17 SiO ₂ 40.3 0.106λ 18 TiO ₂ 12.0 0.052λ Substrate (II) 19 TiO ₂ 12.0 0.052λ 20 SiO ₂ 40.3 0.106λ twenty one TiO ₂ 120.2 0.525 λ twenty two SiO ₂ 184.6 0.485λ twenty three TiO ₂ 114.0 0.497λ twenty four SiO ₂ 195.7 0.514 λ 25 TiO ₂ 113.8 0.497λ 26 SiO ₂ 184.7 0.485λ 27 TiO ₂ 109.3 0.477λ 28 SiO ₂ 177.7 0.467λ 29 TiO ₂ 106.2 0.463 λ 30 SiO ₂ 183.5 0.482 λ 31 TiO ₂ 115.9 0.506 λ 32 SiO ₂ 189.2 0.497λ 33 TiO ₂ 112.1 0.489 λ 34 SiO ₂ 191.6 0.503 λ 35 TiO ₂ 110.0 0.480λ 36 SiO ₂ 88.8 0.233 λ *λ=550nm

The spectral transmittance measured from the vertical direction of the optical filter and at an angle of 30° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 3 and Table 17.

In addition, camera modules were fabricated using the obtained optical filters, and evaluations of ghosting and color shading of camera images were performed. The results are shown in Table 17. The obtained camera images have good results in color shading and ghosting.

[Example 2] In Example 2, an optical filter having a single-layer base material including a transparent resin substrate was produced.

In Example 1, 0.02 parts by mass of compound (n-1) represented by the following formula (n-1) (absorption maximum wavelength in dichloromethane is 882 nm) was additionally used as compound (N), except Otherwise, under the same procedures and conditions as in Example 1, a single-layer base material including a transparent resin substrate containing the compound (S) and the compound (Z) was obtained. [Chem 3]

The spectral transmittance of the base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in FIG. 4 and Table 17.

Next, the dielectric multilayer film was designed using the same design parameters as in Example 1, and in the same manner as in Example 1, a dielectric including 18 silicon dioxide (SiO ₂ ) layers/titanium dioxide (TiO ₂ ) layers was formed on both sides. multilayer film. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 5 and Table 17.

[Example 3] In Example 3, an optical filter having a laminated base material having overcoat layers on both sides of a transparent resin-made substrate was fabricated.

A transparent resin substrate was produced in the same manner as in Example 2, and then the outer coating resin composition (1) of the following composition was applied to one side of the obtained transparent resin substrate by using a bar coater, and then dried in an oven with The solvent was evaporated and removed by heating at 70° C. for 2 minutes. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying became 2 micrometers. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to harden the resin composition for overcoat (1) to form an overcoat layer on a transparent resin substrate. Similarly, an overcoat layer comprising the resin composition (1) for overcoating is also formed on the other side of the transparent resin substrate to obtain a compound (S) and a compound (Z) on both sides of the transparent resin substrate with Laminate substrate for topcoat.

Resin composition for exterior coating (1): 60 parts by mass of tricyclodecane dimethanol acrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent , solid component concentration (total solid concentration (TSC)): 30%)

The spectral transmittance of the laminated base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in Table 17.

Next, the dielectric multilayer film was designed using the same design parameters as in Example 1, and in the same manner as in Example 1, a dielectric including 18 silicon dioxide (SiO ₂ ) layers/titanium dioxide (TiO ₂ ) layers was formed on both sides. multilayer film. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in Table 17.

[Example 4] In Example 4, an optical filter having a laminated base material including a transparent resin-made substrate having an overcoat layer on both sides was produced.

In Example 1, 0.15 parts by mass of compound (z-2) represented by the following formula (z-2) (absorption maximum wavelength in dichloromethane is 825 nm) was additionally used as compound (Z), except Other than that, a transparent resin substrate containing the compound (S) and the compound (Z) was obtained under the same procedure and conditions as in Example 1.

[chemical 4]

Next, in the same manner as in Example 3, an overcoat layer using the resin composition (1) was formed to obtain a laminated base material having an overcoat layer on both sides of a transparent resin substrate containing compound (S) and compound (Z). . The spectral transmittance of the laminated base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in FIG. 6 and Table 17.

Then, a dielectric multilayer film (III) was formed on one side of the obtained laminated substrate, and a dielectric multilayer film (IV) was further formed on the other side of the substrate to obtain an optical filter with a thickness of about 0.110 mm. The dielectric multilayer film (III) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (18 layers in total). The dielectric multilayer film (IV) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (18 layers in total).

Regarding the design of the dielectric multilayer film (III) and the dielectric multilayer film (IV), in Example 1, the input parameters (target values) to the software were changed as shown in Table 3 below, and it was the same as in Example 1. conduct.

[table 3] Embodiment 4 uses target Dielectric Multilayer Film wavelength (nm) Input parameters to the software angle of incidence Required value target tolerance Types of (III), (IV) 400～700 0 100 1 Transmittance 880～970 0 100 0.5 Transmittance 1050～1200 0 0 0.8 Transmittance

The result of film structure optimization is that in Example 1, both the dielectric multilayer film (III) and the dielectric multilayer film (IV) are silicon dioxide layers with a film thickness of 33 nm to 213 nm and titanium dioxide layers with a film thickness of 24 nm to 133 nm. A multilayer vapor-deposited film in which layers are alternately laminated with a stack number of 18. An example of the optimized membrane structure is shown in Table 4.

[Table 4] Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (III) 1 SiO ₂ 105.3 0.277λ 2 TiO ₂ 123.3 0.538 λ 3 SiO ₂ 197.7 0.520λ 4 TiO ₂ 123.7 0.540λ 5 SiO ₂ 209.6 0.551 λ 6 TiO ₂ 125.4 0.547λ 7 SiO ₂ 202.1 0.531 λ 8 TiO ₂ 123.1 0.537λ 9 SiO ₂ 205.0 0.539 λ 10 TiO ₂ 122.4 0.534 λ 11 SiO ₂ 198.6 0.522 λ 12 TiO ₂ 127.2 0.555 λ 13 SiO ₂ 212.5 0.558 λ 14 TiO ₂ 128.9 0.563 λ 15 SiO ₂ 190.5 0.500λ 16 TiO ₂ 132.9 0.580 λ 17 SiO ₂ 32.5 0.085λ 18 TiO ₂ 24.1 0.105λ Substrate (IV) 19 TiO ₂ 24.1 0.105λ 20 SiO ₂ 32.5 0.085λ twenty one TiO ₂ 132.9 0.580 λ twenty two SiO ₂ 190.5 0.500λ twenty three TiO ₂ 128.9 0.563 λ twenty four SiO ₂ 212.5 0.558 λ 25 TiO ₂ 127.2 0.555 λ 26 SiO ₂ 198.6 0.522 λ 27 TiO ₂ 122.4 0.534 λ 28 SiO ₂ 205.0 0.539 λ 29 TiO ₂ 123.1 0.537λ 30 SiO ₂ 202.1 0.470λ 31 TiO ₂ 125.4 0.547λ 32 SiO ₂ 209.6 0.551 λ 33 TiO ₂ 123.7 0.540λ 34 SiO ₂ 197.7 0.520λ 35 TiO ₂ 123.3 0.538 λ 36 SiO ₂ 105.3 0.277λ *λ=550nm

For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 7 and Table 17.

[Example 5] In Example 5, an optical filter including a laminated base material having overcoat layers on both sides of a transparent resin-made substrate was fabricated.

