JP7040362B2 - Optical filters, solid-state image sensors, camera modules and biometrics - Google Patents

Description

The present invention relates to an optical filter and an application using the optical filter. More specifically, the present invention relates to an optical filter that selectively transmits visible light and a part of near infrared rays, and a solid-state imaging device, a camera module, and a biometric authentication device using the optical filter.

A CCD or CMOS image sensor, which is a solid-state image sensor for color images, is used in solid-state image sensors such as video cameras, digital still cameras, mobile phones with camera functions, and smartphones. In, a silicon photodiode having sensitivity to near infrared rays, which cannot be perceived by the human eye, is used. In these solid-state image sensors, it is necessary to perform luminosity factor correction that makes the hue look natural to the human eye, and an optical filter that selectively transmits or cuts light rays in a specific wavelength region (for example, near-infrared cut). Filter) is often used.

As such a near-infrared cut filter, those manufactured by various methods have been conventionally used. For example, Patent Document 1 describes a near-infrared cut filter in which a substrate made of a transparent resin is used and a near-infrared absorber is contained in the transparent resin, and Patent Document 2 describes a glass substrate containing copper ions. A near-infrared cut filter using the above is described.

In recent years, attempts have been made to add sensing functions such as motion capture using near infrared rays and distance recognition (spatial recognition) to camera modules in addition to visible light. In such an application, it is necessary to selectively transmit visible light and a part of near-infrared rays, so that it is not possible to use a conventional near-infrared cut filter that uniformly blocks near-infrared rays.

As an optical filter that selectively transmits visible light and a part of near infrared rays, for example, the optical filter described in Patent Document 3 is known. Toa Rikagaku Research Institute Co., Ltd. and Ceratech Japan Co., Ltd. sell filters in which a dielectric multilayer film is formed on a glass substrate. Further, Patent Documents 4 to 7 describe an optical filter that selectively transmits visible light containing a near-infrared absorber and a part of near-infrared light.

Japanese Unexamined Patent Publication No. 6-200113 Japanese Patent No. 5036229 JP-A-2015-227963 International Publication No. 2015/056734 Japanese Unexamined Patent Publication No. 2016-142891 Japanese Unexamined Patent Publication No. 2016-162946 Japanese Unexamined Patent Publication No. 2016-200771

However, with conventional optical filters that selectively transmit visible light and some near-infrared rays, noise is generated by the sensitivity of the blue, green, and red pixels to near-infrared rays when detecting under sunlight. It was found that the signal-to-noise ratio (S / N ratio) deteriorated. In particular, in recent years, there has been a tendency for solid-state image sensors and the like to be thinner, and the angle of light incident on the solid-state image sensor and the like is large regardless of whether a lens unit is used or an image is obtained by another mechanism. , The maximum may be about 35 degrees. For this reason, an optical filter provided in a solid-state image sensor or the like is also required to have a configuration in which light incident at a high angle is taken into consideration.

However, in the conventional optical filter, when light is incident on the filter at a high angle, the transmittance of near-infrared rays other than the near-infrared rays to be transmitted is increased, which is set in consideration of the vertical incident on the optical filter. , It turned out that the noise gets worse. In particular, when the near infrared rays to be selectively transmitted are 900 nm or more and an optical filter having a large incident angle dependence on the shorter wavelength side than the selective transmission band is used, when light rays are obliquely incident on the filter, It was found that the amount of noise (N / S ratio) of the near-infrared rays (near-infrared rays that were selectively transmitted) used for the sensing function increased, and that problems such as adverse effects on camera image quality and color reproducibility at the edges of the image occurred. rice field.

FIG. 1 shows an example of a conventional optical filter that selectively transmits conventional visible light and a part of near-infrared rays that transmit light having a wavelength of 910 to 999 nm incident from a direction perpendicular to the surface direction of the filter. When light is incident from a direction perpendicular to the plane direction of the optical filter that selectively transmits this visible light and some near infrared rays, and when light is incident at an angle of 35 degrees from the vertical direction, it is near. The shortest wavelength at which the transmittance in the infrared transmission band is 50% is shifted to the 42 nm short wavelength side. That is, when the incident angle of the light to the filter becomes 35 ° (35 ° incident), the selective transmission band (near infrared selective transmission band) in the near infrared region is significantly shifted to the short wavelength side, and the original light ray. It was confirmed that the transmittance in the wavelength region to be cut (around 850 to 900 nm in the example of this figure) becomes high.

In addition, light with a wavelength of 800 to 900 nm has been used in the past for sensing in motion capture using near infrared rays, distance recognition (spatial recognition), biometric authentication, etc., but the light source to be sensed is more invisible to the human eye. As described above, light having a longer wavelength of 900 to 1100 nm has come to be used.

An object of the present invention is an optical filter having a function of selectively transmitting visible light and a part of near infrared rays (wavelength 900 to 1100 nm) and having little dependence on an incident angle, and the optical filter is used. It is an object of the present invention to provide an optical filter capable of providing an apparatus having a small amount of infrared noise even when used in sunlight, and an apparatus using the optical filter.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a specific optical filter, and have completed the present invention. An example of the embodiment of the present invention is shown below.

[1] A compound (A) having an absorption maximum at a wavelength of 800 to 930 nm is contained, and the compound (A) is contained.
In light incident from the direction perpendicular to the surface direction of the optical filter,
The average transmittance of light having a wavelength of 800 to 1200 nm other than the wavelength (region) I is 30% or less so that light having a wavelength (region) I of at least a part of the wavelengths of 900 to 1100 nm and visible light are transmitted. To shut off,
Optical filter.

[2] Satisfy the following requirements (a) to (c) and
In light incident from the direction perpendicular to the surface direction of the optical filter,
The average transmittance of light having a wavelength of 800 to 1200 nm other than the wavelength (region) I is 30% or less so that light having a wavelength (region) I of at least a part of the wavelengths of 900 to 1100 nm and visible light are transmitted. An optical filter that blocks light.
(A) At wavelengths of 430 to 580 nm, the average value of the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 60% or more. (B) At wavelengths of 800 to 900 nm, with respect to the surface direction of the optical filter. The average value of the transmittance of light incident from the vertical direction is 10% or less. (C) The shortest wavelength at which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% at a wavelength of 800 to 1200 nm. When λIRT ₀ (nm), the wavelength λIRT ₀ is in the range of 900 to 1100 nm.
At wavelengths of 800 nm to (λIRT _0-50 ) nm, the maximum value of the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter is 15% or less.

[3] The optical filter according to [2], which comprises the compound (A) having an absorption maximum at a wavelength of 800 to 930 nm.

[4] The optical filter according to any one of [1] to [3], which contains the compound (B) having an absorption maximum wavelength in a wavelength of 600 nm or more and less than 800 nm.
[5] The optical filter according to any one of [1] to [4], which comprises a compound (X) having an absorption maximum wavelength at a wavelength of 300 to 425 nm.

[6] At least one layer containing the compound (A) having an absorption maximum at a wavelength of 800 to 930 nm is provided.
Satisfy the following formula (A1),
The optical filter according to any one of [1] to [5].

［式（Ａ１）中の符号は、以下のことを示す。
化合物（Ａ）を含む層をｎ層有する光学フィルターにおいて、
ＣＡｎはｎ層中の化合物（Ａ）の濃度（ｗｔ％）を示し、ｌＡｎは該ｎ層の厚み（μｍ）を示す。］

[The reference numerals in the formula (A1) indicate the following.
In an optical filter having n layers containing the compound (A),
CAN indicates the concentration (wt%) of the compound (A) in the n layer, and lAn indicates the thickness (μm) of the n layer. ]

[7] At wavelengths of 800 to 1200 nm, the total wavelength (range) at which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% or more is 20 to 150 nm, [1] to [ 6] The optical filter according to any one of.

[8] The optical filter according to any one of [1] to [7], which satisfies the following requirement (d).
(D) At wavelengths of 800 to 1200 nm, the shortest wavelength at which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% is λIRT ₀ (nm).
When λIRT ₃₅ is the shortest wavelength at which the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter at a wavelength of 800 to 1200 nm is 50%, the following equation (d1) is satisfied. ｜ λIRT ₀ －λIRT ₃₅ ｜ ≦ 30nm (d1)

[9] [1] to [8] having a dielectric multilayer film and having four or more laminated portions in which two or more layers having a thickness of 60 nm or less are continuous among the layers constituting the dielectric multilayer film. ] The optical filter described in any of.

[10] It has a dielectric multilayer film and has
When the number of layers of all the dielectric multilayer films contained in the optical filter is A and the number of layers of layers having a thickness of 60 nm or less is B, B / A> 0.2 is satisfied, [1] to [9]. ] The optical filter described in any of.

[11] A solid-state image sensor including the optical filter according to any one of [1] to [10].
[12] A camera module including the optical filter according to any one of [1] to [10].
[13] A biometric authentication device including the optical filter according to any one of [1] to [10].

According to the present invention, it has a function of selectively transmitting visible light and a part of near-infrared light (wavelength 900 to 1100 nm), and is on the long wavelength side of the visible light transmission band or in the near-infrared selective transmission band. It is an optical filter that is less dependent on the incident angle on the short wavelength side, and even when the optical filter is used in sunlight, it is possible to obtain good camera image quality with a small amount of infrared noise. It is possible to provide an optical filter that can be used.

FIG. 1 is a spectral transmission spectrum of an optical filter that selectively transmits the conventional visible light obtained in Comparative Example 1 and a part of near infrared rays. FIG. 2 is a schematic cross-sectional schematic diagram showing a configuration example of the optical filter of the present invention. FIG. 3 is a schematic cross-sectional schematic diagram showing an example of a solid-state image sensor and a module including the optical filter of the present invention. FIG. 4 is a schematic cross-sectional schematic diagram showing an example of a solid-state imaging device including an optical filter of the present invention, a camera module, and a biometric authentication device. FIG. 5A is a schematic diagram showing a method of measuring the transmittance of light incident from a direction perpendicular to the surface direction of the optical filter. FIG. 5B is a schematic view showing a method of measuring the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter. FIG. 6 is a schematic cross-sectional schematic diagram showing an example of a sensor portion in a solid-state image sensor including the optical filter of the present invention. FIG. 7 is the irradiation dose data of Gifu at a certain date and time released by the New Energy and Industrial Technology Development Organization. FIG. 8 is an example of wavelength-specific sensitivity of each of the blue, green, red, and infrared sensor pixels. FIG. 9 is a spectral transmission spectrum of the optical filter 1 obtained in Example 1. FIG. 10 is a spectral transmission spectrum of the optical filter 2 obtained in Example 2. FIG. 11 is a spectral transmission spectrum of the optical filter 3 obtained in Example 3. FIG. 12 is a spectral transmission spectrum of the optical filter 4 obtained in Example 4. FIG. 13 is a spectral transmission spectrum of the optical filter 5 obtained in Example 5. FIG. 14 is a spectral transmission spectrum of the optical filter 6 obtained in Example 6. FIG. 15 is a spectral transmission spectrum of the optical filter 7 obtained in Example 7. FIG. 16 is a spectral transmission spectrum of the optical filter 8 obtained in Example 8. FIG. 17 is a spectral transmission spectrum of the optical filter 9 obtained in Example 9. FIG. 18 is a spectral transmission spectrum of the optical filter 11 obtained in Comparative Example 2. FIG. 19 is a spectral transmission spectrum of the optical filter 12 obtained in Comparative Example 3. FIG. 20 is a spectral transmission spectrum of the optical filter 13 obtained in Comparative Example 4. FIG. 21 is a spectral transmission spectrum of the optical filter 14 obtained in Comparative Example 5. FIG. 22 is a spectral transmission spectrum of the optical filter 15 obtained in Comparative Example 6.

≪Optical filter≫
The optical filter according to the present invention (hereinafter, also referred to as “the present filter”) is a light incident from a direction perpendicular to the plane direction of the optical filter, and has a wavelength (region) I of at least a part of the wavelengths of 900 to 1100 nm. An optical filter that transmits light and visible light and blocks light having a wavelength of 800 to 1200 nm other than the wavelength (region) I so that the average transmission rate is 30% or less, and is the following requirement (I) or ( II) is satisfied.
Hereinafter, the optical filter satisfying the following requirement (I) is also referred to as the present filter 1, and the optical filter satisfying the following requirement (II) is also referred to as the present filter 2.

Requirement (I): Containing the compound (A) having an absorption maximum at a wavelength of 800 to 930 nm Requirement (II): Satisfying the following requirements (a) to (c) (a) Surface direction of an optical filter at a wavelength of 430 to 580 nm The average value of the transmittance of light incident from the vertical direction is 60% or more. (B) At a wavelength of 800 to 900 nm, the average value of the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 10. % Or less (c) When the shortest wavelength at which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% at a wavelength of 800 to 1200 nm is λIRT ₀ (nm), the wavelength λIRT ₀ . Is at 900 to 1100 nm,
At wavelengths of 800 nm to (λIRT _0-50 ) nm, the maximum value of the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter is 15% or less.

In the present invention, the description of wavelengths X to Ynm indicates that the wavelength is X nm or more and Y nm or less. The average value (average transmittance) of the transmittances of wavelengths X to Ynm is the number of measured transmittances obtained by measuring the transmittances at each wavelength of Xnm or more and Ynm or less in 1 nm increments. It is calculated by dividing by (wavelength range, YX + 1).

One of the features of this filter is that it transmits visible light. Examples of the visible light include light in the wavelength region of 430 to 580 nm.
In the present invention, "transmitting" light of a certain wavelength means that the light transmittance, which is the ratio of the transmitted luminous flux (including the diffusion component) to the incident luminous flux of the light of that wavelength, is 50% or more. To say.

When this filter is used in a solid-state image sensor or the like, it is preferable that the visible light transmittance is high. Specifically, at a wavelength of 430 to 580 nm, the average value of the transmittance when measured from the direction perpendicular to the surface direction of the optical filter is preferably 60% or more, more preferably 65% or more, still more preferably 70. % Or more, more preferably 75% or more, and particularly preferably 80% or more. When the average value of the transmittance is in the above range in this wavelength range, excellent image pickup sensitivity can be achieved when this filter is used in a solid-state image sensor or the like.

In this filter, the average value of the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter at a wavelength of 430 to 580 nm is preferably 57% or more, more preferably 62% or more. It is more preferably 67% or more, and particularly preferably 72% or more. It can be said that a filter having an average transmittance in the above range is an optical filter having little dependence on the incident angle in the visible light transmission band, and when the filter is used in a solid-state image sensor or the like, or in an oblique direction to the filter. Excellent image pickup sensitivity can be achieved even when light is incident from the light beam.

One of the features of this filter is that light incident from a direction perpendicular to the surface direction of the optical filter transmits light having a wavelength (region) I of at least a part of the wavelengths of 900 to 1100 nm.
The wavelength (range) I indicates a wavelength or a wavelength range, and includes a case where the wavelength width of the transmission portion is less than 2 nm.

