JP7405228B2 - Resin compositions for optical filters, optical filters, camera modules and electronic devices - Google Patents

Description

The present invention relates to a resin composition for an optical filter, an optical filter, a camera module, and an electronic device. More specifically, the present invention relates to a resin composition for an optical filter containing a specific compound, an optical filter having specific optical properties, a camera module using the optical filter, and an electronic device including the camera module.

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 image sensors use silicon photodiodes in their light receiving portions, which 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 visibility correction to make colors look natural to the human eye, and optical filters that selectively transmit or cut light in specific wavelength ranges (for example, near-infrared cut filters) are often used.

Conventionally, such near-infrared cut filters manufactured by various methods have been 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 does not always have sufficient near-infrared absorption characteristics.

In Patent Document 2, the present applicant has discovered that by using a transparent resin substrate containing a near-infrared absorbing dye that has an absorption maximum in a specific wavelength region, the optical characteristics change little even when the incident angle is changed, and proposed a near-infrared cut filter with high visible light transmittance. In addition, Patent Document 3 discloses that by using a phthalocyanine dye with a specific structure, near-infrared rays can achieve both excellent visible light transmittance and long absorption maximum wavelength at a high level, which were conventional problems. It is stated that a cut filter can be obtained.

However, in the near-infrared cut filters described in Patent Documents 2 and 3, although the applied base material has a sufficiently strong absorption band around 700 nm, it has a strong absorption band in the near-infrared wavelength region of, for example, 900 to 1200 nm. has almost no absorption. Therefore, light rays in the near-infrared wavelength range are mostly cut only by reflection from the dielectric multilayer film, but with this configuration, slight stray light due to internal reflection in the optical filter or reflection between the optical filter and the lens is eliminated. , which sometimes caused ghosts and flares when shooting in dark environments. In particular, in recent years, there has been a strong demand for higher image quality cameras even for mobile devices such as smartphones, and conventional optical filters may not be suitable for use.

On the other hand, an infrared shielding filter as disclosed in Patent Document 4 has been proposed as an optical filter using a base material having broad absorption in the near-infrared wavelength region. 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 incidence) due to the recent reduction in the height of camera modules.

Further, Patent Document 5 discloses a near-infrared cut filter having a near-infrared absorbing glass base material and a layer containing a near-infrared absorbing dye, but the configuration described in Patent Document 5 also sufficiently improves color shading. There were times when it was not possible to do so. For example, FIG. 5 of Patent Document 5 shows optical characteristic graphs at 0-degree incidence and 30-degree incidence. ), a large wavelength shift has been observed.

Japanese Patent Application Publication No. 6-200113 Japanese Patent Application Publication No. 2011-100084 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 also considering a new module configuration in which the functions of a conventional optical filter, which combines absorption by a dye and reflection by a dielectric multilayer film, are separated into separate components. There is a need for an optical filter that can accommodate such configurations.

An object of the present invention is to provide an optical filter that can suppress both color shading and ghosting of camera images at a high level, which conventional optical filters have not been able to do.

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

[1] Optical filter that satisfies the following requirements (a) and (b):
(a) In the wavelength range 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 a direction oblique to the vertical direction at 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 optical density OD _a-0 for light incident from the vertical direction of the optical filter and the average optical density for light incident from a direction oblique to the vertical direction at 30 degrees. Both the value OD _a-30 and the average value OD _a-60 of optical density for light incident from a direction diagonal at 60 degrees with respect to the vertical direction are 1.8 or more.

[2] The optical filter according to item [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 from the vertical direction of the optical filter is 60% or more.

[3] The optical filter according to item [1] or [2], which 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 from the vertical direction of the optical filter and the average transmittance of light incident from a direction oblique to the vertical direction at 30 degrees The value T _a-30 and the average value T _a-60 of the transmittance of light incident at an angle of 60 degrees with respect to the vertical direction are both 65% or more and less than 90%.

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

[5] The optical filter according to item [4], wherein the base material further satisfies the following requirement (f):
(f) In the wavelength range of 600 to 900 nm, the longest wavelength X _a where the transmittance for light incident from the vertical direction of the base material ranges from more than 10% to less than 10% 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 and the transmittance for light incident from the vertical direction of the base material from the short wavelength side to the long wavelength side from 10% or less to over 10% | X _b −X _a | is 100 nm or more.

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

[7] The base material contains, as the compound (A), a compound (A-a) having an absorption maximum in a wavelength range of 650 m or more and 715 nm or less, and a compound (A-a) having an absorption maximum in a wavelength range of more than 715 nm and 750 nm or less. b), and the optical filter according to any one of items [4] to [6], which contains a compound (A-c) having an absorption maximum in a wavelength region of more than 750 nm and 800 nm or less.

[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 resin, polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy 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 The optical filter according to item [8], wherein the optical filter is at least one resin selected from the group consisting of mold resins and resins whose main component is silica 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 [10], further comprising a cover member that protects an internal mechanism of the camera module from the outside, and wherein the cover member has a near-infrared 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 that has excellent near-infrared cut characteristics, low incidence angle dependence, and excellent transmittance characteristics in the visible light wavelength range, color shading suppressing effect, and ghost suppressing effect.

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

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

[Optical filter]
The optical filter of the present invention is characterized by satisfying the following requirements (a) and (b), and preferably satisfies the following requirements (C) and/or (D).
(a) In the wavelength range 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 a direction oblique to the vertical direction at 30 degrees The value T _b-30 and the minimum value T _b-60 of the transmittance of light incident at an angle of 60 degrees with respect to the vertical direction are both 55% or more and less than 90%.
(b) In the wavelength range of 700 to 780 nm, the average optical density OD _a-0 for light incident from the vertical direction of the optical filter and the average optical density for light incident from a direction oblique to the vertical direction at 30 degrees. Both the value OD _a-30 and the average value OD _a-60 of optical density for light incident from a direction diagonal at 60 degrees with respect to the vertical direction are 1.8 or more.
(c) In the wavelength range of 900 to 1200 nm, the average transmittance T _IR of light incident from the vertical direction of the optical filter 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 from the vertical direction of the optical filter and the average transmittance of light incident from a direction oblique to the vertical direction at 30 degrees The value T _a-30 and the average value T _a-60 of the transmittance of light incident obliquely at 60 degrees with respect to the vertical direction 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.

A method for satisfying requirement (a), that is, a method for adjusting the minimum value of each transmittance, is, for example, by adjusting the type and amount of compound (A) described below so as to obtain the minimum value of transmittance within a specified range. Examples include methods of selecting and adjusting as appropriate.

By satisfying requirement (a), even when the incident angle is high such as 30 degrees or 60 degrees, the change in RGB balance is small, so a high quality camera image can be obtained.

<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. It is 4.5 or less, more preferably 2.2 or more and 4.0 or less.

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

By satisfying 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, resulting in no or reduced color shading. Camera images can be obtained.

Here, the OD value is a common logarithm value of transmittance, and can be calculated using the following formula (1). A high average OD value in a specified wavelength range indicates that the optical filter has a high ability to cut light in that wavelength range.

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

As a method for satisfying requirement (c), that is, a method for adjusting the average value of light transmittance, for example, the type and amount of compound (A) to be described later are appropriately selected and added so as to obtain transmittance within a specified range. One way to do this is to make adjustments.