In Example 4, 0.02 parts by mass of compound (n-2) represented by the following formula (n-2) (absorption maximum wavelength in dichloromethane is 1000 nm) was additionally used as compound (N), except Otherwise, under the same procedures and conditions as in Example 4, a laminated base material having an overcoat layer on both surfaces of a transparent resin substrate containing the compound (S) and the compound (Z) was obtained.

[chemical 5]

The spectral transmittance of the base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in FIG. 8 and Table 17.

Next, the dielectric multilayer film was designed using the same design parameters as in Example 4, and in the same manner as in Example 4, a dielectric multilayer including 18 silicon dioxide (SiO ₂ ) layers/titanium dioxide (TiO ₂ ) layers was formed on both sides. membrane.

For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 9 and Table 17.

[Example 6] In Example 6, an optical filter including a laminated base material having overcoat layers on both sides of a transparent resin-made substrate was manufactured.

Under the same procedure and conditions as in Example 5, a laminated base material having an overcoat layer on both surfaces of a transparent resin substrate containing compound (S), compound (Z), and compound (N) was obtained.

Then, a dielectric multilayer film (V) was formed on one side of the obtained substrate, and a dielectric multilayer film (VI) was further formed on the other side of the substrate to obtain an optical filter with a thickness of about 0.105 mm. The dielectric multilayer film (V) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (8 layers in total). The dielectric multilayer film (VI) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (8 layers in total).

Regarding the design of the dielectric multilayer film (V) and the dielectric multilayer film (VI), in Example 1, the input parameters (target values) to the software were changed as shown in Table 5 below, and it was the same as in Example 1. conduct.

[table 5] Dielectric Multilayer Film wavelength (nm) Input parameters to the software angle of incidence Required value target tolerance Types of (V), (VI) 400～700 0 100 0.8 Transmittance 880～970 0 100 0.2 Transmittance

The result of film structure optimization is that in Example 1, both the dielectric multilayer film (V) and the dielectric multilayer film (VI) are silicon dioxide layers with a film thickness of 12 nm to 107 nm and titanium dioxide layers with a film thickness of 12 nm to 78 nm. A multilayer vapor-deposited film in which layers are alternately laminated with a stack number of 8. An example of the optimized membrane structure is shown in Table 6.

[Table 6] Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (V) 1 SiO ₂ 106.7 0.280λ 2 TiO ₂ 23.5 0.103λ 3 SiO ₂ 18.8 0.050λ 4 TiO ₂ 78.4 0.342 λ 5 SiO ₂ 12.2 0.032λ 6 TiO ₂ 31.0 0.135 λ 7 SiO ₂ 38.2 0.100λ 8 TiO ₂ 11.9 0.052λ Substrate (VI) 9 TiO ₂ 11.9 0.052λ 10 SiO ₂ 38.2 0.100λ 11 TiO ₂ 31.0 0.135 λ 12 SiO ₂ 12.2 0.032λ 13 TiO ₂ 78.4 0.342 λ 14 SiO ₂ 18.8 0.050λ 15 TiO ₂ 23.5 0.103λ 16 SiO ₂ 106.7 0.280λ *λ=550nm

For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 10 and Table 17.

[Example 7] In Example 7, an optical filter including a laminated base material having overcoat layers on both sides of a transparent resin-made substrate was fabricated.

Under the same procedure and conditions as in Example 5, a substrate including an overcoat layer on both surfaces of a transparent resin substrate containing compound (S), compound (Z), and compound (N) was obtained. In Example 7, the base material was used as an optical filter as it was, and the optical characteristics in each wavelength range, and the ghost and color shading of the camera image were evaluated in the same manner as in Example 1. The results are shown in Table 17.

[Example 8] In Example 8, an optical filter including a laminated base material having overcoat layers on both sides of a transparent resin-made substrate was fabricated.

Instead of compound (s-2), 0.04 parts by mass of compound (s-3) represented by the following formula (s-3) (maximum absorption wavelength in dichloromethane is 739 nm) was used as compound (S) instead of Compound (z-2) and 0.02 parts by mass of compound (z-3) represented by the following formula (z-3) (maximum absorption wavelength in dichloromethane is 825 nm) was used as compound (Z), and the compound Except that the addition amount of (z-1) was changed to 0.12 parts by mass, under the same procedure and conditions as in Example 7, a transparent compound containing compound (S), compound (Z), and compound (N) was obtained. A laminated substrate with overcoats on both sides of a resin substrate. In Example 8, the base material was used as it is as an optical filter, and the optical characteristics in each wavelength range, and the ghost and color shading of the camera image were evaluated in the same manner as in Example 1. The results are shown in FIG. 11 and Table 17.

[chemical 6]

[Example 9] In Example 9, an optical filter including a laminated substrate having resin layers containing the compound (S) and the compound (Z) on both sides of a resin support was manufactured.

Resin A and methyl chloride obtained in Synthesis Example 1 were added to a container to obtain a solution having a resin concentration of 20% by mass (that is, not containing compound (S) or compound (Z)). A resin support was produced in the same manner as in Example 1 except for using the above solution.

Using the same method as in Example 3, a resin layer comprising the resin composition (A) of the following composition was formed on both sides of the obtained resin support, and a compound (S) and a compound (Z) were formed on both sides. The resin layer to obtain a laminated substrate.

The spectral transmittance of the base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in Table 17.

Resin composition (A): 100 parts by mass of tricyclodecane dimethanol acrylate, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone, 1.0 parts by mass of compound (s-1), 2.0 parts by mass of compound (s-2) , compound (z-1) 2.75 parts by mass, compound (z-2) 3.75 parts by mass, compound (n-2) 3.75 parts by mass, methyl ethyl ketone (solvent, TSC: 25%)

Next, the dielectric multilayer film was designed using the same design parameters as in Example 6, and in the same manner as in Example 6, a dielectric including 8 silicon dioxide (SiO ₂ ) layers/titanium dioxide (TiO ₂ ) layers was formed on both sides. multilayer film. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in Table 17.

[Example 10] In Example 10, an optical filter including a laminated substrate having a resin layer containing a compound (S) and a compound (Z) on one side of a glass support was manufactured. On a glass support "OA-10G (thickness 200 μm)" (manufactured by NEC Glass Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width, a resin composition having the following composition was coated with a spin coater ( B) Heat on a heating plate at 80°C for 2 minutes to remove the solvent. At this time, the coating conditions of the spin coater were adjusted so that the thickness after drying became 4 μm. Next, exposure was performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW), and the resin composition (B) was cured to obtain a resin layer containing the compound (S) and the compound (Z). A laminated substrate formed on one side of a glass support.

The spectral transmittance of the base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in Table 17.

Resin composition (B): 20 parts by mass of tricyclodecane dimethanol acrylate, 80 parts by mass of dipentaerythritol hexaacrylate, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone, 1.0 parts by mass of compound (s-1), Compound (s-2) 2.0 parts by mass, Compound (z-1) 3.5 parts by mass, Compound (n-1) 0.50 parts by mass, methyl ethyl ketone (solvent, TSC: 35%)

Then, a dielectric multilayer film (VII) was formed on one side of the obtained substrate, and a dielectric multilayer film (VIII) was further formed on the other side of the substrate to obtain an optical filter with a thickness of about 0.105 mm. The dielectric multilayer film (VII) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (8 layers in total). The dielectric multilayer film (VIII) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (8 layers in total).

Regarding the design of the dielectric multilayer film (VII) and the dielectric multilayer film (VIII), in Example 1, the input parameters (target values) to the software were changed as shown in Table 7 below, and it was the same as in Example 1. conduct.

