JP7200985B2 - Optical filters, camera modules and electronics - Google Patents

Description

The present invention relates to optical filters, camera modules and electronic devices. More specifically, the present invention relates to an optical filter having specific optical properties, a camera module using the optical filter, and an electronic device having the camera module.

2. Description of the Related Art Solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions use CCD and CMOS image sensors, which are solid-state imaging devices for color images. These solid-state imaging devices use silicon photodiodes in their light receiving portions that are sensitive to near-infrared rays that cannot be detected by the human eye. For these solid-state image sensors, it is necessary to perform luminosity correction so that colors look natural when viewed by the human eye. filter) is often used.

As such near-infrared cut filters, those manufactured by various methods have been conventionally used. For example, a near-infrared cut filter is known in which a transparent resin is used as a base material and a near-infrared absorbing dye is contained in the transparent resin (see, for example, Patent Document 1). However, the near-infrared cut filter described in Patent Document 1 may not necessarily have sufficient near-infrared absorption characteristics.

In Patent Document 2, the present applicant uses a transparent resin substrate containing a near-infrared absorbing dye that has an absorption maximum in a specific wavelength region, so that even if the incident angle is changed, the change in optical characteristics is small, and proposed a near-infrared cut filter with high visible light transmittance. Further, in Patent Document 3, by using a phthalocyanine-based dye having a specific structure, near-infrared light that achieves both excellent visible light transmittance and lengthening of the maximum absorption wavelength at a high level, which has been a problem in the past. It is described that a cut filter can be obtained.

However, in the near-infrared cut filters described in Patent Documents 2 and 3, the base material applied has a sufficiently strong absorption band near 700 nm, but in the near-infrared wavelength region such as 900 to 1200 nm. has almost no absorption. Therefore, light rays in the near-infrared wavelength region are cut only by the reflection of the dielectric multilayer film, but with such a configuration, a small amount of stray light is generated due to internal reflection in the optical filter and reflection between the optical filter and the lens. , it may cause ghosting and flare when shooting in dark environments. In particular, in recent years, there has been a strong demand for high image quality cameras even in mobile devices such as smartphones, and conventional optical filters may not be suitable for use.

On the other hand, as an optical filter using a substrate having broad absorption in the near-infrared wavelength region, an infrared shielding filter as disclosed in Patent Document 4 has been proposed. In Patent Document 4, broad absorption in the near-infrared wavelength region is achieved by mainly applying a compound having a dithiolene structure, but the absorption intensity around 700 nm is not sufficient. In particular, image deterioration due to color shading may occur when used under high incident angle conditions (for example, 45-degree incident angle) as camera modules become thinner in recent years.

Further, Patent Document 5 discloses a near-infrared cut filter having a near-infrared absorbing glass substrate and a layer containing a near-infrared absorbing dye. Sometimes it was not possible. For example, FIG. 5 of Patent Document 5 shows optical characteristic graphs at 0-degree incidence and at 30-degree incidence. ), a large wavelength shift is observed.

JP-A-6-200113 JP 2011-100084 A International publication 2015/025779 pamphlet International publication 2014/168190 pamphlet International publication 2014/030628 pamphlet

In addition to the above-mentioned issues, recently, with the aim of further improving the performance of camera modules, we are considering a new module configuration that separates the functions of the conventional optical filter, which combines the absorption by the dye and the reflection by the dielectric multilayer film, into separate members. Therefore, there is a demand for an optical filter that can accommodate such a configuration.

SUMMARY OF THE INVENTION An object of the present invention is to provide an optical filter capable of simultaneously suppressing color shading and ghosting of a camera image at a high level, which conventional optical filters could not sufficiently achieve.

As a result of intensive studies by the present inventors in order to solve the above problems, in a specific wavelength region, from the vertical direction of the optical filter, the direction diagonal to the vertical direction at 30 degrees, and the direction diagonal to the vertical direction at 60 degrees The minimum value of the transmittance of incident light is all within a specific range, and in a specific wavelength range, the optical filter is perpendicular, 30 degrees oblique to the vertical direction, and 60 degrees oblique to the vertical direction. By using an optical filter whose average optical density (OD value) for light incident from any direction is within a specific range, the desired near-infrared cut characteristics, visible light transmittance, color shading suppression effect, and ghost suppression can be achieved. The inventors have found that the effect can be achieved, and have completed the present invention. Examples of aspects of the invention are provided below.

[1] An optical filter that satisfies the following requirements (a) and (b):
(a) In the wavelength region of 430 to 580 nm, the minimum value T _b-0 of the transmittance of light incident from the vertical direction of the optical filter and the minimum transmittance of light incident from the direction oblique to the vertical direction by 30 degrees The value T _b-30 and the minimum value T _b-60 of the transmittance of light incident from a direction oblique to the vertical direction at 60 degrees are both 55% or more and less than 90%;
(b) In the wavelength range of 700 to 780 nm, the average value OD _a-0 of the optical density for light incident on the optical filter from the vertical direction and the average optical density for light incident at an angle of 30 degrees to the vertical direction. Both the value OD _a-30 and the average value OD _a-60 of optical densities for light incident from a direction oblique to the vertical direction of 60 degrees are 1.8 or more.

[2] The optical filter according to [1], which further satisfies the following requirement (c):
(c) In the wavelength range of 900 to 1200 nm, the average transmittance T _IR of light incident on the optical filter in the vertical direction is 60% or more.

[3] The optical filter according to item [1] or [2] that further satisfies the following requirement (d):
(d) In the wavelength range of 430 to 580 nm, the average value T _a-0 of the transmittance of light incident on the optical filter in the vertical direction and the average transmittance of light incident from the direction oblique to the vertical direction at 30 degrees. The value Ta _-30 and the average value _Ta-60 of the transmittance of light incident from a direction oblique to the vertical direction at 60 degrees are both 65% or more and less than 90%.

[4] The optical filter according to any one of items [1] to [3], which contains a substrate that satisfies the following requirement (e):
(e) A layer containing a compound (A) having an absorption maximum in the wavelength range of 650 to 800 nm.

[5] The optical filter according to item [4], wherein the substrate further satisfies the following requirement (f):
(f) At a wavelength of 600 to 900 nm, the wavelength X _a on the longest wavelength side at which the transmittance for light incident from the vertical direction of the substrate is from more than 10% to 10% or less from the short wavelength side to the long wavelength side. and the absolute value of the difference between the wavelength X _b on the shortest wavelength side at which the transmittance for light incident from the vertical direction of the substrate is 10% or less to more than 10% from the short wavelength side to the long wavelength side | X _b −X _a | is 100 nm or more.

[6] An item characterized in that the compound (A) is at least one compound selected from the group consisting of squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, croconium-based compounds, and cyanine-based compounds. The optical filter according to [4] or [5].

[7] The base material includes, as the compound ( A ), a compound (Aa) having an absorption maximum in a wavelength range of 650 nm or more and 715 nm or less, a compound having an absorption maximum in a wavelength range of more than 715 nm and 750 nm or less ( Ab), and the optical filter according to any one of items [4] to [6], characterized by containing a compound (Ac) having an absorption maximum in a wavelength range of more than 750 nm and not more than 800 nm. .

[8] The optical filter according to any one of items [4] to [7], wherein the layer containing the compound (A) is a transparent resin layer.

[9] The resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, or an aramid resin. , polysulfone-based resin, polyethersulfone-based resin, polyparaphenylene-based resin, polyamideimide-based resin, polyethylene naphthalate-based resin, fluorinated aromatic polymer-based resin, (modified) acrylic-based resin, epoxy-based resin, silsesqui Oxane-based UV-curable resin, maleimide-based resin, alicyclic epoxy thermosetting resin, polyetheretherketone-based resin, polyarylate-based resin, allyl ester-based curable resin, acrylic-based UV-curable resin, vinyl-based UV-curable resin Item [8], wherein the optical filter is at least one resin selected from the group consisting of mold resins and resins containing silica as a main component formed by a sol-gel method.

[10] The optical filter according to item [8] or [9], wherein the resin constituting the transparent resin layer has a refractive index (n20d) of 1.50 to 1.53.

[11] A camera module comprising the optical filter according to any one of items [1] to [10].

[12] The camera module according to item [ 11 ], further comprising a cover member for protecting the internal mechanism of the camera module from the outside, wherein the cover member has a near-infrared ray reflecting function.

[13] An electronic device comprising the camera module according to item [10].

According to the present invention, it is possible to provide an optical filter which is excellent in near-infrared cut properties, less dependent on incident angles, and excellent in transmittance properties in the visible light wavelength range, color shading suppression effect, and ghost suppression effect.

FIG. 10 is a diagram showing a configuration for measuring transmission spectra in a vertical direction, a 30-degree oblique direction, and a 60-degree oblique direction; FIG. 3 is a schematic diagram showing the configuration of a camera module used for color shading evaluations performed in Examples and Comparative Examples; FIG. 4 is a schematic diagram for explaining color shading evaluation of camera images performed in Examples and Comparative Examples; FIG. 5 is a schematic diagram for explaining ghost evaluation of camera images performed in Examples and Comparative Examples. 4 is a spectral transmission spectrum of the optical filter obtained in Example 1. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 2. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 3. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 4. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 5. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 6. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 7. FIG. 3 is a spectral transmission spectrum of the optical filter obtained in Example 8. FIG. 3 is a spectral transmission spectrum of the optical filter obtained in Example 9. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 10. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Example 11. FIG. 3 is a spectral transmission spectrum of the optical filter obtained in Example 15. FIG. 10 is a spectral transmission spectrum of the optical filter obtained in Example 16. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 1. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 2. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 3. FIG. 4 is a spectral transmission spectrum of the optical filter obtained in Comparative Example 4. FIG.

An optical filter, a camera module using the optical filter, and an electronic device having the camera module according to the present invention will be described below in detail.

[Optical filter]
The optical filter of the present invention is characterized by satisfying requirements (a) and (b) below, and preferably satisfies requirements ( c ) and/or ( d ) below.
(a) In the wavelength region of 430 to 580 nm, the minimum value T _b-0 of the transmittance of light incident from the vertical direction of the optical filter and the minimum transmittance of light incident from the direction oblique to the vertical direction by 30 degrees The value T _b-30 and the minimum value T _b-60 of the transmittance of light incident from a direction oblique to the vertical direction at 60 degrees are both 55% or more and less than 90%.
(b) In the wavelength range of 700 to 780 nm, the average value OD _a-0 of the optical density for light incident on the optical filter from the vertical direction and the average optical density for light incident at an angle of 30 degrees to the vertical direction. Both the value OD _a-30 and the average value OD _a-60 of optical densities for light incident from a direction oblique to the vertical direction of 60 degrees are 1.8 or more.
(c) In the wavelength range of 900 to 1200 nm, the average transmittance T _IR of light incident on the optical filter in the vertical direction is 60% or more.
(d) In the wavelength range of 430 to 580 nm, the average value T _a-0 of the transmittance of light incident on the optical filter in the vertical direction and the average transmittance of light incident from the direction oblique to the vertical direction at 30 degrees. The value Ta _-30 and the average value _Ta-60 of the transmittance of light incident from a direction oblique to the vertical direction at 60 degrees are both 65% or more and less than 90%.

Each requirement will be explained below.

<Requirement (a)>
The T _b-0 and the T _b-30 are preferably 63% or more and 86% or less, more preferably 67% or more and 82% or less, and the T _b-60 is preferably 58% or more and 80% or less. More preferably, it is 60% or more and 75% or less.