Since this filter has such characteristics, by using the filter, sensing such as motion capture, distance recognition (spatial recognition), and biometric authentication can be performed by light that is more invisible to the human eye.
According to FIG. 8, the upper limit wavelength of the wavelength (region) I is preferably 1050 nm, more preferably 1025 nm, from the viewpoint of improving the sensor sensitivity of the infrared pixel (IR pixel) for sensing. .. Further, according to FIG. 7, considering the case of using under the sun's rays, the lower limit wavelength of the wavelength (region) I is preferably 905 nm or more, more preferably 908 nm or more from the viewpoint of the intensity distribution of the sun's rays. Particularly preferably, it is 910 nm or more. The λIRT ₀ is preferably in the same range as the lower limit wavelength of the wavelength (region) I.

According to FIG. 7, this filter suppresses the influence of noise caused by light exceeding 780 nm due to the sun's rays, and according to FIG. 8, the sensor sensitivity of the infrared pixel (IR pixel) for sensing is obtained. A wavelength (range) in which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% or more at a wavelength of 800 to 1200 nm, preferably a wavelength of 900 to 1100 nm. The total of I is preferably 20 to 150 nm, more preferably 30 to 140 nm.
The wavelength (the wavelength (region) I) can be easily obtained even for light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the filter. The total of the regions (regions) I is preferably 40 nm or more, preferably 150 nm or less, and more preferably 140 nm or less.
When the total of the wavelengths (regions) I is in the above range, it is possible to further reduce the noise due to the wavelengths not sensed while ensuring the sensitivity of the wavelengths to be sensed.

For example, when the total of the wavelengths (regions) I is 20 nm, there are a plurality of portions where the width of the wavelengths (regions) I having a transmittance of 50% or more is less than 2 nm, and a total of 20 nm is present. However, at a wavelength of 800 to 1200 nm, it is preferable that there is one portion having a wavelength width of 20 nm such that the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% or more. In the present invention, a width having a wavelength width of 2 nm or more at which the transmittance of light incident from a direction perpendicular to the surface direction of the optical filter at a wavelength of 800 to 1200 nm is 50% or more is referred to as a transmission width.
For the same reason as described above, the transmission width is preferably 20 nm or more, more preferably 30 nm or more, particularly preferably 40 nm or more, preferably 150 nm or less, and more preferably 140 nm or less.

In addition, this filter may block light having a wavelength of 800 to 1200 nm other than the wavelength (region) I of the light incident from the direction perpendicular to the surface direction of the optical filter so that the average transmittance is 30% or less. It is one of the features.
Here, the "average transmittance of light having a wavelength of 800 to 1200 nm other than the wavelength (region) I of the light incident from the direction perpendicular to the surface direction of the optical filter" is defined as a wavelength in increments of 1 nm at a wavelength of 800 to 1200 nm. (Region) It is calculated by measuring the transmittance of light in a wavelength range other than I and dividing the total transmittance by the number of measured wavelength ranges.
The average transmittance is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and particularly preferably 8% or less.
When the average transmittance is in the above range, light having a wavelength of 800 to 1200 nm other than the light having a desired wavelength to be used for sensing or the like can be blocked, and by using an optical filter having an average transmittance in the above range, it is possible to block light. A large S / N ratio can be obtained.

The present filter preferably transmits light having a wavelength (region) II of at least a part of the wavelengths of 850 to 1100 nm in the light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter.
The wavelength (region) II indicates a wavelength or wavelength range through which light is transmitted at a wavelength of 850 to 1100 nm in light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter, and the wavelength width of the transmitted portion. Including the case where is less than 2 nm.
When the λIRT ₃₅ has a wavelength of 850 nm or more, the lower limit wavelength of the wavelength (region) II is synonymous with λIRT ₃₅ .

Further, in this filter, the average transmittance of light having a wavelength of 800 to 1200 nm other than the wavelength (region) II of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter is 30% or less. It is preferable to block the light.
The average transmittance is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and particularly preferably 8% or less.
When the average transmittance is in the above range, light having a wavelength of 800 to 1200 nm other than the light having a desired wavelength to be used for sensing or the like can be blocked, and by using an optical filter having an average transmittance in the above range, it is possible to block light. A large S / N ratio can be obtained.

Here, "the average transmittance of light having a wavelength of 800 to 1200 nm other than the wavelength (region) II of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter" is defined at a wavelength of 800 to 1200 nm. It is calculated by measuring the transmittance of light in a wavelength range other than wavelength (range) II in 1 nm increments and dividing the total transmittance by the number of measured wavelength ranges.

In the present invention, "blocking" light of a certain wavelength means that the light transmittance, which is the ratio of the transmitted luminous flux (including the diffusion component) to the incident luminous flux of the light of that wavelength, is 30% or less. To say.

In this filter, the average value of the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter at a wavelength of 800 to 900 nm is preferably 15% from the viewpoint of efficiently removing noise caused by sunlight. Below, it is more preferably 10% or less, still more preferably 9% or less, still more preferably 5% or less, and particularly preferably 3% or less.
When the average value of the transmittance is in the above range, light having a wavelength of 800 to 1200 nm other than the light having a desired wavelength to be used for sensing or the like can be blocked, and an optical filter having an average value of the transmittance in the above range can be used. By using it, a large S / N ratio can be obtained.

In this filter, the average value of the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter at a wavelength of 800 to 900 nm is preferably 25% or less, more preferably 20% or less. It is more preferably 15% or less, still more preferably 13% or less, and particularly preferably 5% or less. It can be said that a filter having an average transmittance in the above range is an optical filter having little dependence on the incident angle in the near infrared band, and when the filter is used for sensing or the like, the amount of near infrared noise (N / S ratio). It is possible to obtain an image or the like having excellent camera image quality and color reproducibility at the edge of the image.

In this filter, when the shortest wavelength at which the transmittance of light incident from the direction perpendicular to the plane direction of the optical filter is 50% at a wavelength of 800 to 1200 nm is λIRT ₀ (nm), the wavelength λIRT ₀ is set. It is preferably in the range of 900 to 1100 nm, and more preferably in the same range as the lower limit wavelength of the wavelength (region) I.
At a wavelength of 800 nm to (λIRT _0-50 ) nm, the maximum value of the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter is preferably 15% or less, more preferably 10%. Hereinafter, it is more preferably 8% or less, and particularly preferably 5% or less.
It can be said that a filter having the maximum transmittance in the above range is an optical filter having little dependence on the incident angle in the near infrared band, and when the filter is used for sensing or the like, the amount of near infrared noise (N / S ratio). It is possible to obtain an image or the like having excellent camera image quality and color reproducibility at the edge of the image.

It is preferable that this filter further satisfies the following requirement (d).
(D) At wavelengths of 800 to 1200 nm, the shortest wavelength at which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% is λIRT ₀ (nm).
When λIRT ₃₅ is the shortest wavelength at which the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter at a wavelength of 800 to 1200 nm is 50%, the following equation (d1) is satisfied. ..
｜ λIRT ₀ －λIRT ₃₅ ｜ ≦ 30nm (d1)

The right side of the formula (d1) is more preferably 25 nm, still more preferably 20 nm, still more preferably 15 nm, and particularly preferably 13 nm.
By satisfying the above formula (d1), it is possible to maintain the blocking performance at a wavelength of 800 to 900 nm even when incident at 35 degrees, and image pickup is performed using a solid-state image sensor including this filter, a camera module, a biometric authentication device, or the like. At that time, it is possible to reduce noise due to a wavelength of more than 780 nm in the peripheral portion of the image corresponding to the light beam incident on the optical filter at a high angle.
An optical filter having this optical characteristic contains, for example, the following compound (A) at an appropriate concentration, and appropriately sets the wavelength of the near infrared transmission region (a part of the wavelength of 900 to 1100 nm) of the dielectric multilayer film. Can be obtained by

The λIRT ₃₅ is preferable because the sun rays that cause noise tend to have a high intensity at a wavelength of 800 to 900 nm, for example, from the viewpoint of preventing noise from entering the sensor. Is 875 nm or more, more preferably 880 nm or more, still more preferably 890 nm or more, still more preferably 895 nm or more, and particularly preferably 900 nm or more.

It is preferable that this filter further satisfies the following requirement (f).
(F) At wavelengths of 460 to 780 nm, the wavelength of the shortest wavelength at which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% is λRT ₀ (nm).
When the wavelength of the shortest wavelength at which the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter at a wavelength of 460 to 780 nm is 50% is λRT ₃₅ , the following equation (f1) is used. Meet.
｜ λRT ₀ －λRT ₃₅ ｜ ≦ 25nm (f1)

The right side of the formula (f1) is more preferably 20 nm, still more preferably 15 nm, still more preferably 10 nm, and particularly preferably 7 nm.
By satisfying the above formula (f1), the change in the amount of visible light of a color near red is small even when incident at 35 degrees, and an image is taken using a solid-state imaging device including this filter, a camera module, a biometric authentication device, or the like. At the same time, it is possible to suppress a change in the color of the visible light pixel in the peripheral portion of the image corresponding to the light beam incident on the optical filter at a high angle.
An optical filter having this optical characteristic can be obtained, for example, by containing the following compound (B) at an appropriate concentration and appropriately setting the wavelength of the near-infrared ray blocking region of the dielectric multilayer film.

The λRT ₀ is preferably 610 to 720 nm, more preferably 620 to 670 nm, still more preferably 620 to 660 nm, and particularly preferably 625 to 650 nm from the viewpoint of being superior in color reproducibility of a color image by visible light. Is desirable.
Further, it is desirable that the λRT ₃₅ is preferably 610 to 700 nm, more preferably 620 to 660 nm, still more preferably 620 to 655 nm, and particularly preferably 625 to 650 nm, like λRT ₀ .

It is preferable that this filter further satisfies the following requirement (h).
(H) At a wavelength of 300 to 450 nm, the wavelength of the shortest wavelength at which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% is defined as λBT ₀ (nm).
When λBT ₃₅ is the shortest wavelength wavelength at which the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter at a wavelength of 300 to 450 nm is 50%, the following equation (h1) is used. Meet.
｜ λBT ₀ －λBT ₃₅ ｜ ≦ 15nm (h1)

The right side of the formula (h1) is preferably 10 nm, more preferably 8 nm, still more preferably 6 nm, still more preferably 4 nm, and particularly preferably 2 nm.
By satisfying the above formula (h1), the change in the amount of visible light of a color near blue is small even when incident at 35 degrees, and an image is taken using a solid-state imaging device including this filter, a camera module, a biometric authentication device, or the like. At the same time, it is possible to suppress a change in the color of the visible light pixel in the peripheral portion of the image corresponding to the light beam incident on the optical filter at a high angle.
An optical filter having this optical characteristic can be obtained, for example, by containing the following compound (X) at an appropriate concentration and appropriately setting the wavelength of the near-infrared ray blocking region of the dielectric multilayer film.

The λBT ₀ is preferably 380 to 440 nm, more preferably 390 to 436 nm, still more preferably 395 to 430 nm, and particularly preferably 400 to 428 nm from the viewpoint of excellent color reproducibility of a color image by visible light. Is desirable.
Further, it is desirable that the λBT ₃₅ is preferably 380 to 440 nm, more preferably 390 to 436 nm, still more preferably 395 to 430 nm, and particularly preferably 400 to 428 nm, like λBT ₀ .

In this filter, the noise amount at 0 degree incident described in the following examples is preferably 15% or less, more preferably 13% or less, still more preferably 10% or less, still more preferably 8% or less, and particularly preferably 5. % Or less, and the noise amount at 35 degree incident described in the following examples is preferably 18% or less, more preferably 13% or less, still more preferably 9% or less, and particularly preferably 4% or less.
When a filter having a noise amount within the above range is used for sensing or the like, it is possible to obtain an image or the like having a small amount of near-infrared noise (N / S ratio) and excellent camera image quality and color reproducibility at the image edge.

The thickness of this filter may be appropriately selected according to the desired application, but it is preferably thin according to the recent trend of thinning and weight reduction of solid-state image sensors and the like. This filter can be made thinner, and in particular, it can be made thinner when the following base material (i) is used.
The thickness of the filter is, for example, preferably 200 μm or less, more preferably 180 μm or less, further preferably 150 μm or less, particularly preferably 120 μm or less, and the lower limit is not particularly limited, but is preferably 20 μm or more, for example.

<Compound (A)>
The filter 1 may contain a compound (A) having predetermined optical characteristics and an absorption maximum at a wavelength of 800 to 930 nm, and the filter 2 preferably contains the compound (A).
By using the compound (A), an optical filter satisfying the above requirements (a) to (c) can be easily obtained.

Compound (A) has an absorption maximum wavelength in the range of 800 to 930 nm. When the optical filter has a maximum absorption wavelength of 800 nm or more and transmits near infrared rays having a wavelength of 900 to 1100 nm incident from the direction perpendicular to the surface direction of the optical filter, the optical filter transmits the near infrared rays with respect to the surface direction of the optical filter. By absorbing light with a wavelength of 800 to 900 nm when light is incident at an angle of 35 degrees from the vertical direction (incident at 35 degrees), light with a wavelength of 800 to 900 nm that enters the visible light pixel at the time of high angle incident is blocked. be able to.

Compound (A) also tends to absorb light in a region having a long wavelength of about 10 to 70 nm from its absorption maximum wavelength. Therefore, in an optical filter that transmits near infrared rays with a wavelength of 900 to 1100 nm, light with a wavelength of 800 to 900 nm is more efficient when light is incident at an angle of 35 degrees from the direction perpendicular to the plane direction of the optical filter. The absorption maximum wavelength of the compound (A) is preferably 830 nm or more, more preferably 840 nm or more, still more preferably 851 nm or more, and particularly preferably 852 nm or more, from the viewpoint of being able to block light.

As shown in FIG. 7, for example, the sun rays that cause noise tend to have a high intensity at a wavelength of 800 to 900 nm and a low intensity at a wavelength of about 930 to 980 nm. Therefore, it is important to more efficiently block the noise caused by the light having a wavelength of 800 to 900 nm that enters the visible light pixel of the sun's rays in order to reduce the amount of noise, and to efficiently reduce the transmittance at the wavelength of 800 to 900 nm. The absorption maximum wavelength of the compound (A) is preferably 930 nm or less, more preferably 920 nm or less, and particularly preferably 910 nm or less. According to FIG. 7, the intensity of the sun's rays rises again at a wavelength of 980 nm or more and has a peak, but according to FIG. 8, for light having a wavelength of 980 nm or more, the sensor sensitivity is low, so that the wavelength is 930 nm or less. It is effective to block the light.

