WO2020255927A1

WO2020255927A1 - Optical filter, imaging device, and optical sensor

Info

Publication number: WO2020255927A1
Application number: PCT/JP2020/023450
Authority: WO
Inventors: さゆり山田; 和彦塩野
Original assignee: Ａｇｃ株式会社
Priority date: 2019-06-20
Filing date: 2020-06-15
Publication date: 2020-12-24
Also published as: JP7484911B2; CN114008494A; JPWO2020255927A1

Abstract

The present invention relates to an optical filter comprising an absorption layer and a reflection layer constituted of a dielectric multilayer film, the absorption layer comprising: a transparent resin having a glass transition point of 130°C or higher; and a near-infrared-ray-absorbing colorant (A) which, in the transparent resin, has a maximum absorption wavelength in the wavelength range of 850-1,100 nm, which has an average internal transmittance of 90% or higher for light having wavelengths of 490-560 nm, which has an average internal transmittance of 90% or higher for light having wavelengths of 590-630 nm, and which, in the wavelength range of 650-1,150 nm, has an internal transmittance of 50% at wavelengths, the difference between which is 180 nm or greater. The near-infrared-ray-absorbing colorant (A) has a difference in average transmittance of 490-560 nm light of 10% or less between in dichloromethane and in the transparent resin and has a difference in average transmittance of 590-630 nm light of 10% or less between in dichloromethane and in the transparent resin.

Description

Optical filters, imaging devices and optical sensors

The present invention relates to an optical filter that transmits light in the visible wavelength region and shields light in the near-infrared wavelength region, and an image pickup device and an optical sensor provided with the optical filter.

An image sensor using a solid-state image sensor transmits light in the visible region (hereinafter also referred to as "visible light") and transmits light in the near infrared region (hereinafter "near red") in order to reproduce color tones well and obtain a clear image. An optical filter that blocks (also called "outside light") is used. The optical filter includes a near-infrared cut filter in which an absorption layer containing a near-infrared absorbing dye and a resin and a reflecting layer made of a dielectric multilayer film that shields near-infrared light are provided on a glass substrate. Are known.

Such a near-infrared cut filter is used for applications such as an ambient light sensor, in which case it absorbs light in a specific long wavelength region of near-infrared light and has a high transmittance in the visible light region. Was required.

As an optical filter for an ambient light sensor, for example, Patent Document 1 discloses an optical filter using a dye having an absorption ability in a wavelength range of 850 to 1050 nm, which is a long wavelength range of near infrared light.

Further, in Patent Document 2, instead of the absorbing glass having absorption in the long wavelength region of near infrared light, a shape having good absorption characteristics in the wavelength region and a small size and a thin wall can be easily obtained. Moreover, the technology of the near-infrared cut filter, which is less likely to generate minute defects during polishing and is excellent in cost and productivity, is described. Patent Document 2 discloses a technique for obtaining a near-infrared cut filter having the above characteristics by using an optical film containing a transparent resin and a dye that combines a diimonium dye, a cyanine dye, and an onium salt.

International Publication No. 2017/094672 Japanese Patent Application Laid-Open No. 2008-303130

However, in the above optical filter using an absorption layer containing a specific dye and a transparent resin capable of absorbing near-infrared light in a long wavelength region, the transmittance of visible light, particularly green, which strongly affects the visual perception. It could not be said that the transmittance of red and red was sufficiently high.

The present invention can effectively block light in the long wavelength range of near-infrared light, particularly in the wavelength range of 850 to 1100 nm, and maintains a sufficiently high transmittance of visible light, particularly green and red. It is an object of the present invention to provide an optical filter capable of the present invention, and an image pickup device and an optical sensor having excellent color reproducibility using the optical filter.

The optical filter according to one aspect of the present invention contains a transparent resin having a glass transition point of 130 ° C. or higher and a near-infrared absorbing dye (A) that satisfies all of the following requirements (1-1) to (1-6). It has an absorbing layer and a reflective layer made of a dielectric multilayer film.
(1-1) In the spectral transmittance curve SC _TR having a wavelength of 350 to 1200 nm measured by containing the near-infrared absorbing dye (A) in the transparent resin, the maximum absorption wavelength λ _{max (A) TR} is 850 to 1100 nm. It is in the wavelength range of.
(1-2) Average internal transmittance of light having a wavelength of 490 to 560 nm when the internal transmittance at the maximum absorption wavelength λ _{max (A) TR} is 10% in the spectral transmittance curve SC _TR T _{AVE490-560 (A) TR} is 90% or more.
(1-3) Average internal transmittance of light having a wavelength of 590 to 630 nm when the internal transmittance at the maximum absorption wavelength λ _{max (A) TR} is 10% in the spectral transmittance curve SC _TR T _{AVE590-630 (A) TR} is 90% or more.
(1-4) The spectral transmittance curve SC _TR has an internal transmittance of 50% in a wavelength region of 650 to 1150 nm, where the internal transmittance at the maximum absorption wavelength λ _{max (A) TR} is 10%. It has two wavelengths, and the width between the two wavelengths is 180 nm or more.
(1-5) the transmittance of light at the maximum absorption wavelength lambda _{max (A) DCM} in the spectral transmittance curve _{SC DCM} wavelength 350 ~ 1200 nm to be measured the near-infrared absorbing dye (A) was dissolved in dichloromethane The value obtained by subtracting the average internal transmittance T _{AVE490-560 (A) TR} from the average transmittance T _{AVE490-560 (A) DCM} of light having a wavelength of 490 to 560 nm at 10% is 10% or less.
(1-6) Maximum absorption wavelength λ _{max (A)} in the spectral transmittance curve SC _DCM The average transmittance of light having a wavelength of 590 to 630 nm when the transmittance of light in _DCM is 10% T _{AVE590-630 ( A) The} value obtained by subtracting the average internal transmittance T _{AVE590-630 (A) TR} from _DCM is 10% or less.

The present invention also provides an image pickup apparatus and an optical sensor provided with the optical filter of the present invention.

According to the present invention, it is possible to effectively block light in the long wavelength range of near-infrared light, particularly in the wavelength range of 850 to 1100 nm, and to sufficiently reduce the transmittance of visible light, particularly the transmittance of green and red. It is possible to provide an optical filter that can be maintained at a high level, and an image pickup device and an optical sensor that use the optical filter and have excellent color reproducibility.

FIG. 1 is a cross-sectional view schematically showing an example of an optical filter of one embodiment. FIG. 2 is a cross-sectional view schematically showing another example of the optical filter of one embodiment. FIG. 3 is a cross-sectional view schematically showing another example of the optical filter of one embodiment. FIG. 4 is a cross-sectional view schematically showing another example of the optical filter of one embodiment. FIG. 5 is a cross-sectional view schematically showing another example of the optical filter of one embodiment. FIG. 6 is a cross-sectional view schematically showing another example of the optical filter of one embodiment. FIG. 7 is a diagram showing spectral transmittance curves of the dye (A1a-5NS) in Test Example 2 in the transparent resin P and dichloromethane. FIG. 8 is a diagram showing spectral transmittance curves of the dye (A1a-5NS) in Test Example 19 in a transparent resin other than the transparent resin P and in dichloromethane. FIG. 9 is a diagram showing a spectral transmittance curve of the absorption layer in the optical filter of the example (Example 1; Example). FIG. 10 is a diagram showing a spectral transmittance curve of the optical filter of the example (Example 1; Example). FIG. 11 is a diagram showing a spectral transmittance curve of the absorption layer in the optical filter of the example (Example 4; Example). FIG. 12 is a diagram showing a spectral transmittance curve of the optical filter of the example (Example 4; Example). FIG. 13 is a diagram showing a spectral transmittance curve of the absorption layer in the optical filter of the example (Example 6; Example). FIG. 14 is a diagram showing a spectral transmittance curve of the optical filter of the example (Example 6; Example). FIG. 15 is a diagram showing a spectral transmittance curve of the absorption layer in the optical filter of the example (Example 8; comparative example). FIG. 16 is a diagram showing a spectral transmittance curve of the optical filter of the example (Example 8; comparative example).