As a method of satisfying the requirement (a), that is, a method of adjusting the minimum value of each transmittance, for example, the type and addition amount of the compound (A) described later are adjusted so that the minimum value of the transmittance within a specified range is obtained. A method of appropriately selecting and adjusting is included.

By satisfying the requirement (a), a high-quality camera image can be obtained because the change in RGB balance is small even at high incident angles such as 30 degrees and 60 degrees.

<Requirement (b)>
The OD _a-0 and the OD _a-30 are preferably 1.8 or more and 4.0 or less, more preferably 1.9 or more and 3.5 or less, and the OD _a-60 is preferably 2.1. 4.5 or less, more preferably 2.2 or more and 4.0 or less.

As a method of satisfying the requirement (b), that is, a method of adjusting the average optical density (OD value), for example, the type and A method of appropriately selecting and adjusting the amount to be added is included.

By satisfying the requirement (b), the optical filter can sufficiently cut not only the near-infrared rays transmitted in the vertical direction but also the near-infrared rays transmitted at high incident angles, so that there is no or reduced color shading. A camera image can be obtained.

Here, the OD value is a common logarithmic value of transmittance and can be calculated by the following formula (1). A high average OD value for a given wavelength range indicates that the optical filter has high cut properties for light in that wavelength range.

Average OD value in a certain wavelength range=-Log ₁₀ (Average transmittance (%) in a certain wavelength range/100) Equation (1)
<Requirement (c)>
The _TIR is preferably 70% to 98%, more preferably 80% to 95%, even more preferably 85% to 94%, and particularly preferably 89% to 93%.

As a method of satisfying the requirement (c), that is, a method of adjusting the average value of light transmittance, for example, the type and addition amount of the compound (A) described later are appropriately selected and added so that the transmittance in the specified range is obtained. There is a method of adjustment.

By satisfying the requirement (c), the transmittance in the near-infrared region is high and the reflected light in the near-infrared region can be reduced, so that a camera image with reduced ghost can be obtained.

<Requirement (d)>
The _Ta-0 is preferably 73% or more and 88% or less, more preferably 76% or more and 86% or less, and the _Ta-30 is preferably 72% or more and 87% or less, more preferably 75% or more. 85% or less, and the _Ta-60 is preferably 68% or more and 85% or less, more preferably 70% or more and 80% or less.

As a method of satisfying the requirement (d), that is, a method of adjusting the average value of each transmittance, for example, the type and addition amount of the compound (A) described later are adjusted so as to obtain the average value of the transmittance within a specified range. A method of appropriately selecting and adjusting is included.

By satisfying the requirement (d), a high-quality camera image can be obtained because the change in RGB balance is small even at high incident angles such as 30 degrees and 60 degrees.

<Thickness of optical filter>
The thickness of the optical filter of the present invention is preferably 210 µm or less, more preferably 190 µm or less, still more preferably 160 µm or less, and particularly preferably 130 µm or less.

[Base material]
The configuration of the optical filter of the present invention is not particularly limited as long as an optical filter exhibiting the optical properties described above can be obtained. f) is preferably satisfied.
(e) A layer containing a compound (A) having an absorption maximum in the wavelength range of 650 to 800 nm.
(f) At a wavelength of 600 to 900 nm, the wavelength X _a on the longest wavelength side at which the transmittance for light incident from the vertical direction of the substrate is from more than 10% to 10% or less from the short wavelength side to the long wavelength side. and the absolute value of the difference between the wavelength X _b on the shortest wavelength side at which the transmittance for light incident from the vertical direction of the substrate is 10% or less to more than 10% from the short wavelength side to the long wavelength side | X _b −X _a | is 100 nm or more.

Each requirement will be explained below.

<Requirement (e)>
In the requirement (e), the component constituting the layer containing the compound (A) is not particularly limited. From the viewpoint of compatibility with A), a transparent resin is preferable.

The substrate may be a single layer or multiple layers as long as it has a layer containing the compound (A).

<Requirement (f)>
The difference |X _b −X _a | between the wavelengths X _a and X _b is preferably 110 nm or more, more preferably 115 nm or more, even more preferably 120 nm or more, and particularly preferably 125 nm or more. The upper limit is not particularly limited, but if the value is too large, the visible light transmittance may decrease depending on the properties of the compound (A) or other near-infrared absorbents. If the difference |X _b −X _a | This is preferable because color shading can be suppressed even under conditions where the incident angle is large, such as degrees.

The wavelength value (X _a +X _b )/2 between X _a and X _b can be said to be the central wavelength of the absorption band in the near-infrared wavelength region close to the visible light region, preferably 650 nm or more and 850 nm or less, more preferably is 680 nm or more and 820 nm or less, more preferably 700 nm or more and 800 nm or less. When the wavelength value represented by (X _a +X _b )/2 is within the above range, light in the wavelength region near the long wavelength end of the visible light region can be cut more efficiently, which is preferable.

Xa preferably has _a wavelength of 610 nm or more and 720 nm or less, more preferably a wavelength of 625 nm or more and 710 nm or less, and even more preferably a wavelength of 630 nm or more and 700 nm or less. When X _a is in such a range, it is preferable because there is a tendency to obtain a camera image with less noise and excellent color reproducibility.

<Thickness of base material>
The thickness of the substrate can be appropriately selected according to the desired application, and is not particularly limited, but is preferably 10 to 200 μm, more preferably 20 to 180 μm, still more preferably 25 to 150 μm. When the thickness of the base material is within the above range, the optical filter using the base material can be made thinner and lighter, and can be suitably used for various applications such as solid-state imaging devices. In particular, when the substrate made of the transparent resin substrate is used for a lens unit such as a camera module, the lens unit can be reduced in height and weight, which is preferable.

<<Compound (A)>>
The compound (A) is not particularly limited as long as it has an absorption maximum in the wavelength range of 650 to 800 nm, but at least it is selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds and cyanine compounds. One type of compound is preferable, and squarylium-based compounds, phthalocyanine-based compounds and cyanine-based compounds are particularly preferable. In addition, compound (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

A squarylium-based compound has excellent visible light transmittance, steep absorption characteristics, and a high molar extinction coefficient, but it may generate fluorescence that causes scattered light when absorbing light. In such a case, by using a combination of the squarylium-based compound and the other compound (A), an optical filter with less scattered light and better camera image quality can be obtained.

The maximum absorption wavelength of compound (A) is preferably 660 nm or more and 795 nm or less, more preferably 680 nm or more and 790 nm or less.

The compound (A) is not particularly limited as long as it has an absorption maximum in the wavelength region of 650 to 800 nm, but from the viewpoint of heat resistance of the optical filter, a compound (Aa ), a compound (Ab) having an absorption maximum in a wavelength region of more than 715 nm and 750 nm or less, and a compound (Ac) having an absorption maximum in a wavelength region of more than 750 nm and 800 nm or less. . When the compound (A) has such a structure, the near-infrared absorption band can be efficiently widened while minimizing the decrease in visible light transmittance. It is preferable because it tends to improve the weather resistance.

When the compound (A) is a combination of two or more compounds, the difference in absorption maximum wavelength between the compound (A) having the shortest absorption maximum wavelength and the longest absorption maximum wavelength is preferably 20 to 20. It is 100 nm, more preferably 30-90 nm, still more preferably 40-80 nm. When the difference in maximum absorption wavelength is within the above range, scattered light due to fluorescence can be sufficiently reduced, and both a wide absorption band around 700 nm and excellent visible light transmittance can be achieved, which is preferable.

The content of the compound (A) as a whole is, for example, a substrate made of a transparent resin substrate containing the compound (A), or a curable resin on a transparent resin substrate containing the compound (A). When using a base material laminated with a resin layer such as an overcoat layer made of etc., it is preferably 0.04 to 2.0 parts by mass, more preferably 0.06 to 100 parts by mass of the transparent resin. It is 1.5 parts by mass, more preferably 0.08 to 1.0 parts by mass, and the substrate contains the compound (A) on a support such as a glass support or a base resin support. In the case of using a substrate laminated with a transparent resin layer such as an overcoat layer made of a curable resin or the like, it is preferably 0.00 to 100 parts by mass of the resin forming the transparent resin layer containing the compound (A). 4 to 5.0 parts by mass, more preferably 0.6 to 4.0 parts by mass, still more preferably 0.8 to 3.5 parts by mass.

(squarylium-based compound)
The squarylium-based compound is not particularly limited, but at least one selected from the group consisting of a squarylium-based compound represented by the following formula (I) and a squarylium-based compound represented by the following formula (II): are preferred. Hereinafter, they are also referred to as "compound (I)" and "compound (II)", respectively.

式（Ｉ）中、Ｒ^a、Ｒ^bおよびＹａは、下記条件（α）または（β）を満たす。

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

Condition (α):
each of a plurality of R ^a independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L ¹ or -NR ^e R ^f group;
each of a plurality of R ^b independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L ¹ or -NR ^g R ^h group;
each of a plurality of Ya's independently represents a -NR ^j R ^k group;
L ¹ represents L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h ;
R ^e and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ;
R ^g and R ^h are each independently a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C(O)R ⁱ group (R ⁱ is -L ^a , represents -L ^b , -L ^c , -L ^d or -L ^e );
R ^j and R ^k each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ;
L ^a represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L;
L ^b represents a halogen-substituted alkyl group having 1 to 12 carbon atoms which may have a substituent L;
L ^c represents an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L;
L ^d represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent L;
L ^e represents a heterocyclic group having 3 to 14 carbon atoms which may have a substituent L;
L ^f represents an alkoxy group having 1 to 9 carbon atoms which may have a substituent L;
L ^g represents an acyl group having 1 to 9 carbon atoms which may have a substituent L;
L ^h represents an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L;
L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms. , a heterocyclic group having 3 to 14 carbon atoms, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group and an amino group.

Condition (β):
At least one of the two R ^a on one benzene ring is mutually bonded to Y on the same benzene ring to form a 5- or 6-membered heterocyclic ring containing at least one nitrogen atom;
The heterocyclic ring may have a substituent, and R ^b and R ^a that does not participate in the formation of the heterocyclic ring are each independently synonymous with R ^b and R ^a in the condition (α).

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

Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms in L ^a and L include methyl group (Me), ethyl group (Et), n-propyl group (n-Pr), isopropyl group (i-Pr ), n-butyl group (n-Bu), sec-butyl group (s-Bu), tert-butyl group (t-Bu), pentyl group, hexyl group, octyl group, nonyl group, decyl group and dodecyl group, etc. alkenyl groups such as vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, 2-pentenyl group, hexenyl group and octenyl group and alkynyl groups such as ethynyl, propynyl, butynyl, 2-methyl-1-propynyl, hexynyl and octynyl groups.

Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms in L ^b and L include trichloromethyl group, trifluoromethyl group, 1,1-dichloroethyl group, pentachloroethyl group, pentafluoroethyl group, heptachloro Mention may be made of propyl and heptafluoropropyl groups.

Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms in L ^c and L include cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; norbornane group and adamantane group; and polycyclic alicyclic groups such as

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L ^d and L include phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, Mention may be made of phenanthryl, acenaphthyl, phenalenyl, tetrahydronaphthyl, indanyl and biphenylyl radicals.

Examples of heterocyclic groups having 3 to 14 carbon atoms in L ^e and L include furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, thiadiazole, indole, indoline, indolenine, and benzofuran. , benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, acridine, morpholine and phenazine.

Examples of the alkoxy group having 1 to 12 carbon atoms in L ^f include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group and an octyloxy group. can.

Examples of the acyl group having 1 to 9 carbon atoms in L ^g include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group and benzoyl group.