The compound (A) is not particularly limited as long as it is a compound having the maximum absorption wavelength, but is preferably a solvent-soluble dye compound, and is preferably a squarylium-based compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, or croconium. Compounds, hexaphyllin compounds, azo compounds, naphthoquinone compounds, oxonol compounds, pyrolopyrrole compounds, triarylmethane dyes, diimonium compounds, dithiol complex compounds, dithiolene complex compounds, mercaptophenol complex compounds , At least one selected from the group consisting of mercaptonaphthol complex-based compounds and polymethine-based compounds is more preferable. Among these, in the present invention, it is more preferable to use a polymethine-based compound or a squarylium-based compound from the viewpoints of having excellent visible light transmission characteristics, steep absorption characteristics, and a high molar extinction coefficient.

[Polymethine compounds]
The polymethine-based compound is not particularly limited as long as it is a compound having the absorption maximum wavelength, but is a compound represented by any of the following formulas (S-1) to (S-5) (hereinafter, each "compound (S-)". 1) ”to“ compound (S-5) ”) is preferable.

The X ^- represents a monovalent anion. The monovalent anion is not particularly limited, but is, for example, Cl ⁻ , Br ⁻ , I ⁻ , PF ₆ ⁻ , N (SO ₂ CF ₃ ) ₂ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , and nickel diion. Examples thereof include thiolate-based complex ions and copper dithiolate-based complex ions.

The Y ⁺ represents a monovalent cation. The monovalent cation is not particularly limited, and examples thereof include Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Rb ⁺ , NH ₄ ⁺ , and NR ₄ ⁺ . Here, R is an alkyl group having 1 to 4 carbon atoms.

The plurality of Ds independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom.
The plurality of Xs independently represent an oxygen atom, a sulfur atom, a selenium atom or -NH-.

Multiple R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i are independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, respectively. Amide group, imide group, cyano group, silyl group, -L ¹ , -S-L ² , -SS-L ² , -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 at least one combination of R _h and R _i , according to the following formulas (A) to (H). Represents at least one group selected from the group consisting of the represented groups.

In addition, D- (R _b ) (R _c ) in the above formulas (S-1) to (S-4) is described in this way for convenience, and R _b and R _c are not necessarily included in D. Are not combined. For example, if D is a nitrogen atom, then one of R _b and R _c is absent, if D is an oxygen atom, then both R _b and R _c are absent, and if D is a sulfur atom, then R _b and R _c . Both do not exist, or the total of R _b and R _c is four.

The amino group, amide group, imide group and silyl group are an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, and an alicyclic hydrocarbon group having 3 to 14 carbon atoms. Selected from the group consisting of 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. It may have at least one substituent L.

The L ¹ is L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g , L ^h or L ⁱ below.
(L ^a ) An aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have the substituent L (L ^b ) A halogen-substituted alkyl group having 1 to 12 carbon atoms which may have the substituent L (L a). L ^c ) An alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have the substituent L (L ^d ) An aromatic hydrocarbon group having 6 to 14 carbon atoms which may have the substituent L. (L ^e ) A heterocyclic group having 3 to 14 carbon atoms which may have the substituent L (L ^f ) An alkoxy group having 1 to 9 carbon atoms which may have the substituent L (L ^g ). It has an acyl group (L ^h ) having 1 to 9 carbon atoms which may have a substituent L and an alkoxycarbonyl group ( ^Li ) substituent L which may have the substituent L and has 1 to 9 carbon atoms. May be a sulfide group or a disulfide group having 1 to 12 carbon atoms.

The L ² represents either a hydrogen atom or L ^a to L ^e in the L ¹ .
The L ³ represents either a hydrogen atom or L ^a to L ^e in the L ¹ .
The L ⁴ represents any of ^La to L ^e in the L ¹ .

In formulas (A) to (H), R _x and R _y represent carbon atoms.
Multiple _RA to _RL are independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -S-L ² , _-SS -L ² , -SO ₂ -L ³ or -N ₌ N-L ⁴ (L ¹ to L ⁴ are synonymous with L ¹ to L ⁴ in Ra to Ri). The amino group, amide group, imide group and silyl group may have the substituent L.

Z _a to Z _c and Y _a to Y _d are independently hydrogen atom; halogen atom; hydroxyl group; carboxy group; nitro group; amino group; amide group; imide group; cyano group; silyl group; -L ¹ ;- S-L ² ; -SS-L ² ; -SO ₂ -L ³ ; -N = N-L ⁴ (L ¹ to L ⁴ are synonymous with L ¹ to L ⁴ in _Ra to R _i . ); An aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding two adjacent Zs or Ys to each other; two adjacent Zs or Ys are bonded to each other. A 5- to 6-membered alicyclic hydrocarbon group, which may contain at least one nitrogen atom, oxygen atom or sulfur atom, which is formed; or two adjacent Z-to-Y-to-Y bonds to each other. A complex aromatic hydrocarbon group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, which is formed; represents these aromatic hydrocarbon groups, alicyclic hydrocarbon groups and complex. The aromatic hydrocarbon group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the amino group, the amide group, the imide group and the silyl group have the substituent L. You may.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding Z to each other or Y to each other in Z _a to Z _c and Y _a to Y _d include a phenyl group and a tolyl group. , Xylyl group, mesityl group, cumenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, phenanthryl group, acenaphthyl group, phenalenyl group, tetrahydronaphthyl group, indanyl group and biphenylyl group.

A 5- to 6-membered ring of Z _a to Z _c and Y _a to Y _d , which may contain at least one nitrogen atom, oxygen atom or sulfur atom formed by bonding Z to each other or Y to each other. Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; polycyclic alicyclic group such as norbornan group and adamantan group; tetrahydrofuran and piperidine. , Pyrrolidine, imidazoline, piperidine, piperazine, morpholine and other heterocycles.

Examples of the heteroaromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding Z to each other or Y to each other in Z _a to Z _c and Y _a to Y _d include furan and thiophene. Pyrazole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, thiazyl, indol, indolin, indolenin, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, aclysine. Alternatively, a group consisting of phenazine may be mentioned.

Examples of the amino group which may have the substituent L include an amino group, an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group and a diisopropylamino group.

Examples of the amide group which may have the substituent L include an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group, a propyltrifluoromethylamide group, a diisopropylamide group, a dibutylamide group and α-. Examples thereof include a lactam group, a β-lactam group, a γ-lactam group, and a δ-lactam group.

Examples of the imide group which may have the substituent L include an imide group, a methylimide group, an ethylimide group, a diethylimide group, a dipropylimide group, a diisopropylimide group and a dibutylimide group.

Examples of the silyl group which may have the substituent L include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group and a triethylsilyl group.

Examples of -S-L ² include a thiol group, a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, an iso butyl sulfide group, a sec-butyl sulfide group, a tert-butyl sulfide group, and a phenyl sulfide group. Examples thereof include 2,6-di-tert-butylphenyl sulfide group, 2,6-diphenyl phenyl sulfide group and 4-cumyl phenyl sulfide group.

Examples of the -SS-L ² include 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, a tert-butyl disulfide group, and a phenyl disulfide group. Examples thereof include 2,6-di-tert-butylphenyl disulfide group, 2,6-diphenylphenyl disulfide group and 4-cumylphenyl disulfide group.

Examples of the -SO ₂ -L ³ include a sulfo group, a mesyl group, an ethyl sulfonyl group, an n-butyl sulfonyl group, and a p-toluene sulfonyl group.

Examples of the -N = N-L ⁴ include a methyl azo group, a phenyl azo group, a p-methyl phenyl azo group, and a p-dimethylamino phenyl azo group.

The compounds (S-1) to (S-5) may be synthesized by a generally known method, and can be synthesized, for example, by the method described in JP-A-2009-108267. ..

[Squarylium compound]
The squarylium-based compound is not particularly limited as long as it is a compound having the absorption maximum wavelength, but is a squarylium-based compound represented by the following formulas (Sq1) to (Sq2) (hereinafter, these are collectively referred to as "compound (Sq)". It is also preferable that it is a compound selected from (also referred to as).

In the formulas (Sq1) and (Sq2), X independently represents a sulfur atom, a selenium atom or -NH-, and R ¹ to R ⁷ and R ₁ to R ₈ independently represent a hydrogen atom, a halogen atom and a sulfo. Represents a group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -L ¹ or -NR ^g R ^h group. R ^g and R ^h are independently hydrogen atoms, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e , -L ^f , -L ^g , -L ^h or -C (O). Represents an R ⁱ group (R ⁱ represents -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ), and R ₉ independently represents a hydrogen atom, -L ^a , -L ^b . , -L ^c , -L ^d , -L ^e , -L ^f , -L ^g or -L ^h .
L ¹ is L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g or L ^h .
The L ^a to L ^h represent the following groups.
(L ^a ) An aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have the substituent L (L ^b ) A halogen-substituted alkyl group having 1 to 12 carbon atoms which may have the substituent L (L a). L ^c ) An alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have the substituent L (L ^d ) An aromatic hydrocarbon group having 6 to 14 carbon atoms which may have the substituent L. (L ^e ) A heterocyclic group having 3 to 14 carbon atoms which may have the substituent L (L ^f ) An alkoxy group having 1 to 12 carbon atoms which may have the substituent L (L ^g ). An acyl group (L ^h ) having 1 to 12 carbon atoms which may have a substituent L. An alkoxycarbonyl group (L ⁱ ) having 1 to 12 carbon atoms which may have the substituent L. May be a sulfide group or a disulfide group having 1 to 12 carbon atoms.

The R ¹ , R ₁ and R ₂ are independently hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-. Butyl group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group and nitro group are preferable, and hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group and hydroxyl group are more preferable. ..

The R ² to R ⁷ and R ₃ to R ₈ are independently hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and sec-butyl group. , Tart-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, penta Fluoroetanoylamino group, tert-butanoylamino group and cyclohexinoylamino group are preferable, and hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group and hydroxyl group are preferable. , Dimethylamino group, nitro group, acetylamino group, propionylamino group, trifluoromethanoylamino group, pentafluoroetanoylamino group, tert-butanoylamino group, cyclohexinoylamino group are more preferable.

The compound (Sq) can adjust the absorption maximum wavelength by a substituent, but the X is preferably a sulfur atom because it tends to be a compound having a maximum absorption wavelength of 800 to 930 nm.

The structure of the compound (Sq1) can be expressed by a description method such as the following formula (Sq1-1) or a description method having a resonance structure such as the following formula (Sq1-2). That is, the difference between the following formula (Sq1-1) and the following formula (Sq1-2) is only the method of describing the structure, and both represent the same compound. Unless otherwise specified in the present specification, the structure of a squarylium-based compound shall be represented by a description method such as the following formula (Sq1-1). The same applies to (Sq2).

Further, for example, the compound represented by the following formula (Sq1-3) and the compound represented by the following formula (Sq1-4) can be regarded as the same compound. The same applies to (Sq2).

The structure of the compound (Sq) is not particularly limited as long as it satisfies the above formulas (Sq1) and (Sq2). For example, when the structure is expressed as in the above formula (Sq1), the left and right substituents bonded to the central four-membered ring may be the same or different, but the ones that are the same are synthetically the same. It is preferable because it is easy. The same applies to (Sq2).

The compound (A) may be synthesized by a generally known method, and for example, the methods described in JP-A No. 1-2289960, JP-A-2001-40234, Patent No. 3196383 and the like. It can be synthesized by referring to.

In the present invention, the absorption maximum wavelength of the compound may be measured by dissolving the compound in an appropriate solvent such as dichloromethane and then measuring the obtained solution using a spectrophotometer.

<Compound (B)>
This filter preferably contains a compound (B) having an absorption maximum wavelength in a wavelength of 600 nm or more and less than 800 nm, and more preferably a compound (A) and a compound (B) in combination.
The absorption maximum wavelength of compound (B) is preferably 650 nm or more and less than 800 nm, more preferably 690 nm or more and less than 800 nm, and particularly preferably 700 nm or more and less than 800 nm.
By using such a compound (B), it is possible to efficiently block light at a wavelength of 700 to 780 nm, which causes noise in a color image, and visible light of a color near red even when incident at 35 degrees. Visible light pixels in the peripheral part of the image corresponding to the light rays incident on the optical filter at a high angle when the image is taken using a solid-state image pickup device including this filter, a camera module, a biometric authentication device, etc. The change in the color of the light can be easily suppressed.
Further, by using such a compound (B) together with the compound (A), it is possible to efficiently block light at a wavelength of 700 to 900 nm, which causes noise in both a color image and a near-infrared image, and color reproduction is possible. A solid-state image sensor, a camera module, and a biometric authentication device having good properties and a small amount of noise can be obtained, which is preferable.

The compound (B) is not particularly limited as long as the absorption maximum wavelength is in the above range, but is preferably a squarylium-based compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, a croconium-based compound, a hexaphyllin-based compound, and an azo-based compound. Examples thereof include naphthoquinone compounds, oxonol compounds, pyrolopyrrole compounds, triarylmethane dyes, dithiol complex compounds, dithiolene complex compounds, mercaptophenol complex compounds, mercaptonaphthol complex compounds and polymethine compounds. Among these, in the present invention, it is more preferable to use a polymethine-based compound, a phthalocyanine-based compound, and a squarylium-based compound from the viewpoints of having excellent visible light transmission characteristics, steep absorption characteristics, and a high molar extinction coefficient.
Compound (B) may be used alone or in combination of two or more.

It is more preferable that the compound (B) contains one or more of each of the squarylium-based compound and the other compound (B), and when the squarylium-based compound and the other compound (B) are used, the squarylium-based compound is the other compound. It is preferable to have an absorption maximum wavelength on the shorter wavelength side than (B), and it is more preferable that the difference in absorption maximum wavelength between the squarylium-based compound and at least one of the other compounds (B) is 5 to 50 nm.

When a squarylium-based compound and another compound (B) are used as the compound (B), the content ratio of the squarylium-based compound is preferably 10 to 95% by mass when the total content of the compound (B) to be used is 100% by mass. It is more preferably 15 to 85% by mass, and particularly preferably 20 to 80% by mass.

Depending on the structure, the squarylium-based compound may generate fluorescence that causes scattered light when absorbing light, but when a squarylium-based compound and another compound (B) are used as the compound (B), the absorption maximum wavelength of these compounds is used. When the compound (B) whose difference is in the above range is used, or when the squarylium-based compound is used in the above amount, preferably when all of these are satisfied, unnecessary light including scattered light is used in the visible to near-infrared wavelength range. Since the light rays can be cut efficiently, good camera image quality can be achieved due to the excellent incident angle-dependent improvement performance and the scattered light reduction effect.

[Squarylium compound]
The squarylium-based compound used as the compound (B) preferably contains at least one selected from the group consisting of the squarylium-based compound represented by the formula (I) and the squarylium-based compound represented by the formula (II). .. Hereinafter, they are also referred to as “Compound (I)” and “Compound (II)”, respectively.

In formula (I), R ^a , R ^b and Y satisfy the condition of the following (i) or (ii).