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

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

A method for satisfying requirement (d), that is, a method for adjusting the average value of each transmittance, is, for example, by adjusting the type and amount of compound (A) described below so as to obtain an average value of transmittance within a specified range. Examples include methods of selecting and adjusting as appropriate.

By satisfying the requirement (d), even when the incident angle is high such as 30 degrees or 60 degrees, the change in RGB balance is small, so a high quality camera image can be obtained.

<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, even more preferably 160 μm or less, particularly preferably 130 μm or less, and although the lower limit is not particularly limited, it is preferably 20 μm or more.

[Base material]
The configuration of the optical filter of the present invention is not particularly limited as long as an optical filter exhibiting the above-mentioned optical properties can be obtained, but it is preferable that the base material includes a base material that satisfies the following requirement (e). It is preferable that f) is satisfied.
(e) A layer containing a compound (A) having an absorption maximum in a wavelength range of 650 to 800 nm.
(f) In the wavelength range of 600 to 900 nm, the longest wavelength X _a where the transmittance for light incident from the vertical direction of the base material ranges from more than 10% to less than 10% 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 and the transmittance for light incident from the vertical direction of the base material from the short wavelength side to the long wavelength side from 10% or less to over 10% | X _b −X _a | is 100 nm or more.

Each requirement will be explained below.

<Requirement (e)>
In requirement (e), the components constituting the layer containing the compound (A) are not particularly limited, and examples thereof include transparent resins, sol-gel materials, and low-temperature curing glass materials. A transparent resin is preferable from the viewpoint of compatibility with A).

The base material may be a single layer or a multilayer, 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, 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 characteristics of the compound (A) and other near-infrared absorbers, so it is preferably 300 nm or less, for example. If the difference |X _b −X _a | is within the above range, it will have an absorption band with sufficient intensity (width) in the near-infrared wavelength region close to the visible light region, for example, at an incident angle of 30 degrees or 60 degrees. This is preferable because color shading can be suppressed even under conditions where the incident angle is large, such as in degrees.

The wavelength _{value (} X _{a +} is 680 nm or more and 820 nm or less, more preferably 700 nm or more and 800 nm or less. It is preferable that the value of the wavelength expressed by (X _a +X _b )/2 is within the above range because light in the wavelength region near the long wavelength end of the visible light region can be more efficiently cut.

Said X _a is preferably 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. It is preferable that X _a be within such a range because it tends to produce camera images with less noise and excellent color reproducibility.

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

≪Compound (A)≫
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 one selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds. One type of compound is preferred, and squarylium compounds, phthalocyanine compounds, and cyanine compounds are particularly preferred. In addition, compound (A) may be used individually by 1 type, and may be used in combination of 2 or more types.

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

The absorption maximum 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 range of 650 to 800 nm, but from the viewpoint of heat resistance of the optical filter, a compound (A-a) that has an absorption maximum in the wavelength range of 650 nm to 715 nm ), a compound (A-b) that has an absorption maximum in a wavelength range of more than 715 nm and 750 nm or less, and a compound (A-c) that has an absorption maximum in a wavelength range of more than 750 nm and 800 nm or less. . When compound (A) has such a configuration, it is possible to efficiently widen the near-infrared absorption band while minimizing the decrease in visible light transmittance, and also to improve heat resistance and This is preferable because it tends to improve weather resistance.

When compound (A) is a combination of two or more types of compounds, the difference in absorption maximum wavelength between the compound (A) that has the shortest absorption maximum wavelength and the longest absorption maximum wavelength among the applied compounds (A) is preferably 20 to 20%. The wavelength is 100 nm, more preferably 30 to 90 nm, even more preferably 40 to 80 nm. It is preferable that the difference in absorption maximum wavelength is within the above range, since it is possible to sufficiently reduce scattered light due to fluorescence, and also to achieve both a wide absorption band around 700 nm and excellent visible light transmittance.

The overall content of the compound (A) is determined by applying a curable resin to the substrate, 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 the The amount is 1.5 parts by mass, more preferably 0.08 to 1.0 parts by mass, and the compound (A) is contained on a support such as a glass support or a base resin support as the base material. When using a base material laminated with a transparent resin layer such as an overcoat layer made of a curable resin or the like, the amount is preferably 0.00 parts by mass based on 100 parts by mass of the resin forming the transparent resin layer containing the compound (A). The amount is 4 to 5.0 parts by weight, more preferably 0.6 to 4.0 parts by weight, and even more preferably 0.8 to 3.5 parts by weight.

(Squarylium compound)
The squarylium compound is not particularly limited, but at least one selected from the group consisting of squarylium compounds represented by the following formula (I) and squarylium compounds represented by the following formula (II). Compounds 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 the 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 the 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 the plural 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 , -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 that 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 that 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, or an aromatic hydrocarbon group having 6 to 14 carbon atoms. , a heterocyclic group having 3 to 14 carbon atoms, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, and an amino group.

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

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

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), and 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, dodecyl group, etc. Alkyl group; alkenyl group 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.

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, and heptachloroethyl group. Mention may be made of the propyl group and the heptafluoropropyl group.

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. Examples include 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.

Examples of the heterocyclic group 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, 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 methoxy group, ethoxy group, n-propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, and octyloxy group. can.

Examples of the acyl group having 1 to 9 carbon atoms in L ^g include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a 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 group. Mention may be made of oxycarbonyl group.

The L ^a is preferably a 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 group. and 2-cyclohexylethyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl.

The 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 a trichloroethyl group. They are a methyl group, a pentachloroethyl group, a trifluoromethyl group, and a pentafluoroethyl group.

The 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. It is.

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

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

The 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, or a hexyloxy group. group, octyloxy group, and more preferably methoxy group, ethoxy group, propoxy group, isopropoxy group, and butoxy group.

The L ^g is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group, or a trifluoromethylcarbonyl group, and more preferably an acetyl group, a propionyl group, or a 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, and more preferably They are methoxycarbonyl group and ethoxycarbonyl group.

The L ^a to L ^h further contain 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. You can. Examples of such groups include 4-sulfobutyl group, 4-cyanobutyl group, 5-carboxypentyl group, 5-aminopentyl group, 3-hydroxypropyl group, 2-phosphorylethyl group, 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 above condition (α) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. , cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, and nitro group, and more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, and hydroxyl group. .

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

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

In condition (β) of the formula (I), at least one of the two R ^a on one benzene ring has at least one nitrogen atom formed by mutually bonding with Y on the same benzene ring. Examples of the heterocycle having 5 or 6 constituent atoms include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine and pyrazine. Among these heterocycles, a heterocycle in which one atom adjacent to the carbon atom constituting the heterocycle and constituting the benzene ring is a nitrogen atom is preferred, 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 ); each of the plurality of R ^c independently represents a hydrogen atom, L ^a , L ^b , Represents L ^c , L ^d or L ^e ; each of the plurality of R ^d 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 represents an R ^f group, and adjacent R ^d may be linked to form a ring which may have a substituent; L ^a to L ^e , L ¹ , R ^e and R ^f are the above-mentioned It has the same meaning as 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, or an n-pentyl group. , n-hexyl group, cyclohexyl group, phenyl group, trifluoromethyl group, and pentafluoroethyl group, and more preferably a 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, or a tert-butyl group. group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, methoxy group, trifluoromethyl group, pentafluoroethyl group, 4-aminocyclohexyl group, more preferably hydrogen atom, chlorine atom, fluorine atom , methyl group, ethyl group, n-propyl group, isopropyl group, trifluoromethyl group, and pentafluoroethyl group.