Examples of the alkoxycarbonyl group having 1 to 9 carbon atoms in L ^h include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group and octyl Oxycarbonyl groups may be mentioned.

L ^a is preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 4-phenylbutyl 2-cyclohexylethyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

L ^b is preferably a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, or a 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, more preferably trichloro A methyl group, a pentachloroethyl group, a trifluoromethyl group, and a pentafluoroethyl group.

L ^c is preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cyclooctyl group, or a 4-phenylcycloheptyl group, and more preferably a cyclopentyl group, a cyclohexyl group, or a 4-ethylcyclohexyl group. is.

L ^d is preferably a phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 3,5-di-tert-butylphenyl group, 4-cyclopentylphenyl group. , 2,3,6-triphenylphenyl group and 2,3,4,5,6-pentaphenylphenyl group, more preferably phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,3 , 4,5,6-pentaphenylphenyl group.

L ^e is preferably a group consisting of furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene and morpholine, more preferably a group consisting of furan, thiophene, pyrrole and morpholine.

L ^f is preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a methoxymethyl group, a methoxyethyl group, a 2-phenylethoxy group, a 3-cyclohexylpropoxy group, a pentyloxy group and a hexyloxy group. octyloxy group, more preferably methoxy group, ethoxy group, propoxy group, isopropoxy group and butoxy group.

L ^g is preferably acetyl group, propionyl group, butyryl group, isobutyryl group, benzoyl group, 4-propylbenzoyl group or trifluoromethylcarbonyl group, more preferably acetyl group, propionyl group or benzoyl group. .

The L ^h is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group, more preferably Methoxycarbonyl group and ethoxycarbonyl group.

The L ^a to L ^h further have at least one atom or group selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group and an amino group. may Examples of such include 4-sulfobutyl, 4-cyanobutyl, 5-carboxypentyl, 5-aminopentyl, 3-hydroxypropyl, 2-phosphorylethyl, 6-amino-2,2-dichloro hexyl group, 2-chloro-4-hydroxybutyl group, 2-cyanocyclobutyl group, 3-hydroxycyclopentyl group, 3-carboxycyclopentyl group, 4-aminocyclohexyl group, 4-hydroxycyclohexyl group, 4-hydroxyphenyl group, pentafluorophenyl group, 2-hydroxynaphthyl group, 4-aminophenyl group, 4-nitrophenyl group, group consisting of 3-methylpyrrole, 2-hydroxyethoxy group, 3-cyanopropoxy group, 4-fluorobenzoyl group, 2 -hydroxyethoxycarbonyl group and 4-cyanobutoxycarbonyl group.

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

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

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

At least one of the two R ^a on one benzene ring in the condition (β) of the formula (I) has at least one nitrogen atom formed by mutual bonding with Y on the same benzene ring Examples of heterocyclic rings containing 5 or 6 atoms include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine and pyrazine. Among these heterocyclic rings, preferred are heterocyclic rings in which one atom adjacent to the carbon atom forming the benzene ring is a nitrogen atom, and pyrrolidine is more preferred.

式（ＩＩ）中、Ｘは独立に、Ｏ、Ｓ、Ｓｅ、Ｎ－Ｒ^cまたはＣ（Ｒ^dＲ^d）を表し；複数あるＲ^cはそれぞれ独立に、水素原子、Ｌ^a、Ｌ^b、Ｌ^c、Ｌ^dまたはＬ^eを表し；複数あるＲ^dはそれぞれ独立に、水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、－Ｌ¹または－ＮＲ^eＲ^f基を表し、隣り合うＲ^d同士は連結して置換基を有していてもよい環を形成してもよく；Ｌ^a～Ｌ^e、Ｌ¹、Ｒ^eおよびＲ^fは、前記式（Ｉ）において定義したＬ^a～Ｌ^e、Ｌ¹、Ｒ^eおよびＲ^fと同義である。

In formula (II), X independently represents O, S, ^Se , N—R ^c or ^C (R ^d R ^{d )} ; represents L ^c , L ^d or L ^e ; each of a plurality of R ^d is independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L ¹ or -NR; ^e represents an R ^f group, and adjacent R ^d may be linked to form a ring optionally having a substituent; L ^a to L ^e , L ¹ , R ^e and R ^f are the It is synonymous with L ^a to L ^e , L ¹ , R ^e and R ^f defined in formula (I).

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

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

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

In the above formula (II), adjacent R ^d may be linked to form a ring. Examples of such rings include benzoindolenine ring, α-naphthimidazole ring, β-naphthimidazole ring, α-naphthoxazole ring, β-naphthoxazole ring, α-naphthothiazole ring, β-naphthothiadiazole ring, Examples include α-naphthoselenazole ring and β-naphthoselenazole ring.

Compound (I) and compound (II) can be obtained by the following formula (I-2) and the following formula (II-2) in addition to the description methods such as the following formula (I-1) and the following formula (II-1). The structure can also be represented by a description method such as taking a resonance structure. That is, the difference between the following formula (I-1) and the following formula (I-2), and the difference between the following formula (II-1) and the following formula (II-2) are only the method of describing the structure. also represent the same compound. In the present invention, unless otherwise specified, structures of squarylium-based compounds are represented by methods of description such as the following formulas (I-1) and (II-1) below.

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

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

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

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

Specific examples of the compounds (I) and (II) include compounds (a-1) described in Tables 1 to 3 below, which have basic skeletons represented by the following formulas (IA) to (IH): ) to (a-36).

前記化合物（Ｉ）および（ＩＩ）は、一般的に知られている方法で合成すればよく、例えば、特開平１－２２８９６０号公報、特開２００１－４０２３４号公報、特許第３１９６３８３号公報等に記載されている方法などを参照して合成することができる。

The compounds (I) and (II) may be synthesized by a generally known method. Synthesis can be performed by referring to the described methods and the like.

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

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

In formula (III), M represents a substituted metal atom containing two hydrogen atoms, two monovalent metal atoms, divalent metal atoms, or trivalent or tetravalent metal atoms, and a plurality of R _a , R _b , R _c and R _d each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , -S -L ² , -SS-L ² , -SO ₂ -L ³ , -N=N-L ⁴ or at least one combination of R _a and R _b , R _b and R _c and R _c and R _d represents at least one group selected from the group consisting of groups represented by formulas (A) to (H) below. However, at least one of R _a , R _b , R _c and R _d bonded to the same aromatic ring is not a hydrogen atom.

The amino group, amide group, imide group and silyl group may have the substituent L defined in the formula (I),
L ¹ has the same definition as L ¹ defined in formula (I) above,
L ² represents a hydrogen atom or any of L ^a to L ^e defined in formula (I) above;
L ³ represents a hydroxyl group or any one of L ^a to L ^e ;
L ⁴ represents any one of the above L ^a to L ^e .

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

In formulas (A) to (H), R _x and R _y represent carbon atoms, and a plurality of R _A to R _L each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amide group, imido group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N=N-L ⁴ ; The groups and silyl groups may have a substituent L defined in formula (I) above, and L ¹ to L ⁴ have the same definitions as L ¹ to L ⁴ defined in formula (III) above.

In the above R _a to R _d and R _A to R _L , the amino group which may have a substituent L includes an amino group, an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group and a diisopropylamino group. and the like.

In the above R _a to R _d and R _A to R _L , the amide group which may have a substituent L includes an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group, a diisopropylamide group, dibutylamide group, α-lactam group, β-lactam group, γ-lactam group, δ-lactam group and the like.

In R _a to R _d and R _A to R _L , the imide group which may have a substituent L includes an imide group, a methylimide group, an ethylimide group, a diethylimide group, a dipropylimide group, a diisopropylimide group, A dibutylimide group and the like can be mentioned.

Examples of the silyl group which may have a substituent _L in R _a to R _d and R _A to R L include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and a triethylsilyl group. .

In the above R _a to R _d and R _A to R _L , —SL ² is a thiol group, methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, isobutyl sulfide group, sec-butyl sulfide group. , tert-butylsulfide group, phenylsulfide group, 2,6-di-tert-butylphenylsulfide group, 2,6-diphenylphenylsulfide group, 4-cumylphenylsulfide group and the like.

In the aforementioned R _a to R _d and R _A to R _L , —SS—L ² is disulfide group, methyl disulfide group, ethyl disulfide group, propyl disulfide group, butyl disulfide group, isobutyl disulfide group, sec-butyl disulfide group. , tert-butyl disulfide group, phenyl disulfide group, 2,6-di-tert-butylphenyl disulfide group, 2,6-diphenylphenyl disulfide group, 4-cumylphenyl disulfide group and the like.

In the aforementioned R _a to R _d and R _A to R _L , —SO ₂ —L ³ includes sulfo group, mesyl group, ethylsulfonyl group, n-butylsulfonyl group, p-toluenesulfonyl group and the like.

In the above R _a to R _d and R _A to R _L , —N═N—L ⁴ includes a methylazo group, a phenylazo group, a p-methylphenylazo group, a p-dimethylaminophenylazo group and the like.

Examples of monovalent metal atoms in M include Li, Na, K, Rb, and Cs.

In M, the divalent metal atoms include Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd, Hg, Sn, Pb etc. are mentioned.

In M, the substituted metal atoms containing trivalent metal atoms include Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, Ga-I, In -F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Fe-Cl, Ru-Cl, Mn-OH and the like.

In M, the substitutional metal atoms containing tetravalent metal atoms include TiF ₂ , TiCl ₂ , TiBr ₂ , TiI ₂ , ZrCl ₂ , HfCl ₂ , CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , _GeF2 , GeCl2, _GeBr2 , _GeI2 , SnF2, SnCl2, _SnBr2 , _SnI2 , Zr(OH) ₂ , Hf(OH) ₂ , Mn ₍ OH) ₂ , Si ₍ OH) ₂ , Ge ₍ OH) ₂ , Sn(OH) ₂ , _TiR2 , _CrR2 , _SiR2 , GeR2, _SnR2 , Ti(OR) ₂ , Cr(OR) ₂ , Si(OR) ₂ , Ge _{(OR)2 ,} Sn (OR) ₂ (R represents an aliphatic group or an aromatic group), TiO, VO, MnO and the like.

The M is a divalent transition metal, trivalent or tetravalent metal halide or tetravalent metal oxide belonging to Groups 5 to 11 of the periodic table and Period 4 to Period 5. Among them, Cu, Ni, Co and VO are particularly preferable because they can achieve high visible light transmittance and stability.

The phthalocyanine-based compound is generally known to be synthesized by a cyclization reaction of a phthalonitrile derivative such as the following formula (V). It is a mixture of four isomers such as VI-4). In the present invention, unless otherwise specified, only one isomer per phthalocyanine compound is exemplified, but the other three isomers can also be used in the same manner. Although these isomers can be separated and used as necessary, the isomer mixture is collectively treated in the present invention.

前記化合物（ＩＩＩ）の具体例としては、下記式（ＩＩＩ－Ａ）～（ＩＩＩ－Ｊ）で表わされる基本骨格を有する、下記表４～７に記載の（ｂ－１）～（ｂ－５６）などを挙げることができる。

Specific examples of the compound (III) include (b-1) to (b- 56 ) described in Tables 4 to 7 below, which have basic skeletons represented by formulas (III-A) to (III-J) below. ) and the like.

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

Compound (III) may be synthesized by a generally known method, for example, the method described in Japanese Patent No. 4081149 or "Phthalocyanine - Chemistry and Function -" (IPC, 1997). Can be referenced and synthesized.