・ Condition (i)
Each of the plurality of Ra independently represents ^a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -L ¹ or -NR ^e R ^f group. R ^e and R ^f independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e , respectively.
Each of the plurality of R ^bs independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, an −L ¹ or an −NR ^g R ^h group. R ^g and R ^h are independently hydrogen atoms, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C (O) R ⁱ group (R ⁱ is -L ^a , Represents -L ^b , -L ^c , -L ^d or -L ^e ).
Each of the plurality of Ys independently represents a -NR ^J R ^k group. R ^J and R ^k independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e , respectively.
L ¹ is L ^a , L ^b , L ^c , L ^d , L ^e , L ^f , L ^g , L ^h or L ⁱ .

The L ^a to L ⁱ represent the following groups.
(L ^a ) An aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L (L ^b ) A halogen-substituted alkyl group (L ^c ) which may have a substituent L and has 1 to 12 carbon atoms. ) Alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L (L ^d ) An aromatic hydrocarbon group (L ^e ) having 6 to 14 carbon atoms which may have a substituent L. It has a heterocyclic group (L ^f ) substituent L having 3 to 14 carbon atoms which may have a substituent L and an alkoxy group (L ^g ) substituent L having 1 to 12 carbon atoms which may have a substituent L. It may have an acyl group (L ^h ) substituent L having 1 to 12 carbon atoms. It may have an alkoxycarbonyl group ( ^Li ) substituent L having 1 to 12 carbon atoms. It may have 1 to 12 carbon atoms. Sulf group or disulfide group

The substituent 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, and an aromatic carbide having 6 to 14 carbon atoms. It is at least one selected from the group consisting of a hydrogen group, 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.

The total number of carbon atoms including the substituents of ^La to ^Li is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. If the number of carbon atoms is more than this range, it may be difficult to synthesize the compound, and the light absorption intensity per unit mass tends to be small.

・ Condition (ii)
At least one of the two Ras on one benzene ring couples with Y on the same benzene ring to form ^a heterocycle with 5 or 6 constituent atoms containing at least one nitrogen atom. The heterocycle may have a substituent L, and R ^b and R ^a not involved in the formation of the heterocycle are independently synonymous with R ^b and R ^a of the condition (i), respectively.

Specific Examples of Each Group Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms in La and L include ^a methyl group (Me), an ethyl group (Et), and an n-propyl group (n-Pr). Isopropyl group (i-Pr), n-butyl group (n-Bu), sec-butyl group (s-Bu), tert-butyl group (t-Bu), pentyl group, hexyl group, octyl group, nonyl group, Alkyl groups such as decyl group and dodecyl group; 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 Alkenyl groups such as an octenyl group; and alkynyl groups such as an ethynyl group, a propynyl group, a butynyl group, a 2-methyl-1-propynyl group, a hexynyl group and an octynyl group can be mentioned.

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

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

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L ^d and L include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 1-naphthyl group, a 2-naphthyl group and an anthrasenyl group. Examples thereof include a phenanthryl group, an acenaphthyl group, a phenalenyl group, a tetrahydronaphthyl group, an indanyl group and a biphenylyl group.

Examples of the heterocyclic groups having 3 to 14 carbon atoms in Le and L include ^furan , thiophene, pyrazole, pyrazole, imidazole, triazole, oxazole, oxadiazol, thiazole, thiadiazol, indol, indoline, indolenin, and benzofuran. , Benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, acridin, morpholine, phenazine and the like.

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

Examples of the acyl group having 1 to 12 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 12 carbon atoms in L ^h include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group and an octyl. Examples include oxycarbonyl groups.

Examples of the sulfide group having 1 to 12 carbon atoms in Li have an ⁿ -octyl sulfide group and an n-dodecyl sulfide group. Examples of the ^disulfide group having 1 to 12 carbon atoms in Li have a phenyl disulfide group, a 4-methylphenyl disulfide group, and a 4-aminophenyl disulfide group.

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

The Lb is preferably a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 5- ^cyclohexyl -2,2,3,3-tetrafluoropentyl group, and more preferably a trichloro group. It is 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. Is.

The L ^d is preferably a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a trill 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, trill group, xsilyl group, mesityl group, cumenyl group, 2,3 , 4, 5, 6-Pentaphenylphenyl group.

The Le is preferably a group composed of furan, thiophene, pyrrole, indol, ^indoline , indoline, benzofuran, benzothiophene and morpholin, and more preferably a group composed of furan, thiophene, pyrrole and morpholin.

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. It is a group, an octyloxy group, and more preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group.

The L ^g is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a tert-butanoyl group, a benzoyl group, a 4-propylbenzoyl group, a trifluoromethylcarbonyl group and a pentafluoroethylcarbonyl group, and more preferably. Is an acetyl group, a propionyl group, and 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. It is a methoxycarbonyl group and an ethoxycarbonyl group.

The La to Li ⁱ further have at least one atom or group selected from the group consisting of ^a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group and an amino group. You may. Examples of such are 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, 4-cyanobutoxycarbonyl group and examples.

The Ra in the condition (i) 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, nitro group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl. It is a group and a hydroxyl group.

The ^Rb under the condition (i) 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, pentafluoroetanoylamino group , Tart-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, pentafluoroetanoylamino group, tert-butanoylamino group, cyclohexinoylamino group.

The Y is preferably an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a din-propylamino group, a diisopropylamino group, a din-butylamino group, a di-tert-butylamino group, or 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-tert-butylamino group.

At least one nitrogen atom formed by interconnecting at least one of two ^Ra on one benzene ring with Y on the same benzene ring under the condition (ii) of the formula (I). Examples of the heterocycle containing 5 or 6 constituent atoms include pyrrolidine, pyrrol, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine and pyrazine. Among these heterocycles, a heterocycle which constitutes the heterocycle and whose one atom next to the carbon atom constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.

In formula (II), X independently represents O, S, Se, N-R ^c or C (R ^d R ^d ); the plurality of R ^cs independently represent a hydrogen atom, ^{La, L b ,} respectively. Represents L ^c , L ^d or L ^e ; multiple R ^ds are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxy groups, phosphate groups, -L ¹ or -NR. ^e R ^f groups may be represented and adjacent R ^ds may be linked to each other to form a ring which may have ^a substituent L; La to L ^e , L ¹ , R ^e and R ^f are It is synonymous with ^La to ^Le , L ¹ , R ^e and R ^f defined in the above formula (I).

The 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, tolfluoromethyl group, pentafluoroethyl group, more preferably hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group.

The ^Rd in the formula (II) is preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl. 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, pentafluoroethyl group.

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

In the above formula (II), adjacent R ^ds may be connected to each other to form a ring. Examples of the ring bonded to -CH = bonded to the cyclobutane ring when such adjacent R ^ds are linked include a benzoindolenine ring, an α-naphthoimidazole ring, a β-naphthoimidazole ring, and an α-naphtho. Examples thereof include an oxazole ring, a β-naphthoxazole ring, an α-naphthiazole ring, a β-naphthiazole ring, an α-naphthoselazole ring, and a β-naphthoselazole ring.

The compound (I) and the compound (II) have the following formulas (I-2) and the following formula (II-2) in addition to the description methods such as the following formulas (I-1) and the following formula (II-1). The structure can also be expressed by a description method that takes a resonance structure as described above. That is, the difference between the following formula (I-1) and the following formula (I-2), and the difference between the following formula (II-1) and the following formula (II-2) is only the method of describing the structure. Also represents the same compound. Unless otherwise specified in the present specification, the structure of the squarylium-based compound shall be represented by the description method such as the following formula (I-1) and the following formula (II-1).

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

The structures of the compound (I) and the compound (II) are not particularly limited as long as they satisfy the formulas (I) and (II), respectively. For example, when the structure is expressed as the above formula (I-1) and the above formula (II-1), the left and right substituents bonded to the central four-membered ring may be the same or different. However, it is preferable that they are the same because it is easy to synthesize.

Specific examples of the compound (I) and the compound (II) include compounds having a basic skeleton represented by the following (IA) to (IH).

As the squarylium-based compound used as the compound (B), a squarylium-based compound represented by the formula (iii) or a squarylium-based compound represented by the formula (iv) may be used.

In the formula (iii), R ^a to R ^g are independently synonymous with R ^b of the condition (i) in the formula (I).

In the formula (iv), R ¹ to R ⁷ are independently synonymous with R ¹ to R ⁷ in the formula (Sq1).

The compounds (I) to (II) and the compounds (iii) to (iv) may be synthesized by a generally known method, and for example, JP-A No. 1-2289960 and JP-A-2001-40234 may be synthesized. , Patent No. 3196383 and the like can be referred to for synthesis.

[Pphthalocyanine compound]
The phthalocyanine-based compound used as the compound (B) is preferably a compound represented by the following formula (III) (hereinafter, also referred to as “compound (III)”).

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.
Multiple R _a , R _b , R _c and R _d are independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -S-L ² , -SS-L ² , -SO ₂ -L ³ , -N = N-L ⁴ , or at least R _a and R _b , R _b and R _c , and R _c and R _d . It represents at least one group selected from the group consisting of the groups represented by the following formulas (A) to (H) to which one combination is bound. However, at least one of R _a , R _b , R _c and R _d bonded to the same aromatic ring is not a hydrogen atom.
The amino group, amide group, imide group and silyl group may have the substituent L defined in the above formula (I).
L ¹ is synonymous with L ¹ defined in the above formula (I).
L ² represents either ^a hydrogen atom or La to L ^e defined in the above formula (I).
L ^{3 represents} either ^a hydroxyl group or the above La to Le.
L ⁴ represents any of the above ^La to L ^e .

In formulas (A) to (H), R _x and R _y represent carbon atoms.
Multiple _RA to _RL are independently hydrogen atom, halogen atom, hydroxyl group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -S-L ² , -SS. Represents -L ² , -SO ₂ -L ³ , -N = N-L ⁴ ,
The amino group, amide group, imide group and silyl group may have the substituent L defined in the above formula (I), and L ¹ to L ⁴ are L ¹ to L defined in the above formula (III). It is synonymous with ⁴ .

In the above Ra to R _d and _RA to _RL , examples of the amino group which may have the substituent _L include an amino group, an ethylamino group, a dimethylamino group, a methylethylamino group and a dibutylamino group. Examples include diisopropylamino groups.

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

Examples of the imide group which may have the substituent _L in R _a to R _d and _RA to RL include an imide group, a methylimide group, an ethylimide group, a diethylimide group, a dipropylimide group and a diisopropylimide. Examples include a group and a dibutylimide group.

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

In R _a to R _d and _RA to RL, -S- _L ² may be, for example, a thiol group, a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, an isobutyl sulfide group, or sec-butyl. Examples thereof include a sulfide group, a tert-butyl sulfide group, a phenyl sulfide group, a 2,6-di-tert-butyl phenyl sulfide group, a 2,6-diphenyl phenyl sulfide group and a 4-cumyl phenyl sulfide group.

In the above Ra to R _d and _RA to RL, _-SS - _L ² may be, for example, a disulfide group, a methyl disulfide group, an ethyl disulfide group, a propyl disulfide group, a butyl disulfide group, an isobutyl disulfide group, or sec-butyl. Examples thereof include a disulfide group, a tert-butyl disulfide group, a phenyl disulfide group, a 2,6-di-tert-butylphenyl disulfide group, a 2,6-diphenylphenyl disulfide group and a 4-cumylphenyl disulfide group.

In R _a to R _d and _RA to RL, examples of -SO ₂ - _L ³ include a sulfo group, a mesyl group, an ethyl sulfonyl group, an n-butyl sulfonyl group, and a p-toluene sulfonyl group.

In the above Ra to R _d and _RA to RL 4, examples of −N ₌ N— _L ⁴ include a methyl azo group, a phenyl azo group, a p-methyl phenyl azo group, and a p-dimethylamino phenyl azo group.

In M, examples of the monovalent metal atom include Li, Na, K, Rb, and Cs.

In the above M, examples of the divalent metal atom include Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd and Hg. Examples include Sn and Pb.

In the above M, examples of the substituted metal atom containing a trivalent metal atom include Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, and Ga-I. , In-F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Fe-Cl, Ru-Cl, Mn-OH.

In the above M, examples of the substituted metal atom containing a tetravalent metal atom include TiF ₂ , TiCl ₂ , TiBr ₂ , TiI ₂ , ZrCl ₂ , HfCl ₂ , CrCl ₂ , SiC ₂ , SiCl ₂ , SiBr ₂ , and 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 M is a divalent transition metal, a trivalent or tetravalent metal halide, or a tetravalent metal oxide belonging to the 4th to 5th periods of the Periodic Table Group 5 to 11. Of these, Cu, Ni, Co and VO are particularly preferable because high visible light transmittance and stability can be achieved.

A method for synthesizing the phthalocyanine compound by a cyclization reaction of a phthalonitrile derivative as shown in the following formula (V) is generally known, and the obtained phthalocyanine compounds are described in the following formulas (VI-1) to (V). It is a mixture of four isomers such as VI-4). Unless otherwise specified, this specification exemplifies only one isomer per one phthalocyanine compound, but the other three isomers can be used in the same manner. Although these isomers can be separated and used as needed, the present specification deals with isomer mixtures collectively.

Specific examples of the compound (III) include compounds having a basic skeleton represented by the following formulas (III-A) to (III-J).

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

<Compound (X)>
This filter preferably contains a compound (X) having an absorption maximum wavelength at a wavelength of 300 to 425 nm, more preferably a compound (A) and a compound (X) in combination, and the compound (A) and the compound (B). ) And compound (X) in combination are particularly preferable.
The absorption maximum wavelength of compound (X) is preferably 350 to 415 nm, more preferably 360 to 410 nm, and particularly preferably 365 to 405 nm.
By using such a compound (X), the change in the amount of visible light of a color near blue is small even when incident at 35 degrees, and a solid-state imaging device including this filter, a camera module, a biometric authentication device, or the like can be used. When an image is taken, it is possible to easily suppress a change in the color of the visible light pixel in the peripheral portion of the image corresponding to the light beam incident on the optical filter at a high angle.

The compound (X) is not particularly limited as long as it is a compound having the absorption maximum wavelength, but for example, oxazole-based, merocyanine-based, cyanine-based, naphthalimide-based, oxadiazole-based, oxazine-based, oxazolidine-based, and naphthalic acid. Examples thereof include dyes such as a system, a styryl system, an anthracene system, a cyclic carbonyl system, and a triazole system.
Compound (X) may be used alone or in combination of two or more.

Commercially available products of the compound (X) include, for example, Uvitex OB (manufactured by Ciba Specialty Chemicals Co., Ltd.), HakkolRF-K (manufactured by Showa Chemical Industry Co., Ltd.), NikkafluorEFS, and NikkafluoroSB-conc (above, Nippon Chemical Industrial Co., Ltd.). ), S0511 (FewChemicals), SMP370 (Hayashihara Co., Ltd.), BONASORB UA3701, UA3911 (above, Orient Chemical Industry Co., Ltd.), Lumogen Fviolet570 (BASF), ABS407 (Exiton). , UV381A, UV381B, UV382A, UV386A (all manufactured by QCR Solutions Corp.).