Hereinafter, embodiments of the present invention will be described.
In the present specification, the near-infrared absorbing dye may be abbreviated as "NIR dye" and the ultraviolet absorbing dye may be abbreviated as "UV dye".

In the present specification, the compound represented by the formula (A1) is referred to as a compound (A1). The same applies to compounds represented by other formulas. The dye composed of the compound (A1) is also referred to as a dye (A1), and the same applies to other dyes. Further, for example, a group represented by the formula (1x) is also described as a group (1x), and the same applies to a group represented by another formula.

In the present specification, the internal transmittance is a transmittance obtained by subtracting the influence of interfacial reflection from the actually measured transmittance, which is represented by the formula of measured transmittance / (100-reflectance). In the present specification, the transmittance of a transparent substrate made of a resin and the spectroscopy of the transmittance of a resin layer including the case where a dye such as an absorption layer is contained in the resin are all described as "transmittance". "Internal transmittance". On the other hand, the transmittance measured by dissolving the dye in a solvent such as dichloromethane and the transmittance of the optical filter having the dielectric multilayer film are the measured transmittance.

In the present specification, for a specific wavelength region, for example, a transmittance of 90% or more means that the transmittance does not fall below 90% in the entire wavelength region, that is, the minimum transmittance is 90% or more in the wavelength region. To say. Similarly, for a specific wavelength region, for example, a transmittance of 1% or less means that the transmittance does not exceed 1% in the entire wavelength region, that is, the maximum transmittance is 1% or less in the wavelength region. .. The same applies to the internal transmittance. The average transmittance and the average internal transmittance in a specific wavelength region are arithmetic means of the transmittance and internal transmittance for each 1 nm in the wavelength region.
In the present specification, "-" representing a numerical range includes upper and lower limits.

<Optical filter>
The optical filter of one embodiment of the present invention (hereinafter, also referred to as “the present filter”) is a transparent resin (hereinafter, transparent resin (P)) having a glass transition point (hereinafter, also referred to as “Tg”) of 130 ° C. or higher. It also has an absorption layer containing the NIR dye (A) that satisfies all the following requirements (1-1) to (1-6), and a reflection layer made of a dielectric multilayer film.

(1-1) In the spectral transmittance curve SC _TR having a wavelength of 350 to 1200 nm measured by containing the NIR dye (A) in the transparent resin (P), the maximum absorption wavelength λ _{max (A) TR} is 850 to 1100 nm. It is in the wavelength range.
(1-2) Spectral Transmittance Curve The average internal transmittance of light with a wavelength of 490 to 560 nm when the internal transmittance at the maximum absorption wavelength λ _{max (A) TR} is 10% in the SC _TR T _{AVE490-560 (A). ) TR} is 90% or more.

(1-3) Average internal transmittance of light having a wavelength of 590 to 630 nm when the internal transmittance at the maximum absorption wavelength λ _{max (A) TR} is 10% in the spectral transmittance curve SC _TR T _{AVE590-630 (A) ) TR} is 90% or more.
(1-4) The spectral transmittance curve SC _TR has an internal transmittance of 50% in the wavelength region of 650 to 1150 nm when the internal transmittance at the maximum absorption wavelength λ _{max (A) TR} is 10%. It has two wavelengths, and the width between the two wavelengths is 180 nm or more.

(1-5) Spectral Transmittance Curve Measured by Dissolving NIR Dye (A) in dichloromethane and Having a Wavelength of 350 to 1200 nm Maximum Absorption Wavelength in SC _DCM λ _{max (A)} Light transmittance in _DCM is 10%. The value obtained by subtracting the average internal transmittance T _{AVE490-560 (A) TR} from the average transmittance T _{AVE490-560 (A) DCM} of light having a wavelength of 490 to 560 nm is 10% or less.
(1-6) Spectral transmittance curve SC Maximum absorption wavelength in _DCM λ _{max (A)} Average transmittance of light having a wavelength of 590 to 630 nm when the transmittance of light in _DCM is 10% T _{AVE590-630 (A) ) The} value obtained by subtracting the average internal transmittance T _{AVE590-630 (A) TR} from _DCM is 10% or less.

In this filter, the absorption layer contains the NIR dye (A) and the transparent resin (P) having the characteristics of (1-1) to (1-6), so that the long wavelength range of near infrared light, particularly , Light in the wavelength range of 850 to 1100 nm can be effectively shielded, and the transmittance of visible light, particularly the transmittance of green and red, can be maintained sufficiently high. In general, it is known that it is difficult to reproduce the high transmittance of visible light in dichloromethane in a transparent resin due to the contribution of association in the NIR dye having the maximum absorption wavelength in the long wavelength region. As shown in (1-5) to (1-6) above, the NIR dye (A) maintains a high transmittance of visible light in dichloromethane in relation to the transparent resin (P). I understand.

The NIR dye (A) further preferably satisfies 1 or more selected from the following (1-7) to (1-9), more preferably 2 or more, and particularly satisfies all. preferable.

(1-7) Spectral transmittance curve SC Maximum absorption wavelength in _DCM λ _{max (A)} Average transmittance of light having a wavelength of 435 to 480 nm when the transmittance of light in _DCM is 10% T _{AVE435-480 (A) ) From DCM} , the average internal transmittance of light with a wavelength of 435 to 480 nm when the internal transmittance at the maximum absorption wavelength λ _{max (A) TR} on the spectral transmittance curve SC _TR is 10% T _{AVE435-480 (A). The} value obtained by subtracting _TR is 10% or less.
(1-8) The value obtained by subtracting the average internal transmittance T _{AVE490-560 (A) TR} from the average transmittance T _{AVE490-560 (A) DCM} is 5% or less.
(1-9) The value obtained by subtracting the average internal transmittance T _{AVE590-630 (A) TR} from the average transmittance T _{AVE590-630 (A) DCM} is 5% or less.

This filter may further have a transparent substrate. In this case, the absorption layer and the reflection layer are provided on the main surface of the transparent substrate. The present filter may have the absorption layer and the reflection layer on the same main surface of the transparent substrate, or may have the absorption layer and the reflection layer on different main surfaces. When the absorption layer and the reflection layer are provided on the same main surface, the stacking order thereof is not particularly limited.

This filter may also have another functional layer. Examples of other functional layers include an antireflection layer that suppresses the loss of visible light transmittance. In particular, when the absorption layer has the outermost surface structure, a visible light transmittance loss due to reflection occurs at the interface between the absorption layer and air, so it is preferable to provide an antireflection layer on the absorption layer.

Next, a configuration example of this filter will be described using drawings. FIG. 1 is a configuration example of an optical filter 10A having a reflection layer 12 on one main surface of the absorption layer 11. In the optical filter 10A, the absorption layer 11 can be composed of a layer containing the NIR dye (A) and the transparent resin (P). The absorption layer 11 may further contain the NIR dye (B) and / or the NIR dye (C) described later. In that case, the absorption layer 11 may have a structure in which a plurality of layers are laminated, and each layer contains an NIR dye (A), a NIR dye (B) and / or an NIR dye (C) in an appropriate combination. .. The phrase "providing the reflective layer 12 on one main surface (upper) of the absorbing layer 11" is not limited to the case where the reflective layer 12 is provided in contact with the absorbing layer 11, and the absorbing layer 11 and the reflective layer 12 The following configuration is also the same, including the case where another functional layer is provided between.

FIG. 2 is a cross-sectional view schematically showing an example of an optical filter of an embodiment having a transparent substrate, an absorption layer, and a reflection layer. The optical filter 10B has an absorption layer 11 arranged on one main surface of the transparent substrate 13 and the transparent substrate 13, and a reflection layer 12 provided on the other main surface of the transparent substrate 13. In the optical filter 10B, the absorption layer 11 can have the same configuration as the optical filter 10A.