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

In the formula (II), adjacent R ^d may be connected to each other to form a ring. Examples of such rings include benzindolenine ring, α-naphthoimidazole ring, β-naphthoimidazole 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 expressed in the following formulas (I-1) and (II-1) as well as in the following formulas (I-2) and (II-2). The structure can also be represented by a description method that takes a resonance structure. In other words, 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) is only in the method of describing the structure. also represent the same compound. In the present invention, unless otherwise specified, the structure of the squarylium compound will be represented by the following formulas (I-1) and (II-1).

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

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

前記化合物（Ｉ）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 structures of the compounds (I) and (II) are not particularly limited as long as they satisfy the requirements of the formulas (I) and (II), respectively. For example, when the structures are represented as in 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 be the same because it is easier to synthesize.

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

The compounds (I) and (II) may be synthesized by a generally known method, for example, as described in JP-A-1-228960, JP-A-2001-40234, and Japanese Patent No. 3,196,383. It can be synthesized by referring to the methods described.

(phthalocyanine compound)
The phthalocyanine 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, a divalent metal atom, or a trivalent or tetravalent metal atom; _a , R _b , R _c and R _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imido group, a cyano group, a silyl group, -L ¹ , -S -L ² , -SS-L ² , -SO ₂ -L ³ , -N=N-L ⁴ , or at least one 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 the following formulas (A) to (H), to which is bonded. However, at least one of R _a , R _b , R _c and R _d bonded to the same aromatic ring is not a hydrogen atom.

The amino group, amide group, imide group and silyl group may have a substituent L defined in the formula (I),
L ¹ has the same meaning as L ¹ defined in the above formula (I),
L ² represents a hydrogen atom or any one of L ^a to L ^e defined in formula (I) above,
L ³ represents a hydroxyl group or any of the above 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 each of the plurality of R _A to R _L independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amide group, Represents 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 , and represents the amino group, amide group, imide group, The group and the silyl group may have a substituent L as defined in the above formula (I), and L ¹ to L ⁴ have the same meanings as L ¹ to L ⁴ defined in the above formula (III).

In R _a to R _d and R _A to R _L , examples of the amino group which may have a substituent L include an amino group, an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group, and a diisopropylamino group. Examples include groups.

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

In the above 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, Examples include dibutylimide group.

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

In R _a to R _d and R _A to R _L , -S-L 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-butyl sulfide group, phenyl sulfide group, 2,6-di-tert-butylphenyl sulfide group, 2,6-diphenylphenyl sulfide group, 4-cumylphenyl sulfide group, and the like.

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

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

In 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.

In the above M, examples of the monovalent metal atom 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, Examples include Pb.

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 the above M, the substituted 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 , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF _{2 , SnCl 2 ,} SnBr ₂ , SnI ₂ , Zr(OH) ₂ , Hf(OH) ₂ , Mn(OH) ₂ , Si(OH) ₂ , Ge( OH) ₂ , Sn(OH) ₂ , TiR _{2 , CrR 2} , SiR ₂ , GeR ₂ , SnR ₂ , 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 above M is a divalent transition metal, a trivalent or tetravalent metal halide, or a tetravalent metal oxide belonging to Groups 5 to 11 of the periodic table and from the 4th period to the 5th period. are preferred, and among these, Cu, Ni, Co, and VO are particularly preferred because they can achieve high visible light transmittance and stability.

It is generally known that the phthalocyanine compounds are synthesized by a cyclization reaction of phthalonitrile derivatives as shown in the following formula (V). It is a mixture of four isomers such as VI-4). In the present invention, unless otherwise specified, only one type of isomer per type of phthalocyanine compound is illustrated, but the other three types of isomers can be used in the same manner. Although these isomers can be separated and used if necessary, the present invention deals with a mixture of isomers all at once.

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－６１）などを挙げることができる。

Specific examples of the compound (III) include (b-1) to (b-61) listed in Tables 4 to 7 below, which have basic skeletons represented by the following formulas (III-A) to (III-J). ), etc.

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). It can be referenced and synthesized.

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

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 D's independently represent a carbon atom, nitrogen atom, oxygen atom, or 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, Imide 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 represented by the above formulas (A) to (H) represents at least one group selected from the group consisting of groups, and the amino group, amide group, imido group and silyl group may have a substituent L defined in the formula (I),
L ¹ has the same meaning as L ¹ defined in the above formula (I),
L ² represents a hydrogen atom or any one of L ^a to L ^e defined in formula (I) above,
L ³ represents a hydrogen atom or any of the above L ^a to L ^e ,
L ⁴ represents any one of the above 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 imido 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 Z or Y selected from two adjacent ones of these; nitrogen atom, oxygen atom or sulfur atom a 5- to 6-membered alicyclic hydrocarbon group that may contain at least one; or a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms and 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.

In Z _a to Z _c and Y _a to Y _d , the aromatic hydrocarbon group having 6 to 14 carbon atoms and formed by mutual bonding of Z or Y is, for example, the aromatic hydrocarbon group in the substituent L. Examples include compounds exemplified by aromatic hydrocarbon groups.

A 5- to 6-membered ring which may contain at least one nitrogen atom, oxygen atom or sulfur atom and is formed by mutually bonding Zs or Ys in Z _{a to} Z _c and Y a to Y _d . Examples of the alicyclic hydrocarbon group include the compounds exemplified for the alicyclic hydrocarbon group and heterocycle in the substituent L (excluding heteroaromatic hydrocarbon groups).

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

In the formulas (IV-1) to (IV-3), -S-L ² , -SS-L ² , -SO ₂ -L ³ , -N=N-L ⁴ , even if it has a substituent L Examples of good amino groups, amide groups, imido groups, and silyl groups 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, and examples include I ^- , Br ^- , PF ₆ ^- , N(SO ₂ CF ₃ ) ₂ ^- , B(C ₆ F ₅ ) ₄ ^- , nickel dithiolate. Examples include copper dithiolate complexes and copper dithiolate complexes.

Specific examples of the compounds (IV-1) to (IV-3) include (c-1) to (c-24) listed 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 No. 2009-108267.

<Transparent resin>
The transparent resin is not particularly limited as long as it does not impair the effects of the present invention, but for example, in order to ensure thermal stability and formability into a film, the transparent resin preferably has a glass transition temperature (Tg) of 110 to 110. Examples include resins having a temperature of 380°C, more preferably 110 to 370°C, and even more preferably 120 to 360°C. Further, since it is suitable for a reflow process, the glass transition temperature of the resin is preferably 140°C or higher, more preferably 230°C or higher.

It is particularly preferable that the refractive index (n20d) of the transparent resin is 1.53 or less. Transparent resins with a refractive index (n20d) of more than 1.53 tend to have many aromatic rings in the molecule, but resins with this structure have a strong interaction with the π-conjugated system in the compound (A) molecule. Too much water may deteriorate weather resistance.

The transparent resin has a total light transmittance (JIS K7105) of preferably 75 to 95%, more preferably 78 to 95 when a resin plate with a thickness of 0.1 mm is formed from the resin. %, particularly preferably 80 to 95%. If a resin having a total light transmittance within this range is used, the resulting substrate will exhibit good transparency as an optical film.