[Table 7] Embodiment 10 uses target Dielectric Multilayer Film wavelength (nm) Input parameters to the software angle of incidence Required value target tolerance Types of (VII), (VIII) 400～700 0 100 0.8 Transmittance 790～880 0 100 0.2 Transmittance

The result of film structure optimization is that in Example 10, both the dielectric multilayer film (VII) and the dielectric multilayer film (VIII) have a silicon dioxide layer with a film thickness of 12 nm to 104 nm and a titanium dioxide film with a film thickness of 12 nm to 76 nm. A multilayer vapor-deposited film in which layers are alternately laminated with a stack number of 8. An example of the optimized membrane structure is shown in Table 8.

[Table 8] Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (VII) 1 SiO ₂ 103.5 0.272λ 2 TiO ₂ 22.8 0.099λ 3 SiO ₂ 18.3 0.048 λ 4 TiO ₂ 76.0 0.332 λ 5 SiO ₂ 11.8 0.031λ 6 TiO ₂ 30.0 0.131 λ 7 SiO ₂ 37.0 0.097λ 8 TiO ₂ 11.6 0.051λ Substrate (VIII) 9 TiO ₂ 11.6 0.051λ 10 SiO ₂ 37.0 0.097λ 11 TiO ₂ 30.0 0.131 λ 12 SiO ₂ 11.8 0.031λ 13 TiO ₂ 76.0 0.332 λ 14 SiO ₂ 18.3 0.048 λ 15 TiO ₂ 22.8 0.099λ 16 SiO ₂ 103.5 0.272λ *λ=550nm

For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in Table 17.

[Example 11] In Example 11, an optical filter including a laminated substrate having a resin layer containing the compound (S) and the compound (Z) on one side of the glass support was manufactured. In Example 10, except that the resin composition (A) was used instead of the resin composition (B), in the same procedure and conditions as in Example 10, a compound containing compound (S) and compound (Z) was obtained. A glass support substrate of the resin layer.

The spectral transmittance of the base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in Table 17.

Next, the dielectric multilayer film was designed using the same design parameters as in Example 6, and in the same manner as in Example 6, a dielectric multilayer including 8 silicon dioxide (SiO ₂ ) layers/titanium dioxide (TiO ₂ ) layers was formed on both sides. membrane. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in Table 17.

[Example 12 to Example 14] In Examples 12 to 14, optical filters including laminated base materials having overcoat layers on both sides of a transparent resin substrate were produced.

In Example 6, the transparent resin type, solvent, and drying conditions were changed as described in Table 17. In addition, in the same procedure and conditions as in Example 6, a composite material containing an overcoat layer on both sides was obtained. The base material of the transparent resin substrate of compound (S), compound (Z), and compound (N).

Next, the dielectric multilayer film was designed using the same design parameters as in Example 6, and in the same manner as in Example 6, a dielectric multilayer including 8 silicon dioxide (SiO ₂ ) layers/titanium dioxide (TiO ₂ ) layers was formed on both sides. membrane. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in Table 17. [Comparative Example 1] In Comparative Example 1, an optical filter having a base material including a transparent resin substrate having an overcoat layer on both surfaces was fabricated.

In Example 3, except not using the compound (Z) and the compound (N), it carried out similarly to Example 3, and produced the base material containing the transparent resin-made board|substrate which has an overcoat layer on both surfaces. The spectral transmittance of the base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in FIG. 12 and Table 17.

Then, a dielectric multilayer film (IX) was formed on one surface of the obtained substrate, and a dielectric multilayer film (X) was formed on the other surface of the substrate to obtain an optical filter with a thickness of about 0.109 mm. The dielectric multilayer film (IX) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (18 layers in total). The dielectric multilayer film (X) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (28 layers in total).

Regarding the design of the dielectric multilayer film (IX) and the dielectric multilayer film (X), in Example 1, the input parameters (target values) to the software were changed as shown in Table 9 below, and it was the same as in Example 1. conduct.

[Table 9] Dielectric Multilayer Film wavelength (nm) Input parameters to the software angle of incidence Required value target tolerance Types of (IX) 400～700 0 100 1 Transmittance 800～870 0 100 0.5 Transmittance 950～1200 0 0 0.8 Transmittance (X) 400～680 0 100 1 Transmittance 710～750 0 0 0.3 Transmittance 800～870 0 100 0.5 Transmittance

As a result of the optimization of the film structure, in Comparative Example 1, the dielectric multilayer film (IX) was formed by alternately stacking silicon dioxide layers with a film thickness of 40 nm to 196 nm and titanium dioxide layers with a film thickness of 12 nm to 120 nm The multilayer vapor-deposited film with a number of 18, the dielectric multilayer film (X) is a multilayer vapor-deposited film with a stack number of 28 in which silicon dioxide layers with a film thickness of 15 nm to 534 nm and titanium dioxide layers with a film thickness of 12 nm to 111 nm are alternately laminated . An example of the optimized membrane structure is shown in Table 10.

[Table 10] Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (IX) 1 SiO ₂ 88.8 0.233 λ 2 TiO ₂ 110.0 0.480λ 3 SiO ₂ 191.6 0.503 λ 4 TiO ₂ 112.1 0.489 λ 5 SiO ₂ 189.2 0.497λ 6 TiO ₂ 115.9 0.506 λ 7 SiO ₂ 183.5 0.482 λ 8 TiO ₂ 106.2 0.463 λ 9 SiO ₂ 177.7 0.467λ 10 TiO ₂ 109.3 0.477λ 11 SiO ₂ 184.7 0.485λ 12 TiO ₂ 113.8 0.497λ 13 SiO ₂ 195.7 0.514 λ 14 TiO ₂ 114.0 0.497λ 15 SiO ₂ 184.6 0.485λ 16 TiO ₂ 120.2 0.525 λ 17 SiO ₂ 40.3 0.106λ 18 TiO ₂ 12.0 0.052λ Substrate (X) 19 TiO ₂ 16.04 0.070λ 20 SiO ₂ 24.79 0.065λ twenty one TiO ₂ 73.07 0.319 λ twenty two SiO ₂ 21.93 0.058 λ twenty three TiO ₂ 18.71 0.082λ twenty four SiO ₂ 533.95 1.403 λ 25 TiO ₂ 17.86 0.078 λ 26 SiO ₂ 14.9 0.039λ 27 TiO ₂ 75.28 0.329 λ 28 SiO ₂ 164.37 0.432 λ 29 TiO ₂ 81.86 0.357λ 30 SiO ₂ 15.6 0.041λ 31 TiO ₂ 12.12 0.053 λ 32 SiO ₂ 190.99 0.502 λ 33 TiO ₂ 13.52 0.059λ 34 SiO ₂ 40.17 0.106λ 35 TiO ₂ 104.96 0.458 λ 36 SiO ₂ 156.46 0.411 λ 37 TiO ₂ 92.31 0.403 λ 38 SiO ₂ 196.82 0.517λ 39 TiO ₂ 12.67 0.055λ 40 SiO ₂ 239.9 0.630λ 41 TiO ₂ 15.94 0.070λ 42 SiO ₂ 43.02 0.113 λ 43 TiO ₂ 110.54 0.482 λ 44 SiO ₂ 163.32 0.429 λ 45 TiO ₂ 89.27 0.390λ 46 SiO ₂ 76.55 0.201λ *λ=550nm

For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 13 and Table 17. The resulting optical filter has a large dependence on the angle of incidence as a result of ghosting or poor color shading.

[Comparative example 2] In Comparative Example 2, an optical filter having a base material including a transparent resin-made substrate having overcoat layers on both sides was prepared.

Under the same procedure and conditions as in Comparative Example 1, a base material comprising a transparent resin substrate having an overcoat layer on both surfaces and containing the compound (S) was obtained.