<Other absorbent (Z)>
The filter may further contain an absorbent (Z) other than the compound (A), the compound (B) and the compound (X).
Depending on the absorption characteristics of the compound (A) and the target near-infrared transmission wavelength, by using the compound (A) in combination with another absorbent (Z), the length of the near-infrared transmission band is increased in addition to the visible wavelength range. The dependence on the incident angle can be reduced even on the wavelength side, and there is a tendency that better infrared sensing performance can be achieved.

Examples of the other absorbent (Z) include squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, porphyrin compounds and metal dithiolate compounds, diimonium compounds, and azo compounds. , Polymethine-based compounds, phthalide-based compounds, naphthoquinone-based compounds, anthraquinone-based compounds, indophenol compounds, pyrylium-based compounds, thiopyrylium-based compounds, triphenylmethane-based compounds, and aminium-based compounds.

<Structure of optical filter>
The present filter is not particularly limited as long as it satisfies the requirements of the present filter 1 or 2, but is preferably an optical filter including a base material and a dielectric multilayer film.
The filter may have a dielectric multilayer film on one surface of the substrate as shown in the uppermost figure of FIG. 2, and a plurality of dielectric multilayer films as shown in the other figures of FIG. Or may have a plurality of substrates.

[Base material]
The substrate may be a single layer or a multilayer, and when the substrate is a single layer, for example, a substrate (i) made of a transparent resin substrate can be mentioned, and in the case of a multilayer. For example, a base material (ii) in which one or more overcoat layers are laminated on one or more layers of a support such as a glass support or a resin support as a base can be mentioned.
A base material containing an overcoat layer is preferable from the viewpoints of manufacturing cost, ease of adjusting optical characteristics, achievement of scratch erasing effect of the resin support, improvement of scratch resistance of the base material, and the like.

The thickness of the base material can be appropriately selected depending on the desired application and is not particularly limited, but is preferably appropriately selected so as to reduce the incident angle dependence of the obtained optical filter, preferably 10 to 10 to. It is 200 μm, more preferably 20 to 150 μm, and particularly preferably 15 to 120 μm.
When the thickness of the base material is within the above range, the optical filter using the base material can be made thinner and lighter, and can be suitably used for various applications such as a solid-state image sensor. In particular, when the base material (i) is used for a lens unit such as a camera module, it is preferable because the lens unit can be reduced in height and weight.

In the case of the base material (i), the transparent resin substrate preferably contains the transparent resin and the compound (A). Further, in the case of the base material (ii), when the support is a glass support, the overcoat layer preferably contains the transparent resin and the compound (A), and the base material (ii). In the above case, when the support is a resin support, it is preferable that at least one of the resin support or the overcoat layer contains a transparent resin and the compound (A).

When the compound (B) or the compound (X) is used, these compounds may be contained in the same layer or in separate layers.
When these are contained in the same layer, for example, a substrate made of a transparent resin substrate containing the compounds (A), (B) and (X), and a transparent material containing the compounds (A), (B) and (X). Examples thereof include a base material having an overcoat layer laminated on a resin support, and a base material having an overcoat layer containing compounds (A), (B) and (X) laminated on the support.
When the compound is contained in separate layers, for example, a group in which an overcoat layer containing the compound (B) and the compound (X) is laminated on a transparent resin support containing the compound (A). Examples thereof include a material and a base material in which an overcoat layer containing the compound (A) is laminated on a support made of a transparent resin containing the compound (B) and the compound (X).
It is more preferable that the compound (A) and the compound (B) and / or the compound (X) are contained in the same layer, and in this case, the compound (A) to be used is more preferable than the case where the compound (A) and the compound (B) and / or the compound (X) are contained in separate layers. ), (B), (X), it becomes easier to control the content ratio.

The concentration of the compound (A) in the layer containing the compound (A) is preferably 0.001 to 50 parts by mass, more preferably 0.005 to 40 parts by mass with respect to 100 parts by mass of the resin contained in the layer. Particularly preferably 0.01 to 35 parts by mass.
When the concentration of the compound (A) is in the above range, even if the light is incident on the optical filter at 35 degrees, the light having a wavelength of 800 to 900 nm can be more easily blocked.

Further, the concentration of the compound (A) preferably satisfies the following formula (A1).

［式（Ａ１）中の符号は、以下のことを示す。
化合物（Ａ）を含む層をｎ層有する光学フィルターにおいて、
ＣＡｎはｎ層中の化合物（Ａ）の濃度（ｗｔ％）を示し、ｌＡｎは該ｎ層の厚み（μｍ）を示す。］

[The reference numerals in the formula (A1) indicate the following.
In an optical filter having n layers containing the compound (A),
CAN indicates the concentration (wt%) of the compound (A) in the n layer, and lAn indicates the thickness (μm) of the n layer. ]

In the formula (A1), the present filter has a layer 1 (thickness aμm) containing the compound (A) at a concentration of α wt% and a layer 2 (thickness b μm) containing the compound (A) at a concentration of β wt%. , "1 ≦ (α × a + β × b) ≦ 50".
Further, when a certain layer contained in this filter contains two or more kinds of the compound (A), the CAN indicates the total concentration (wt%) of the compound (A) contained in the layer.
These are also the same in the following equations (B1) and (X1).

The left side of the formula (A1) is preferably 2, more preferably 3, and the right side is preferably 40, more preferably 30, and particularly preferably 25.
When the concentration of the compound (A) satisfies the above formula (A1), light having a wavelength of 800 to 900 nm, which causes noise due to sunlight, can be sufficiently blocked, and the wavelength other than 800 to 900 nm due to excessive addition can be sufficiently blocked. It is possible to reduce the absorption of light, for example, visible light, and it is possible to easily obtain an optical filter that has both high sensitivity in the visible light region and reduction in the amount of noise.

When the compound (B) is used, the concentration of the compound (B) in the layer containing the compound (B) is preferably 0.001 to 50 parts by mass with respect to 100 parts by mass of the resin contained in the layer. It is preferably 0.005 to 40 parts by mass, and particularly preferably 0.01 to 35 parts by mass.
When the concentration of the compound (B) is within the above range, even if light is incident on the optical filter at 35 degrees, the change in the amount of visible light of a color near red can be further suppressed, and the light can be seen due to excessive absorption. There is little decrease in light transmittance, and when an image is taken using a solid-state image pickup device, camera module, biometric authentication device, etc. that includes the filter, it is visible in the peripheral part of the image corresponding to the light rays incident on the filter at a high angle. It is possible to suppress the change in the tint of the optical pixel.

Further, the concentration of the compound (B) preferably satisfies the following formula (B1).

［式（Ｂ１）中の符号は、以下のことを示す。
化合物（Ｂ）を含む層をｎ層有する光学フィルターにおいて、
ＣＢｎはｎ層中の化合物（Ｂ）の濃度（ｗｔ％）を示し、ｌＢｎは該ｎ層の厚み（μｍ）を示す。］

[The reference numerals in the equation (B1) indicate the following.
In an optical filter having n layers containing the compound (B),
CBn indicates the concentration (wt%) of the compound (B) in the n layer, and lBn indicates the thickness (μm) of the n layer. ]

The left side of the formula (B1) is preferably 2, more preferably 3, and the right side is preferably 30, more preferably 25.
When the concentration of the compound (B) satisfies the above formula (B1), light having a wavelength of 700 to 780 nm, which causes noise due to sunlight, can be sufficiently blocked, and a wavelength other than 700 to 780 nm due to excessive addition can be sufficiently blocked. It is possible to reduce the absorption of light, for example, visible light, and it is possible to easily obtain an optical filter that has both high sensitivity in the visible light region and reduction in the amount of noise.

When the compound (X) is used, the concentration of the compound (X) in the layer containing the compound (X) is preferably 0.001 to 50 parts by mass with respect to 100 parts by mass of the resin contained in the layer. It is preferably 0.005 to 40 parts by mass, and particularly preferably 0.01 to 35 parts by mass.
When the concentration of the compound (X) is in the above range, even if light is incident on the optical filter at 35 degrees, it can be suppressed by the change in the amount of visible light of a color near blue, and visible light due to excessive absorption. There is little decrease in transmittance, and when an image is taken using a solid-state image pickup device, camera module, biometric authentication device, etc. that includes the filter, visible light is visible in the peripheral part of the image corresponding to the light rays incident on the filter at a high angle. It is possible to suppress changes in the color of the pixels.

Further, the concentration of the compound (X) preferably satisfies the following formula (X1).

［式（Ｘ１）中の符号は、以下のことを示す。
化合物（Ｘ）を含む層をｎ層有する光学フィルターにおいて、
ＣＸｎはｎ層中の化合物（Ｘ）の濃度（ｗｔ％）を示し、ｌＸｎは該ｎ層の厚み（μｍ）を示す。］

[The reference numerals in the equation (X1) indicate the following.
In an optical filter having n layers containing compound (X),
CXn indicates the concentration (wt%) of the compound (X) in the n layer, and lXn indicates the thickness (μm) of the n layer. ]

The left side of the formula (X1) is preferably 0.5, more preferably 1, and the right side is preferably 30, more preferably 25.
When the concentration of the compound (X) satisfies the above formula (X1), it is possible to sufficiently block ultraviolet rays that cause noise due to sunlight, and absorption of light other than the ultraviolet region due to excessive addition, for example, visible light. It is possible to easily obtain an optical filter that achieves both high sensitivity in the visible light region and reduction in the amount of noise.

As the base material, for example, a base material made of a transparent resin substrate containing the transparent resin and the compounds (A), (B) and (X), or a transparent resin and the compounds (A), (B). ) And (X), the total content of the compounds (A), (B) and (X) is 100 parts by mass of the transparent resin when a base material containing a transparent resin support containing (X) is used. It is preferably 0.01 to 2.0 parts by mass, more preferably 0.02 to 1.5 parts by mass, and particularly preferably 0.03 to 1.0 parts by mass.

When a base material in which an overcoat layer containing the compounds (A), (B) and (X) is laminated on a glass support or a resin support as a base is used as the base material, the overcoat is used. The total content of the compounds (A), (B) and (X) is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 0.2 parts by mass with respect to 100 parts by mass of the resin forming the layer. It is 4.0 parts by mass, particularly preferably 0.3 to 3.0 parts by mass.

When the total content of the compounds (A), (B) and (X) is within the above range, high visible light transmission and desired near-infrared transmission characteristics, and other light blocking properties at wavelengths of 800 to 1200 nm are obtained. It is possible to easily obtain an optical filter that has both excellent and excellent properties.

Further, it is preferable that the concentrations of the compounds (A), (B) and (X) contained in the substrate satisfy the following formula (ABX).

When the left side of the formula (ABX) is 0.5, an optical filter capable of sufficiently blocking light having a wavelength of 800 to 900 nm can be easily obtained. The left side of the formula (ABX) is preferably 1, more preferably 2, and particularly preferably 3.
Further, when the right side of the above formula (ABX) is 60, an optical filter having both high visible light transmission and desired near-infrared transmission characteristics and excellent light blocking property of other wavelengths of 800 to 1200 nm is achieved. Can be easily obtained. The right side of the formula (ABX) is preferably 45, more preferably 35, and particularly preferably 25.

As the base material, for example, a base material made of a transparent resin substrate containing the transparent resin and the other absorbent (Z), or a transparent resin containing the transparent resin and the other absorbent (Z). When a substrate containing a substrate is used, the content of the absorbent (Z) is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 to 1. It is 0 parts by mass, particularly preferably 0.03 to 0.7 parts by mass.
Further, when a base material in which an overcoat layer containing the absorbent (Z) is laminated on a glass support or a resin support as a base is used as the base material, the resin forming the overcoat layer is used. The content of the absorbent (Z) is preferably 0.1 to 4.0 parts by mass, more preferably 0.2 to 3.0 parts by mass, and particularly preferably 0.3 to 0.3 parts by mass with respect to 100 parts by mass. 2.0 parts by mass.

When the content of the absorbent (Z) is in the above range, the optics has both high visible light transmission and desired near-infrared transmission characteristics, and excellent light blocking property of other wavelengths of 800 to 1200 nm. The filter can be easily obtained.

<Transparent resin>
The overcoat layer and the transparent resin substrate to be laminated on the resin support, the glass support, and the like can be formed by using the transparent resin.
As the transparent resin used for the base material, one type may be used alone, or two or more types may be used.

The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. Examples thereof include resins having a glass transition temperature (Tg) of preferably 110 to 380 ° C., more preferably 110 to 370 ° C., and even more preferably 120 to 360 ° C. in order to use a substrate capable of forming a body multilayer film.
Further, when the glass transition temperature of the resin is 140 ° C. or higher, a film (transparent resin substrate, transparent resin support and overcoat layer) capable of forming a dielectric multilayer film by vapor deposition at a higher temperature can be obtained. Especially preferable.
Specifically, Tg can be measured by the method described in the following Examples.

As the transparent resin, when a resin support having a thickness of 0.1 mm made of the resin is formed, the total light transmittance (JIS K7375) of the resin support is preferably 75% or more, more preferably 75% or more. A resin having a content of 78% or more, particularly preferably 80% or more can be used. If a resin having a total light transmittance in such a range is used, the obtained base material exhibits good transparency as an optical film.

When a solvent-soluble resin is used as the transparent resin, the polystyrene-equivalent weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method of the transparent resin is usually 15,000 to 350,000. It is preferably 30,000 to 250,000, and the number average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.
Specifically, Mw and Mn can be measured by the method described in the following Examples.

Examples of the transparent resin include cyclic (poly) olefin resin, aromatic polyether resin, polyimide resin, fluorene polyester resin, polycarbonate resin, polyamide (aramid) resin, polyarylate resin, and polysulphon resin. , Polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate (PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin Examples thereof include a curable resin, a silsesquioxane-based ultraviolet curable resin, an acrylic-based ultraviolet curable resin, and a vinyl-based ultraviolet curable resin.

-Cyclic (poly) olefin resin The cyclic (poly) olefin resin is selected from the group consisting of the monomer represented by the following formula (X ₀ ) and the monomer represented by the following formula (Y ₀ ). A resin obtained from at least one of these monomers and a resin obtained by hydrogenating the resin are preferable.

In the formula (X ₀ ), R ^x1 to R ^x4 represent atoms or groups selected from the following (i') to (ix') independently, and k ^x , m ^x and ^px are independently 0. Or represents a positive integer.
(I') Hydrogen atom (iii') Halogen atom (iii') Trialkylsilyl group (iv') Substituent or unsubstituted carbon number 1 having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. Hydrocarbon group (v') substituted or unsubstituted hydrocarbon group (vi') polar group having 1 to 30 carbon atoms (excluding (iv')).
(Vii') Alkylidene groups 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 independently described in (i'). )-(Vi') represents an atom or group selected.)
(Viii') A monocyclic or polycyclic hydrocarbon ring or heterocycle formed by mutually bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 (however, R ^x1 to R not involved in the bond). ^x4 represents an atom or group independently selected from the above (i') to (vi').)
(Ix') A monocyclic hydrocarbon ring or heterocycle formed by bonding R ^x2 and R ^x3 to each other (however, R ^x1 and R ^x4 not involved in the bond are independently described in (i). Represents an atom or group selected from') to (vi').)