FIG. 3 is a configuration example of an optical filter 10C having an absorbing layer 11 and having

reflective layers

12a and 12b on both main surfaces of the absorbing layer 11. FIG. 4 shows an optical filter 10D having an absorption layer 11 on one main surface of the transparent substrate 13 and

reflection layers

12a and 12b on the other main surface of the transparent substrate 13 and on the main surface of the absorption layer 11. This is a configuration example. In the

optical filters

10C and 10D, the absorption layer 11 can have the same configuration as the optical filter 10A.

FIG. 5 is a configuration example of an optical filter 10E provided with

absorption layers

11a and 11b on both main surfaces of the transparent substrate 13 and further provided with

reflection layers

12a and 12b on the main surfaces of the absorption layers 11a and 11b.

In FIGS. 3, 4 and 5, the two

reflective layers

12a and 12b to be combined may be the same or different. For example, the reflecting

layers

12a and 12b have a property of reflecting ultraviolet light and near-infrared light and transmitting visible light, and the reflecting layer 12a reflects ultraviolet light and light in the first near-infrared region. The reflective layer 12b may be configured to reflect ultraviolet light and light in the second near-infrared region.

Further, in FIG. 5, at least one of the two

absorption layers

11a and 11b is an absorption layer having the above configuration in the present filter. The absorption layers 11a and 11b may be the same or different. When the absorption layers 11a and 11b are different, for example, the absorption layers 11a and 11b may be a combination of a near-infrared absorbing layer and an ultraviolet absorbing layer, or may be a combination of an ultraviolet absorbing layer and a near-infrared absorbing layer, respectively.

Further, in the optical filter 10E, when the absorption layers 11a and 11b contain the NIR dye (B) and / or the NIR dye (C) described later in addition to the NIR dye (A), they are contained in the absorption layers 11a and 11b, respectively. The NIR dyes can be combined as appropriate. For example, when the optical filter 10E contains NIR dyes (A) to (C), one of the absorption layers 11a and 11b contains one selected from NIR dyes (A) to (C), and the other 2 The composition may contain seeds. Further, the absorption layers 11a and 11b may be a single layer or a plurality of layers may be laminated.

FIG. 6 is a configuration example of the optical filter 10F provided with the antireflection layer 14 on the main surface of the absorption layer 11 of the optical filter 10B shown in FIG. When the reflective layer is not provided and the absorbing layer has the outermost surface structure, it is preferable to provide an antireflection layer on the absorbing layer. The antireflection layer may cover not only the outermost surface of the absorption layer but also the entire side surface of the absorption layer. In that case, the moisture-proof effect of the absorption layer can be enhanced.

Hereinafter, the absorption layer, the reflection layer, the transparent substrate, and the antireflection layer will be described.
(Absorption layer)
The absorption layer has the above-mentioned properties (1-1) to (1-6), and preferably the NIR dye (A) having one or more properties further selected from the above-mentioned (1-7) to (1-9). And a transparent resin (P).

The absorption layer is typically a layer or (resin) substrate in which the NIR dye (A) is uniformly dissolved or dispersed in the transparent resin (P). The absorption layer may contain other NIR dyes in addition to the NIR dye (A) as long as the effects of the present invention are not impaired. Further, the absorption layer may contain a dye other than the NIR dye, particularly a UV dye, as long as the effect of the present invention is not impaired.

Other NIR dyes include NIR dyes (B) having the maximum absorption wavelength in the wavelength region of 1100 to 1200 nm in the spectral transmittance curve having a wavelength of 350 to 1200 nm measured by containing the transparent resin (P). The NIR dye (C), which is a squarylium dye having a maximum absorption wavelength in the wavelength region of 630 to 750 nm, is preferable. Depending on the required characteristics of the filter, the absorption layer may contain either one of the NIR dye (B) and the NIR dye (C) in addition to the NIR dye (A), or may contain both. ..

Since the absorption layer contains the NIR dye (B), it is possible to absorb near-infrared light in a wavelength range longer than the absorption wavelength range of the NIR dye (A), and the absorption layer absorbs the wavelength range corresponding to the absorption glass. can get. Since the absorption layer contains the NIR dye (C), the influence of the incident angle dependence of the reflection layer made of the dielectric multilayer film in this filter can be reduced.

[NIR dye (A)]
The NIR dye (A) has a maximum absorption wavelength λ _{max (A) TR in} the wavelength region of 850 to 1100 nm as defined in (1-1). The maximum absorption wavelength λ _{max (A) TR} is preferably in the wavelength region of 900 to 1050 nm.

The NIR dye (A) has a _{TAVE490-560 (A) TR} of 90% or more as defined in (1-2). The T _{AVE 490-560 (A) TR} is preferably 92% or more, more preferably 94% or more. The NIR dye (A) has a _{TAVE590-630 (A) TR} of 90% or more as defined in (1-3). T _{AVE590-630 (A) T}
_R is preferably 91% or more, more preferably 94% or more.

As specified in (1-4), the NIR dye (A) has a spectral transmittance curve SC _TR of 650 to 1150 nm when the internal transmittance at the maximum absorption wavelength λ _{max (A) TR} is 10%. It has two wavelengths in which the internal transmittance is 50% in the wavelength region of, and the width WT _50% between the two wavelengths is 180 nm or more. The WT _50% is preferably 200 nm or more, more preferably 300 nm or more. Of the wavelengths of 50%, the wavelength on the short wavelength side is preferably 650 nm or more, more preferably 700 nm or more. The upper limit of WT _50% is preferably about 380 nm, more preferably about 370 nm, and even more preferably about 320 nm.

The NIR dye (A) has a T _{AVE 490-560 (A) DCM-} T _{AVE 490-560 (A) TR} of 10% or less as specified in (1-5), and is specified in (1-6). As you can see, T _{AVE590-630 (A) DCM-} T _{AVE590-630 (A) TR} is 10% or less. T _{AVE490-560 (A) DCM-} T _{AVE490-560 (A) TR} and T _{AVE590-630 (A) DCM-} T _{AVE590-630 (A) TR} are each preferably 8% or less.

Here, T _{AVE 490-560 (A) DCM} and T _{AVE 590-630 (A) DCM} are the maximum absorption in the spectral transmittance curve SC _DCM at a wavelength of 350 to 1200 nm measured by dissolving NIR dye (A) in dichloromethane. Wavelength λ _{max (A)} The average transmittance of light having a wavelength of 490 to 560 nm and the average transmittance of light having a wavelength of 590 to 630 nm, respectively, when the transmittance of light at the _DCM is 10%. The λ _{max (A) DCM} is preferably in the wavelength region of 850 to 1100 nm, more preferably in the wavelength region of 900 to 1000 nm.

The NIR dye (A) preferably has T _{AVE435-480 (A) DCM-} T _{AVE435-480 (A) TR} shown in (1-7) of 10% or less, more preferably 9% or less, and 7%. The following is more preferable. The NIR dye (A) preferably has T _{AVE 490-560 (A) DCM-} T _{AVE 490-560 (A) TR} shown in (1-8) of 5% or less, more preferably 4% or less, and 3%. The following is more preferable. The NIR dye (A) preferably has T _{AVE590-630 (A) DCM-} T _{AVE590-630 (A) TR} shown in (1-9) of 5% or less, more preferably 4% or less, and 3%. The following is more preferable.

The molecular structure of the NIR dye (A) is not particularly limited as long as it satisfies the requirements (1-1) to (1-6) in relation to the transparent resin (P). Specifically, at least one pigment selected from the group consisting of cyanine pigments, croconium pigments, phthalocyanine pigments, squarylium pigments, diimonium pigments, tris-type immonium pigments, and diketopyrrolopyrrole pigments can be mentioned, and high transmission of visible light can be mentioned. Tris-type imonium dyes are particularly preferable from the viewpoint of sex and the width of the absorption layer.