(cyanine compound)
The cyanine compound is not particularly limited, but compounds represented by any of the following formulas (IV-1) to (IV-3) (hereinafter referred to as "compounds (IV-1) to (IV-3 )”.) is preferred.

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

In formulas (IV-1) to (IV-3), X _a ^- represents a monovalent anion, multiple Ds independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and multiple R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, imido group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ³ , -SO ₂ -L ³ , -N=N-L ⁴ , or R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h , and R _h and R _i are combined, represented by the formulas (A) to (H) represents at least one group selected from the group consisting of groups, the amino group, amido group, imide group and silyl group may have the substituent L defined in the formula (I),
L ¹ has the same definition as L ¹ defined in formula (I) above,
L ² represents a hydrogen atom or any of L ^a to L ^e defined in formula (I) above;
L ³ represents a hydrogen atom or any one of L ^a to L ^e ;
L ⁴ represents any one of L ^a to L ^e ;
Z _a to Z _c and Y _a to Y _d each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ , - SL ² , -SS-L ² , -SO ₂ -L ³ , -N=N-L ⁴ (L ¹ to L ⁴ have the same meanings as L ¹ to L ⁴ in R _a to R _i above. ), or an aromatic hydrocarbon group having 6 to 14 carbon atoms, formed by mutually bonding Zs or Ys selected from two adjacent ones of these; a nitrogen atom, an oxygen atom or a sulfur atom a 5- to 6-membered alicyclic hydrocarbon group which may contain at least one; or a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, These aromatic hydrocarbon groups, alicyclic hydrocarbon groups and heteroaromatic hydrocarbon groups may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms formed by mutual bonding between Zs or Ys in Z _a to Z _c and Y _a to Y _d include Compounds exemplified for the aromatic hydrocarbon group can be mentioned.

a 5- to 6-membered ring optionally containing at least one nitrogen atom, oxygen atom or sulfur atom, formed by mutually bonding Zs or Ys in Z _a to Z _c and Y _a to Y _d ; The alicyclic hydrocarbon group includes, for example, the compounds exemplified for the alicyclic hydrocarbon group and the heterocyclic ring in the substituent L (excluding the heteroaromatic hydrocarbon group).

Examples of the heteroaromatic hydrocarbon group having 3 to 14 carbon atoms, which is formed by mutually bonding Zs or Ys in Z _a to Z _c and Y _a to Y _d , include the substituent L (excluding alicyclic hydrocarbon groups containing at least one nitrogen atom, oxygen atom or sulfur atom) exemplified as the heterocyclic group in .

In formulas (IV-1) to (IV-3), —SL ² , —SS-L ² , —SO ₂ —L ³ , —N=NL ⁴ , substituent L Examples of the good amino group, amido group, imide group and silyl group include the same groups as those exemplified in formula (III) above.

X _a ^- is not particularly limited as long as it is a monovalent anion, but I ^- , Br ^- , PF ₆ ^- , N(SO ₂ CF ₃ ) ₂ ^- , B(C ₆ F ₅ ) ₄ ^- , nickel dithiolate and copper dithiolate-based complexes.

Specific examples of the compounds (IV-1) to (IV-3) include (c-1) to (c-24) shown in Table 8 below.

前記化合物（ＩＶ－１）～（ＩＶ－３）は、一般的に知られている方法で合成すればよく、たとえば特開２００９－１０８２６７号公報に記載されている方法で合成することができる。

The compounds (IV-1) to (IV-3) may be synthesized by a generally known method, for example, by the method described in JP-A-2009-108267.

<Transparent resin>
The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. Resins having a temperature of 380°C, more preferably 110 to 370°C, and even more preferably 120 to 360°C are mentioned. In addition, the glass transition temperature of the resin is preferably 140° C. or higher, more preferably 230° C. or higher, because it is suitable for the reflow process.

The refractive index (n20d) of the transparent resin is particularly preferably 1.53 or less. A transparent resin having a refractive index (n20d) of more than 1.53 tends to have many aromatic rings in the molecule. Too much and may deteriorate the weather resistance.

As the transparent resin, when a resin plate having a thickness of 0.1 mm is formed from the resin, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95. %, particularly preferably 80 to 95%. If a resin having a total light transmittance within such a range is used, the obtained substrate exhibits good transparency as an optical film.

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

Examples of transparent resins include cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polysulfone resins, poly Ethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane ultraviolet curable resins resins, maleimide resins, alicyclic epoxy thermosetting resins, polyetheretherketone resins, polyarylate resins, allyl ester curing resins, acrylic ultraviolet curing resins, vinyl ultraviolet curing resins, and by the sol-gel method Mention may be made of the formed silica-based resins. Among these, cyclic polyolefin resin, aromatic polyether resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, and polyarylate resin are used to improve transparency (optical properties), heat resistance, and reflow resistance. A cyclic polyolefin resin is particularly preferable from the viewpoint of the refractive index of the resin. The transparent resin may be used singly or in combination of two or more.

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

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

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

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

In formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i′) to (vi′), or R ^y1 and R ^y2 are mutually bonded to Each of k ^y and p ^y independently represents an integer from 0 to 4, representing a formed monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring.

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

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

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

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

In formula (2), R ¹ to R ⁴ and a to d are each independently defined as R ¹ to R ⁴ and a to d in formula ( ₁ ) above; Y is a single bond; - or -CO-, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, g and h each independently represent 0 to 4 It represents an integer, and m represents 0 or 1. However, when m is 0, ^R7 is not a cyano group.

In addition, the aromatic polyether-based resin further has at least one structural unit selected from the group consisting of structural units represented by the following formula (3) and structural units represented by the following formula (4). is preferred.

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

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

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

In formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in formula (2); ⁵ , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in the above formula (3).

≪Polyimide resin≫
The polyimide resin is not particularly limited as long as it is a polymer compound containing an imide bond in a repeating unit. Can be synthesized.

≪Fluorene polycarbonate resin≫
The fluorene polycarbonate-based resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety.

≪Fluorene polyester resin≫
The fluorene polyester-based resin is not particularly limited, and may be a polyester resin containing a fluorene moiety. can be done.

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

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

≪Epoxy resin≫
Epoxy-based resins are not particularly limited, but can be broadly classified into ultraviolet-curable and heat-curable types. As the UV-curable epoxy resin, for example, it is synthesized from a composition containing a compound having one or more epoxy groups in the molecule and a compound that generates an acid when exposed to UV rays (hereinafter also referred to as a "photoacid generator"). Examples of thermosetting epoxy resins include those synthesized from a composition containing a compound having one or more epoxy groups in the molecule and an acid anhydride. can be done. The epoxy UV-curable resin contains, as the base material, a base material in which a transparent resin layer containing the compound (A) is laminated on a glass support or a base resin support, or a base material containing the compound (A). When using a substrate in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate, the curable resin can be particularly preferably used.

<<Resin mainly composed of silica formed by sol-gel method>>
Silica-based resins produced by the sol-gel method include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane , dimethoxydiethoxysilane, and methoxytriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyldimethoxysilane. , phenylalkoxysilane such as diphenyldiethoxysilane, and the like, can be used as the resin.

≪Commercial product≫
Examples of commercially available transparent resins include the following commercially available products. Examples of commercially available cyclic polyolefin resins include Arton manufactured by JSR Corporation, Zeonor manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics. Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. and the like can be mentioned as commercial products of polyether sulfone-based resins. Commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. Commercial products of polycarbonate-based resins include Pure Ace manufactured by Teijin Limited. Commercially available fluorene polycarbonate-based resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Inc., and the like. OKP4HT manufactured by Osaka Gas Chemicals Co., Ltd. and the like can be cited as commercial products of fluorene polyester-based resins. Examples of commercially available acrylic resins include Acryvure manufactured by Nippon Shokubai Co., Ltd., and the like. Commercially available silsesquioxane-based UV-curable resins include Silplus manufactured by Nippon Steel Chemical Co., Ltd., and the like.

<Other dyes (X)>
The substrate may further contain other dye (X) that does not correspond to the compound (A).

Other dyes (X) are not particularly limited as long as they have a maximum absorption wavelength of less than 650 nm or more than 800 nm and 1250 nm or less. At least one compound selected from the group consisting of phthalocyanine-based compounds, croconium-based compounds, octaphylline-based compounds, diimmonium-based compounds, pyrrolopyrrole-based compounds, boron dipyrromethene (BODIPY)-based compounds, perylene-based compounds, and metal dithiolate-based compounds is mentioned. By using such dyes, it is possible to achieve absorption characteristics in a wide near-infrared wavelength region and excellent visible light transmittance.

The absorption maximum wavelength of the other dye (X) is preferably 805 nm or more and 1200 nm or less, more preferably 810 nm or more and 1150 nm or less, still more preferably 815 nm or more and 1100 nm or less, and particularly preferably 820 nm or more and 1050 nm or less. When the absorption maximum wavelength of the other dye (X) is within such a range, unnecessary near-infrared rays can be efficiently cut, and the incident angle dependency of incident light can be reduced.

The content of the other dye (X) is, for example, when a substrate made of a transparent resin substrate containing the other dye (X) is used as the substrate, with respect to 100 parts by mass of the transparent resin, It is preferably 0.005 to 1.0 parts by mass, more preferably 0.01 to 0.9 parts by mass, and particularly preferably 0.02 to 0.8 parts by mass. A substrate in which a transparent resin layer such as an overcoat layer made of a curable resin containing another dye (X) is laminated on a support such as a resin support, or a substrate containing the compound (A) When using a substrate in which a resin layer such as an overcoat layer made of a curable resin containing other dye (X) is laminated on a transparent resin substrate, a transparent resin containing the other dye (X) is used. It is preferably 0.05 to 4.0 parts by mass, more preferably 0.1 to 3.0 parts by mass, and particularly preferably 0.2 to 2.0 parts by mass based on 100 parts by mass of the resin forming the layer. be.

<Other ingredients>
The substrate may further contain an antioxidant, a near-ultraviolet absorber, a fluorescence quencher, and the like as other components within a range that does not impair the effects of the present invention. These other components may be used individually by 1 type, and may use 2 or more types together.

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

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

These other components may be mixed together with the resin or the like when manufacturing the base material, or may be added when synthesizing the resin. Further, the amount to be added is appropriately selected according to the desired properties, but it is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass, per 100 parts by mass of the resin. Department.

<Method for manufacturing base material>
When the substrate is a substrate containing a transparent resin substrate containing the compound (A), the transparent resin substrate can be formed, for example, by melt molding or cast molding. By coating a coating agent such as an antireflection agent, a hard coating agent and/or an antistatic agent after molding, a substrate having an overcoat layer laminated thereon can be produced.

An overcoat comprising a curable resin or the like containing the compound (A) on a support such as a glass support or a base resin support, or on a transparent resin substrate not containing the compound (A). In the case where the substrate is a laminated transparent resin layer such as a layer, for example, a resin solution containing the compound (A) is melt-molded or cast-molded on the support or the transparent resin substrate, preferably by spinning. After coating by a method such as coating, slit coating, or inkjet, the solvent is removed by drying, and if necessary, light irradiation or heating is performed to form the compound (A) on the support or the transparent resin substrate. A substrate on which a transparent resin layer containing is formed can be produced.

≪Melt molding≫
Specifically, the melt-molding is a method of melt-molding pellets obtained by melt-kneading a resin, a compound (A), and optionally other components; A method of melt-molding a resin composition containing other components according to the method; Examples include a method of melt-molding pellets. Examples of melt molding methods include injection molding, melt extrusion molding, and blow molding.