Then, a dielectric multilayer film (XI) was formed on one side of the obtained substrate, and a dielectric multilayer film (XII) was further formed on the other side of the substrate to obtain an optical filter with a thickness of about 0.110 mm. The dielectric multilayer film (XI) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (18 layers in total). The dielectric multilayer film (XII) was formed by laminating silicon dioxide (SiO ₂ ) layers and titanium dioxide (TiO ₂ ) layers alternately at a deposition temperature of 100° C. (26 layers in total).

Regarding the design of the dielectric multilayer film (XI) and the dielectric multilayer film (XII), in Example 1, the input parameters (target values) to the software were changed as shown in Table 11 below, and it was the same as in Example 1. conduct.

[Table 11] Dielectric Multilayer Film wavelength (nm) Input parameters to the software angle of incidence Required value target tolerance Types of (XI) 400～700 0 100 1 Transmittance 880～970 0 100 0.5 Transmittance 1050～1200 0 0 0.8 Transmittance (XII) 400～680 0 100 1 Transmittance 710～850 0 0 0.4 Transmittance 880～970 0 100 0.5 Transmittance

As a result of the optimization of the film structure, in Comparative Example 2, the dielectric multilayer film (XI) is a laminate in which silicon dioxide layers with a film thickness of 33 nm to 213 nm and titanium dioxide layers with a film thickness of 24 nm to 133 nm are alternately laminated The multilayer vapor-deposited film with a number of 18, the dielectric multilayer film (XII) is a multilayer vapor-deposited film with a stacking number of 26 in which silicon dioxide layers with a film thickness of 12 nm to 228 nm and titanium dioxide layers with a film thickness of 4 nm to 106 nm are alternately laminated . An example of the optimized membrane structure is shown in Table 12.

[Table 12] Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (XI) 1 SiO ₂ 105.3 0.277λ 2 TiO ₂ 123.3 0.538 λ 3 SiO ₂ 197.7 0.520λ 4 TiO ₂ 123.7 0.540λ 5 SiO ₂ 209.6 0.551 λ 6 TiO ₂ 125.4 0.547λ 7 SiO ₂ 202.1 0.531 λ 8 TiO ₂ 123.1 0.537λ 9 SiO ₂ 205.0 0.539 λ 10 TiO ₂ 122.4 0.534 λ 11 SiO ₂ 198.6 0.522 λ 12 TiO ₂ 127.2 0.555 λ 13 SiO ₂ 212.5 0.558 λ 14 TiO ₂ 128.9 0.563 λ 15 SiO ₂ 190.5 0.500λ 16 TiO ₂ 132.9 0.580 λ 17 SiO ₂ 32.5 0.085λ 18 TiO ₂ 24.1 0.105λ Substrate (XII) 19 TiO ₂ 9.7 0.042λ 20 SiO ₂ 33.6 0.088λ twenty one TiO ₂ 105.8 0.462 λ twenty two SiO ₂ 187.1 0.492 λ twenty three TiO ₂ 28.5 0.124λ twenty four SiO ₂ 45.4 0.119 λ 25 TiO ₂ 13.0 0.057λ 26 SiO ₂ 143.2 0.376λ 27 TiO ₂ 10.1 0.044λ 28 SiO ₂ 197.0 0.518 λ 29 TiO ₂ 92.6 0.404λ 30 SiO ₂ 151.5 0.398 λ 31 TiO ₂ 92.8 0.405λ 32 SiO ₂ 194.6 0.511 λ 33 TiO ₂ 13.9 0.060λ 34 SiO ₂ 228.1 0.599 λ 35 TiO ₂ 11.4 0.050λ 36 SiO ₂ 219.6 0.577λ 37 TiO ₂ 4.2 0.018 λ 38 SiO ₂ 21.0 0.055λ 39 TiO ₂ 9.3 0.041λ 40 SiO ₂ 194.3 0.510λ 41 TiO ₂ 9.4 0.041λ 42 SiO ₂ 12.3 0.032λ 43 TiO ₂ 97.4 0.425 λ 44 SiO ₂ 87.6 0.230λ *λ=550nm

For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 14 and Table 17. The resulting optical filter has a large dependence on the angle of incidence as a result of ghosting or poor color shading.

[Comparative example 3] In Comparative Example 3, an optical filter having a base material including a transparent resin-made substrate having overcoat layers on both sides was prepared.

In Example 3, the compound (z-1) was added in an amount of 0.03 parts by mass, and the compound (N) was not used. In the same manner as in Example 3, it was prepared including Base material for transparent resin substrates. The spectral transmittance of the base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in FIG. 15 and Table 17.

Then, use the same design parameters as in Comparative Example 1 to design the dielectric multilayer film. In the same way as in Comparative Example 1, 18 layers of silicon dioxide (SiO ₂ ) layers/titanium dioxide (TiO ₂ ) layers and 28 layers of Dielectric multilayer film of silicon (SiO ₂ ) layer/titanium dioxide (TiO ₂ ) layer. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 16 and Table 17.

[Comparative example 4] In Comparative Example 4, an optical filter having a base material including a transparent resin-made substrate having overcoat layers on both sides was prepared.

Under the same procedure and conditions as in Comparative Example 3, a base material comprising a transparent resin substrate having an overcoat layer on both surfaces and containing the compound (S) and the compound (Z) was obtained.

Then, use the same design parameters as in Comparative Example 2 to design the dielectric multilayer film. In the same way as in Comparative Example 2, 18 layers of silicon dioxide (SiO ₂ ) layers/titanium dioxide (TiO ₂ ) layers and 26 layers of Dielectric multilayer film of silicon (SiO ₂ ) layer/titanium dioxide (TiO ₂ ) layer. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 17 and Table 17.

[Comparative Example 5] In Comparative Example 5, an optical filter having a base material including a transparent resin-made substrate having overcoat layers on both surfaces was prepared.

In Example 3, except not using the compound (S) and the compound (N), it carried out similarly to Example 3, and produced the base material containing the transparent resin-made board|substrate which has an overcoat layer on both surfaces. The spectral transmittance of the base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in FIG. 18 and Table 17.

Then, use the same design parameters as in Comparative Example 1 to design the dielectric multilayer film. In the same way as in Comparative Example 1, 18 layers of silicon dioxide (SiO ₂ ) layers/titanium dioxide (TiO ₂ ) layers and 28 layers of Dielectric multilayer film of silicon (SiO ₂ ) layer/titanium dioxide (TiO ₂ ) layer. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 19 and Table 17.

[Comparative Example 6] In Comparative Example 6, an optical filter having a base material including a transparent resin-made substrate having overcoat layers on both sides was prepared.

Under the same procedure and conditions as in Comparative Example 5, a base material including a transparent resin substrate having an overcoat layer on both surfaces and containing the compound (Z) was obtained.

Then, use the same design parameters as in Comparative Example 2 to design the dielectric multilayer film. In the same way as in Comparative Example 2, 18 layers of silicon dioxide (SiO ₂ ) layers/titanium dioxide (TiO ₂ ) layers and 26 layers of Dielectric multilayer film of silicon (SiO ₂ ) layer/titanium dioxide (TiO ₂ ) layer. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 20 and Table 17.

[Example 15] In Example 15, an optical filter having a single-layer base material including a transparent resin substrate was produced.

Under the same procedures and conditions as in Example 1, a transparent resin substrate containing the compound (S) and the compound (Z) was obtained. The spectral transmittance of the base material was measured, and (Xa), (Xb), and the average value of the transmittance at a wavelength of 450 nm to 570 nm were obtained. The results are shown in Table 17.