As the Tris-type imonium dye which is the NIR dye (A), specifically, one or more selected from the compound represented by the following formula (A1) and the compound represented by the following formula (A2) is preferable.

The symbols in the formulas (A1) and (A2) are as follows.
R ²⁰¹ to R ²⁰⁶ and R ²²¹ to R ²²⁶ have independent hydrogen atoms, halogen atoms, sulfo groups, hydroxy groups, cyano groups, nitro groups, carboxyl groups, phosphate groups, and oxygen atoms between carbon atoms. The alkyl group or alkoxy group having 1 to 20 carbon atoms which may be substituted, or the aryl group having 6 to 14 carbon atoms and the aralkyl group having 7 to 14 carbon atoms which may be substituted, may be substituted. Alternatively, it is a heterocyclic group having 3 to 14 members. However, groups in which a substituted or unsubstituted amino group is bonded to a phenyl group are excluded. Further, in R ²⁰¹ to R ²⁰⁶ and R ²²¹ to R ²²⁶ , two groups bonded to the same nitrogen atom may be bonded to each other to form a heterocycle having 3 to 8 members together with the nitrogen atom. The hydrogen atom bonded to the ring may be substituted with an alkyl group having 1 to 12 carbon atoms.

R ²⁰⁷ to R ²¹⁸ and R ²²⁷ to R ²³⁸ are independently substituted with a hydrogen atom, a halogen atom, an optionally substituted amino group, an amide group, a cyano group, a nitro group, a carboxyl group, or a halogen atom. It is an alkyl group or an alkoxy group having 1 to 12 carbon atoms which may be used. In R ²⁰⁷ to R ²¹⁸ and R ²²⁷ to R ²³⁸ , the two groups adjacent to each other may be bonded to each other to form a ring having 3 to 8 members together with the two carbon atoms of the phenyl group. The hydrogen atom to be bonded may be substituted with an alkyl group having 1 to 12 carbon atoms.

In R ²⁰¹ to R ²⁰⁶ and R ²²¹ to R ²²⁶ , an alkyl group or an alkoxy group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 14 carbon atoms which may be substituted, and 7 carbon atoms which may be substituted. As the substituent in the aralkyl group of to 14 or the heterocyclic group having 3 to 14 members, an amino group, a carboxyl group or a sulfo group which may be substituted with a halogen atom, a hydroxyl group or an alkyl group having 1 to 6 carbon atoms. , Cyano group and acyloxy group having 1 to 6 carbon atoms.

In the case where no ring is formed, R ²⁰⁷ to R ²¹⁸ and R ²²⁷ to R ²³⁸ are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 12 carbon atoms. The alkyl group or alkoxy group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

In R ²⁰⁷ to R ²¹⁸ and R ²²⁷ to R ²³⁸ , the ring formed by bonding two groups adjacent to each other together with the two carbon atoms of the phenyl group may be an alicyclic ring or an aromatic ring. It may be a heterocycle. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

In R ²⁰⁷ to R ²¹⁸ and R ²²⁷ to R ²³⁸ , the combination in which two groups that are adjacent to each other are bonded is in the three phenyl groups bonded to the central nitrogen atom in the formulas (A1) and (A2). There are a total of 6 sets, 2 sets each. Specifically, in the formula (A1), there are six sets of R ²⁰⁷ and R ²⁰⁸ , R ²⁰⁹ and R ²¹⁰ , R ²¹¹ and R ²¹² , R ²¹³ and R ²¹⁴ , R ²¹⁵ and R ²¹⁶ , and R ²¹⁷ and R ²¹⁸ . Is. In the formula (A2), there are 6 sets of R ²²⁷ and R ²²⁸ , R ²²⁹ and R ²³⁰ , R ²³¹ and R ²³² , R ²³³ and R ²³⁴ , R ²³⁵ and R ²³⁶ , and R ²³⁷ and R ²³⁸ .

In R ²⁰⁷ to R ²¹⁸ of the formula (A1) and R ²²⁷ to R ²³⁸ of the formula (A2), the number of pairs to which two adjacent groups are bonded may be one set or two or more sets. All up to 6 pairs may be combined. For each of the three phenyl groups, it is preferable that a total of three groups are bonded.

As a divalent group in which the above two adjacent groups are bonded, specifically, one or two nitrogen atoms may be contained as a hetero atom, or an unsaturated bond may be formed between the atoms, and the number of carbon atoms is 1. Examples thereof include up to 6 alkylene groups. More specifically, the following groups (X-1) to (X-4) can be mentioned. The hydrogen atom contained in these divalent groups may be substituted with an alkyl group having 1 to 12 carbon atoms.

-(CH ₂ ) _n- (n is an integer from 1 to 6) ... (X-1)
-CH = CH-CH = CH-... (X-2)
-CH _2- CH = CH-... (X-3)
-N = CH-NH-... (X-4)

R ²⁰⁷ to R ²¹⁸ and R ²²⁷ to R ²³⁸ are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms or an alkoxy group, and each has a hydrogen atom or an alkyl having 1 to 12 carbon atoms. A group or an alkoxy group is preferable. The alkyl group or alkoxy group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

Also, R ²⁰¹ and R ²⁰⁷ , R ²⁰² and R ²¹⁰ , R ²⁰³ and R ²¹¹ , R ²⁰⁴ and R ²¹⁴ , R ²⁰⁵ and R ²¹⁵ , R ²⁰⁶ and R ²¹⁸ , R ²²¹ and R ²²⁷ , R ²²² and R ²³⁰ , R ²²³ and R ²³¹ and R ²²⁴ and R ²³⁴ , R ²²⁵ and R ²³⁵ , and R ²²⁶ and R ²³⁸ are 4 members together with a nitrogen atom bonded to a phenyl group and two carbon atoms of the phenyl group. A heterocycle of to 8 may be formed, and the hydrogen atom bonded to the ring may be substituted with an alkyl group having 1 to 12 carbon atoms.
Xa ^- and Xb ^- each independently represents a monovalent anion.

In the above, the alkyl group may be linear, branched, cyclic or a combination of these structures. The same applies to the alkyl group when the following aryl group has an alkyl group and the alkyl group of the aralkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom and a chlorine atom are preferable.

In the above, the aryl group refers to a group bonded via a carbon atom constituting an aromatic ring (however, a hetero atom is not contained) of an aromatic compound, for example, a benzene ring, a naphthalene ring, a biphenyl, or the like. The aryl group includes a structure in which a hydrogen atom bonded to a ring-constituting atom other than the carbon atom contributing to the bond is substituted with an alkyl group, for example, a tolyl group or a xsilyl group.

In the above, the aralkyl group refers to a group in which an alkyl group is bonded to an aromatic ring (however, it does not contain a hetero atom) and is bonded via a carbon atom constituting the alkyl group. The aralkyl group includes a structure in which a hydrogen atom bonded to a ring-constituting atom other than the atom to which the alkyl group contributing to the bond is bonded is substituted with an alkyl group.

In the above, the heterocyclic group is a group in which the atoms constituting the ring are bonded via the atoms constituting the alicyclic or aromatic ring composed of carbon atoms and atoms other than carbon atoms. The heterocyclic group includes a structure in which a hydrogen atom bonded to a ring-constituting atom other than the atom contributing to the bond is substituted with an alkyl group. Examples of the atom other than the carbon atom contained in the heterocycle include an oxygen atom, a nitrogen atom, and a sulfur atom, and the number is preferably 1 or 2.