The mass average molecular weight (Mw) of the transparent resin measured by gel permeation chromatography (GPC) in terms of polystyrene is usually 15,000 to 350,000, preferably 30,000 to 250,000, and the number The average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 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, and polysulfone resins. Ethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioxane ultraviolet curing type Resin, maleimide resin, alicyclic epoxy thermosetting resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin, and sol-gel method. Mention may be made of resins formed mainly of silica. Among these, cyclic polyolefin resins, aromatic polyether resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, and polyarylate resins are preferred because of their transparency (optical properties), heat resistance, and reflow resistance. Cyclic polyolefin resins are preferred from the viewpoint of obtaining an optical filter with excellent balance of properties, and cyclic polyolefin resins are particularly preferred from the viewpoint of the refractive index of the resin. The transparent resins may be used alone 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 the 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 the following (i') to (ix'), and k ^x , m ^x and p ^x each independently represent 0 Represents an integer between ~4.
(i') Hydrogen atom (ii') Halogen atom (iii') Trialkylsilyl group (iv') Substituted or unsubstituted carbon number 1 having a linking group containing an oxygen atom, sulfur atom, nitrogen atom or silicon atom ~30 hydrocarbon groups (v') Substituted or unsubstituted hydrocarbon groups having 1 to 30 carbon atoms (vi') Polar groups (excluding (ii') and (iv'))
(vii') An alkylidene group formed by mutual bonding of R ^x1 and R ^x2 or R ^x3 and R ^x4 (However, R ^x1 to R ^x4 that do not participate in the bond are each independently ) to (vi') represents an atom or group selected from
(viii') A monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring formed by mutual bonding of R ^x1 and R ^x2 or R ^x3 and R ^x4 (provided that R ^x1 to R ^x4 each independently represents an atom or group selected from (i') to (vi') above.)
(ix') A monocyclic hydrocarbon ring or a heterocyclic ring formed by R ^x2 and R ^x3 bonding with each other (However, R ^x1 and R ^x4 that do not participate in the bond are each independently of the above (i Represents an atom or group selected from ') to (vi').)

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

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

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

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

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

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

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

Further, the aromatic polyether resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). 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, and Z is a single bond, -O-, -S-, -SO ₂ -, - CO-, -CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1.

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

In formula (4), R ⁷ , R ⁸ , Y, m, g and h each independently have the same meaning as R ⁷ , R ⁸ , Y, m, g and h in formula (2), and R ⁵ , R ⁶ , Z, n, e and f each independently have the same meaning as 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 the repeating unit, and for example, it can be used by the method described in JP-A No. 2006-199945 and JP-A No. 2008-163107. Can be synthesized.

≪Fluorene polycarbonate resin≫
The fluorene polycarbonate resin is not particularly limited and may be any polycarbonate resin containing a fluorene moiety, and can be synthesized, for example, by the method described in JP-A-2008-163194.

≪Fluorene polyester resin≫
The fluorene polyester resin is not particularly limited and may be any polyester resin containing a fluorene moiety, for example, it can be synthesized by the method described in JP-A No. 2010-285505 or JP-A No. 2011-197450. I can do it.

≪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. The polymer 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 ultraviolet curing resin≫
The acrylic UV-curable resin is not particularly limited, but it can be synthesized from a resin composition containing a compound that has one or more acrylic or methacrylic groups in the molecule and a compound that decomposes with UV rays to generate active radicals. I can list things that are done. The acrylic ultraviolet curable resin can be used as the base material, such as a base material 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 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 resins are not particularly limited, but can be broadly classified into ultraviolet curing types and thermosetting types. As an ultraviolet 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 ultraviolet light (hereinafter also referred to as a "photoacid generator"). Examples of thermosetting epoxy resins include those synthesized from a compound having one or more epoxy groups in the molecule and a composition containing an acid anhydride. I can do it. The epoxy ultraviolet curable resin may be 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 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, it can be particularly suitably used as the curable resin.

≪Resin whose main component is silica formed by sol-gel method≫
Examples of resins whose main component is silica produced by the sol-gel method include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxylane, and methoxytriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, A compound obtained by a sol-gel reaction resulting from hydrolysis of one or more silanes selected from phenylalkoxysilanes such as diphenyldiethoxysilane can be used as the resin.

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

<Other dyes (X)>
The base material may further contain other dyes (X) that do 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, such as squarylium compounds, phthalocyanine compounds, cyanine compounds, At least one compound selected from the group consisting of phthalocyanine compounds, croconium compounds, octaphylline compounds, diimonium compounds, pyrrolopyrrole compounds, borondipyrromethene (BODIPY) compounds, perylene compounds, and metal dithiolate compounds. can be mentioned. By using such a dye, absorption characteristics in a wide range of near-infrared wavelengths and excellent visible light transmittance can be achieved.

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, even 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 dependence of incident light on the angle of incidence can be reduced.

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

<Other ingredients>
The base material 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 alone or in combination of two or more.

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

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

Note that these other components may be mixed with the resin etc. when manufacturing the base material, or may be added when synthesizing the resin. The amount added is selected appropriately depending on the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, per 100 parts by weight of the resin. Department.

<Method for manufacturing base material>
When the base material is a base material including a transparent resin substrate containing the compound (A), the transparent resin substrate can be formed, for example, by melt molding or cast molding, and further, if necessary, After molding, a base material on which an overcoat layer is laminated can be manufactured by coating with a coating agent such as an antireflection agent, a hard coating agent, and/or an antistatic agent.

The base material is an overcoat made of a curable resin containing the compound (A), etc. 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 of a base material having transparent resin layers laminated thereon, for example, a resin solution containing the compound (A) is melt-molded or cast-molded onto the support or the transparent resin substrate, preferably by spin-forming. After coating by a method such as coating, slit coating, or inkjet, the solvent is dried and removed, and if necessary, further light irradiation or heating is performed to coat the compound (A) on the support or the transparent resin substrate. A base material on which a transparent resin layer containing the following can be manufactured.

≪Melt molding≫
Specifically, the melt-molding method includes a method of melt-molding a pellet obtained by melt-kneading a resin, a compound (A), and other components as necessary; A method of melt-molding a resin composition containing the compound (A), a resin, a solvent, and other components as necessary; Examples include a method of melt-molding pellets. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

≪Cast molding≫
The cast molding is a method in which a resin composition containing the compound (A), a resin, a solvent, and other components as necessary is cast onto a suitable support and the solvent is removed; After casting a curable composition containing a photocurable resin and/or a thermosetting resin and other components as necessary on a suitable support and removing the solvent, the composition is subjected to ultraviolet irradiation, heating, etc. It can also be manufactured by a method of curing using an appropriate method.

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 the coating film from the support after cast molding, In addition, the base material is made of a curable resin 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). In the case of a base material on which a transparent resin layer such as an overcoat layer is laminated, the base material can be obtained by not peeling off the coating film after cast molding.

The support may be, for example, a near-infrared absorbing glass plate (for example, a phosphate-based glass plate containing a copper component such as "BS-11" manufactured by Matsunami Glass Industry Co., Ltd. or "NF-50T" manufactured by AGC Techno Glass Co., Ltd.). glass plates), transparent glass plates (for example, alkali-free glass plates such as "OA-10G" made by Nippon Electric Glass Co., Ltd. and "AN100" made by Asahi Glass Co., Ltd.), steel belts, steel drums, and transparent resins (for example, polyester films) , cyclic olefin resin film).

Furthermore, an optical component made of glass plate, quartz, transparent plastic, etc. is coated with the resin composition and the solvent is dried, or the curable composition is coated, 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 is preferably as small as possible. Specifically, the residual solvent amount is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0. 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 not easily deformed or changes in properties and can easily exhibit desired functions can be obtained.