In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i') to (vi'), or R ^y1 and R ^y2 are bonded to each other. Represents the formed monocyclic or polycyclic alicyclic hydrocarbons, aromatic hydrocarbons or heterocycles, where ^ky and ^py each independently represent 0 or a positive integer.

-Aromatic polyether resin The aromatic polyether resin is at least one structural unit selected from the group consisting of the structural unit represented by the following formula (1) and the structural unit represented by the following formula (2). It is preferable to have.

（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 the formula (1), R ¹ to R ⁴ independently represent a monovalent organic group having 1 to 12 carbon atoms, and a to d 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＞Ｃ＝Ｏ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 the formula (2), R ¹ to R ⁴ and a to d are independently synonymous with R ¹ to R ⁴ and a to d in the formula (1), and Y is a single bond, −SO. ₂ -or> C = O, R ⁷ and R ⁸ independently represent a halogen atom, a monovalent organic group or a nitro group having 1 to 12 carbon atoms, and g and h independently represent 0 to 0, respectively. It indicates an integer of 4, 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 the structural unit represented by the following formula (3) and the structural unit represented by the following formula (4). May be.

（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－、＞Ｃ＝Ｏ、－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 the 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- , > C = O, -CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms, e and f independently indicate an integer of 0 to 4, and n indicates 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 the formula (4), R ⁷ , R ⁸ , Y, m, g and h are independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in the formula (2). R ⁵ , R ⁶ , Z, n, e and f are independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in the above formula (3).)

Fluorene polyester-based resin The fluorene polyester-based resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety. For example, the methods described in JP-A-2010-285505 and JP-A-2011-197450. Can be synthesized with.

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

Polycarbonate-based resin The polycarbonate-based resin is not particularly limited, but a resin having a glass transition temperature of 140 ° C. or higher is preferable. , Japanese Patent Application Laid-Open No. 2011-246583, can be synthesized by the method described in JP-A-2011-246583.

-Fluorinated aromatic polymer-based resin The fluorinated aromatic polymer-based resin is not particularly limited, but has 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. It is preferably a polymer containing a repeating unit containing at least one bond selected from the group consisting of bonds, and can be synthesized, for example, by the method described in JP-A-2008-181121.

-Acrylic-based ultraviolet curable resin The acrylic ultraviolet-curable resin is not particularly limited, but contains a compound having one or more acrylic groups or methacrylic groups in the molecule and a compound that is decomposed by ultraviolet rays to generate active radicals. Examples thereof include those synthesized from the resin composition to be used. The acrylic ultraviolet curable resin can be particularly preferably used as the base material as a resin used for an overcoat layer formed on a glass support or a base resin support.

-Commercial products Examples of commercial products of transparent resin include the following commercial products. Examples of commercially available cyclic (poly) olefin resins include Arton manufactured by JSR Co., Ltd., Zeonoa manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals Co., Ltd., and TOPAS manufactured by Polyplastics Co., Ltd. Examples of commercially available products of the polyether sulfone-based resin include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available polycarbonate-based resins include Pure Ace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate-based resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available fluorene polyester-based resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available polycarbonate-based resins include Panlite SP-3810 manufactured by Teijin Limited. Examples of commercially available acrylic resins include Acriviewer manufactured by Nippon Shokubai Co., Ltd. Examples of commercially available products of the silsesquioxane-based ultraviolet curable resin include Silplus manufactured by Nippon Steel Chemical Co., Ltd.

<Additive>
As long as the effect of the present invention is not impaired, the base material further comprises an antioxidant, a light-resistant improver, a mold release agent, a surfactant, an antistatic agent, an adhesion aid, a light diffusing material, a fluorescent quenching agent and a metal. It may contain an additive such as a complex compound. Further, when the base material is manufactured by cast molding described later, it is possible to facilitate the manufacture of the base material by adding a leveling agent or an antifoaming agent.
These additives may be used alone or in combination of two or more.

Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5'-dimethyldiphenylmethane, and the like. Tetrakiss [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane can be mentioned.

The additive may be mixed with a resin or the like when the base material is produced, or may be added when the resin is synthesized. The amount to be added is appropriately selected according to the desired characteristics, but is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the resin. It is a department.

<Manufacturing method of base material>
The transparent resin substrate or resin support can be formed by, for example, melt molding or cast molding, and if necessary, a coating such as an antireflection agent, a hard coating agent and / or an antistatic agent is applied after molding. By coating the agent, a base material on which an overcoat layer is laminated can be produced.

When the base material is a base material in which an overcoat layer is laminated on a glass support or a resin support as a base, for example, an overcoat layer is formed on the glass support or the resin support as a base. By melt molding or cast molding of the composition, preferably after coating by a method such as spin coating, slit coating, inkjet, etc., the solvent is dried and removed, and if necessary, further light irradiation or heating is performed. , It is possible to manufacture a base material in which an overcoat layer is formed on a glass support or a resin support as a base.

-Melting molding The melt molding specifically includes, for example, a method of melt-molding a pellet obtained by melt-kneading a resin and other components used as necessary; a resin and other components used as necessary. Examples thereof include a method of melt-molding a resin composition containing an ingredient; or a method of melt-molding a pellet obtained by removing a solvent from a resin composition containing a resin, a solvent and other components used as necessary. ..
Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

Cast molding The cast molding is, for example, a method of casting a resin composition containing a resin, a solvent and other components used as necessary on an appropriate support to remove the solvent; or a photocurable resin. And / or a curable composition containing a thermosetting resin and other components used as necessary is cast on a suitable support to remove the solvent, and then by an appropriate method such as ultraviolet irradiation or heating. Examples include a method of curing.

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. When the base material is a base material in which an overcoat layer containing the compound (A) is laminated on a support such as a glass support or a resin support as a base, the base material is used. It can be obtained by not peeling off the coating film after casting.

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

Further, an optical component made of a glass plate, quartz, transparent plastic, or the like is coated with the resin composition to dry the solvent, or the curable composition is coated to be cured and dried. A transparent resin layer can also be formed on the component.

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

[Dielectric multilayer film]
The filter preferably has a dielectric multilayer film. The dielectric multilayer film is preferably a film having an ability to cut unnecessary near-infrared rays by reflection and to transmit necessary near-infrared rays.
The dielectric multilayer film may be provided on one side or both sides of the base material. When it is provided on one side, it is excellent in manufacturing cost and ease of manufacture, and when it is provided on both sides, it is possible to obtain an optical filter having high strength and less likely to warp.

When this filter is applied to an application such as a solid-state image sensor, it is preferable that the warp of the optical filter is small. Therefore, it is preferable to provide a dielectric multilayer film on both sides of the base material. The spectral characteristics may be the same or different. When the spectral characteristics of the dielectric multilayer films provided on both sides are the same, the transmittance of light having a wavelength of 800 to 1200 nm other than the wavelength (region) I in the near infrared wavelength region can be efficiently reduced, and both sides can be used. When the provided dielectric multilayer films have different spectral characteristics, it tends to be easy to extend the near-infrared ray blocking region exceeding the wavelength (region) I to the longer wavelength side.

Examples of the dielectric multilayer film include a laminated body 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 more than 1.6 can be used, and a material having a refractive index of more than 1.6 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 oxide, indium oxide and the like as main components, and titanium oxide, tin oxide and /. Alternatively, those containing a small amount of cerium oxide or the like (for example, 0 to 10% by mass with respect to the main component) can be mentioned.

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. Examples of such a material include silica, alumina, lanthanum fluoride, magnesium fluoride and sodium hexafluoride, which are filled with an appropriate porosity.

The method of laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, a high refractive index material layer and a low refractive index material layer are alternately alternately formed on a substrate by a CVD method, a sputtering method, a vacuum vapor deposition method, an ion-assisted vapor deposition method or an ion plating method, a radical-assisted sputtering method, or the like. It is possible to form a dielectric multilayer film laminated on the surface.

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

The total number of layers of the high-refractive index material layer and the low-refractive index material layer in the dielectric multilayer film is preferably 16 to 120 layers as a whole, and more preferably 20 to 80 layers. When the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of layers are within the above ranges, a sufficient manufacturing margin can be secured and warpage of the optical filter and cracks of the dielectric multilayer film are reduced. can do.

In the present invention, the material types constituting the high refractive index material layer and the low refractive index material layer, the thickness of each layer of the high refractive index material layer and the low refractive index material layer, the order of lamination, and the number of laminations are appropriately selected. Therefore, it is possible to obtain an optical filter having a light blocking band and a light transmitting band having a desired wavelength in the near infrared wavelength region while ensuring sufficient transmittance in the visible region.

Here, in order to optimize the above conditions, for example, optical thin film design software (for example, Essential Macleod, manufactured by Thin Film Center) is used, and the transmittance in the wavelength range in which the transmission of light rays is desired to be suppressed in the near infrared wavelength range is desired. The parameters may be set so as to lower the transmittance and increase the transmittance in the wavelength range in which the light rays are to be transmitted. For example, when a light transmission band is provided in the vicinity of 940 nm by a dielectric multilayer film formed on both sides, the above software is used to set the target transmission rate of light at a wavelength of 800 to 900 nm of one of the dielectric multilayer films to 0% and a wavelength. Set the target transmission rate of light of 920 to 960 nm to 100%, set the Target Distance value of each wavelength range to 0.5 or less, and set the target of light with a wavelength of 920 to 960 nm of the other dielectric multilayer film. A parameter setting method may be mentioned in which the transmission rate is 100%, the target transmission rate of light having a wavelength of 961 to 1200 nm is 0%, and the Target Measurement value in each wavelength range is 0.5 or less.

When a blocking region is provided in the near infrared rays by a dielectric multilayer film, conventionally, a laminated body of layers having an optical film thickness that is one-fourth of the blocking region is provided. However, in a laminated body of layers having an optical film thickness of one-fourth of the conventional cut-off region, the wavelength region of one-third of the cut-off region tends to be a reflection band. When the design is such that a part of the wavelength is transmitted at a wavelength of 900 to 1100 nm, the cutoff region is, for example, 1000 to 1350 nm when a transmission band is formed at a wavelength of 950 nm in order to form a transmission region in the wavelength region. In that case, the transmittance of light having a wavelength of 450 nm, which corresponds to one-third of the wavelength of 1350 nm, decreases, and it becomes difficult to maintain a high visible light transmittance.
On the other hand, the dielectric multilayer film preferably has four or more laminated portions in which two or more layers (only) having a thickness of 60 nm or less are continuous among the layers constituting the dielectric multilayer film. By including 5 or more, more preferably 6 or more, still more preferably 7 or more, and particularly preferably 8 or more, the transmittance of light having a wavelength of 430 to 580 nm is high, and the wavelength is in the range of 900 to 1100 nm. It is possible to easily obtain a dielectric multilayer film that has a transmittance in a part but blocks other near-infrared rays having a wavelength of 800 to 1200 nm.
The number of the laminated portions is preferably 12 or less from the viewpoint of manufacturing cost.

In the dielectric multilayer film, when the number of layers of all the dielectric multilayer films contained in the optical filter is A and the number of layers having a thickness of 60 nm or less is B, the B / A is preferably 0. It is more than 2, more preferably more than 0.27, still more preferably more than 0.3, preferably less than 0.6, and more preferably 0.5 or less.
When the B / A is in the above range, it is possible to easily obtain an optical filter having both high visible light transmission and desired near-infrared transmission characteristics and excellent light blocking property of other wavelengths of 800 to 1200 nm. Can be done.

[Light-shielding film]
As shown in FIG. 2, the present filter may have a light-shielding film that blocks light.
The light-shielding film included in this filter may be one place or a plurality of places.

The thickness of the light-shielding film is preferably 1 to 10 μm, and more preferably 1 to 5 μm from the viewpoint that diffraction and reflection on the surface and end face of the light-shielding film can be easily suppressed. Further, the thickness of the light-shielding film is preferably 2 μm or more from the viewpoint of forming a film having sufficient blocking performance.
When there is a change in thickness between light-shielding films with different thicknesses or one light-shielding film, the height difference between the thickest part and the thinnest part of the light-shielding film is different from the viewpoint of preventing reflection on the surface of the light-shielding film. It is preferable to provide unevenness of about 0.1 to 2 μm. More preferably, it is about 0.1 to 0.25 μm.

The material that forms the light-shielding film is not particularly limited, but is selected from carbon materials such as dyes, carbon black, carbon nanotubes, fullerenes, graphene, HOPG (highly oriented pyrolytic graphite), metals, and visible light absorption. It is preferable that the resin composition is an ultraviolet curable type or a thermocurable resin composition containing at least one agent. Above all, the ultraviolet curable resin composition is more preferable from the viewpoint of excellent adhesion to the base material and the dielectric multilayer film.

As the metal or metal oxide which is a visible light absorber, a metal containing at least one kind of iron, copper, chromium, molybdenum, tungsten, nickel, and titanium or an oxide of the metal is preferable, and a lower metal oxide or a metal is particularly preferable. Suboxides are preferable because they have excellent light-shielding properties.
The content of the visible light absorber in the light-shielding film is at least 1 ppm or more, preferably 50% or less in terms of mass.

The optical density (OD value) of the light-shielding film at a wavelength of 300 to 1200 nm is not particularly limited, but is 1 or more, preferably 2 or more, more preferably 3 or more from the viewpoint of the effect of removing stray light, the formation of a Fresnel zone plate, and the like. Is.

[Other functional membranes]
The optical filter of the present invention has a surface between the base material and the dielectric multilayer film, a surface opposite to the surface provided with the dielectric multilayer film of the base material, or a dielectric multilayer film, as long as the effect of the present invention is not impaired. Antireflection film, hard, on the surface opposite to the surface on which the substrate of the film is provided, for the purpose of improving the surface hardness of the substrate and the dielectric multilayer film, improving chemical resistance, antistatic and scratch erasing. A functional film such as a coat film or an antistatic film can be appropriately provided.

This filter may contain one layer made of the functional film, or may contain two or more layers. When the present filter contains two or more layers made of the functional film, it may contain two or more similar layers or two or more different layers.

The method for laminating the functional film is not particularly limited, but for example, a coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent is melt-molded on the base material or the dielectric multilayer film in the same manner as described above. Alternatively, a cast molding method can be mentioned.

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

Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resins and heat-curable resins, and specific examples thereof include vinyl compounds, urethane-based, urethane acrylate-based, acrylate-based, and epoxy. Examples include based and epoxy acrylate based 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 the photopolymerization initiator and the thermal polymerization initiator may be used in combination. The polymerization initiator may be used alone or in combination of two or more.