Xa ^- and Xb ^- as are each ^{^{^{^{independently, Cl -, Br -, I}}}} -, F -, ClO 4 -, BF 4 -, PF 6 -, SbF 6 -, CF 3 SO 3 -, CH 3 C _{_{_{^{_{6 H 4 SO 3 -, N}}}}} [SO 2 R f] 2 -, C [SO 2 R f] 3 - , and the like.

Here, R _f is a fluoroalkyl group having 1 to 4 carbon atoms, preferably a fluoroalkyl group having 1 to 2 carbon atoms, and more preferably a fluoroalkyl group having 1 carbon atom. When the number of carbon atoms is within the above range, durability such as heat resistance and moisture resistance, and solubility in an organic solvent described later are good. Examples of such R _f include perfluoroalkyl groups such as -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , and -C ₂ F ₄ H, -C ₃ F _6. Examples include H, -C ₂ F ₈ H and the like.

From the viewpoint of moisture resistance, the fluoroalkyl group is preferably a perfluoroalkyl group, more preferably a trifluoromethyl group.

Xa ^- and Xb ^- as are ^each ^{_{^{_{^{independently, I -, BF 4-, SbF}}}}} 6 -, PF 6 -, ClO 4 -, N [SO 2 CF 3] 2 -, C [SO 2 CF 3] 3 ^- and the like are preferable, from the viewpoint difference in optical characteristics between dichloromethane solution and resin is _small, ^SbF 6 -, PF ₆ ^- and _{_{_{N [SO 2 CF 3] 2}}} - are more _preferable, ^SbF 6 -, N [SO ₂ CF ₃ ] ₂ ^- is particularly preferable. From the viewpoint of light ^{_{^{_{resistance, BF 4-, PF 6 -,}}}} N [SO 2 CF 3] 2 - are preferred.

Regarding the dye (A1), the following formulas (A1a), (A1b), and (A1c) are based on the structure of the group bonded to the nitrogen atom bonded to the 4-position of the three phenyl groups bonded to the central nitrogen atom. ), They were classified into three types of dyes (A1a) to (A1c). Similarly, for the dye (A2), the following formulas (A2a) and (A2b), based on the structure of the group bonded to the nitrogen atom bonded to the 4-position of the three phenyl groups bonded to the central nitrogen atom, It was classified into three types of dyes (A2a) to (A2c) represented by the formula (A2c), respectively.

The dye (A1a) and the dye (A2a) have a structure in which the nitrogen atom bonded to the 4-position of the three phenyl groups (hereinafter, the nitrogen atom at the 4-position) does not form a heterocycle.

The dye (A1b) and the dye (A2b) have a structure in which at least one set of two groups bonded to each of the three nitrogen atoms at the 4-position is bonded to each other to form a heterocycle. Two sets of two groups each bonded to the three 4-position nitrogen atoms may be bonded to each other, or all three sets may be bonded.

The dye (A1c) and dye (A2c) formed a heterocycle in which at least one of the two groups attached to the three nitrogen atoms at the 4-position was bonded to the group attached to the 3- or 5-position of the phenyl group. It is a structure. The dye (A1c) and the dye (A2c) may have 2 to 6 heterocycles.

In formulas (A1a) and (A2a), R ²⁰¹ to R ²⁰⁶ and R ²²¹ to R ²²⁶ are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxy groups, cyano groups, nitro groups, and carboxyl groups, respectively. An alkyl group or an alkoxy group having 1 to 20 carbon atoms which may have an oxygen atom between a phosphate group and a carbon atom and may be substituted, or an alkyl group or an alkoxy group having 6 to 14 carbon atoms which may be substituted. It is an aryl group, an aralkyl group having 7 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. However, groups in which a substituted or unsubstituted amino group is bonded to a phenyl group are excluded. R ²⁰¹ to R ²⁰⁶ and R ²²¹ to R ²²⁶ are each independently preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. R ²⁰⁷ ~ ^{R 218} and ^R 227 ^{~ R 238} are each independently, it can be like the ^R 207 ^{~ R 218} and ^R 227 ^{~ R 238} in formula (A1) and formula (A2).

In formula (A1b), Q ¹ , Q ² and Q ³ are such that R ²⁰¹ and R ²⁰² , R ²⁰³ and R ²⁰⁴ and R ²⁰⁵ and R ²⁰⁶ in formula (A1) are bonded, respectively, and these groups are bonded. It shows a divalent group when a heterocycle having 3 to 8 members is formed together with the nitrogen atom. In formula (A2b), Q ¹¹ , Q ¹² and Q ¹³ are such that R ²²¹ and R ²²² , R ²²³ and R ²²⁴ and R ²²⁵ and R ²²⁶ in formula (A2) are bonded, respectively, and these groups are bonded. It shows a divalent group when a heterocycle having 3 to 8 members is formed together with the nitrogen atom.

Formula (A1b) and formula (A2b) may if it has at least one of ^Q 1 ~ ^{Q 3} and ^Q 11 ^{~ Q 13} each may have two or more, may have three .. The ^hydrogen atom bonded to Q 1 ~ ^{Q 3} and ^Q 11 ^{~ Q 13} may be substituted by an alkyl group having 1 to 12 carbon atoms independently.

It is preferable that Q ¹ to Q ³ and Q ¹¹ to Q ¹³ are independently alkylene groups represented by − (CH ₂ ) _n1 − (n1 is an integer of 2 to 7), and hydrogen of the alkylene group. The atom may be substituted with an alkyl group having 1 to 12 carbon atoms.

In the case where the heterocycle is not formed, R ²⁰¹ to R ²⁰⁶ and R ²²¹ to R ²²⁶ are independently similar to R ²⁰¹ to R ²⁰⁶ and R ²²¹ to R ^{226 in} the formulas (A1a) and (A2a), respectively. it can. R ²⁰⁷ to R ²¹⁸ and R ²²⁷ to R ²³⁸ can be independently made similar to R ²⁰⁷ to R ²¹⁸ and R ²²⁷ to R ²³⁸ in formulas (A1) and (A2), respectively.

In formula ^{^{(A1c), Q 4 ~ Q}} 9 are ^{each, R 201} and ^R ^{207, R 202} and ^R ^{210, R 203} and ^R ^{211, R 204} and ^R ^{214, R 205} and ^R ^{215, R 206} and ^{R 218} Shows a divalent group in the case where is bonded to form a heterocycle having 4 to 8 members together with the nitrogen atom and the carbon atom of the phenyl group to which these groups are bonded. In formula ^{^{(A2c), Q 14 ~ Q}} 19 , ^{respectively, R 221} and ^R ^{227, R 222} and ^R ^{230, R 223} and ^R ^{231, R 224} and ^R ^{234, R 225} and ^R ^{235, R 226} and ^{R 238} Shows a divalent group in the case where is bonded to form a heterocycle having 4 to 8 members together with the nitrogen atom and the carbon atom of the phenyl group to which these groups are bonded.

Formula (A1c) and formula (A2c) may if it has at least one of ^Q 4 ~ ^{Q 9} and ^Q 14 ^{~ Q 19} each may have two or more, have up to 6 Good. The ^hydrogen atom bonded to Q 4 ~ ^{Q 9} and ^Q 14 ^{~ Q 19} may be substituted by an alkyl group having 1 to 12 carbon atoms independently.

Q ⁴ ~ ^{Q 9} and ^Q 14 ^{~ Q 19} are each _{_{independently, - (CH 2) n2 -}} (n2 is an integer of 1-5) is preferably an alkylene group represented by hydrogen of the alkylene group The atom may be substituted with an alkyl group having 1 to 12 carbon atoms.

In the case of not forming the hetero ^ring, R 201 ^{~ R 218} and ^R 221 ^{~ R 238} are each independently, it can be like the ^R 201 ^{~ R 218} and ^R 221 ^{~ R 238} in formula (A1) and formula (A2) ..