≪Cast molding≫
As the cast molding, a method of casting a resin composition containing the compound (A), a resin, a solvent and, if necessary, other components onto a suitable support to remove the solvent; A curable composition comprising a photocurable resin and/or a thermosetting resin and optionally other components is cast onto a suitable support, and the solvent is removed, followed by ultraviolet irradiation, heating, or the like. It can also be produced by a method of curing by an appropriate method of.

When the base material is a base material made of a transparent resin substrate containing the compound (A), the base material can be obtained by peeling off the coating film from the support after cast molding, In addition, the substrate is made of a curable resin or the like containing the compound (A) on a support such as a glass support or a base resin support or on a transparent resin substrate that does not contain the compound (A). When the base material is laminated with a transparent resin layer such as an overcoat layer, the base material can be obtained by not peeling off the coating film after cast molding.

Examples of the support include near-infrared absorbing glass plates (e.g., phosphate-based glass containing a copper component such as "BS-11" manufactured by Matsunami Glass Industry Co., Ltd. and "NF-50T" manufactured by AGC Techno Glass Co., Ltd.). glass plate), transparent glass plate (e.g., non-alkali glass plate such as "OA-10G" manufactured by Nippon Electric Glass Co., Ltd. and "AN100" manufactured by Asahi Glass Co., Ltd.), steel belt, steel drum and transparent resin (e.g., polyester film , cyclic olefin resin film).

Furthermore, optical parts such as glass plates, quartz or transparent plastics are coated with the resin composition and the solvent is dried, or the curable composition is coated and cured and dried. A transparent resin layer can also be formed on the component.

The amount of residual solvent in the transparent resin layer (transparent resin substrate) obtained by the above method should be as small as possible. Specifically, the amount of the residual solvent is preferably 3 parts by mass or less, more preferably 1 part by mass or less, further preferably 0.1 part by mass or less, with respect to 100 parts by mass of the transparent resin layer (transparent resin substrate). It is 5 parts by mass or less. When the amount of residual solvent is within the above range, a transparent resin layer (transparent resin substrate) that is resistant to deformation and changes in properties and can easily exhibit desired functions can be obtained.

[Dielectric multilayer film]
The optical filter of the present invention preferably does not have a dielectric multilayer film, but may have a dielectric multilayer film on at least one surface of the substrate as long as the effects of the present invention are not impaired. A dielectric multilayer film in the present invention is a film having an antireflection effect in the visible light region.

The dielectric multilayer film preferably has antireflection properties over the entire wavelength range of 400 to 610 nm, more preferably 410 to 600 nm, and even more preferably 420 to 590 nm.

A form having dielectric multilayer films on both sides of the base material, which has dielectric multilayer films on both sides of the base material having anti-reflection properties mainly in the vicinity of wavelengths of 400 to 610 nm when measured from the vertical direction of the optical filter. etc.

The thickness of the dielectric multilayer film having an antireflection effect in the visible light region is not particularly limited as long as it does not impair the effects of the present invention. 5 μm. By setting the thickness within the above range, an optical filter with little warpage or distortion can be obtained.

Dielectric multilayer films include those in which high refractive index material layers and low refractive index material layers are alternately laminated. A material having a refractive index of 1.7 or more can be used as a material constituting the high refractive index material layer, and a material having a refractive index of 1.7 to 2.5 is usually selected. Such materials include, for example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, etc., and tin oxide and/or oxide. Examples include those containing a small amount of cerium (for example, 0 to 10 parts by mass with respect to 100 parts by mass of the main component).

A material having a refractive index of 1.6 or less can be used as a material constituting the low refractive index material layer, and a material having a refractive index of 1.2 to 1.6 is usually selected. Such materials include, for example, silica, alumina, lanthanum fluoride, magnesium fluoride and sodium aluminum hexafluoride.

The method of stacking the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film is formed by stacking these material layers. For example, dielectrics in which high refractive index material layers and low refractive index material layers are alternately laminated directly on a base material by CVD, sputtering, vacuum deposition, ion-assisted deposition, ion plating, or the like. A multilayer film can be formed.

The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ to 0.5λ, where λ (nm) is the near-infrared wavelength to be blocked. The value of λ (nm) is, for example, 700-1400 nm, preferably 750-1300 nm. When the thickness is within this range, the product (n × d) of the refractive index (n) and the film thickness (d) is calculated as λ / 4, and the optical film thickness, the high refractive index material layer and the low refractive index The thickness of each layer of the index material layer becomes almost the same value, and there is a tendency that the blocking and transmission of a specific wavelength can be easily controlled from the relationship between the optical characteristics of reflection and refraction.

The total number of laminated layers of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film is preferably 1 to 20 layers, more preferably 2 to 12 layers for the entire optical filter. By setting the number of laminations within the above range, an optical filter with little warpage or distortion can be obtained.

In the present invention, the material species constituting the high refractive index material layer and the low refractive index material layer, the high refractive index material layer and the low refractive index material layer are selected according to the absorption characteristics of the compound (A) and other dyes (X). By appropriately selecting the thickness of each layer, the order of lamination, and the number of layers, it has sufficient transmittance in the visible light region and has sufficient light cut characteristics in the near-infrared wavelength region. It is possible to reduce the reflectance when near-infrared rays enter from the direction.

Here, in order to optimize the above conditions, for example, optical thin film design software (for example, Essential Macleod, manufactured by Thin Film Center) is used to achieve both an antireflection effect in the visible light region and a light cut effect in the near infrared region. You should be able to set the parameters accordingly. In the case of the above software, for example, when designing the first optical layer, the target transmittance at a wavelength of 400 to 700 nm is 100%, the Target Tolerance value is 1, and the target transmittance at a wavelength of 705 to 950 nm is 0%. A parameter setting method such as setting the value of Target Tolerance to 0.5 can be mentioned. For these parameters, the wavelength range can be divided more finely according to various properties of the base material (i), and the Target Tolerance value can be changed.

[Other functional films]
In the optical filter of the present invention, at least one surface of the base material, between the base material and the dielectric multilayer film, and the surface of the base material opposite to the surface on which the dielectric multilayer film is provided, as long as the effects of the present invention are not impaired. side, or the side opposite to the side on which the base material of the dielectric multilayer film is provided, the surface hardness of the base material or dielectric multilayer film is improved, the chemical resistance is improved, and antistatic and scratch-removing properties are applied. For the purpose, a functional film such as an antireflection film, a hard coat film, or an antistatic film can be appropriately provided.

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

The method for laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and/or an antistatic agent is applied to the base material or the dielectric multilayer film, and melt molding or casting is performed in the same manner as described above. A molding method and the like can be mentioned.

It can also be produced by applying a curable composition containing the coating agent and the like onto a base material or a dielectric multilayer film using a bar coater or the like, and then curing the film by ultraviolet irradiation or the like.

Examples of the coating agent include ultraviolet (UV)/electron beam (EB) curable resins and thermosetting resins. Specifically, vinyl compounds, urethane, urethane acrylate, acrylate, epoxy and epoxy acrylate resins. Examples of the curable composition containing these coating agents include vinyl-based, urethane-based, urethane-acrylate-based, acrylate-based, epoxy-based and epoxy-acrylate-based curable compositions.

Moreover, the curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or thermal polymerization initiator can 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.

The mixing ratio of the polymerization initiator in the curable composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, when the total amount of the curable composition is 100 parts by mass. More preferably, it is 1 to 5 parts by mass. When the blending ratio of the polymerization initiator is within the above range, the curing properties and handling properties of the curable composition are excellent, and functional films such as antireflection films, hard coat films and antistatic films having desired hardness can be obtained. can.

Furthermore, an organic solvent may be added as a solvent to the curable composition, and known organic solvents can be used. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone and propylene. esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, N- Amides such as methylpyrrolidone can be mentioned. A solvent may be used individually by 1 type, and may use 2 or more types together.

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

In addition, for the purpose of improving the adhesion between the base material and the functional film and/or the dielectric multilayer film, and the adhesion between the functional film and the dielectric multilayer film, the surface of the base material, the functional film, or the dielectric multilayer film may be coated with corona. Surface treatment such as treatment or plasma treatment may be performed.

[Applications of optical filters]
The optical filter of the present invention has a wide viewing angle and excellent near-infrared cutting ability. Therefore, it is useful for visibility correction of a solid-state imaging device such as a CCD of a camera module or a CMOS image sensor. In particular, digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automobile cameras, televisions, car navigation systems, personal digital assistants, video game machines, and portable game machines , fingerprint authentication systems, digital music players, etc. Furthermore, it is also useful as a heat ray cut filter attached to glass plates of automobiles, buildings, and the like.

Here, the solid-state imaging device is an image sensor equipped with a solid-state imaging device such as a CCD or CMOS image sensor. Specifically, it includes digital still cameras, smartphone cameras, mobile phone cameras, wearable device cameras, digital It can be used for applications such as video cameras. For example, a camera module of the invention comprises an optical filter of the invention. Here, the camera module is a device that includes an image sensor, a focus adjustment mechanism, a phase detection mechanism, a distance measurement mechanism, or the like, and outputs an image and distance information as electrical signals.

It is particularly preferable that the camera module has a cover member that protects the internal mechanism from the outside, and that the cover member has a near-infrared reflective function. The near-infrared wavelength band in which the cover member has a function of reflecting light incident from the direction perpendicular to the cover member is preferably 900 to 1100 nm, more preferably 850 to 1150 nm, and particularly preferably 800 to 1200 nm. The means for imparting the near-infrared reflective function to the cover member is not particularly limited, but a dielectric multilayer film in which a high refractive index material and a low refractive index material are alternately laminated is formed by a CVT method, a sputtering method, a vacuum deposition method, or an ion-assisted deposition method. A method of forming on the cover member by a method or the like is preferable.

When the camera module is configured as described above, light rays enter the camera module while part of the near-infrared rays are cut off by the cover member. Unnecessary near-infrared reflection between the optical filter and the solid-state imaging device can be reduced, and noise and ghosts in camera images tend to be reduced, which is preferable. Furthermore, since the camera module of the present invention is provided with an optical filter that efficiently cuts near-infrared rays with a wavelength of 700 to 780 nm by absorption of the compound (A), it achieves high image quality that is difficult to achieve with conventional camera modules. be able to.

Further, an electronic device of the present invention has the camera module of the present invention. Examples of electronic devices include, but are not particularly limited to, smartphones, mobile phones, and PCs used in the applications described above.

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

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

For the resin synthesized in Resin Synthesis Example 3, which will be described later, the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the above method.
(c) A portion of the polyimide resin solution was poured into anhydrous methanol to precipitate the polyimide resin, which was separated from unreacted monomers by filtration. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. using a Canon-Fenske viscometer is calculated by the following formula. asked.

μ={ln( _ts / _t0 )}/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., the temperature was measured at a rate of temperature increase of 20°C per minute under a nitrogen stream.

<Spectral transmittance>
The transmittance of the substrate and the optical filter at each wavelength was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.

Here, for the transmittance measured in the vertical direction of the optical filter, the light 1 transmitted vertically through the optical filter 2 as shown in FIG. In the transmittance measured at an angle of 30 degrees with respect to the direction, the spectrophotometer 3 detects light 1′ transmitted at an angle of 30 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG. When the transmittance is measured at an angle of 60 degrees with respect to the vertical direction of the optical filter, as shown in FIG. '' was measured with a spectrophotometer 3.

<Color shading evaluation of camera image>
Color shading evaluation when the optical filter was incorporated into the camera module was performed by the following method. A camera module as shown in FIG. 2 was produced in the same manner as in JP-A-2016-110067. Using the obtained camera module, a white plate of 300 mm × 400 mm was illuminated with a D65 light source (X-Rite standard The image was taken under the light source device "Macbeth Judge II"), and the difference in color between the center and the edge of the white plate in the camera image was evaluated according to the following criteria.