Then, use the design parameters shown in the following Table 13 to design the dielectric multilayer film, and form silicon dioxide (SiO ₂ ) layers on both sides of the obtained substrate using the same evaporation conditions as in the above examples. and a dielectric multilayer film (XIII) and a dielectric multilayer film (XIV) with a total of 18 layers in which titanium dioxide (TiO ₂ ) layers and Al ₂ O ₃ layers are alternately laminated. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 21 and Table 17.

[Table 13] Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (XIII) 1 SiO ₂ 97.1 0.256λ 2 TiO ₂ 113.0 0.480λ 3 Al ₂ O ₃ 174.9 0.516 λ 4 TiO ₂ 113.8 0.500λ 5 Al ₂ O ₃ 170.7 0.504λ 6 TiO ₂ 112.1 0.492 λ 7 Al ₂ O ₃ 170.3 0.502 λ 8 TiO ₂ 112.7 0.495 λ 9 Al ₂ O ₃ 170.3 0.502 λ 10 TiO ₂ 112.4 0.494λ 11 Al ₂ O ₃ 170.0 0.501 λ 12 TiO ₂ 113.4 0.498 λ 13 Al ₂ O ₃ 174.1 0.514 λ 14 TiO ₂ 114.2 0.501 λ 15 Al ₂ O ₃ 171.9 0.507λ 16 TiO ₂ 120.0 0.527λ 17 Al ₂ O ₃ 34.0 0.100λ 18 TiO ₂ 16.2 0.071λ Substrate (XIV) 19 TiO ₂ 16.2 0.071λ 20 Al ₂ O ₃ 34.0 0.100λ twenty one TiO ₂ 120.0 0.527λ twenty two Al ₂ O ₃ 171.9 0.507λ twenty three TiO ₂ 114.2 0.501 λ twenty four Al ₂ O ₃ 174.1 0.514 λ 25 TiO ₂ 113.4 0.498 λ 26 Al ₂ O ₃ 170.0 0.501 λ 27 TiO ₂ 112.4 0.494λ 28 Al ₂ O ₃ 170.3 0.502 λ 29 TiO ₂ 112.7 0.495 λ 30 Al ₂ O ₃ 170.3 0.502 λ 31 TiO ₂ 112.1 0.492 λ 32 Al ₂ O ₃ 170.7 0.504λ 33 TiO ₂ 113.8 0.500λ 34 Al ₂ O ₃ 174.9 0.516 λ 35 TiO ₂ 113.0 0.480λ 36 SiO ₂ 97.1 0.256λ *λ=550nm

[Example 16] In Example 16, an optical filter having a single-layer base material including a transparent resin substrate was produced.

In the same procedure and conditions as in Example 15, a transparent resin substrate containing the compound (S) and the compound (Z) was obtained. Then, use the design parameters in Table 14 below to design the dielectric multilayer film, and form silicon dioxide (SiO ₂ ) layers and Ta ₂ O Dielectric multilayer film (XV) and dielectric multilayer film (XVI) with a total of 22 layers in which ₅ layers and ₃ layers of Al ₂ O are laminated alternately. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 22 and Table 17.

[Table 14] Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (XV) 1 SiO ₂ 91.8 0.241λ 2 Ta ₂ O ₅ 123.2 0.480λ 3 Al ₂ O ₃ 163.0 0.481 λ 4 Ta ₂ O ₅ 121.6 0.469 λ 5 Al ₂ O ₃ 159.6 0.471λ 6 Ta ₂ O ₅ 118.5 0.457λ 7 Al ₂ O ₃ 157.3 0.464λ 8 Ta ₂ O ₅ 118.4 0.457λ 9 Al ₂ O ₃ 158.1 0.466λ 10 Ta ₂ O ₅ 119.0 0.459 λ 11 Al ₂ O ₃ 157.6 0.465λ 12 Ta ₂ O ₅ 116.7 0.450λ 13 Al ₂ O ₃ 154.6 0.456 λ 14 Ta ₂ O ₅ 117.5 0.453 λ 15 Al ₂ O ₃ 159.8 0.471λ 16 Ta ₂ O ₅ 122.1 0.471λ 17 Al ₂ O ₃ 164.5 0.485λ 18 Ta ₂ O ₅ 125.6 0.484λ 19 Al ₂ O ₃ 167.5 0.494λ 20 Ta ₂ O ₅ 129.7 0.500λ twenty one Al ₂ O ₃ 46.5 0.137λ twenty two Ta ₂ O ₅ 10.7 0.041λ Substrate (XVI) twenty three Ta ₂ O ₅ 10.7 0.041λ twenty four Al ₂ O ₃ 46.5 0.137λ 25 Ta ₂ O ₅ 129.7 0.500λ 26 Al ₂ O ₃ 167.5 0.494λ 27 Ta ₂ O ₅ 125.6 0.484λ 28 Al ₂ O ₃ 164.5 0.485λ 29 Ta ₂ O ₅ 122.1 0.471λ 30 Al ₂ O ₃ 159.8 0.471λ 31 Ta ₂ O ₅ 117.5 0.453 λ 32 Al ₂ O ₃ 154.6 0.456 λ 33 Ta ₂ O ₅ 116.7 0.450λ 34 Al ₂ O ₃ 157.6 0.465λ 35 Ta ₂ O ₅ 119.0 0.459 λ 36 Al ₂ O ₃ 158.1 0.466λ 37 Ta ₂ O ₅ 118.4 0.457λ 38 Al ₂ O ₃ 157.3 0.464λ 39 Ta ₂ O ₅ 118.5 0.457λ 40 Al ₂ O ₃ 159.6 0.471λ 41 Ta ₂ O ₅ 121.6 0.469 λ 42 Al ₂ O ₃ 163.0 0.481 λ 43 Ta ₂ O ₅ 123.2 0.480λ 44 SiO ₂ 91.8 0.241λ *λ=550nm

[Example 17] In Example 17, an optical filter having a single-layer base material including a transparent resin substrate was produced.