More specifically, the dye (A1a) and the dye (A2a) include compounds in which R ²⁰¹ to R ²¹⁸ and R ²²¹ to R ²³⁸ are shown in Tables 1 and 2 below, respectively. In the example dye (A1a), since R ²⁰¹ , R ²⁰³ , and R ²⁰⁵ have the same group, they are collectively shown in one column in Table 1. R ²⁰² , R ²⁰⁴ , and R ²⁰⁶ are also shown together in the same manner. For R ²⁰⁷ to R ²¹⁸ , in the three phenyl groups bonded to the central nitrogen atom, the substituents at the same position are grouped together as "R ²⁰⁷ , R ²¹¹ , R ²¹⁵ ", "R ²⁰⁸ , R ²¹² , R". ²¹⁶ ”,“ R ²⁰⁹ , R ²¹³ , R ²¹⁷ ”,“ R ²¹⁰ , R ²¹⁴ , R ²¹⁸ ”. The same description method was used for the dye (A2a).

In Table 1, for the dye (A1a-21) and the dye (A1a-23), there are three sets of two groups, R ²⁰⁷ and R ²⁰⁸ , R ²¹¹ and R ²¹² , and R ²¹⁵ and R ^{216, which} are adjacent to each other. The divalent groups formed by binding to each other are described in the columns of "R ²⁰⁷ , R ²¹¹ , R ²¹⁵ " and the columns of "R ²⁰⁸ , R ²¹² , R ²¹⁶ ". For the dye (A1a-22), a divalent group formed by combining three sets of two groups, R ²⁰⁹ and R ²¹⁰ , R ²¹³ and R ²¹⁴ , and R ²¹⁷ and R ²¹⁸ , which are adjacent to each other. ^Was described in the column in which the columns of "R ²⁰⁹ , R ²¹³ , R ²¹⁷ " and the columns of "R ²¹⁰ , R ²¹⁴ , R ²¹⁸ " were combined. The same description method was used for the dye (A2a-21), the dye (A2a-22) and the dye (A2a-23) in Table 2.

Table 1, 2, Xa ^- and Xb ^- show no, in even Xa any compound ^- or Xb ^- are each ^{^{^{independently, Cl -, Br -, I}}} -, F -, ClO 4 -, _{^{_{^{_{BF 4 -, PF 6 -,}}}}} SbF 6 -, CF 3 SO 3 -, CH 3 C 6 H 4 SO 3 -, N [SO 2 R f] 2 -, _{_{_{or, C [SO 2 R f]}}} 3 - in is there. Xa ^- and Xb ^- are ^each ^{_{^{_{^{independently, I -, BF 4-, SbF}}}}} 6 -, PF 6 -, ClO 4 -, N [SO 2 CF 3] 2 - or _{_{_{C [SO 2 CF 3] 3}}} - Is preferable.

The abbreviations for the dyes corresponding to the preferred monovalent anions are shown below. In the dye (A1a-1), when Xa ⁻ is I ⁻ , the dye (A1a-1I), BF ^4- is the dye (A1a-1B), SbF ₆ ⁻ is the dye (A1a-1Sb), and PF. ₆ ^- dye (A1a-1P) in the case of, ClO ₄ ^- dye (A1a-1Cl) the case _{_{_{of, N [SO 2 CF 3]}}} 2 - in the case where the colorant (A1a-1NS), C [ SO 2 CF 3 ] ₃ ^- shows the case of the dye (A1a-1CS). The same applies to the other dyes shown in Tables 1 and 2. In Table 1, 2, Ph represents a phenyl group, an alkyl group such as _-C 3 _{H 7} is an alkyl group of all linear.

Examples of the dye (A1b), more ^{^{^{specifically, Q 1 ~ Q 3, R}}} 207 ~ R 218 is, compounds shown in Table 3 below. In illustrative dye ^(A1b), because they have the same groups as ^{^{Q 1, Q 2, Q 3}} , shown in Table 3 are collectively into one column. R ²⁰⁷ to R ²¹⁸ are described in the same manner as in Table 1. More specifically, as the dye (A2b), Q ¹¹ to Q ¹³ and R ²²⁷ to R ²³⁸ include compounds shown in Table 4 below. In illustrative dye ^(A2b), because they have the same groups as ^{^{Q 11, Q 12, Q 13}} , shown in Table 4 are collectively into one column. ^R227 to ^R238 have the same description as in Table 2.

Table 3, 4, Xa ^- and Xb ^- show no, in any of the compound Xa ^- or Xb ^- is similar to the dye shown in Table 1 (A1a). In Tables 3 and 4, all alkyl groups such as -C ₄ H ₉ are linear alkyl groups.

Examples of the dye (A1c), more ^{specifically,} Q 4 ~ ^{Q 9,} ^{^"R ^202,} ^R ^204, ^R ^206", ^{^"R ^208,} ^R ^212, ^R ^216", ^{^"R ^209,} ^R ^213, ^R ²¹⁷ , "R ²¹⁰ , R ²¹⁴ , R ²¹⁸ " are listed in Table 5 below. In illustrative dye ^(A1c), because they have the same groups as ^{^{Q 4, Q 6, Q 8}} , shown in Table 5 are collectively into one column. ^Furthermore, when having Q ^5, Q 7, ^{Q ^9,} to have the same group as Q ^5, Q 7, ^{Q 9,} shown in Table 5 are collectively into one column. "R ²⁰² , R ²⁰⁴ , R ²⁰⁶ " and "R ²¹⁰ , R ²¹⁴ , R ²¹⁸ " are groups that are present when the dye (A1c) does not have Q ⁵ , Q ⁷ , Q ⁹ .

Dye (A2c) as is more ^{specifically,} Q 14 ^{~ Q 19,} ^{^"R ^222,} ^R ^224, ^R ^226", ^{^"R ^228,} ^R ^232, ^R ^236", ^{^"R ^229,} ^R ^233, ^R ²³⁷ , "R ²³⁰ , R ²³⁴ , R ²³⁸ " are listed in Table 6 below. In illustrative dye ^(A2c), because they have the same groups as ^{^{Q 14, Q 16, Q 18}} , shown in Table 6 are collectively into one column. ^Furthermore, when having a ^{^{Q 15, Q 17, Q 19}} , to have the same group as ^{^{Q 15, Q 17, Q 19}} , shown in Table 6 are collectively into one column. "R ²²² , R ²²⁴ , R ²²⁶ " and "R ²³⁰ , R ²³⁴ , R ²³⁸ " are groups that are present when the dye (A2c) does not have Q ¹⁵ , Q ¹⁷ , Q ¹⁹ .

“R ²⁰² , R ²⁰⁴ , R ²⁰⁶ ”, “R ²⁰⁸ , R ²¹² , R ²¹⁶ ”, “R ²⁰⁹ , R ²¹³ , R ²¹⁷ ”, “R ²¹⁰ , R ²¹⁴ , R ²¹⁸ ” are the same as in Table 1. It was described as. “ ^R222 , ^R224 , ^R226 ”, “ ^R228 , ^R232 , ^R236 ”, “ ^R229 , ^R233 , ^R237 ”, “ ^R230 , ^R234 , ^R238 ” are the same as in Table 2. It was described as.

The left and right symmetrical compounds of the dye (A1c) and the dye (A2c), for example, the dye (A1c-1) and "Q ⁵ , Q ⁷ , Q ⁹ " are -CH _2- CH _2- CH _2- CH. _2- , "R ²⁰¹ , R ²⁰³ , R ²⁰⁵ " is -C ₂ H ₅ , "R ²⁰⁷ , R ²¹¹ , R ²¹⁵ ", "R ²⁰⁸ , R ²¹² , R ²¹⁶ ", "R ²⁰⁹ " , R ²¹³ , R ²¹⁷ ", are treated as the same compound as the compound in which H is.