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

An organic solvent may be added to the curable composition as a solvent, and a known solvent can be used as the organic solvent. Specific examples of the organic solvent 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- Examples thereof include amides such as methylpyrrolidone.
These solvents may be used alone or in combination of two or more.

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

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

<Use of optical filter>
This filter has a wide viewing angle and can selectively transmit visible light and some near infrared rays. Therefore, it is useful for correcting the luminosity factor of a solid-state image sensor such as a CCD or CMOS image sensor having both a camera function and a near-infrared sensing function. In particular, digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automobile cameras, dark vision cameras, motion captures, laser range meters, virtual fittings, number plates. Recognition device, TV, car navigation, mobile information terminal, video game machine, portable game machine, digital music player, face authentication device, vein authentication device, iris authentication device, fingerprint authentication device, body temperature detection device, space object detection device, expansion It is useful for reality display devices, virtual reality display devices, and the like.

[Solid image sensor]
The solid-state image sensor according to the present invention includes the present filter. Here, the solid-state image sensor is preferably an image sensor equipped with a solid-state image sensor such as a CCD or a CMOS image sensor having both a camera function and a near-infrared sensing function, specifically for a digital still camera and a smartphone. Examples thereof include cameras, cameras for mobile phones, cameras for wearable devices, camera modules such as digital video cameras, and biometric authentication devices.

An example of a solid-state image sensor, a camera module, and a biometric authentication device is shown in FIG. A near-infrared light source 102, a sensor 112, and a lens unit 121 are provided for sensing, and the optical filter 1 is provided on the entire surface of the sensor 112. The light source, the sensor, and the lens unit may be one or more for the device.
The lens included in the light source or the lens unit may be a structure having a so-called refractive index of 1.1 or more and a diffractive optical element. From the viewpoint of thinness and optical control such as diffusing a light source to a plurality of places, it is more preferable that the lens unit of the solid-state imaging device, the camera module, and the biometric authentication device has a diffractive optical element. As the diffractive optical element, for example, silicon, titania, germanium, aluminum oxide, silicon oxide, gold, silver, copper, and aluminum are used. From the viewpoint of visible light transmittance, the material constituting the diffractive optical element preferably includes a material containing silicon, titania, aluminum oxide, and silicon oxide.

FIG. 3 shows an example of the position of the optical filter in the solid-state image sensor. The arrangement position is not particularly limited, but as shown in FIG. 3, the optical filter 1 may be provided either behind or in front of the lens unit 32. If the optical filter has a light-shielding film and the light-shielding film has a lens effect such as a mosaic mask or Fresnel zone plate, or if the captured image can be obtained by another mechanism such as when scanning the sensor detection position, a lens unit is provided. You don't have to.

FIG. 6 shows an example of the sensor portion in the solid-state image sensor. The components are not particularly limited, but the sensor may have near-infrared pixels in addition to the three-color pixels of blue pixels, green pixels, and red pixels. When this filter, which has a high transmittance for some near-infrared transmission bands for sensing, is used, and when used for a sensor having near-infrared pixels, detection using light invisible to the human eye becomes possible. ..
As the light receiving element, for example, a photodiode can be used, and as the photodiode, a silicon photodiode or black silicon is preferable.
The surface of the insulating layer preferably has an antireflection structure such as a cone, a triangular pyramid, or a quadrangular pyramid from the viewpoint of improving the sensitivity of the photodiode.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The following "part" means "part by mass" unless otherwise specified.

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

(A) Using a gel permeation chromatography (GPC) device (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS, weight in terms of standard polystyrene. The average molecular weight (Mw) and the number average molecular weight (Mn) were measured.
(B) Using a GPC device (HLC-8220 type, column: TSKgelα-M, developing solvent: tetrahydrofuran) manufactured by Tosoh Corporation, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were measured. ..

<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies Co., Ltd., the temperature was measured at a heating rate of 20 ° C. per minute under a nitrogen stream.

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

Here, the transmittance of the light incident from the direction perpendicular to the surface direction of the substrate and the optical filter (0 degree incident) is the light transmitted perpendicularly to the substrate or the filter as shown in FIG. 5 (A). Was measured. Further, the transmittance of the light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter (incident at 35 degrees) is an angle of 35 degrees with respect to the vertical direction of the filter as shown in FIG. 5 (B). The light transmitted by was measured.

<Noise amount>
The amount of noise when incident at 35 degrees is the wavelength-specific transmission T ₃₅ (λ) of the optical filter when incident at 35 degrees, the wavelength-specific intensity I (λ) of the sunbeam, and the wavelength-specific sensitivity B (λ) of the blue pixel in the sensor pixel. ), The wavelength-specific sensitivity G (λ) of the green pixel, and the wavelength-specific sensitivity R (λ) of the red pixel were calculated from the following equations.
Noise amount (%) = N / S x 100

N is an alternative index of the total amount of light received by the sensor pixel under the sun's rays at wavelengths of 781 to 1200 nm, which is a near-infrared wavelength with relatively low human luminous efficiency. Specifically, N is the wavelength-specific transmission T ₃₅ (λ) of the optical filter, the wavelength-specific intensity I (λ) of the sunbeam, and the wavelength-specific sensitivity B (λ) of each of the blue, green, and red sensor pixels. ), G (λ) or R (λ), and the sum of the calculated values for each 1 nm was calculated based on the following formula.

S is an alternative index of the total amount of light received by the sensor pixel under the sun's rays at a wavelength of 380 to 780 nm. Specifically, S is the wavelength-specific transmission T ₃₅ (λ) of the optical filter, the wavelength-specific intensity I (λ) of the sunbeam, and the wavelength-specific sensitivity B (λ) of each of the blue, green, and red sensor pixels. ), G (λ) or R (λ), and the sum of the calculated values for each 1 nm was calculated based on the following formula.

As shown in Fig. 7, the wavelength-specific intensity I (λ) of the sun's rays used the irradiation amount data of Gifu at a certain date and time released by the New Energy and Industrial Technology Development Organization. The values shown in FIG. 8 were used for the wavelength-specific sensitivities of the blue, green, and red sensor pixels based on the description in JP-A-2017-216678.

The noise amount at 0 degree incident was calculated in the same manner as the noise amount at 35 degree incident except that the transmittance T ₀ (λ) for each wavelength at 0 degree incident of the optical filter was used.

[Composite example]
The compound (A), the compound (B) and the compound (X) used in the following examples can be synthesized by a generally known method, and for example, Japanese Patent No. 3366697 and Japanese Patent No. 2846091 can be synthesized. , Patent No. 2864475, Japanese Patent No. 3094037, Japanese Patent No. 3703869, Japanese Patent Application Laid-Open No. 60-228448, Japanese Patent Application Laid-Open No. 1-146846, Japanese Patent Application Laid-Open No. 1-2289960, Japanese Patent Application Laid-Open No. 4081149, JP-A-63-124054, "Futarusinin-Chemistry and Function-" (IPC, 1997), JP-A-2007-169315, JP-A-2009-108267, JP-A-2010-241873, Patent. It can be synthesized by referring to the methods described in Japanese Patent No. 3699464, Japanese Patent No. 4740631, and the like.

<Compound (A)>

<Compound (B)>

<Compound (X)>
(X-1): BONASORB-UA3911 (manufactured by Orient Chemical Industry Co., Ltd.)

<Resin synthesis example 1>
8-Methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] 100 parts of dodeca-3-ene, 18 parts of 1-hexene (molecular weight modifier) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were placed in a reaction vessel substituted with nitrogen, and this solution was charged at 80 ° C. Heated to. Next, in the solution in the reaction vessel, 0.2 part of a toluene solution of triethylaluminum (concentration 0.6 mol / liter) and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) 0 as a polymerization catalyst. .9 parts were added, and the obtained 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%.

1,000 parts of the ring-opening polymer solution thus obtained 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 a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C., the hydrogenation reaction was carried out by heating and stirring for 3 hours. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the 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 weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.

[Example 1]
To the container, 100 parts of the resin A obtained in Synthesis Example 1, 0.12 parts of the compound (a-1) (absorption maximum wavelength 843 nm in dichloromethane) and methylene chloride as the compound (A) are added, and the resin concentration is 20. A mass% solution was obtained. The resulting solution was then cast onto a smooth glass plate, dried at 20 ° C. for 8 hours and then stripped from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 8 hours to obtain a substrate made of a transparent resin having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

Subsequently, the dielectric multilayer film (I) shown in Table 1 is formed on one surface of the obtained substrate, and the dielectric multilayer film (II) shown in Table 1 is formed on the other surface of the substrate. , An optical filter 1 having a thickness of about 0.105 mm was obtained.

The dielectric multilayer film (I) is a laminated body in which silica (SiO ₂ ) layers and titanium (TiO ₂ ) layers are alternately laminated at a vapor deposition temperature of 100 ° C. The dielectric multilayer film (II) is a laminated body in which silica layers and titania layers are alternately laminated at a vapor deposition temperature of 100 ° C. In both the dielectric multilayer films (I) and (II), the silica layer and the titania layer are in the order of the titania layer, the silica layer, the titania layer, ..., the silica layer, the titania layer, and the silica layer from the substrate side. The layers were alternately laminated, and the outermost layer of the optical filter was a silica layer.

The spectral transmittance of light incident on the optical filter 1 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 9 and Table 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 90.2% and the average value of the transmittance at a wavelength of 800 to 900 nm is 2.6% when the optical filter 1 is incident at 0 degrees, and when the optical filter 1 is incident at 35 degrees. The average value of the transmittance at a wavelength of 430 to 580 nm is 88.8%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 13.2%. Had had. The amount of noise at the time of incident at 35 degrees in the optical filter 1 was 9%, and the amount of noise was small.

[Example 2]
In Example 1, 0.104 parts of compound (a-2) (absorption maximum wavelength 903 nm in dichloromethane) was used instead of 0.12 parts of compound (a-1), and a dielectric provided on both sides of the substrate. An optical filter 2 was obtained under the same procedure and conditions as in Example 1 except that the multilayer film was changed to (III) and (IV) shown in Table 1.

The spectral transmittance of light incident on the optical filter 2 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIGS. 10 and 6.
When the optical filter 2 is incident at 0 degree, the average value of the transmittance at a wavelength of 430 to 580 nm is 80.3%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.1%. The average value of the transmittance at a wavelength of 430 to 580 nm is 78.8%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.8%. Had had. The amount of noise in the optical filter 2 when incident at 35 degrees was 2%, and the amount of noise was small.

[Example 3]
In Example 1, 0.065 part of compound (a-3) (absorption maximum wavelength in dichloromethane, 886 nm) was used instead of 0.12 part of compound (a-1), and a dielectric provided on both sides of the substrate. An optical filter 3 was obtained under the same procedure and conditions as in Example 1 except that the multilayer film was changed to (V) and (VI) shown in Table 1.

The spectral transmittance of light incident on the optical filter 3 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIGS. 11 and 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 81.3% and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.0% when the optical filter 3 is incident at 0 degrees, and when the optical filter 3 is incident at 35 degrees. The average value of the transmittance at a wavelength of 430 to 580 nm is 78.4%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.2%. Had had. The amount of noise at the time of incident at 35 degrees in the optical filter 3 was 1%, and the amount of noise was small.

[Example 4]
100 parts of the resin A obtained in Synthesis Example 1, 0.042 parts of the compound (a-4) (absorption maximum wavelength 868 nm in dichloromethane) and methylene chloride were added to the container to add the resin concentration. Obtained a 20% by weight solution. The resulting solution was then cast onto a smooth glass plate, dried at 20 ° C. for 8 hours and then stripped from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 0.1 mm, a length of 150 mm and a width of 200 mm.

The following resin composition (1) was applied to both sides of the transparent resin substrate using a bar coater (manufactured by Yasuda Seiki Seisakusho Co., Ltd., automatic film applicator, model number 542-AB), and the film thickness after drying was increased by the coater bar. It was applied so as to be 0.002 mm each. Using an inertia oven (Inert oven DN410I manufactured by Yamato Kagaku Co., Ltd.), dry at 80 ° C. for 3 minutes, and then use a UV conveyor (Eye Graphics Co., Ltd., eye ultraviolet curing device, model US2-X0405 60 Hz). The metal halide lamp was UV-cured at an illuminance of 270 mW / cm ² and an exposure of 500 mJ / cm ² to obtain a substrate on which a transparent cured layer was formed.

Resin composition (1): Composition containing 60 parts of tricyclodecanedimethanol acrylate, 40 parts of dipentaerythritol hexaacrylate, 5 parts of 1-hydroxycyclohexylphenyl ketone, and methyl ethyl ketone (used so that the solid content concentration is 30% by mass). object

An optical filter 4 was obtained under the same procedure and conditions as in Example 1 except that the dielectric multilayer films provided on both sides of the obtained substrate were changed to (VII) and (VIII) shown in Table 2.

The spectral transmittance of light incident on the optical filter 4 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 12 and Table 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 88.3% and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.2% when the optical filter 4 is incident at 0 degrees, and when the optical filter 4 is incident at 35 degrees. The average value of the transmittance at a wavelength of 430 to 580 nm is 87.4%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 2.4%. Had had. The amount of noise at the time of incident at 35 degrees in the optical filter 4 was 4%, and the amount of noise was small.

[Example 5]
The following resin composition (2) is applied to a glass plate (manufactured by SCHOTT, BK7, thickness 0.1 mm) by spin coating, and then heated on a hot plate at 80 ° C. for 2 minutes to volatilize and remove the solvent. Formed a layer. At this time, the application conditions of the spin coater were adjusted so that the film thickness of the cured layer was about 0.8 μm.

Resin composition (2): Isocyanuric acid ethylene oxide-modified triacrylate (trade name: Aronix M-315, manufactured by Toa Synthetic Chemical Co., Ltd.) 30 parts, 1,9-nonanediol diacrylate 20 parts, methacrylic acid 20 parts, 30 parts of glycidyl methacrylate, 5 parts of 3-glycidoxypropyltrimethoxysilane, 5 parts of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by Ciba Specialty Chemical Co., Ltd.) and Sun Aid SI-110 main agent (Sanshin) A solution obtained by mixing 1 part (manufactured by Chemical Industry Co., Ltd.), dissolving it in propylene glycol monomethyl ether acetate so that the solid content concentration becomes 50% by mass, and then filtering it with a millipore filter having a pore size of 0.2 μm.

Next, in a container, 100 parts of the resin A obtained in Synthesis Example 1, 0.48 parts of the compound (a-4), 0.54 parts of the compound (b-1) (absorption maximum wavelength 771 nm in dichloromethane) and 0.54 parts. Methylene chloride was added to obtain a solution (A) having a resin concentration of 20% by mass. A bar coater (manufactured by Yasuda Seiki Seisakusho Co., Ltd., automatic film applicator, model number 542-AB) is used on one side of the cured layer, and the solution (A) is applied to the solution (A) so that the film thickness after drying is 10 μm by the coater bar. A transparent resin layer was formed by applying and heating on a hot plate at 80 ° C. for 5 minutes to volatilize and remove the solvent. Next, the glass plate was exposed from the glass plate side using a UV conveyor type exposure machine (exposure amount: 500 mJ / cm ² , illuminance: 200 mW), and then baked in an oven at 210 ° C. for 5 minutes to obtain a glass substrate, a cured layer and a transparent resin layer. A substrate having the above was obtained.