[Dielectric multilayer film]
Although the optical filter of the present invention preferably does not have a dielectric multilayer film, it may have a dielectric multilayer film on at least one surface of the base material within a range that does not impair the effects of the present invention. The dielectric multilayer film in the present invention is a film that has an antireflection effect in the visible light region.

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

A form that has a dielectric multilayer film on both sides of the base material, which has antireflection properties mainly at wavelengths around 400 to 610 nm when measured from the vertical direction of the optical filter. Examples include.

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, but is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.0 μm. It is 5 μm. By setting the thickness within the above range, an optical filter with less warpage and distortion can be obtained.

Examples of the dielectric multilayer film include those in which high refractive index material layers and low refractive index material layers are alternately laminated. As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and 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 or indium oxide as main components, and titanium oxide, tin oxide and/or indium oxide. Alternatively, it may contain a small amount of cerium oxide or the like (for example, 0 to 10 parts by mass per 100 parts by mass of the main component).

As the material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, 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.

There is no particular restriction on the method of laminating the high refractive index material layer and the low refractive index material layer as long as a dielectric multilayer film is formed by laminating these material layers. For example, a dielectric material 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 evaporation, ion-assisted evaporation, ion plating, etc. A multilayer film can be formed.

The thickness of each layer of the high refractive index material layer and the low refractive index material layer is usually 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 to 1400 nm, preferably 750 to 1300 nm. When the thickness is within this range, the product (n x d) of the refractive index (n) and the film thickness (d) is the optical film thickness calculated as λ/4, and the high refractive index material layer and the low refractive The thickness of each layer of the index material layer is approximately the same, and the blocking and transmission of specific wavelengths tends to be easily controlled due to the relationship of optical characteristics of reflection and refraction.

The total number of laminated layers of high refractive index material layers and low refractive index material layers 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 laminated layers within the above range, an optical filter with less warpage and distortion can be obtained.

In the present invention, the material types 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), etc. By appropriately selecting the thickness of each layer, the order of lamination, and the number of laminated layers, it is possible to ensure sufficient transmittance in the visible light region and sufficient light-cutting characteristics in the near-infrared wavelength region. It is possible to reduce the reflectance when near-infrared rays are incident from any direction.

Here, in order to optimize the above conditions, for example, optical thin film design software (e.g., Essential Macleod, manufactured by Thin Film Center) is used to achieve both anti-reflection effect in the visible light region and light ray cutting effect in the near-infrared region. You just need to set the parameters so that it can be done. In the case of the above software, for example, when designing the first optical layer, the target transmittance for the wavelength range of 400 to 700 nm is set to 100%, the Target Tolerance value is set to 1, the target transmittance for the wavelength range of 705 to 950 nm is set to 0%, Examples of parameter setting methods include setting the Target Tolerance value to 0.5. These parameters can also be used to change the Target Tolerance value by further dividing the wavelength range into smaller areas according to various characteristics of the base material (i).

[Other functional membranes]
The optical filter of the present invention may be provided on at least one surface of the base material, between the base material and the dielectric multilayer film, or on the opposite side of the base material to the surface on which the dielectric multilayer film is provided, to the extent that the effects of the present invention are not impaired. The side surface, or the surface opposite to the surface on which the base material of the dielectric multilayer film is provided, is coated with properties such as improving the surface hardness of the base material or dielectric multilayer film, improving chemical resistance, preventing static electricity, and eliminating scratches. For this purpose, a functional film such as an antireflection film, a hard coat film, or an antistatic film can be provided as appropriate.

The optical filter of the present invention may include one layer or two or more layers made of the functional film. When the optical filter of the present invention includes two or more layers made 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 may include melt molding or casting in the same manner as above by applying coating agents such as antireflection agents, hard coating agents, and/or antistatic agents to the base material or dielectric multilayer film. Examples include a method of molding.

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

Examples of the coating agent include ultraviolet (UV)/electron beam (EB) curable resins and thermosetting resins, and specifically, vinyl compounds, urethane-based, urethane-acrylate-based, acrylate-based, and 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.

Further, 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 together. The polymerization initiators may be used alone or in combination of two or more.

In the curable composition, the blending ratio of the polymerization initiator 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 handleability of the curable composition are excellent, and it is possible to obtain functional films such as antireflection films, hard coat films, and antistatic films having desired hardness. can.

Furthermore, an organic solvent may be added to the curable composition as a solvent, and known organic solvents can be used. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; 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. One type of solvent may be used alone, or two or more types may be used in combination.

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

In addition, in order to improve the adhesion between the base material and the functional film and/or dielectric multilayer film, or between the functional film and the dielectric multilayer film, corona is applied to the surface of the base material, functional film, or dielectric multilayer film. 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 correcting the visibility of solid-state imaging devices such as CCDs and CMOS image sensors in camera modules. 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 consoles, and portable game consoles. , fingerprint authentication systems, digital music players, etc. Furthermore, it is useful as a heat ray cut filter attached to glass plates of automobiles, buildings, etc.

Here, the solid-state imaging device is an image sensor equipped with a solid-state imaging element such as a CCD or CMOS image sensor, and specifically includes a digital still camera, a smartphone camera, a mobile phone camera, a wearable device camera, and a digital camera. It can be used for applications such as video cameras. For example, the camera module of the present invention includes the optical filter of the present invention. Here, the camera module is a device that includes an image sensor, a focus adjustment mechanism, a phase detection mechanism, a distance measurement mechanism, etc., and outputs images 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 reflecting function. The near-infrared wavelength band in which the cover member has a reflective function for light incident perpendicularly to the cover member is preferably 900 to 1100 nm, more preferably 850 to 1150 nm, particularly preferably 800 to 1200 nm. The means for imparting a near-infrared reflective function to the cover member is not particularly limited, but a dielectric multilayer film in which high refractive index materials and low refractive index materials are alternately laminated can be formed by CVT method, sputtering method, vacuum evaporation method, or ion-assisted evaporation method. A preferred method is to form it on the cover member by a method or the like.

When the camera module has the above configuration, the near-infrared rays enter the camera module with some of the near-infrared rays being cut off by the cover member, so that the near-infrared rays enter the camera module. This is preferable because unnecessary near-infrared reflection between the optical filter and the solid-state image sensor can be reduced, and noise and ghosts in camera images tend to be reduced. Furthermore, since the camera module of the present invention is equipped with an optical filter that efficiently cuts near-infrared rays with a wavelength of 700 to 780 nm through absorption of compound (A), it achieves high image quality that is difficult to achieve with conventional camera modules. be able to.

Moreover, the electronic device of the present invention includes the camera module of the present invention. Examples of electronic devices include, but are not limited to, smartphones, mobile phones, PCs, and the like for the above-mentioned applications.

EXAMPLES Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples at all. Note that "parts" means "parts by mass" unless otherwise specified. Moreover, the measurement method of each physical property value and the evaluation method of physical property are as follows.

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

Note that for the resin synthesized in Resin Synthesis Example 3, which will be described later, the molecular weight was not measured by the above method, but the logarithmic viscosity was measured by the following method (c).
(c) A portion of the polyimide resin solution was poured into anhydrous methanol to precipitate the polyimide resin, which was filtered and separated from unreacted monomers. 0.1 g of polyimide obtained by vacuum drying at 80 °C for 12 hours was dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 °C was calculated using the following formula using a Cannon-Fenske viscometer. I asked for it.