Table 5, 6, Xa ^- and Xb ^- show no, in any of the compound Xa ^- or Xb ^- is similar to the dye shown in Table 1 (A1a). In Table 5 and 6, an alkyl group such as _-C 3 _{H 7} is an alkyl group of all linear. Also, in Tables 5 and 6, "Q ⁴ , Q ⁶ , Q ⁸ ", "Q ⁵ , Q ⁷ , Q ⁹ ", "Q ¹⁴ , Q ¹⁶ , Q ¹⁸ ", and "Q ¹⁵ , Q ¹⁷ , Q" ^The divalent group shown in the column of " ¹⁹ " is a mode in which the left side is bonded to a nitrogen atom and the right side is bonded to a carbon atom of a phenyl group.

Among these, the dye (A1) includes the dye (A1a-5Sb), the dye (A1a-5NS), the dye (A1a-5P), the dye (A1a-5Cl), and the dye (A1a-5B) as the dye (A1a). ), Dye (A1a-1NS), Dye (A1a-4Sb), Dye (A1a-4NS), Dye (A1a-4P), Dye (A1a-7NS), Dye (A1a-7P), etc. A1a-5Sb), dye (A1a-5NS), dye (A1a-5P), dye (A1a-4Sb), dye (A1a-4NS), dye (A1a-4P) are more preferable.

Further, as the dye (A1b), a dye (A1b-1Sb), a dye (A1b-1NS), a dye (A1b-1P) and the like are preferable. As the dye (A1c), a dye (A1c-3NS), a dye (A1c-3P), a dye (A1c-4NS), a dye (A1c-4P), a dye (A1c-10NS), a dye (A1c-10P) and the like are preferable. , Dye (A1b-1NS), Dye (A1b-1NS), Dye (A1c-4NS), Dye (A1c-4P), Dye (A1c-10NS), Dye (A1c-10P) are more preferable.

Among these, the dye (A2) includes the dye (A2a-5Sb), the dye (A2a-5NS), the dye (A2a-5P), the dye (A2a-5Cl), and the dye (A2a-5B) as the dye (A2a). ), Dye (A2a-1NS), Dye (A2a-4Sb), Dye (A2a-4NS), Dye (A2a-4P), Dye (A2a-7NS), Dye (A2a-7P), etc. A2a-5Sb), dye (A2a-5NS), dye (A2a-5P), dye (A2a-4Sb), dye (A2a-4NS), dye (A2a-4P) are more preferable.

Further, as the dye (A2b), a dye (A2b-1Sb), a dye (A2b-1NS), a dye (A2b-1P) and the like are preferable. As the dye (A2c), a dye (A2c-3NS), a dye (A2c-3P), a dye (A2c-4NS), a dye (A2c-4P), a dye (A2c-10NS), a dye (A2c-10P) and the like are preferable. , Dye (A2b-1NS), Dye (A2b-1NS), Dye (A2c-4NS), Dye (A2c-4P), Dye (A2c-10NS), Dye (A2c-10P) are more preferred.

The NIR dye (A) may consist of one kind of compound or two or more kinds of compounds. When composed of two or more kinds of compounds, each compound does not necessarily have the property of NIR dye (A), and may have the property of NIR dye (A) as a mixture.

The dye (A1) and the dye (A2) can be produced by known methods, respectively. The dyes (A1a) to dyes (A1c) can be produced, for example, by the methods described in Japanese Patent Application Laid-Open No. 2007-197492. The dyes (A2a) to dyes (A2c) can be produced, for example, by the method described in Japanese Patent Application Laid-Open No. 2009-221146.

[NIR dye (B)]
The NIR dye (B) is a dye having a maximum absorption wavelength λ _{max (B) TR} in a wavelength region of 1100 to 1200 nm in a spectral transmittance curve having a wavelength of 350 to 1200 nm measured by containing it in a transparent resin (P). is there. The maximum absorption wavelength λ _{max (B) TR} is preferably in the wavelength region of 1100 to 1150 nm.

It is preferable that the NIR dye (B) has a high visible transmittance in the resin.

As the NIR dye (B), the molecular structure is not particularly limited as long as the maximum absorption wavelength λ _{max (B) TR} is in the range of 1100 to 1200 nm. Specific examples thereof include at least one pigment selected from the group consisting of cyanine pigments, croconium pigments, phthalocyanine pigments, squarylium pigments, diimonium pigments, diketopyrrolopyrrole pigments, metal complex pigments, and metal oxides, which are visible. The diimonium dye is particularly preferable from the viewpoint of high light transmission.

Specifically, as the diimonium dye which is the NIR dye (B), one or more selected from the compound represented by the following formula (B1) and the compound represented by the following formula (B2) is preferable.

The symbols in the formulas (B1) and (B2) are as follows.
R ²⁴¹ to R ²⁴⁸ and R ²⁶¹ to R ²⁶⁸ are independently unsaturated bonds between hydrogen atom, halogen atom, sulfo group, hydroxy group, cyano group, nitro group, carboxyl group, phosphoric acid group and carbon atom. Alternatively, an alkyl group or an alkoxy group having 1 to 20 carbon atoms which may have an oxygen atom or may be substituted, or an aryl group having 6 to 14 carbon atoms and 7 to 14 carbon atoms which may be substituted. Alkoxy group, or a heterocyclic group having 3 to 14 members. In R ²⁴¹ to R ²⁴⁸ and R ²⁶¹ to R ²⁶⁸ , two groups bonded to the same nitrogen atom may be bonded to each other to form a heterocycle having 3 to 8 members together with the nitrogen atom. The hydrogen atom bonded to may be substituted with an alkyl group having 1 to 12 carbon atoms.

In R ²⁴¹ to R ²⁴⁸ and R ²⁶¹ to R ²⁶⁸ , an alkyl group or an alkoxy group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 14 carbon atoms which may be substituted, and 7 carbon atoms which may be substituted. As the substituent in the aralkyl group of to 14 or the heterocyclic group having 3 to 14 members, an amino group, a carboxyl group or a sulfo group which may be substituted with a halogen atom, a hydroxyl group or an alkyl group having 1 to 6 carbon atoms. , Cyano group and acyloxy group having 1 to 6 carbon atoms.

When the ring is not formed, R ²⁴¹ to R ²⁴⁸ and R ²⁶¹ to R ²⁶⁸ are each independently preferably an alkyl group or an alkoxy group having 1 to 12 carbon atoms. The alkyl group or alkoxy group preferably has 1 to 8 carbon atoms.

As R ²⁴¹ to R ²⁴⁸ and R ²⁶¹ to R ²⁶⁸ , linear or branched alkyl groups having 4 to 6 carbon atoms are preferable from the following viewpoints. When the number of carbon atoms is 4 or more, the solubility in an organic solvent is improved, and when the number of carbon atoms is 6 or less, the heat resistance is improved. It is considered that the reason why the heat resistance is improved is that the melting point of the dye is increased.

A divalent group when two groups bonded to the same nitrogen atom are bonded to each other, that is, R ²⁴¹ and R ²⁴² , R ²⁴³ and R ²⁴⁴ , R ²⁴⁵ and R ²⁴⁶ , and R ²⁴⁷ and R ²⁴⁸ are bonded, respectively. In this case, the divalent group is preferably an alkylene group represented _by- (CH ₂ ) _n3- (n3 is an integer of 2 to 7), and the hydrogen atom of the alkylene group has 1 to 12 carbon atoms. It may be substituted with the alkyl group of.

R ²⁴⁹ to R ²⁵³ and R ²⁶⁹ to R ²⁷³ are independently hydrogen atoms, halogen atoms, optionally substituted amino groups, amide groups, cyano groups, nitro groups, carboxyl groups, or halogen atoms. It is an alkyl group or an alkoxy group having 1 to 12 carbon atoms which may be substituted. The four R ²⁴⁹ to R ²⁵³ and R ²⁶⁹ to R ^{273, respectively,} may be the same or different.