A is an acceptable level with no problems at all, B is an acceptable level with no practical problems as a high-quality camera module even though there is a slight color difference, and an acceptable level is an acceptable level for a high-quality camera module with a difference in color. A possible level is C, and a level D is unacceptable even for general camera module applications due to a clear difference in color tone.

As shown in FIG. 3, the positional relationship between the white plate 112 and the camera module was adjusted so that the white plate 112 occupied 90% or more of the area of the camera image 111 when photographing. Also, as the cover member 210 in FIG. 2, a cover member having a film configuration shown in Table 9 below was used, and as the optical filter 240, optical filters produced in Examples and Comparative Examples below were used.

＜カメラ画像のゴースト評価＞
光学フィルターをカメラモジュールに組み込んだ際のゴースト評価は下記の方法で行った。カメラ画像の色シェーディング評価と同様の方法でカメラモジュールを作成し、作成したカメラモジュールを用いて暗室中ハロゲンランプ光源（林時計工業社製「ルミナーエースＬＡ－１５０ＴＸ」）下で撮影し、カメラ画像における光源周辺のゴースト発生具合を以下の基準で評価した。

<Ghost Evaluation of Camera Image>
The ghost evaluation when the optical filter was incorporated into the camera module was performed by the following method. A camera module was created in the same way as the color shading evaluation of camera images, and the created camera module was used to photograph under a halogen lamp light source (Hayashi Tokei Kogyo Co., Ltd. "Luminar Ace LA-150TX") in a dark room. The degree of ghost generation around the light source was evaluated according to the following criteria.

A is an acceptable level with no problem, B is an acceptable level with no problem in practical use as a high-quality camera module with a slight amount of ghosting, and unacceptable level for a high-quality camera module with ghosting. A possible level is C, and a level D is unacceptable even for a general camera module application because the degree of ghosting is severe.

In addition, as shown in FIG. 4, when photographing, the light source 122 was adjusted to be the upper right end of the camera image 121 .

[Synthesis example]
Compound (A) and near-infrared absorbing dye (X) used in the following examples were synthesized by a generally known method. General synthesis methods include, for example, JP-A-60-228448, JP-A-1-146846, JP-A-1-228960, JP-A-4081149, JP-A-63-124054, " Phthalocyanine -Chemistry and Function-" (IPC, 1997), JP-A-2007-169315, JP-A-2009-108267, JP-A-2010-241873, and the like. .

<Resin Synthesis Example 1>
8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene (hereinafter also referred to as “DNM”) 100 parts, 1-hexene (molecular weight modifier) 18 parts and toluene (solvent for ring-opening polymerization reaction) 300 parts were replaced with nitrogen. A vessel was charged and the solution was heated to 80°C. Next, 0.2 part of a toluene solution of triethylaluminum (0.6 mol/liter) and 0.2 part of a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol/liter) were added as polymerization catalysts to the solution in the reaction vessel. 9 parts were added, and this solution was heated and stirred at 80° C. for 3 hours to carry out ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

このようにして得られた開環重合体溶液１，０００部をオートクレーブに仕込み、この開環重合体溶液に、ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃を０．１２部添加し、水素ガス圧１００ｋｇ／ｃｍ²、反応温度１６５℃の条件下で、３時間加熱撹拌して水素添加反応を行った。得られた反応溶液（水素添加重合体溶液）を冷却した後、水素ガスを放圧した。この反応溶液を大量のメタノール中に注いで凝固物を分離回収し、これを乾燥して、水素添加重合体（以下「樹脂Ａ」ともいう。）を得た。得られた樹脂Ａは、数平均分子量（Ｍｎ）が３２，０００、質量平均分子量（Ｍｗ）が１３７，０００であり、ガラス転移温度（Ｔｇ）が１６５℃、屈折率（ｎ２０ｄ）が１．５１であった。

An autoclave was charged with 1,000 parts of the ring-opened polymer solution thus obtained, and 0.12 part of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution. Then, under the conditions of a hydrogen gas pressure of 100 kg/cm ² and a reaction temperature of 165° C., a hydrogenation reaction was carried out by heating and stirring for 3 hours. After cooling the resulting reaction solution (hydrogenated polymer solution), hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a solidified product, which was dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The resulting resin A had a number average molecular weight (Mn) of 32,000, a mass average molecular weight (Mw) of 137,000, a glass transition temperature (Tg) of 165°C, and a refractive index (n20d) of 1.51. Met.

<Resin Synthesis Example 2>
35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis(4-hydroxyphenyl)fluorene, 41.46 g of potassium carbonate ( 0.300 mol), 443 g of N,N-dimethylacetamide (hereinafter also referred to as "DMAc") and 111 g of toluene were added. Subsequently, the four-necked flask was equipped with a thermometer, a stirrer, a three-way cock with a nitrogen inlet tube, a Dean-Stark tube and a cooling tube. Then, after the inside of the flask was replaced with nitrogen, the obtained solution was reacted at 140° C. for 3 hours, and the generated water was removed from the Dean-Stark tube at any time. When the formation of water was no longer observed, the temperature was gradually raised to 160° C., and the reaction was carried out at that temperature for 6 hours. After cooling to room temperature (25° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol to reprecipitate, and the filtrate (residue) was isolated by filtration. The obtained filter cake was vacuum-dried overnight at 60° C. to obtain a white powder (hereinafter also referred to as “resin B”) (yield 95%). The resulting resin B had a number average molecular weight (Mn) of 75,000, a mass average molecular weight (Mw) of 188,000, a glass transition temperature (Tg) of 285°C, and a refractive index (n20d) of 1.66. Met.

<Resin Synthesis Example 3>
1,4-bis(4-amino-α,α -Dimethylbenzyl)benzene 27.66 g (0.08 mol) and 4,4'-bis(4-aminophenoxy)biphenyl 7.38 g (0.02 mol) were charged, and γ-butyrolactone 68.65 g and N, It was dissolved in 17.16 g of N-dimethylacetamide. The resulting 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 and an imidization catalyst were added while maintaining the same temperature. 0.50 g (0.005 mol) of triethylamine was added all at once. After the addition was completed, the temperature was raised to 180° C., and the mixture was refluxed for 6 hours while distilling off the distillate as needed. After completion of the reaction, the mixture was air-cooled until the internal temperature reached 100° C., diluted with 143.6 g of N,N-dimethylacetamide, cooled with stirring, and 264.16 g of a polyimide resin solution with a solid content concentration of 20% by mass. got A portion of this polyimide resin solution was poured into 1 L of methanol to precipitate polyimide. The filtered polyimide was washed with methanol and dried in a vacuum dryer at 100° C. for 24 hours to obtain a white powder (hereinafter also referred to as “resin C”). When the IR spectrum of the obtained resin C was measured, absorption at 1704 cm ^-1 and 1770 cm ^-1 peculiar to the imide group was observed. Resin C had a glass transition temperature (Tg) of 310° C., a refractive index (n20d) of 1.68, and a logarithmic viscosity of 0.87.

[Example 1]
In a container, 100 parts of the resin A obtained in Resin Synthesis Example 1, the compound (Aa-1) represented by the following formula (Aa-1) as the compound (Aa) (maximum absorption in dichloromethane wavelength 712 nm) 0.05 parts, compound (Ab) represented by the following formula (Ab-1) as compound (Ab-1) (absorption maximum wavelength 738 nm in dichloromethane) 0.12 parts , and a compound (Ac-1) represented by the following formula (Ac-1) as a compound (Ac) (absorption maximum wavelength 776 nm in dichloromethane) 0.05 parts, and methylene chloride A solution having a resin concentration of 20% by mass was prepared. 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. The peeled coating film was further dried at 100° C. for 8 hours under reduced pressure to obtain a substrate made of a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 5 and Table 15-1 (hereinafter both Tables 15-1 and 15-2 are referred to as "Table 15" for convenience) .

［実施例２］
実施例１において、化合物（Ａ－ａ）として下記式（Ａ－ａ－２）で表わされる化合物（Ａ－ａ－２）（ジクロロメタン中での吸収極大波長６８６ｎｍ）０．０３部を用いたこと、化合物（Ａ－ｂ）を用いなかったこと、ならびに、化合物（Ａ－ｃ）として化合物（Ａ－ｃ－１）０．０４部および下記式（Ａ－ｃ－２）で表わされる化合物（Ａ－ｃ－２）（ジクロロメタン中での吸収極大波長７６０ｎｍ）０．０６部を用いたこと以外は、実施例１と同様の手順および条件で透明樹脂製基板を得た。

[Example 2]
In Example 1, 0.03 parts of a compound (Aa-2) represented by the following formula (Aa-2) (maximum absorption wavelength in dichloromethane: 686 nm) was used as the compound (Aa). , that the compound (Ab) was not used, and 0.04 parts of the compound (Ac-1) as the compound (Ac) and the compound represented by the following formula (Ac-2) (A -c-2) A transparent resin substrate was obtained in the same procedure and under the same conditions as in Example 1, except that 0.06 part of (absorption maximum wavelength 760 nm in dichloromethane) was used.

得られた透明樹脂製基板の片面に、下記組成の樹脂組成物（１）をバーコーターで塗布し、オーブン中７０℃で２分間加熱して溶剤を揮発除去した。この際、乾燥後の厚みが２μｍとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光（露光量：５００ｍＪ／ｃｍ²，２００ｍＷ）を行って樹脂組成物（１）を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物（１）からなる樹脂層を形成して透明樹脂製基板の両面に樹脂層を有する基材を得た。この基材からなる光学フィルターの分光透過率を測定して光学特性を評価した。また、得られた光学フィルターを用いてカメラモジュールを作成し、カメラ画像の色シェーディングおよびゴーストの評価を行った。結果を図６および表１５に示す。

A resin composition (1) having the following composition was applied to one side of the obtained transparent resin substrate using a bar coater and heated in an oven at 70° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 μm. Next, exposure was performed using a conveyor type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure the resin composition (1) to form a resin layer on the transparent resin substrate. Similarly, a resin layer composed of the resin composition (1) was formed on the other side of the transparent resin substrate to obtain a substrate having resin layers on both sides of the transparent resin substrate. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 6 and Table 15.

Resin composition (1): 60 parts of tricyclodecanedimethanol diacrylate, 40 parts of dipentaerythritol hexaacrylate, 5 parts of 1-hydroxycyclohexylphenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30% by mass)
[Example 3]
In Example 1, 0.04 parts of compound (Aa-1) and 0.03 parts of compound (Aa-2) were used as compound (Aa), and compound (Ab) was (Ab-1) that 0.10 parts were used, and 0.04 parts of compound (Ac-1) and 0.05 parts of compound (Ac-2) as compound (Ac) A substrate made of a transparent resin substrate was obtained in the same procedure and under the same conditions as in Example 1, except that the was used. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 7 and Table 15.

[Example 4]
In Example 1, 0.04 parts of compound (Aa-1) and 0.03 parts of compound (Aa-2) were used as compound (Aa), and compound (Ab) was 0.01 part of (Ab-1) was used, and 0.03 part of compound (Ac-1) and 0.04 part of compound (Ac-2) were used as compound (Ac) and, as another near-infrared absorbing dye (X), 0.04 parts of a near-infrared absorbing dye (X-1) represented by the following formula (X-1) (maximum absorption wavelength in dichloromethane: 813 nm) A substrate made of a transparent resin substrate containing the compound (A) and the near-infrared absorbing dye (X) was obtained in the same procedure and under the same conditions as in Example 1, except for the addition. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 8 and Table 15.