μ={ln(t _s /t ₀ )}/C
t ₀ : Flow time of solvent t _s : Flow time of dilute polymer solution C: 0.5 g/dL
<Glass transition temperature (Tg)>
Measurement was performed using a differential scanning calorimeter (DSC6200) manufactured by SII Nanotechnologies Co., Ltd. at a temperature increase rate of 20° C. per minute under a nitrogen stream.

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

Here, for the transmittance when measured from the vertical direction of the optical filter, the light 1 transmitted perpendicularly to the optical filter 2 is measured with a spectrophotometer 3 as shown in FIG. In terms of transmittance when measured from an angle of 30 degrees with respect to the direction, the spectrophotometer 3 measures the light 1' transmitted through the optical filter 2 at an angle of 30 degrees with respect to the vertical direction, as shown in Figure 1 (B). The transmittance measured at an angle of 60 degrees with respect to the vertical direction of the optical filter shows that the light 1 transmitted through the optical filter 2 at an angle of 60 degrees with respect to the vertical direction as shown in FIG. '' was measured with a spectrophotometer 3.

<Color shading evaluation of camera images>
Color shading evaluation when an optical filter was incorporated into a camera module was performed using the following method. A camera module as shown in FIG. 2 was manufactured using the same method as in JP-A-2016-110067, and the resulting camera module was used to attach a white plate of 300 mm x 400 mm to a D65 light source (standard manufactured by X-Rite). Photographs were taken under the light source device "Macbeth Judge II"), and the difference in color between the center and edges of the white board in the camera image was evaluated using the following criteria.

A is acceptable level with no problems at all, B is acceptable level with no problems in practical use as a high-resolution camera module although there is a slight difference in color, B is not acceptable for use as a high-resolution camera module due to a difference in color. The possible level was determined to be C, and the level where there was a clear difference in color and was unacceptable even for general camera module use was determined to be D.

As shown in FIG. 3, when photographing, 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 in the camera image 111. Further, as the cover member 210 in FIG. 2, a cover member having a film structure shown in Table 9 below was used, and as the optical filter 240, an optical filter produced in the following Examples and Comparative Examples was 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 images>
Ghost evaluation when an optical filter was incorporated into a camera module was performed using the following method. A camera module was created using the same method as for color shading evaluation of camera images, and the created camera module was used to take pictures in a dark room under a halogen lamp light source ("Lumina Ace LA-150TX" manufactured by Hayashi Watch Industry Co., Ltd.). The degree of ghost occurrence around the light source was evaluated using the following criteria.

A is an acceptable level with no problems at all, and B is an acceptable level with no problems in practical use as a high-resolution camera module, although some ghosting is observed, and B is an acceptable level with ghosts occurring. The possible level was determined to be C, and the degree of ghosting was determined to be severe and the level to be unacceptable even for general camera module use was determined to be D.

Note that, as shown in FIG. 4, when photographing, the light source 122 was adjusted to be at 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, Japanese Patent No. 4081149, JP-A-63-124054, Examples include methods described in "Phthalocyanine - Chemistry and Function" (IPC, 1997), JP 2007-169315, JP 2009-108267, JP 2010-241873, etc. .

<Resin synthesis example 1>
8-Methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] Dodec-3-ene (hereinafter also referred to as "DNM") 100 parts, 1-hexene (molecular weight regulator) 18 parts and toluene (ring-opening polymerization reaction solvent) 300 parts were replaced with nitrogen. The solution was heated to 80°C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol/liter) and 0.2 parts of a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol/liter) were added to the solution in the reaction vessel as polymerization catalysts. 9 parts of the solution was added, and the solution was heated and stirred at 80° C. for 3 hours to carry out a 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。

1,000 parts of the ring-opening polymer solution obtained in this manner was charged into an autoclave, and 0.12 parts of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, under the conditions of hydrogen gas pressure of 100 kg/cm ² and reaction temperature of 165° C., the mixture was heated and stirred for 3 hours to carry out a hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), the pressure of hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and collect a coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The obtained 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>
In a 3L four-neck flask, add 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis(4-hydroxyphenyl)fluorene, and 41.46 g (0.250 mol) 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, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube, and a cooling tube were attached to the four-necked flask. Next, after purging the inside of the flask with nitrogen, the resulting solution was reacted at 140° C. for 3 hours, and the produced water was removed from the Dean-Stark tube as needed. When water generation was no longer observed, the temperature was gradually raised to 160° C., and the reaction was continued at that temperature for 6 hours. After cooling to room temperature (25° C.), the generated salts were removed using filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60° C. overnight to obtain a white powder (hereinafter also referred to as “resin B”) (yield: 95%). The obtained 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 27.66g (0.08 mol) and 4,4'-bis(4-aminophenoxy)biphenyl 7.38g (0.02 mol) were added, and γ-butyrolactone 68.65g and N, It was dissolved in 17.16 g of N-dimethylacetamide. The obtained solution was cooled to 5°C using an ice-water bath, and while maintaining the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and the imidization catalyst were added. 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 occasionally distilling off the distillate. After the reaction was completed, the internal temperature was air cooled to 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 was obtained. I got it. A portion of this polyimide resin solution was poured into 1 L of methanol to precipitate polyimide. After washing the filtered polyimide with methanol, it was 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, absorptions at 1704 cm ^-1 and 1770 cm ^-1 characteristic of imide groups were 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 resin A obtained in Resin Synthesis Example 1, compound (A-a-1) represented by the following formula (A-a-1) as compound (A-a) (maximum absorption in dichloromethane) (wavelength 712 nm) 0.05 part, as compound (Ab), compound (A-b-1) represented by the following formula (A-b-1) (maximum absorption wavelength in dichloromethane 738 nm) 0.12 part , and 0.05 part of the compound (A-c-1) represented by the following formula (A-c-1) (maximum absorption wavelength in dichloromethane: 776 nm), and methylene chloride. A solution having a resin concentration of 20% by mass was prepared. The obtained solution was cast onto 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 under reduced pressure at 100° C. for 8 hours to obtain a base material made of a transparent resin substrate with a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. The optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 5 and Table 15.

［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 part of a compound (A-a-2) represented by the following formula (A-a-2) (maximum absorption wavelength in dichloromethane 686 nm) was used as the compound (A-a). , Compound (A-b) was not used, and Compound (A-c) was 0.04 part of Compound (A-c-1) and Compound (A-c-2) represented by the following formula (A-c-2). A transparent resin substrate was obtained using the same procedure and conditions as in Example 1, except that 0.06 part of -c-2) (maximum absorption wavelength in dichloromethane, 760 nm) 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 coated on 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, the resin composition (1) was cured by exposure (exposure amount: 500 mJ/cm ² , 200 mW) using a conveyor type exposure machine, and a resin layer was formed on the transparent resin substrate. Similarly, a resin layer made of resin composition (1) was formed on the other side of the transparent resin substrate to obtain a base material having resin layers on both sides of the transparent resin substrate. The optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 6 and Table 15.

Resin composition (1): 60 parts of tricyclodecane dimethanol 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 (A-a-1) and 0.03 parts of compound (A-a-2) were used as compound (A-a), and 0.03 parts of compound (A-a-2) were used as compound (A-b). (A-b-1) 0.10 part was used, and as compound (A-c), 0.04 part of compound (A-c-1) and 0.05 part of compound (A-c-2) were used. A base material made of a transparent resin substrate was obtained using the same procedure and conditions as in Example 1, except that . The optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 7 and Table 15.