In the same procedure and conditions as in Example 15, a transparent resin substrate containing the compound (S) and the compound (Z) was obtained. Then, use the design parameters in the following Table 15 to design the dielectric multilayer film, and use the same vapor deposition conditions as in the above example to form the 50 layers shown in the following Table 15 containing silicon dioxide (SiO ₂ ). Dielectric multilayer film (XVII) and dielectric multilayer film (XVIII) of layer/Ta ₂ O ₅ layer/titanium dioxide (TiO ₂ ) layer. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 23 and Table 17. [Table 15] Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (XVII) 1 SiO ₂ 93.0 0.245λ 2 Ta ₂ O ₅ 52.2 0.480λ 3 TiO ₂ 83.1 0.365λ 4 Ta ₂ O ₅ 124.5 0.480λ 5 TiO ₂ 105.4 0.463 λ 6 Ta ₂ O ₅ 122.5 0.472 λ 7 TiO ₂ 110.9 0.487λ 8 Ta ₂ O ₅ 130.5 0.503 λ 9 TiO ₂ 114.5 0.503 λ 10 Ta ₂ O ₅ 132.7 0.512 λ 11 TiO ₂ 113.9 0.500λ 12 Ta ₂ O ₅ 127.6 0.492 λ 13 TiO ₂ 109.1 0.479 λ 14 Ta ₂ O ₅ 124.4 0.480λ 15 TiO ₂ 106.4 0.467λ 16 Ta ₂ O ₅ 120.4 0.464λ 17 TiO ₂ 101.9 0.448 λ 18 Ta ₂ O ₅ 117.4 0.453 λ 19 TiO ₂ 102.1 0.448 λ 20 Ta ₂ O ₅ 119.7 0.462 λ twenty one TiO ₂ 105.5 0.463 λ twenty two Ta ₂ O ₅ 123.1 0.475λ twenty three TiO ₂ 104.2 0.458 λ twenty four Ta ₂ O ₅ 113.9 0.439 λ 25 TiO ₂ 94.7 0.416λ 26 Ta ₂ O ₅ 113.6 0.438 λ 27 TiO ₂ 100.3 0.441 λ 28 Ta ₂ O ₅ 117.8 0.454λ 29 TiO ₂ 100.5 0.442 λ 30 Ta ₂ O ₅ 113.8 0.439 λ 31 TiO ₂ 98.9 0.434λ 32 Ta ₂ O ₅ 119.3 0.460λ 33 TiO ₂ 104.4 0.459 λ 34 Ta ₂ O ₅ 117.4 0.453 λ 35 TiO ₂ 98.4 0.432 λ 36 Ta ₂ O ₅ 115.6 0.446λ 37 TiO ₂ 102.3 0.449 λ 38 Ta ₂ O ₅ 118.8 0.458 λ 39 TiO ₂ 99.5 0.437λ 40 Ta ₂ O ₅ 110.2 0.425 λ 41 TiO ₂ 93.7 0.412 λ 42 Ta ₂ O ₅ 114.8 0.443 λ 43 TiO ₂ 102.8 0.452 λ 44 Ta ₂ O ₅ 122.4 0.472 λ 45 TiO ₂ 109.1 0.479 λ 46 Ta ₂ O ₅ 129.1 0.498 λ 47 TiO ₂ 111.5 0.490λ 48 Ta ₂ O ₅ 204.1 0.787λ 49 SiO ₂ 30.8 0.081λ 50 TiO ₂ 12.7 0.056λ Substrate (XVIII) 51 TiO ₂ 12.7 0.056λ 52 SiO ₂ 30.8 0.081λ 53 Ta ₂ O ₅ 204.1 0.787λ 54 TiO ₂ 111.5 0.490λ 55 Ta ₂ O ₅ 129.1 0.498 λ 56 TiO ₂ 109.1 0.479 λ 57 Ta ₂ O ₅ 122.4 0.472 λ 58 TiO ₂ 102.8 0.452 λ 59 Ta ₂ O ₅ 114.8 0.443 λ 60 TiO ₂ 93.7 0.412 λ 61 Ta ₂ O ₅ 110.2 0.425 λ 62 TiO ₂ 99.5 0.437λ 63 Ta ₂ O ₅ 118.8 0.458 λ 64 TiO ₂ 102.3 0.449 λ 65 Ta ₂ O ₅ 115.6 0.446λ 66 TiO ₂ 98.4 0.432 λ 67 Ta ₂ O ₅ 117.4 0.453 λ 68 TiO ₂ 104.4 0.459 λ 69 Ta ₂ O ₅ 119.3 0.460λ 70 TiO ₂ 98.9 0.434λ 71 Ta ₂ O ₅ 113.8 0.480λ 72 TiO ₂ 100.5 0.264λ 73 Ta ₂ O ₅ 117.8 0.454λ 74 TiO ₂ 100.3 0.441 λ 75 Ta ₂ O ₅ 113.6 0.438 λ 76 TiO ₂ 94.7 0.416λ 77 Ta ₂ O ₅ 113.9 0.439 λ 78 TiO ₂ 104.2 0.458 λ 79 Ta ₂ O ₅ 123.1 0.475λ 80 TiO ₂ 105.5 0.463 λ 81 Ta ₂ O ₅ 119.7 0.480λ 82 TiO ₂ 102.1 0.268 λ 83 Ta ₂ O ₅ 117.4 0.453 λ 84 TiO ₂ 101.9 0.448 λ 85 Ta ₂ O ₅ 120.4 0.464λ 86 TiO ₂ 106.4 0.467λ 87 Ta ₂ O ₅ 124.4 0.480λ 88 TiO ₂ 109.1 0.479 λ 89 Ta ₂ O ₅ 127.6 0.492 λ 90 TiO ₂ 113.9 0.500λ 91 Ta ₂ O ₅ 132.7 0.480λ 92 TiO ₂ 114.5 0.301λ 93 Ta ₂ O ₅ 130.5 0.503 λ 94 TiO ₂ 110.9 0.487λ 95 Ta ₂ O ₅ 122.5 0.472 λ 96 TiO ₂ 105.4 0.463 λ 97 Ta ₂ O ₅ 124.5 0.480λ 98 TiO ₂ 83.1 0.365λ 99 Ta ₂ O ₅ 52.2 0.480λ 100 SiO ₂ 93.0 0.245λ *λ=550nm

[Example 18] In Example 18, an optical filter having a single-layer base material including a transparent resin substrate was produced.

In the same procedure and conditions as in Example 16, a transparent resin substrate containing the compound (S) and the compound (Z) was obtained. Then, use the design parameters in Table 16 to design the dielectric multilayer film, and use the same evaporation conditions to form the silicon dioxide (SiO ₂ ) layer/titanium dioxide (TiO 2 ) layer/titanium dioxide (TiO ₂ ) Dielectric multilayer film (XIX) and dielectric multilayer film (XX) of /Al ₂ O ₃ layers/Ta ₂ O ₅ layers. For the optical filter, evaluations of optical characteristics in each wavelength region, ghosting and color shading of camera images were performed in the same manner as in Example 1. The results are shown in FIG. 24 and Table 17. The dielectric multilayer film (XIX) is a total of 22 layers in which silicon dioxide (SiO ₂ ) layers, titanium dioxide (TiO ₂ ) layers, and Al ₂ O ₃ layers are alternately laminated. The dielectric multilayer film (XX) is a total of 22 layers in which silicon dioxide (SiO ₂ ) layers, Ta ₂ O ₅ layers, and Al ₂ O ₃ layers are alternately laminated.

[Table 16] Dielectric Multilayer Film Floor membrane material Physical film thickness (nm) Optical film thickness (nd) (XIX) 1 SiO ₂ 95.6 0.252λ 2 TiO ₂ 111.4 0.480λ 3 Al ₂ O ₃ 170.8 0.504λ 4 TiO ₂ 110.2 0.484λ 5 Al ₂ O ₃ 164.7 0.486λ 6 TiO ₂ 107.4 0.472 λ 7 Al ₂ O ₃ 165.5 0.488 λ 8 TiO ₂ 108.6 0.477λ 9 Al ₂ O ₃ 163.4 0.482 λ 10 TiO ₂ 104.5 0.459 λ 11 Al ₂ O ₃ 159.8 0.471λ 12 TiO ₂ 105.5 0.464λ 13 Al ₂ O ₃ 163.6 0.482 λ 14 TiO ₂ 107.7 0.473 λ 15 Al ₂ O ₃ 165.1 0.487λ 16 TiO ₂ 109.6 0.481 λ 17 Al ₂ O ₃ 169.1 0.499 λ 18 TiO ₂ 111.9 0.491 λ 19 Al ₂ O ₃ 169.3 0.499 λ 20 TiO ₂ 118.2 0.519 λ twenty one Al ₂ O ₃ 37.6 0.111 λ twenty two TiO ₂ 13.7 0.060λ Substrate (XX) twenty three Ta ₂ O ₅ 11.2 0.049λ twenty four Al ₂ O ₃ 48.7 0.144λ 25 Ta ₂ O ₅ 136.0 0.597λ 26 Al ₂ O ₃ 175.2 0.517λ 27 Ta ₂ O ₅ 131.6 0.578 λ 28 Al ₂ O ₃ 172.0 0.507λ 29 Ta ₂ O ₅ 128.0 0.562 λ 30 Al ₂ O ₃ 167.1 0.493 λ 31 Ta ₂ O ₅ 123.2 0.541 λ 32 Al ₂ O ₃ 161.6 0.477λ 33 Ta ₂ O ₅ 122.3 0.537λ 34 Al ₂ O ₃ 164.8 0.486λ 35 Ta ₂ O ₅ 124.7 0.548 λ 36 Al ₂ O ₃ 165.4 0.488 λ 37 Ta ₂ O ₅ 124.1 0.545 λ 38 Al ₂ O ₃ 164.5 0.485λ 39 Ta ₂ O ₅ 124.2 0.546 λ 40 Al ₂ O ₃ 166.9 0.492 λ 41 Ta ₂ O ₅ 127.5 0.560λ 42 Al ₂ O ₃ 170.5 0.503 λ 43 Ta ₂ O ₅ 129.1 0.480λ 44 SiO ₂ 96.0 0.252λ *λ=550nm