［実施例５］
縦６０ｍｍ、横６０ｍｍの大きさにカットした透明ガラス基板「ＯＡ－１０Ｇ（厚み１５０ｕｍ）」（日本電気硝子（株）製）上に下記組成の樹脂組成物（２）をスピンコーターで塗布し、ホットプレート上８０℃で２分間加熱して溶剤を揮発除去した。この際、乾燥後の厚みが２μｍとなるように、スピンコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光（露光量：５００ｍＪ／ｃｍ²，２００ｍＷ）を行って樹脂組成物（２）を硬化させ、化合物（Ａ）を含む透明樹脂層を有する透明ガラス基板からなる基材を得た。この基材からなる光学フィルターの分光透過率を測定して光学特性を評価した。また、得られた光学フィルターを用いてカメラモジュールを作成し、カメラ画像の色シェーディングおよびゴーストの評価を行った。結果を図９および表１５に示す。

[Example 5]
A transparent glass substrate "OA-10G (thickness 150 um)" (manufactured by Nippon Electric Glass Co., Ltd.) cut to a size of 60 mm long and 60 mm wide was coated with a resin composition (2) having the following composition with a spin coater, The solvent was removed by volatilization by heating on a hot plate at 80° C. for 2 minutes. At this time, the coating conditions of the spin coater were adjusted so that the thickness after drying was 2 μm. Next, exposure is performed using a conveyor type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure the resin composition (2). A base material was obtained. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 9 and Table 15.

Resin composition (2): 20 parts of tricyclodecanedimethanol diacrylate, 80 parts of dipentaerythritol hexaacrylate, 4 parts of 1-hydroxycyclohexylphenyl ketone, 3.00 parts of compound (Aa-1), compound (A -a-2) 1.00 parts, compound (Ab-1) 7.00 parts, compound (Ac-1) 4.00 parts, methyl ethyl ketone (solvent, TSC: 35%)
[Example 6]
In Example 1, 0.04 parts of compound (Aa-1) and 0.03 parts of compound (Aa-2) were used as compound (Aa), and compound (Ab) was (Ab-1) using 0.34 parts, using 0.04 parts of the compound (Ac-1) as the compound (Ac), and changing the thickness of the transparent resin substrate A substrate made of a transparent resin substrate was obtained in the same procedure and under the same conditions as in Example 1, except that the thickness was 0.08 mm. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 10 and Table 15.

[Example 7]
In Example 1, 0.05 parts of compound (Aa-1) was used as compound (Aa), and 0.85 parts of compound (Ab-1) was used as compound (Ab). In addition, except that 0.05 parts of the compound (Ac-1) was used as the compound (Ac), and the thickness of the transparent resin substrate was 0.04 mm, it was the same as in Example 1. A substrate made of a transparent resin substrate was obtained in the same procedure and under the same conditions. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 11 and Table 15.

[Example 8]
Resin A obtained in Resin Synthesis Example 1 and methylene chloride were added to a container to prepare a solution having a resin concentration of 20% by mass, and resin was prepared in the same manner as in Example 1 except that the obtained solution was used. A support was created.

In the same manner as in Example 2, a resin layer composed of a resin composition (3) having the following composition was formed on both sides of the resin support, and compound (A) and near-infrared rays were applied to both sides of the resin support. A substrate having a transparent resin layer containing the absorbing dye (X) was obtained. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 12 and Table 15.

Resin composition (3): 100 parts of tricyclodecanedimethanol diacrylate, 4 parts of 1-hydroxycyclohexylphenyl ketone, compound (Aa-1) 0.50 parts, compound (Ac-1) 0.50 part, compound (Ac-2) 2.50 parts, near-infrared absorbing dye (X-1) 1.40 parts, methyl ethyl ketone (solvent, TSC: 25%)
[Example 9]
A near-infrared absorbing glass substrate "BS-11 (thickness 120 um)" (manufactured by Matsunami Glass Industry Co., Ltd.) cut to a size of 60 mm long and 60 mm wide is coated with a resin composition (4) having the following composition with a spin coater. and heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the spin coater were adjusted so that the thickness after drying was 2 μm. Next, exposure is performed using a conveyor-type exposure machine (exposure amount: 500 mJ/cm ² , 200 mW) to cure the resin composition (4), resulting in a near-infrared absorbing glass having a transparent resin layer containing the compound (A). A substrate consisting of a substrate was obtained. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 13 and Table 15.

Resin composition (4): 20 parts of tricyclodecanedimethanol diacrylate, 80 parts of dipentaerythritol hexaacrylate, 4 parts of 1-hydroxycyclohexylphenyl ketone, compound (Aa-1) 1.00 parts, compound (A -c-1) 1.00 parts, compound (Ac-2) 5.00 parts, methyl ethyl ketone (solvent, TSC: 35 mass%)
[Example 10]
In Example 1, 0.04 parts of compound (Aa-1) and 0.03 parts of compound (Aa-2) were used as compound (Aa), and compound (Ab) was (Ab-1) using 0.14 parts, using 0.04 parts of compound (Ac-1) as compound (Ac), and near-infrared absorbing dye (X-1 ) was used in the same procedure and under the same conditions as in Example 1, except that 0.04 part was used. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. Results are shown in FIG. 14 and Table 15.

[Example 11]
In Example 1, 0.04 parts of compound (Aa-1) and 0.03 parts of compound (Aa-2) were used as compound (Aa), and compound (Ab) was The same procedure as in Example 1 except that 0.34 parts of (Ab-1) was used, and 0.04 parts of compound (Ac-1) was used as compound (Ac). A substrate made of a transparent resin substrate was obtained under the procedures and conditions.

A dielectric multilayer film (I) is formed as a first optical layer on one side of the obtained substrate, and a similar dielectric multilayer film (I) is formed on the other side of the substrate to form an optical filter. Obtained.

As the dielectric multilayer film (I), silica (SiO ₂ ) layers and titania (TiO ₂ ) layers were alternately laminated at a vapor deposition temperature of 120° C. (four layers in total). The silica layer and the titania layer of the dielectric multilayer film (I) were alternately laminated in the order of titania layer, silica layer, titania layer, silica layer from the substrate side, and the silica layer was the outermost layer of the optical filter.

Here, the dielectric multilayer film (I) was a multilayer deposition film having four layers, in which silica layers with a thickness of 33 to 88 nm and titania layers with a thickness of 13 to 111 nm were alternately laminated. The film structure is shown in Table 10 below.

得られた基材および光学フィルターの分光透過率を測定して光学特性を評価した。また、得られた光学フィルターを用いてカメラモジュールを作成し、カメラ画像の色シェーディングおよびゴーストの評価を行った。結果を図１５および表１５に示す。

The spectral transmittance of the obtained substrate and optical filter was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. Results are shown in FIG. 15 and Table 15.

[Examples 12 to 14]
A substrate was prepared in the same manner as in Example 1, except that the resin, solvent, drying conditions for the resin substrate, and compound (A) were changed as shown in Table 15. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. Table 15 shows the results.

[Examples 15 and 16]
A substrate was prepared in the same manner as in Example 2 except that the resin, solvent, drying conditions for the resin substrate, compound (A) and near-infrared absorbing dye (X) were changed as shown in Table 15. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in Figures 16, 17 and Table 15.

[Comparative Example 1]
In Example 1, 0.07 parts of the compound (Aa-1) was used as the compound (Aa), and 0.08 parts of the compound (Ab-1) as the compound (Ab) A substrate made of a transparent resin substrate was obtained in the same procedure and under the same conditions as in Example 1, except that the was used. |X _b −X _a | of the resulting substrate was 61 nm, less than 100 nm.

Subsequently, a dielectric multilayer film (II) formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer (26 layers in total) as a first optical layer was formed on one side of the obtained base material. A dielectric multilayer film (III) formed by alternately laminating a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer as a second optical layer on the other surface of the substrate (20 layers in total) was formed to obtain an optical filter with a thickness of about 0.105 mm.

The dielectric multilayer films (II) and (III) were designed as follows.

Regarding the thickness and number of each layer, the wavelength dependence characteristics of the refractive index of the base material and the absorption of the applied compound (A) are selected so as to achieve an antireflection effect in the visible light region and selective transmission and reflection performance in the near infrared region. The characteristics were optimized using optical thin film design software (Essential Macleod, manufactured by Thin Film Center). When optimizing, in this comparative example, input parameters (target values) to the software were as shown in Table 11 below.

膜構成最適化の結果、比較例１では、誘電体多層膜（ＩＩ）は、膜厚３１～１５５ｎｍのシリカ層と膜厚１０～９４ｎｍのチタニア層とが交互に積層されてなる、積層数２６の多層蒸着膜となり、誘電体多層膜（ＩＩＩ）は、膜厚３８～１８９ｎｍのシリカ層と膜厚１１～１０９ｎｍのチタニア層とが交互に積層されてなる、積層数２０の多層蒸着膜となった。最適化を行った膜構成の一例を下記表１２に示す。

As a result of optimizing the film configuration, in Comparative Example 1, the dielectric multilayer film (II) is composed of alternately laminated silica layers with a thickness of 31 to 155 nm and titania layers with a thickness of 10 to 94 nm. The dielectric multilayer film (III) is a multilayer vapor deposition film having 20 layers, in which a silica layer having a thickness of 38 to 189 nm and a titania layer having a thickness of 11 to 109 nm are alternately laminated. rice field. An example of optimized film configuration is shown in Table 12 below.

得られた光学フィルターの分光透過率を測定して光学特性を評価した。また、得られた光学フィルターを用いてカメラモジュールを作成し、カメラ画像の色シェーディングおよびゴーストの評価を行った。結果を図１８および表１５に示す。比較例１で得られた光学フィルターは、比較的良好な光学濃度を示すものの、高角度入射時の透過率の低下が大きく、誘電体多層膜による近赤外線反射に起因すると考えられるゴーストの発生が確認され、さらに色シェーディング抑制効果が劣ることが確認された。

The spectral transmittance of the obtained optical filter was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. Results are shown in FIG. 18 and Table 15. Although the optical filter obtained in Comparative Example 1 exhibits a relatively good optical density, the transmittance at high-angle incidence is greatly reduced, and a ghost is generated, which is considered to be caused by the reflection of near-infrared rays by the dielectric multilayer film. It was also confirmed that the effect of suppressing color shading was inferior.

[Comparative Example 2]
A substrate made of a transparent resin substrate was obtained in the same procedure and under the same conditions as in Comparative Example 1. forming a dielectric multilayer film (IV) in which a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated (30 layers in total) as a first optical layer on one side of the obtained base material; Furthermore, on the other side of the base material, a dielectric multilayer film (V) was formed as a second optical layer, in which silica (SiO ₂ ) layers and titania (TiO ₂ ) layers were alternately laminated (20 layers in total). , an optical filter with a thickness of about 0.105 mm was obtained.

When optimizing, in this comparative example, input parameters (target values) to the software were as shown in Table 13 below.