[Example 4]
In Example 1, 0.04 parts of compound (A-a-1) and 0.03 parts of compound (A-a-2) were used as compound (A-a), and 0.03 parts of compound (A-a-2) were used as compound (A-b). 0.01 part of (A-b-1) was used, and 0.03 part of compound (A-c-1) and 0.04 part of compound (A-c-2) were used as compound (A-c). In addition, as the other near-infrared absorbing dye (X), 0.04 part of the near-infrared absorbing dye (X-1) represented by the following formula (X-1) (maximum absorption wavelength in dichloromethane 813 nm) was used. A base material made of a transparent resin substrate containing the compound (A) and the near-infrared absorbing dye (X) was obtained using the same procedures and conditions as in Example 1, except for the following. The optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images 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 resin composition (2) having the following composition was applied with a spin coater onto a transparent glass substrate "OA-10G (thickness 150 um)" (manufactured by Nippon Electric Glass Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width, The solvent was evaporated off 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, the resin composition (2) is cured by exposure (exposure amount: 500 mJ/cm ² , 200 mW) using a conveyor type exposure machine, and the transparent glass substrate having the transparent resin layer containing the compound (A) is A base material was obtained. The optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 9 and Table 15.

Resin composition (2): 20 parts of tricyclodecane dimethanol diacrylate, 80 parts of dipentaerythritol hexaacrylate, 4 parts of 1-hydroxycyclohexylphenyl ketone, 3.00 parts of compound (A-a-1), compound (A -a-2) 1.00 parts, compound (A-b-1) 7.00 parts, compound (A-c-1) 4.00 parts, methyl ethyl ketone (solvent, TSC: 35%)
[Example 6]
In Example 1, 0.04 parts of compound (A-a-1) and 0.03 parts of compound (A-a-2) were used as compound (A-a), and 0.03 parts of compound (A-a-2) were used as compound (A-b). (A-b-1), 0.04 part of compound (A-c-1) was used as compound (A-c), and the thickness of the transparent resin substrate was A base material made of a transparent resin substrate was obtained using the same procedure and conditions as in Example 1 except that the thickness was 0.08 mm. The optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 10 and Table 15.

[Example 7]
In Example 1, 0.05 part of compound (A-a-1) was used as compound (A-a), and 0.85 part of compound (A-b-1) was used as compound (A-b). Example 1 except that irako, 0.05 part of compound (A-c-1) was used as compound (A-c), and the thickness of the transparent resin substrate was 0.04 mm. A base material made of a transparent resin substrate was obtained using the same procedure and conditions. The optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images 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 with a resin concentration of 20% by mass, and the resin was prepared in the same manner as in Example 1, except that the resulting solution was used. A support was prepared.

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

Resin composition (3): 100 parts of tricyclodecane dimethanol diacrylate, 4 parts of 1-hydroxycyclohexylphenyl ketone, 0.50 parts of compound (A-a-1), 0.50 parts of compound (A-c-1) 2.50 parts of compound (A-c-2), 1.40 parts of near-infrared absorption dye (X-1), methyl ethyl ketone (solvent, TSC: 25%)
[Example 9]
A resin composition (4) with the following composition was applied using a spin coater on a near-infrared absorbing glass substrate "BS-11 (thickness 120 um)" (manufactured by Matsunami Glass Industries Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width. The solution was then 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, the resin composition (4) is cured by exposure (exposure amount: 500 mJ/cm ² , 200 mW) using a conveyor type exposure machine, and the near-infrared absorbing glass having a transparent resin layer containing the compound (A) is A base material consisting of a substrate was obtained. The optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 13 and Table 15.

Resin composition (4): 20 parts of tricyclodecane dimethanol diacrylate, 80 parts of dipentaerythritol hexaacrylate, 4 parts of 1-hydroxycyclohexylphenyl ketone, 1.00 parts of compound (A-a-1), compound (A -c-1) 1.00 parts, compound (A-c-2) 5.00 parts, methyl ethyl ketone (solvent, TSC: 35% by mass)
[Example 10]
In Example 1, 0.04 parts of compound (A-a-1) and 0.03 parts of compound (A-a-2) were used as compound (A-a), and 0.03 parts of compound (A-a-2) were used as compound (A-b). (A-b-1), 0.04 part of compound (A-c-1) was used as compound (A-c), and near-infrared absorbing dye (X-1 ) A base material made of a transparent resin substrate containing the compound (A) and the near-infrared absorbing dye (X) was obtained using the same procedure and conditions as in Example 1, except that 0.04 part of the compound (A) and the near-infrared absorbing dye (X) were used. The optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 14 and Table 15.

[Example 11]
In Example 1, 0.04 parts of compound (A-a-1) and 0.03 parts of compound (A-a-2) were used as compound (A-a), and 0.03 parts of compound (A-a-2) were used as compound (A-b). Same procedure as in Example 1 except that 0.34 part of (A-b-1) was used and 0.04 part of compound (A-c-1) was used as compound (A-c). A base material made of a transparent resin substrate was obtained according to the procedure and conditions.

A dielectric multilayer film (I) is formed as a first optical layer on one side of the obtained base material, and a similar dielectric multilayer film (I) is further formed on the other side of the base material 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 deposition temperature of 120° C. (4 layers in total). The silica layer and titania layer of the dielectric multilayer film (I) were laminated alternately in the order of titania layer, silica layer, titania layer, and silica layer from the base material side, and the outermost layer of the optical filter was the silica layer.

Here, the dielectric multilayer film (I) was a multilayer vapor-deposited film with 4 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 membrane 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 optical properties of the obtained base material and optical filter were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 15 and Table 15.

[Examples 12 to 14]
A base material was created 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 optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in Table 15.

[Example 15, 16]
A base material was created 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 optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 16, FIG. 17, and Table 15.

[Comparative example 1]
In Example 1, 0.07 part of compound (A-a-1) was used as compound (A-a), and 0.08 part of compound (A-b-1) was used as compound (A-b). A base material made of a transparent resin substrate was obtained using the same procedure and conditions as in Example 1, except that . |X _b −X _a | of the obtained base material was 61 nm, which was less than 100 nm.

Subsequently, a dielectric multilayer film (II) consisting of alternately laminated silica (SiO ₂ ) layers and titania (TiO ₂ ) layers (26 layers in total) was formed as a first optical layer on one side of the obtained base material. A dielectric multilayer film (III) in which silica (SiO ₂ ) layers and titania (TiO ₂ ) layers are alternately laminated (20 layers in total) as a second optical layer on the other surface of the base material. 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.

The thickness and number of each layer are determined based on the wavelength-dependent characteristics of the refractive index of the base material and the absorption of the applied compound (A) in order to achieve an anti-reflection effect in the visible light region and selective transmission/reflection performance in the near-infrared region. Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) according to the characteristics. When performing optimization, in this comparative example, input parameters (target values) to the software were as shown in Table 11 below.

As a result of film configuration optimization, in Comparative Example 1, the dielectric multilayer film (II) had 26 layers in which silica layers with a thickness of 31 to 155 nm and titania layers with a thickness of 10 to 94 nm were alternately laminated. The dielectric multilayer film (III) is a multilayer deposited film with 20 layers, in which silica layers with a thickness of 38 to 189 nm and titania layers with a thickness of 11 to 109 nm are alternately laminated. Ta. An example of the optimized membrane configuration is shown in Table 12 below.