[Table 17] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative example 6 Substrate structure The shape of the substrate (1) (1) (2) (2) (2) (2) (2) (2) (3) (4) (4) (2) (2) (2) (1) (1) (1) (1) (5) (5) (2) (2) (6) (6) Transparent resin substrate or resin layer Transparent resin (mass part) Resin A 100 100 100 100 100 100 100 100 Support body 100 100 100 100 100 100 100 100 100 100 Resin B 100 Resin C 100 Resin D 100 Acrylate※ 100 100 100 Compound (S) (parts by mass) s-1 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 1.00 1.00 1.00 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 s-2 0.08 0.08 0.08 0.08 0.08 0.08 0.08 2.00 2.00 2.00 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 s-3 0.04 Compound (Z) (parts by mass) z-1 0.14 0.14 0.14 0.11 0.11 0.11 0.11 0.12 2.75 3.50 3.50 0.11 0.11 0.11 0.14 0.14 0.14 0.14 0.03 0.03 0.14 0.14 z-2 0.15 0.15 0.15 0.15 3.75 0.15 0.15 0.15 z-3 0.13 Compound (N) (parts by mass) n-1 0.02 0.02 0.50 0.50 n-2 0.15 0.15 0.15 0.15 3.75 0.15 0.15 0.15 solvent (1) (1) (1) (1) (1) (1) (1) (1) (1) - - (2) (2) (3) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) drying conditions (1) (1) (1) (1) (1) (1) (1) (1) (1) - - (2) (2) (3) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) Glass base board - - - - - - - - - Support body Support body - - - - - - - - - - - - - (Transparent) resin layer forming composition - - (1) (1) (1) (1) (1) (1) (A) (B) (B) (1) (1) (1) - - - - (1) (1) (1) (1) (1) (1) Substrate Optical Properties Xa (nm) 690 691 691 691 690 690 690 690 689 690 689 688 688 689 690 690 690 690 702 702 700 700 749 749 Xb (nm) 796 797 797 851 851 851 851 852 851 797 850 852 853 851 796 796 796 796 725 725 729 729 796 796 Difference between Xa and Xb (nm) 106 106 106 160 161 161 161 162 162 107 161 164 165 162 106 106 106 106 twenty three twenty three 29 29 47 47 The average value of the transmittance at a wavelength of 450 nm to 570 nm (%) 88 86 86 87 80 80 80 78 79 85 79 77 76 79 88 88 88 88 90 90 89 89 90 90 Dielectric multilayer film (two-sided structure) Number of layers on one side 18 18 18 18 18 8 0 0 8 8 8 8 8 8 18 twenty two 50 twenty two 18 18 18 18 18 18 Number of layers on one side 18 18 18 18 18 8 0 0 8 8 8 8 8 8 18 twenty two 50 twenty two 28 26 28 26 28 26 Optical Filter Optical Properties The average value of the transmittance at a wavelength of 450 nm to 570 nm (%) 90 88 88 84 77 85 80 78 84 90 85 83 82 84 89 91 84 90 92 91 92 91 93 91 Minimum transmittance Ta in Za (%) less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% Maximum transmittance Tb in Zb (%) 95 62 62 95 70 72 67 64 72 65 71 69 66 69 97 96 93 96 83 92 82 92 75 92 Minimum transmittance Tc in Zc (%) less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% 2 2 2 2 9 2 2 2 3 0.5 1 4 0.3 less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% less than 0.1% ｜Ya-Yb｜（nm） 3 4 4 2 1 1 1 1 2 2 1 1 2 1 3 3 3 3 twenty two 15 20 15 twenty one 9 ｜Yc-Yd｜（nm） 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 2 0 17 43 1 42 3 41 ｜Ye-Yf｜（nm） 38 15 15 41 33 3 2 3 4 3 3 3 3 3 34 36 twenty three 33 39 45 39 45 39 45 Mod Features double image 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 x x △ x △ x color shade 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 x x x x x △

The structures, various compounds, and the like of the substrates used in Examples and Comparative Examples are as follows.

<Form of base material> ･Form (1): Transparent resin substrate containing compound (S) and compound (Z) ･Form (2): Resin layers are formed on both sides of a transparent resin substrate containing compound (S) and compound (Z) ･Form (3): Resin layers containing compound (S) and compound (Z) on both sides of a resin support ･Form (4): A resin layer containing compound (S) and compound (Z) on one side of the glass support ･Form (5): There are resin layers on both sides of a transparent resin substrate containing only the compound (S) (comparative example) ･Form (6): There are resin layers on both sides of a transparent resin substrate containing only compound (Z) (comparative example)

＜Transparent resin＞ ･Resin A: Cyclic olefin-based resin (resin synthesis example 1) ･Resin B: Aromatic polyether resin (resin synthesis example 2) ･Resin C: Polyimide-based resin (resin synthesis example 3) ･Resin D: Cyclic olefin-based resin "Zeonor 1420R" (manufactured by Nippon Zeon Co., Ltd.)

＜Glass support body＞ ･Glass support (1): Transparent glass support "OA-10G (thickness 200 μm)" cut into a size of 60 mm in length and 60 mm in width (manufactured by NEC Glass Co., Ltd.)

"Compound (S)" ･Compound (s-1): a squarylium-based compound represented by the above-mentioned formula (s-1) (absorption maximum wavelength in methylene chloride is 711 nm) ･Compound (s-2): A phthalocyanine compound represented by the above-mentioned formula (s-2) (absorption maximum wavelength in methylene chloride is 736 nm) ･Compound (s-3): A polymethine compound represented by the above-mentioned formula (s-3) (absorption maximum wavelength in methylene chloride is 739 nm)

"Compound (Z)" ･Compound (z-1): A polymethine compound represented by the above-mentioned formula (z-1) (absorption maximum wavelength in methylene chloride is 770 nm) ･Compound (z-2): A polymethine compound represented by the above-mentioned formula (z-2) (absorption maximum wavelength in methylene chloride is 825 nm) ･Compound (z-3): A polymethine compound represented by the above-mentioned formula (z-3) (absorption maximum wavelength in methylene chloride is 825 nm)

"Compound (N)" ･Compound (n-1): A squarylium-based compound represented by the above-mentioned formula (n-1) (absorption maximum wavelength in methylene chloride is 882 nm) ･Compound (n-2): Metal dithioctene complex compound represented by the above formula (n-2) (absorption maximum wavelength in methylene chloride is 1000 nm)

＜Solvent＞ ･Solvent (1): Methane chloride ･Solvent (2): N,N-Dimethylacetamide ･Solvent (3): cyclohexane/xylene (mass ratio: 7/3)