膜構成最適化の結果、比較例２では、誘電体多層膜（ＩＶ）は、膜厚２２～４６７ｎｍのシリカ層と膜厚６～１３０ｎｍのチタニア層とが交互に積層されてなる、積層数３０の多層蒸着膜となり、誘電体多層膜（Ｖ）は、膜厚８４～２０６ｎｍのシリカ層と膜厚８～１０９ｎｍのチタニア層とが交互に積層されてなる、積層数２０の多層蒸着膜となった。最適化を行った膜構成の一例を下記表１４に示す。

As a result of optimizing the film structure, in Comparative Example 2, the dielectric multilayer film (IV) was formed by alternately laminating a silica layer with a thickness of 22 to 467 nm and a titania layer with a thickness of 6 to 130 nm. The dielectric multilayer film (V) is a multilayer vapor deposition film having 20 layers, in which a silica layer with a thickness of 84 to 206 nm and a titania layer with a thickness of 8 to 109 nm are alternately laminated. rice field. An example of optimized film configuration is shown in Table 14 below.

得られた光学フィルターの分光透過率を測定して光学特性を評価した。また、得られた光学フィルターを用いてカメラモジュールを作成し、カメラ画像の色シェーディングおよびゴーストの評価を行った。結果を図１９および表１５に示す。比較例２で得られた光学フィルターは、高角度入射時の透過率の低下が大きく、さらに近赤外線波長領域の吸収も十分ではないため、色シェーディング抑制効果やゴースト抑制効果に劣ることが確認された。

The spectral transmittance of the obtained optical filter was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 19 and Table 15. It has been confirmed that the optical filter obtained in Comparative Example 2 is inferior in the color shading suppressing effect and the ghost suppressing effect because the transmittance is greatly reduced at high angle incidence and the absorption in the near-infrared wavelength region is not sufficient. rice field.

[Comparative Example 3]
A substrate made of a transparent resin substrate was obtained in the same procedure and under the same conditions as in Comparative Example 1. Subsequently, in the same procedure and under the same conditions as in Example 11, the dielectric multilayer film (I) was formed as the first optical layer on one side of the obtained substrate, and the other side of the substrate was formed in the same manner. A dielectric multilayer film (I) was formed to obtain an optical filter with a thickness of about 0.101 mm.

The spectral transmittance of the obtained optical filter was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 20 and Table 15. It was confirmed that the optical filter obtained in Comparative Example 3 had insufficient absorption in the near-infrared wavelength region and was inferior in the ghost suppressing effect.

[Comparative Example 4]
A substrate made of a transparent resin substrate was obtained in the same procedure and under the same conditions as in Comparative Example 1. The spectral transmittance of the optical filter made of this base material was measured to evaluate the optical properties. In addition, a camera module was produced using the obtained optical filter, and color shading and ghost of the camera image were evaluated. The results are shown in FIG. 21 and Table 15. It was confirmed that the optical filter obtained in Comparative Example 4 had insufficient absorption in the near-infrared wavelength region and was inferior in the ghost suppressing effect.

[Comparative Example 5]
A camera module was produced using only the cover member without using the optical filter, and color shading and ghost of the camera image were evaluated. Table 15 shows the results. Since the camera module obtained in Comparative Example 5 does not have an optical filter that absorbs the near-infrared region, both color shading and ghosting are severe, and the level is unacceptable even for general camera module applications. confirmed.

上記表１５中の基材の構成、各種化合物などの記号、および、フィルム［（透明）樹脂製基板もしくは樹脂製支持体］の乾燥条件は下記の通りである。

The structure of the base material, the symbols for various compounds, etc., and the drying conditions for the film [(transparent) resin substrate or resin support] in Table 15 above are as follows.

<Form of base material>
Form (1): Transparent resin substrate containing compound (A) Form (2): Transparent resin substrate containing compound (A) having resin layers on both sides Form (3): Compounds on both sides of resin support Form (4): Having a transparent resin layer containing the compound (A) on one side of the transparent glass substrate Form (5): Having the compound on one side of the near-infrared absorbing glass substrate Form (6) having a transparent resin layer containing (A): Having antireflection layers on both sides of a transparent resin substrate containing compound (A) Form (7): Compound (A) and near-infrared absorbing dye (X) Form (8): A transparent resin substrate containing the compound (A) and having |X _b −X _a |
Form (9): A transparent resin substrate containing compound (A) and having |X _b −X _a |
Mode (10): Transparent resin substrate containing compound (A) and having |X _b −X _a | of less than 100 nm (Comparative Example)
<Transparent resin>
Resin A: Cyclic polyolefin resin (resin synthesis example 1)
Resin B: Aromatic polyether resin (Resin Synthesis Example 2)
Resin C: polyimide resin (Resin Synthesis Example 3)
Resin D: Cyclic olefin resin "Zeonor 1420R" (manufactured by Nippon Zeon Co., Ltd.)
<Glass substrate>
Glass substrate (1): Transparent glass substrate “OA-10G (thickness 150 μm)” cut to a size of 60 mm long and 60 mm wide (manufactured by Nippon Electric Glass Co., Ltd.)
Glass substrate (2): A near-infrared absorbing glass substrate “BS-11 (thickness 120 μm)” cut to a size of 60 mm long and 60 mm wide (manufactured by Matsunami Glass Industry Co., Ltd.)
<Resin support>
Resin support (1): A transparent resin substrate made of resin A having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm <Near-infrared absorption dye>
<<Compound (A)>>
Compound (Aa-1): a compound represented by the formula (Aa-1) (maximum absorption wavelength in dichloromethane: 712 nm)
Compound (Aa-2): a compound represented by formula (Aa-2) (maximum absorption wavelength in dichloromethane: 686 nm)
Compound (Ab-1): compound represented by formula (Ab-1) (maximum absorption wavelength in dichloromethane: 738 nm)
Compound (Ac-1): a compound represented by formula (Ac-1) (maximum absorption wavelength in dichloromethane: 776 nm)
Compound (Ac-2): a compound represented by formula (Ac-2) (maximum absorption wavelength in dichloromethane: 760 nm)
Compound (Ac-3): a compound represented by the following formula (Ac-3) (maximum absorption wavelength in dichloromethane: 773 nm)

≪その他の色素（Ｘ）≫
近赤外線吸収色素（Ｘ－１）：式（Ｘ－１）で表される化合物（ジクロロメタン中での吸収極大波長８１３ｎｍ）
近赤外線吸収色素（Ｘ－２）：下記式（Ｘ－２）で表される化合物（ジクロロメタン中での吸収極大波長８７０ｎｍ）

<<Other dyes (X)>>
Near-infrared absorbing dye (X-1): compound represented by formula (X-1) (maximum absorption wavelength in dichloromethane: 813 nm)
Near-infrared absorbing dye (X-2): a compound represented by the following formula (X-2) (maximum absorption wavelength in dichloromethane: 870 nm)

＜溶媒＞
溶媒（１）：塩化メチレン
溶媒（２）：Ｎ，Ｎ－ジメチルアセトアミド
溶媒（３）：シクロヘキサン／キシレン（質量比：７／３）
＜フィルム乾燥条件＞
条件（１）：２０℃／８ｈｒ→減圧下 １００℃／８ｈｒ
条件（２）：６０℃／８ｈｒ→８０℃／８ｈｒ→減圧下 １４０℃／８ｈｒ
条件（３）：６０℃／８ｈｒ→８０℃／８ｈｒ→減圧下 １００℃／２４ｈｒ
なお、減圧乾燥前に塗膜をガラス板から剥離した。

<Solvent>
Solvent (1): methylene chloride Solvent (2): N,N-dimethylacetamide Solvent (3): cyclohexane/xylene (mass ratio: 7/3)
<Film drying conditions>
Condition (1): 20°C/8hr → 100°C/8hr under reduced pressure
Condition (2): 60°C/8hr → 80°C/8hr → 140°C/8hr under reduced pressure
Condition (3): 60°C/8hr → 80°C/8hr → 100°C/24hr under reduced pressure
The coating film was peeled off from the glass plate before drying under reduced pressure.

Condition (4): 80°C/2min
Condition (5): 70°C/2min

1, 1′, 1″: light 2: optical filter 3: spectrophotometer 111: camera image 112: white plate 113: example of center of white plate 114: example of edge of white plate 121: camera image 122 : Light source 123: Example of ghost around light source 200: Imaging device 210: Cover member 220: Lens group 230: Diaphragm 240: Optical filter 250: Solid-state imaging element 260: Housing

Claims (11)

A substrate having a layer containing a compound (A) having an absorption maximum in the wavelength range of 650 to 800 nm,
The base material has, as the compound (A), a compound (Aa) having an absorption maximum in a wavelength region of 650 nm or more and 715 nm or less, a compound (Ab) having an absorption maximum in a wavelength region of more than 715 nm and 750 nm or less, And containing a compound (Ac) having an absorption maximum in the region of more than 750 nm and 800 nm or less in wavelength,
An optical filter that meets the following requirements (a) and (b):
(a) In the wavelength region of 430 to 580 nm, the minimum value T _b-0 of the transmittance of light incident from the vertical direction of the optical filter and the minimum transmittance of light incident from the direction oblique to the vertical direction by 30 degrees The value T _b-30 and the minimum value T _b-60 of the transmittance of light incident from a direction oblique to the vertical direction at 60 degrees are both 55% or more and less than 90%;
(b) In the wavelength range of 700 to 780 nm, the average value OD _a-0 of the optical density for light incident on the optical filter from the vertical direction and the average optical density for light incident at an angle of 30 degrees to the vertical direction. Both the value OD _a-30 and the average value OD _a-60 of optical densities for light incident from a direction oblique to the vertical direction of 60 degrees are 1.8 or more. The optical filter according to claim 1, further satisfying the following requirement (c):
(c) In the wavelength range of 900 to 1200 nm, the average transmittance T _IR of light incident on the optical filter in the vertical direction is 60% or more. The optical filter according to claim 1 or 2, further satisfying the following requirement (d):
(d) In the wavelength range of 430 to 580 nm, the average value T _a-0 of the transmittance of light incident on the optical filter in the vertical direction and the average transmittance of light incident from the direction oblique to the vertical direction at 30 degrees. The value Ta _-30 and the average value _Ta-60 of the transmittance of light incident from a direction oblique to the vertical direction at 60 degrees are both 65% or more and less than 90%. The optical filter according to any one of claims 1 to 3, wherein the substrate further satisfies the following requirement (f):
(f) At a wavelength of 600 to 900 nm, the wavelength X _a on the longest wavelength side at which the transmittance for light incident from the vertical direction of the substrate is from more than 10% to 10% or less from the short wavelength side to the long wavelength side. and the absolute value of the difference between the wavelength X _b on the shortest wavelength side at which the transmittance for light incident from the vertical direction of the substrate is 10% or less to more than 10% from the short wavelength side to the long wavelength side | X _b −X _a | is 100 nm or more. 1-, wherein the compound (A) is at least one compound selected from the group consisting of squarylium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, croconium-based compounds, and cyanine - based compounds. 5. The optical filter according to any one of 4. 6. The optical filter according to claim 1 , wherein the layer containing compound (A) is a transparent resin layer. The resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, an aramid resin, and a polysulfone resin. Resins, polyether sulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane resins UV curable resins, maleimide resins, alicyclic epoxy thermosetting resins, polyether ether ketone resins, polyarylate resins, allyl ester curable resins, acrylic UV curable resins, vinyl UV curable resins, 7. The optical filter according to claim 6 , wherein the at least one resin is selected from the group consisting of resins containing silica as a main component and formed by a sol-gel method. 8. The optical filter according to claim 6 , wherein the resin constituting the transparent resin layer has a refractive index ( n20d ) of 1.50 to 1.53. A camera module comprising the optical filter according to any one of claims 1 to 8 . 10. The camera module according to claim 9 , further comprising a cover member for protecting the internal mechanism of the camera module from the outside, wherein the cover member has a near-infrared ray reflecting function. An electronic device comprising the camera module according to claim 9 .

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