An optical filter 5 was obtained under the same procedure and conditions as in Example 1 except that the dielectric multilayer films provided on both sides of the obtained substrate were changed to (IX) and (X) shown in Table 2. The dielectric multilayer film was formed so that the dielectric multilayer film in contact with the glass plate became (IX).

The spectral transmittance of light incident on the optical filter 5 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIGS. 13 and 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 75.9% and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.1% when the optical filter 5 is incident at 0 degrees, and when the optical filter is incident at 35 degrees. The average value of the transmittance at a wavelength of 430 to 580 nm is 74.3%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 1.5%. Had had. The amount of noise at the time of incident at 35 degrees in the optical filter 5 was 4%, and the amount of noise was small.

[Example 6]
In Example 1, instead of 0.12 parts of compound (a-1), 0.136 parts of compound (a-1), 0.03 parts of compound (b-2) (absorption maximum wavelength in dichloromethane, 704 nm) and 0.03 parts. Using 0.035 part of compound (b-3) (absorption maximum wavelength in dichloromethane, 733 nm), the dielectric multilayer films provided on both sides of the substrate were changed to (XI) and (XII) shown in Table 2. An optical filter 6 was obtained under the same procedure and conditions as in Example 1 except for the above.

The spectral transmittance of light incident on the optical filter 6 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 14 and Table 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 88.2% and the average value of the transmittance at a wavelength of 800 to 900 nm is 1.6% when the optical filter 6 is incident at 0 degrees, and when the optical filter 6 is incident at 35 degrees. The average value of the transmittance at a wavelength of 430 to 580 nm is 84.1%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 11.1%. Had had. The amount of noise at the time of incident at 35 degrees in the optical filter 6 was 9%, and the amount of noise was small.

[Example 7]
In Example 1, 0.104 parts of compound (a-2), 0.03 part of compound (b-2) and 0.035 parts of compound (b-3) were used instead of compound (a-1). An optical filter 7 was obtained under the same procedure and conditions as in Example 1 except that the dielectric multilayer films provided on both sides of the substrate were changed to (XIII) and (XIV) shown in Table 3.

The spectral transmittance of light incident on the optical filter 7 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIGS. 15 and 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 77.7% when the optical filter 7 is incident at 0 degree, and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.1%. The average value of the transmittance at a wavelength of 430 to 580 nm is 76.1%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.8%. Had had. The amount of noise at the time of incident at 35 degrees in the optical filter 7 was 2%, and the amount of noise was small.

[Example 8]
In Example 1, instead of compound (a-1), 0.041 part of compound (a-4), 0.04 part of compound (b-2), 0.035 part of compound (b-3) and compound (X). -1) Implemented except that 0.045 parts (absorption maximum wavelength in dichloromethane) 0.045 part was used and the dielectric multilayer films provided on both sides of the substrate were changed to (XV) and (XVI) shown in Table 3. An optical filter 8 was obtained under the same procedure and conditions as in Example 1.

The spectral transmittance of light incident on the optical filter 8 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 16 and Table 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 86.7% when the optical filter 8 is incident at 0 degree, and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.3%. The average value of the transmittance at a wavelength of 430 to 580 nm is 82.7%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 2.4%. Had had. The amount of noise at the time of incident at 35 degrees in the optical filter 8 was 4%, and the amount of noise was small.

[Example 9]
In Example 1, instead of compound (a-1), 0.05 part of compound (a-3), 0.031 part of compound (b-2), 0.035 part of compound (b-3) and compound (X). -1) Optical under the same procedure and conditions as in Example 1 except that 0.045 parts were used and the dielectric multilayer films provided on both sides of the substrate were changed to (XVII) and (XVIII) shown in Table 3. Filter 9 was obtained.

The spectral transmittance of light incident on the optical filter 9 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIGS. 17 and 6.
When the optical filter 9 is incident at 0 degrees, the average value of the transmittance at a wavelength of 430 to 580 nm is 81.6%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.0%. The average value of the transmittance at a wavelength of 430 to 580 nm is 78.6%, and the average value of the transmittance at a wavelength of 800 to 900 nm is 0.4%. Had had. The amount of noise at the time of incident at 35 degrees in the optical filter 9 was 1%, and the amount of noise was small.

[Comparative Example 1]
In Example 1, a glass substrate (SKHOTT, BK7, thickness 0.1 mm) was used instead of the substrate made of a transparent resin substrate, and the dielectric multilayer films provided on both sides of the substrate are shown in Table 4. An optical filter 10 was obtained under the same procedure and conditions as in Example 1 except that the components were changed to (XIX) and (XX).

The spectral transmittance of light incident on the optical filter 10 in the direction perpendicular to the plane direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 6.
The obtained optical filter 10 has the same configuration as the conventional two-wavelength bandpass filter, and the average value of the transmittance at a wavelength of 430 to 580 nm when the optical filter 10 is incident at 0 degrees is 95.1% and the wavelength is 800. The average value of the transmittance at ~ 900 nm is 1.0%, the average value of the transmittance at wavelengths of 430 to 580 nm at 35 degrees incident is 94.8%, and the average value of the transmittance at wavelengths of 800 to 900 nm is 32. It was 8.8% and had a high visible light transmittance, but did not have a blocking property with a wavelength of 800 to 900 nm when incident at 35 degrees. The amount of noise at the time of incident at 35 degrees in the optical filter 10 was 13%, which was a large amount of noise.

[Comparative Example 2]
In Example 1, 0.054 parts of compound (b-1) was used instead of 0.12 parts of compound (a-1), and the dielectric multilayer films provided on both sides of the substrate are shown in Table 4 (XXI). ) And (XXII), the optical filter 11 was obtained under the same procedure and conditions as in Example 1.

The spectral transmittance of light incident on the optical filter 11 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 18 and Table 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 83.1% and the average value of the transmittance at a wavelength of 800 to 900 nm is 2.1% when the optical filter 11 is incident at 0 degrees, and when the optical filter is incident at 35 degrees. The average value of the transmittance at the wavelength of 430 to 580 nm is 81.8%, and the average value of the transmittance at the wavelength of 800 to 900 nm is 28.4%. It did not have a blocking property of 800 to 900 nm. The amount of noise at the time of incident at 35 degrees in the optical filter 11 was 19%, which was a large amount of noise.

[Comparative Example 3]
In Example 1, 0.072 parts of compound (b-4) (absorption maximum wavelength in dichloromethane, 770 nm) was used instead of 0.12 parts of compound (a-1), and dielectrics provided on both sides of the substrate. An optical filter 12 was obtained under the same procedure and conditions as in Example 1 except that the multilayer film was changed to (XXIII) and (XXIV) shown in Table 4.

The spectral transmittance of light incident on the optical filter 12 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 19 and Table 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 89.6% and the average value of the transmittance at a wavelength of 800 to 900 nm is 2.2% when the optical filter 12 is incident at 0 degrees, and when the optical filter is incident at 35 degrees. The average value of the transmittance at the wavelength of 430 to 580 nm is 88.8%, and the average value of the transmittance at the wavelength of 800 to 900 nm is 29.8%. It did not have a blocking property of 800 to 900 nm. The amount of noise at the time of incident at 35 degrees in the optical filter 12 was 17%, which was a large amount of noise.

[Comparative Example 4]
In Example 1, 0.03 part of compound (b-2) and 0.035 part of compound (b-3) were used instead of 0.12 part of compound (a-1), and dielectrics provided on both sides of the substrate were used. An optical filter 13 was obtained under the same procedure and conditions as in Example 1 except that the body multilayer film was changed to (XXV) and (XXVI) shown in Table 5.

The spectral transmittance of light incident on the optical filter 13 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 20 and Table 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 94.1% and the average value of the transmittance at a wavelength of 800 to 900 nm is 3.3% when the optical filter 13 is incident at 0 degree. The average value of the transmittance at the wavelength of 430 to 580 nm is 90.3%, and the average value of the transmittance at the wavelength of 800 to 900 nm is 33.5%. It did not have a blocking property of 800 to 900 nm. The amount of noise at the time of incident at 35 degrees in the optical filter 13 was 21%, which was a large amount of noise.

[Comparative Example 5]
In Comparative Example 4, an optical filter 14 was obtained under the same procedure and conditions as in Example 1 except that the dielectric multilayer films provided on both sides of the substrate were changed to (XXVII) and (XXVIII) shown in Table 5.

The spectral transmittance of light incident on the optical filter 14 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 21 and Table 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 90.9% and the average value of the transmittance at a wavelength of 800 to 900 nm is 3.1% when the optical filter 14 is incident at 0 degrees, and when the optical filter is incident at 35 degrees. The average value of the transmittance at the wavelength of 430 to 580 nm is 87.0%, and the average value of the transmittance at the wavelength of 800 to 900 nm is 32.7%. It did not have a blocking property of 800 to 900 nm. The amount of noise at the time of incident at 35 degrees in the optical filter 14 was 22%, which was a large amount of noise.

[Comparative Example 6]
In Example 1, instead of 0.12 parts of compound (a-1), 0.03 parts of compound (b-2), 0.035 parts of compound (b-3) and 0.04 parts of compound (b-4). The optical filter 15 was obtained under the same procedure and conditions as in Example 1 except that the dielectric multilayer films provided on both sides of the substrate were changed to (XXIX) and (XXX) shown in Table 5.

The spectral transmittance of light incident on the optical filter 15 in the direction perpendicular to the surface direction (0 degree) and at an angle of 35 degrees from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 22 and Table 6.
The average value of the transmittance at a wavelength of 430 to 580 nm is 90.9% and the average value of the transmittance at a wavelength of 800 to 900 nm is 66.9% when the optical filter 15 is incident at 0 degrees, and when the optical filter is incident at 35 degrees. The average value of the transmittance at the wavelength of 430 to 580 nm is 86.4%, and the average value of the transmittance at the wavelength of 800 to 900 nm is 46.1%. It did not have a blocking property of 800 to 900 nm. The amount of noise at the time of incident at 35 degrees in the optical filter 15 was 39%, which was a large amount of noise.

This filter can be used for digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automobile cameras, dark vision cameras, motion captures, laser range meters, virtual fittings, etc. Number plate recognition device, TV, car navigation, mobile information terminal, personal computer, video game machine, portable game machine, digital music player, face authentication device, vein authentication device, iris authentication device, fingerprint authentication device, body temperature detection device, spatial object It can be suitably used for a detection device, an extended reality display device, a virtual reality display device, and the like.

1 ... Optical filter 2, 2'... Base material 3, 3'... Dielectric multilayer film 4, 4'... Functional film 5 ... Light-shielding film 6, 6'... Light 7 ... Spectral luminometer 8 ... Optical filter 24 ... Image sensor 25 ... Image sensor frame 26 ... Frame 31 ... Housing 32 ... Lens 101 ... Light source unit 102 ... Light source 103 ... Lens or diffractive optical element or light source scanning unit 111 ... Sensor unit 112 ... Sensor 121 ... Lens unit 122 ... Lens or diffractive optical element 201 ... Micro lens 202 ...・ Flat layer 203a ・ ・ ・ Color filter (blue)
203b ・ ・ ・ Color filter (green)
203c ・ ・ ・ Color filter (red)
203d ・ ・ ・ Color filter (infrared)
204a ・ ・ ・ Photodiode (blue)
204b ・ ・ ・ Photodiode (green)
204c ・ ・ ・ Photodiode (red)
204d ・ ・ ・ Photodiode (infrared)
205 ... Insulation layer 206 ... Substrate

Claims (11)

It contains compound (A) having an absorption maximum at a wavelength of 851 to 930 nm, and contains the compound (A).
Satisfy the following requirements (a) to (c)
In light incident from the direction perpendicular to the surface direction of the optical filter,
The average transmittance of light having a wavelength of 800 to 1200 nm other than the wavelength (region) I is 30% or less so that light having a wavelength (region) I of at least a part of the wavelengths of 900 to 1100 nm and visible light are transmitted. To shut off,
Optical filter.
(A) At wavelengths of 430 to 580 nm, the average value of the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 60% or more. (B) At wavelengths of 800 to 900 nm, with respect to the surface direction of the optical filter. The average value of the transmittance of light incident from the vertical direction is 10% or less. (C) The shortest wavelength at which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% at a wavelength of 800 to 1200 nm. When λIRT ₀ (nm), the wavelength λIRT ₀ is in the range of 900 to 1100 nm.
At wavelengths of 800 nm to (λIRT _0-50 ) nm, the maximum value of the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter is 15% or less. The optical filter according to claim 1 , comprising the compound (B) having an absorption maximum wavelength in a wavelength of 600 nm or more and less than 800 nm. The optical filter according to any one of claims 1 to 2 , which comprises a compound (X) having an absorption maximum wavelength at a wavelength of 300 to 425 nm. It has at least one layer containing the compound (A) having an absorption maximum at a wavelength of 851 to 930 nm.
Satisfy the following formula (A1),
The optical filter according to any one of claims 1 to 3 .

[The reference numerals in the formula (A1) indicate the following.
In an optical filter having n layers containing the compound (A),
CAN indicates the concentration (wt%) of the compound (A) in the n layer, and lAn indicates the thickness (μm) of the n layer. ] Any of claims 1 to 4 , wherein at a wavelength of 800 to 1200 nm, the total wavelength (range) at which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% or more is 20 to 150 nm. The optical filter according to item 1. The optical filter according to any one of claims 1 to 5 , which satisfies the following requirement (d).
(D) At wavelengths of 800 to 1200 nm, the shortest wavelength at which the transmittance of light incident from the direction perpendicular to the surface direction of the optical filter is 50% is λIRT ₀ (nm).
When λIRT ₃₅ is the shortest wavelength at which the transmittance of light incident at an angle of 35 degrees from the direction perpendicular to the surface direction of the optical filter at a wavelength of 800 to 1200 nm is 50%, the following equation (d1) is satisfied. ｜ λIRT ₀ －λIRT ₃₅ ｜ ≦ 30nm (d1) Any one of claims 1 to 6 , which has a dielectric multilayer film and has four or more laminated portions in which two or more layers having a thickness of 60 nm or less are continuous among the layers constituting the dielectric multilayer film. The optical filter described in the section. Has a dielectric multilayer film,
Claims 1 to 7 satisfy B / A> 0.2 when the number of layers of all the dielectric multilayer films contained in the optical filter is A and the number of layers of layers having a thickness of 60 nm or less is B. The optical filter according to any one item. A solid-state image sensor including the optical filter according to any one of claims 1 to 8 . A camera module including the optical filter according to any one of claims 1 to 8 . A biometric authentication device comprising the optical filter according to any one of claims 1 to 8 .

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