<Drying conditions for transparent resin substrates and resin supports> The drying conditions of the transparent resin substrates and resin supports of Examples and Comparative Examples in Table 17 are as follows. In addition, the coating film was peeled from the glass plate before drying under reduced pressure. ･Condition (1): 20°C/8 hr (time) → 100°C/8 hr under reduced pressure ･Condition (2): 60°C/8 hr→80°C/8 hr→140°C/8 hr under reduced pressure ･Condition (3): 60°C/8 hr→80°C/8 hr→100°C/24 hr under reduced pressure

<Resin layer forming composition> The resin composition which forms the resin layer in the Example of Table 17 is as follows. ･Resin composition (1): 60 parts by mass of tricyclodecane dimethanol acrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, TSC : 30%) ･Resin composition (A): 100 parts by mass of tricyclodecane dimethanol acrylate, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone, 1.0 parts by mass of compound (s-1), 2.0 parts by mass of compound (s-2) 2.75 parts by mass of compound (z-1), 3.75 parts by mass of compound (z-2), 3.75 parts by mass of compound (n-2), methyl ethyl ketone (solvent, TSC: 25%) ･Resin composition (B): 20 parts by mass of tricyclodecane dimethanol acrylate, 80 parts by mass of dipentaerythritol hexaacrylate, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone, 1.0 parts by mass of compound (s-1) , compound (s-2) 2.0 parts by mass, compound (z-1) 3.5 parts by mass, compound (n-1) 0.50 parts by mass, methyl ethyl ketone (solvent, TSC: 35%) [industrial availability]

The optical filter of the present invention can be suitably used in digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automotive cameras, night vision cameras, action Capture, laser distance meter, virtual try-on, license plate recognition device, television, car navigation, personal digital assistant, personal computer, video game console, portable game console, fingerprint authentication system, digital music player, etc.

1: Optical filter or substrate 2: Spectrophotometer 3: light 111: camera image 112: white board 113: Example of central part of white board 114:Example of end of white board

(a) of FIG. 1 is a schematic diagram showing a method of measuring transmittance when measured from a direction perpendicular to a substrate. (b) of FIG. 1 is a schematic diagram showing a method of measuring the transmittance when measured from an angle of 30° with respect to the vertical direction of the substrate on which the dielectric multilayer film is provided. (c) of FIG. 1 is a schematic diagram for explaining color shading evaluation of camera images performed in Examples and Comparative Examples. FIG. 2 is the spectral transmission spectrum of the substrate obtained in Example 1. FIG. FIG. 3 is the spectral transmission spectrum of the substrate provided with the dielectric multilayer film obtained in Example 1. FIG. FIG. 4 is the spectral transmission spectrum of the substrate obtained in Example 2. FIG. FIG. 5 is the spectral transmission spectrum of the substrate provided with the dielectric multilayer film obtained in Example 2. FIG. FIG. 6 is the spectral transmission spectrum of the substrate obtained in Example 4. FIG. 7 is the spectral transmission spectrum of the substrate provided with the dielectric multilayer film obtained in Example 4. FIG. FIG. 8 is the spectral transmission spectrum of the substrate obtained in Example 5. FIG. 9 is the spectral transmission spectrum of the substrate provided with the dielectric multilayer film obtained in Example 5. FIG. 10 is the spectral transmission spectrum of the substrate provided with the dielectric multilayer film obtained in Example 6. FIG. FIG. 11 is the spectral transmission spectrum of the substrate obtained in Example 8. FIG. FIG. 12 is the spectral transmission spectrum of the substrate obtained in Comparative Example 1. FIG. 13 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 1. FIG. 14 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 2. FIG. FIG. 15 is the spectral transmission spectrum of the substrate obtained in Comparative Example 3. FIG. 16 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 3. FIG. 17 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 4. FIG. FIG. 18 is a spectral transmission spectrum of the substrate obtained in Comparative Example 5. FIG. 19 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 5. FIG. 20 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Comparative Example 6. FIG. 21 is the spectral transmission spectrum of the substrate provided with the dielectric multilayer film obtained in Example 15. FIG. 22 is the spectral transmission spectrum of the substrate provided with the dielectric multilayer film obtained in Example 16. FIG. 23 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 17. FIG. 24 is a spectral transmission spectrum of a substrate provided with a dielectric multilayer film obtained in Example 18. FIG.

Claims (12)

A kind of base material, be the base material that has the resin layer that comprises resin and pigment, The substrate satisfies the necessary conditions of (a) and (b) below, The resin layer includes a compound (S) having a maximum absorption wavelength at a wavelength of 620 nm to 760 nm, and a compound (Z) having a maximum absorption wavelength at a wavelength of 761 nm to 850 nm, The substrate transmits at least one of light in the visible region and light in the near-infrared region, (a) In the wavelength region of 600 nm to 950 nm, the transmittance when measured from the direction perpendicular to the substrate is the longest wavelength (Xa) at which the transmittance exceeds 2% and becomes 2% or less, and when measured in the direction perpendicular to the substrate The difference in the shortest wavelength (Xb) at which the transmittance becomes more than 2% from less than 2% is 80 nm or more; (b) The average value of the transmittance when measured from the direction perpendicular to the base material in the wavelength region of 450 nm to 570 nm is 70% or more. The substrate according to claim 1, wherein the compound (Z) is selected from squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, cyanine-based compounds, crotonium-based compounds, and at least one compound in the group consisting of polymethine compounds. The substrate according to claim 1 is formed by including two or more compounds (S) in the resin layer. The substrate as claimed in claim 1, wherein the resin is selected from cyclic (poly)olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene poly Ester-based resins, polycarbonate-based resins, polyamide-based resins, polyarylate-based resins, polyamide-based resins, polyether-based resins, polyparaphenylene-based resins, polyamide-imide-based resins, polynaphthalene Ethylene dicarboxylate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curable resins, silsesquioxane UV curable resins, At least one selected from the group consisting of acrylic ultraviolet curable resin and vinyl ultraviolet curable resin. The substrate according to claim 1, wherein the resin layer is provided on a resin substrate or a glass substrate as a support. The substrate according to claim 1, further comprising a compound (N) having a maximum absorption wavelength in the wavelength region of Xb+50 nm to Xb+250 nm. An optical filter, having the substrate as described in claim 1, and satisfying the following requirement (c), (c) It has a light blocking band Za, a light transmitting band Zb, and a light blocking band Zc in the region with a wavelength of 600 nm or more, and the central wavelength of each band is Za<Zb<Zc, and the value of Za in the vertical direction from the substrate is measured The minimum transmittance when measured in Zb is 1% or less, the maximum transmittance (Tb) when measured from the vertical direction of the substrate in Zb is 45% or more, and the minimum transmittance when measured in the vertical direction from the substrate in Zc is rates are below 15%. The optical filter according to claim 7, wherein the optical filter further satisfies the following necessary condition (d), (d) On the long-wavelength side of the light transmission band Zb, the value (Ye) of the shortest wavelength at which the transmittance when measured from the vertical direction of the optical filter becomes half of the above-mentioned Tb, and the value (Ye) from the vertical direction to the optical filter On the other hand, when the transmittance is measured at an angle of 30°, the absolute value |Ye−Yf| of the difference of the shortest wavelength value (Yf) which is half of Tb is less than 35 nm. The optical filter according to claim 7, wherein at least one side of the substrate has a dielectric multilayer film. The optical filter according to claim 9, wherein the dielectric multilayer film is formed by alternately stacking different material layers, and the difference in refractive index between the material layers is 0.8 or less. A solid-state imaging device, comprising the optical filter as claimed in Claim 7. A camera module, comprising the optical filter described in claim 7.

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