The optical properties of the obtained optical filter were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 18 and Table 15. Although the optical filter obtained in Comparative Example 1 showed a relatively good optical density, the transmittance decreased significantly at high angles of incidence, and ghosts were generated, which is thought to be caused by near-infrared reflection by the dielectric multilayer film. It was confirmed that the color shading suppression effect was inferior.

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

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

As a result of film configuration optimization, in Comparative Example 2, the dielectric multilayer film (IV) had 30 layers in which silica layers with a thickness of 22 to 467 nm and titania layers with a thickness of 6 to 130 nm were alternately laminated. The dielectric multilayer film (V) is a multilayer deposited film with 20 layers, in which silica layers with a thickness of 84 to 206 nm and titania layers with a thickness of 8 to 109 nm are alternately laminated. Ta. An example of the optimized membrane 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 optical properties of the obtained optical filter were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 19 and Table 15. It was confirmed that the optical filter obtained in Comparative Example 2 had a large decrease in transmittance at high angles of incidence, and also did not have sufficient absorption in the near-infrared wavelength region, so it was inferior in color shading suppression effect and ghost suppression effect. Ta.

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

The optical properties of the obtained optical filter were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 20 and Table 15. It was confirmed that the optical filter obtained in Comparative Example 3 did not have sufficient absorption in the near-infrared wavelength region and was inferior in ghost suppression effect.

[Comparative example 4]
A base material made of a transparent resin substrate was obtained using the same procedure and conditions as in Comparative Example 1. The optical properties of the optical filter made of this base material were evaluated by measuring the spectral transmittance. In addition, a camera module was created using the obtained optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in FIG. 21 and Table 15. It was confirmed that the optical filter obtained in Comparative Example 4 did not have sufficient absorption in the near-infrared wavelength region and was inferior in ghost suppression effect.

[Comparative example 5]
A camera module was created using only the cover member without using an optical filter, and color shading and ghosting of camera images were evaluated. The results are shown in Table 15. Since the camera module obtained in Comparative Example 5 does not have an optical filter that absorbs near-infrared light, the degree of color shading and ghosting is 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 composition of the base material, the symbols of various compounds, etc., and the drying conditions of 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 the compound (A) Form (2): Resin layers on both sides of the transparent resin substrate containing the compound (A) Form (3): Compound on both sides of the resin support Form (4): having a transparent resin layer containing compound (A) on one side of a transparent glass substrate Form (5): having a transparent resin layer containing compound (A) on one side of a near-infrared absorbing glass substrate Form (6): having an antireflection layer 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 | less than 100 nm has near-infrared reflective layers on both sides (comparative example)
Form (9): A transparent resin substrate containing compound (A) and having |X _b −X _a | less than 100 nm has an antireflection layer on both sides (comparative example)
Form (10): Transparent resin substrate containing compound (A) and having |X _b −X _a | 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)" (manufactured by Nippon Electric Glass Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width.
Glass substrate (2): Near-infrared absorbing glass substrate "BS-11 (thickness 120 μm)" cut to a size of 60 mm in length and 60 mm in width (manufactured by Matsunami Glass Industry Co., Ltd.)
<Resin support>
Resin support (1): Transparent resin substrate made of resin A with a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm <Near-infrared absorbing dye>
≪Compound (A)≫
Compound (A-a-1): Compound represented by formula (A-a-1) (maximum absorption wavelength in dichloromethane 712 nm)
Compound (A-a-2): Compound represented by formula (A-a-2) (maximum absorption wavelength in dichloromethane 686 nm)
Compound (A-b-1): Compound represented by formula (A-b-1) (maximum absorption wavelength in dichloromethane 738 nm)
Compound (A-c-1): Compound represented by formula (A-c-1) (maximum absorption wavelength in dichloromethane 776 nm)
Compound (A-c-2): Compound represented by formula (A-c-2) (maximum absorption wavelength in dichloromethane 760 nm)
Compound (A-c-3): Compound represented by the following formula (A-c-3) (maximum absorption wavelength in dichloromethane 773 nm)

≪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): Compound represented by the following formula (X-2) (maximum absorption wavelength in dichloromethane: 870 nm)

<Solvent>
Solvent (1): Methylene chloride Solvent (2): N,N-dimethylacetamide Solvent (3): Cyclohexane/xylene (mass ratio: 7/3)
<Film drying conditions>
Condition (1): 20℃/8hr → 100℃/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
Note that the coating film was peeled off from the glass plate before drying under reduced pressure.

Condition (4): 80℃/2min
Condition (5): 70℃/2min

1, 1', 1'': Light 2: Optical filter 3: Spectrophotometer 111: Camera image 112: White plate 113: Example of the center of the white plate 114: Example of the edge of the 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: Aperture 240: Optical filter 250: Solid-state image sensor 260: Housing

Claims (11)

A resin composition for an optical filter, comprising a resin and a compound (A) having an absorption maximum in the wavelength range of 650 to 800 nm, and satisfying at least one of the following conditions 1 and 2:
(Condition 1) The compound (A) includes a compound represented by the following formula (A-c-3);
(Condition 2) Further contains a compound represented by the following formula (X-2).
The optical filter according to claim 1, wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds. Resin composition for use. The resin may be 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, a polysulfone resin, or a polyether sulfone. resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane UV-curable resins, maleimide resin, alicyclic epoxy thermosetting resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin, and sol-gel method. The resin composition for an optical filter according to claim 1, which is at least one resin selected from the group consisting of resins containing silica as a main component. The resin composition for an optical filter according to claim 1, wherein the resin has a refractive index (n20d) of 1.50 to 1.53. An optical filter comprising a base material having a layer formed using the resin composition for an optical filter according to any one of claims 1 to 4, and satisfying the following requirements (a) and (b):
(a) In the wavelength range 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 a direction oblique to the vertical direction at 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 optical density OD _a-0 for light incident from the vertical direction of the optical filter and the average optical density for light incident from a direction oblique to the vertical direction at 30 degrees. Both the value OD _a-30 and the average value OD _a-60 of optical density for light incident from a direction diagonal at 60 degrees with respect to the vertical direction are 1.8 or more. The optical filter according to claim 5, further satisfying the following requirement (c):
(c) In the wavelength range of 900 to 1200 nm, the average transmittance T _IR of light incident from the vertical direction of the optical filter is 60% or more. The optical filter according to claim 5, 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 from the vertical direction of the optical filter and the average transmittance of light incident from a direction oblique to the vertical direction at 30 degrees The value T _a-30 and the average value T _a-60 of the transmittance of light incident obliquely at 60 degrees with respect to the vertical direction are both 65% or more and less than 90%. The optical filter according to claim 5, wherein the base material further satisfies the following requirement (f):
(f) In the wavelength range of 600 to 900 nm, the longest wavelength X _a where the transmittance for light incident from the vertical direction of the base material ranges from more than 10% to less than 10% 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 and the transmittance for light incident from the vertical direction of the base material from the short wavelength side to the long wavelength side from 10% or less to over 10% | X _b −X _a | is 100 nm or more. A camera module comprising the optical filter according to claim 5. The camera module according to claim 9, further comprising a cover member that protects an internal mechanism of the camera module from the outside, and wherein the cover member has a near-infrared reflecting function. An electronic device comprising the camera module according to claim 9.