R ²⁴⁹ to R ²⁵³ and R ²⁶⁹ to R ²⁷³ are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 12 carbon atoms. The alkyl group or alkoxy group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

Xc ^- and Xd ^- each independently represents a monovalent anion. Xc ^- and Xd ^- as, for ^{^{^{^{example, Cl -, Br -, I}}}} -, F -, ClO 4 -, BF 4 -, PF 6 -, SbF 6 -, CF 3 SO 3 -, CH 3 C 6 H 4 _{^{_{_{SO 3 -, N [SO 2}}}} R f] 2 - and the like, etc. _{_{^{-, C [SO 2 R f}}} ] 3. Among _{^{_{_{_{these, PF 6 -, N [SO}}}}} 2 R f] 2 -, C [SO 2 R f] 3 - are _{^{_{preferred, PF 6 -, N [SO}}} 2 R f] 2 - is more preferable.

Here, R _f can be set in the same manner as in the cases of Xa ⁻ and Xb ⁻ , including preferred embodiments.

More specifically, as the dye (B1) and the dye (B2), R ²⁴¹ to R ²⁵³ and R ²⁶¹ to R ²⁷³ , respectively, and the compounds shown in Tables 7 and 8 below can be mentioned. In the example dye (B1), since they have the same group as R ²⁴¹ and R ²⁴³ , R ²⁴⁵ and R ²⁴⁷ , they are collectively shown in one column in Table 7. The same applies to R ²⁴² , R ²⁴⁴ , R ²⁴⁶ , and R ²⁴⁸ . For R ²⁴⁹ ₄ to R ²⁵³ ₄ , indicate that R ²⁴⁹ to R ²⁵³ each have 4 groups or atoms, and if the 4 groups or atoms are the same, list only one of those groups or atoms. did. If different, four atoms or groups are listed, such as "H, H, H, -CH ₃ ". The position where the atom or group is bonded is not specified. For example, "H, H, H, -CH ₃ " indicates a case where -CH ₃ is bonded to any of four carbon atoms other than the carbon atom to which the nitrogen atom of the benzene ring is bonded.

In Table 7, in the dye (B1-6), R ²⁴¹ and R ²⁴² , R ²⁴³ and R ²⁴⁴ , R ²⁴⁵ and R ²⁴⁶ , and R ²⁴⁷ and R ²⁴⁸ are bound to each other, and all of them are -CH _2- CH. _{A case of 2-} CH _2- CH _2- is shown. The description method of the dye (B1) in Table 7 was also applied to the dye (B2) in Table 8.

Table 7, 8, Xc ^- and Xd ^- show no, in even Xc any compound ^- or Xd ^- are each ^{^{^{independently, Cl -, Br -, I}}} -, F -, ClO 4 -, _{^{_{^{_{BF 4 -, PF 6 -,}}}}} SbF 6 -, CF 3 SO 3 -, CH 3 C 6 H 4 SO 3 -, N [SO 2 R f] 2 -, _{_{_{or, C [SO 2 R f]}}} 3 - in is there. Xc ^- and Xd ^- are ^each ^{_{^{_{^{independently, I -, BF 4-, SbF}}}}} 6 -, PF 6 -, ClO 4 -, N [SO 2 CF 3] 2 - or _{_{_{C [SO 2 CF 3] 3}}} - Is preferable.

The abbreviations for the dyes corresponding to the preferred monovalent anions are shown below. For example, in the dye (B1-1), the case where Xc ⁻ is I ⁻ is the dye (B1-1I), the case of BF ^4- is the dye (B1-1B), and the case of SbF ₆ ⁻ is the dye (B1-1Sb). , PF ₆ ^- in the case where the colorant (B1-1P), ClO ₄ ^- in the case where the colorant _{(B1-1Cl), N [SO 2} CF 3] 2 - in the case where the colorant (B1-1NS), C [SO ₂ CF _3] ₃ ^- shows the case of the dye (B1-1CS). The same applies to the other dyes shown in Tables 7 and 8. In Table 7, 8, Ph represents a phenyl group, an alkyl group such as _-C 3 _{H 7} is an alkyl group of all linear.

Among these, the dye (B1) includes a dye (B1-5NS), a dye (B1-5Sb), a dye (B1-5P), a dye (B1-4NS), a dye (B1-4Sb), and a dye (B1-). 4P) and the like are preferable. Among these, as the dye (B2), a dye (B2-4NS), a dye (B2-4P), a dye (B2-5NS), a dye (B2-5P) and the like are preferable.

The NIR dye (B) may consist of one kind of compound or two or more kinds of compounds. When composed of two or more kinds of compounds, each compound does not necessarily have the property of NIR dye (B), and may have the property of NIR dye (B) as a mixture.

The dye (B1) and the dye (B2) can be produced by known methods, respectively. The dye (B1) can be produced, for example, by the method described in Japanese Patent Application Laid-Open No. 2009-137894. The dye (B2) can be produced, for example, by the method described in Japanese Patent Application Laid-Open No. 2000-229931.

To give an example of a commercially available product of the dye (B1), for example, Kayasorb IRG-022, IRG-023, IRG-024, IRG-068, IRG-069, and IRG- of Nippon Kayaku Co., Ltd. 079, CIR-1081, CIR-1083, CIR-1085, CIR-RL (all of which are trade names) manufactured by Nippon Carlit Co., Ltd. can be mentioned.

[NIR dye (C)]
The NIR dye (C) is a squarylium dye having a maximum absorption wavelength λ _{max (C) TR} in the wavelength region of 630 to 750 nm in a spectral transmittance curve having a wavelength of 350 to 1200 nm measured by containing it in a transparent resin (P). Is. The maximum absorption wavelength λ _{max (c) TR} is preferably in the wavelength region of 650 to 740 nm.

The NIR dye (C) has a higher visible transmittance in the resin, and when the transmittance increases from the maximum absorption wavelength λ _{max (C) TR} to the short wavelength side, it may show a steep rise. preferable.

The NIR dye (C) is not particularly limited as long as it is a squarylium dye that satisfies the requirements of the maximum absorption wavelength λ _{max (C) TR} . More specifically, as the NIR dye (C), a squarylium dye represented by the following formula (I) or formula (II) is preferable.

However, the symbols in the formula (I) are as follows.
R ²⁴ and R ²⁶ are independently hydrogen atom, halogen atom, hydroxyl group, alkyl group or alkoxy group having 1 to 20 carbon atoms, acyloxy group having 1 to 10 carbon atoms, aryl group having 6 to 11 carbon atoms, respectively. An aralkyl group having 7 to 18 carbon atoms, which may have a substituent or an oxygen atom between carbon atoms, -NR ²⁷ R ²⁸ (R ²⁷ and R ²⁸ are independently hydrogen. Atom, an alkyl group having 1 to 20 carbon atoms, -C (= O) -R ²⁹ (R ²⁹ may have a hydrogen atom, a halogen atom, a hydroxyl group, a substituent, and an unsaturated bond between carbon atoms. , an oxygen atom, a saturated or unsaturated hydrocarbon group of may having 1 to 25 carbon atoms containing a ring structure), - ^{NHR 30,} _{^{^{or,, -SO 2 -R 30 (R}}} 30 are each one or more hydrogen atoms May be substituted with a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, or a cyano group, and may contain an unsaturated bond, an oxygen atom, a saturated or unsaturated ring structure between carbon atoms, and has 1 to 25 carbon atoms. The group (R ⁴¹ , R ⁴² ) represented by the following formula (S) is independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms or an alkoxy. Indicates a group. K is 2 or 3).

R ²¹ and R ²² , R ²² and R ²⁵ , and R ²¹ and R ²³ are linked together to form a heterocycle A, heterocycle B, and heterocycle C with 5 or 6 members, respectively, with nitrogen atoms. May be good.

When a hetero ring A is formed, R ²¹ and R ²² have an alkyl group having a hydrogen atom of 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having a hydrogen atom as a divalent group −Q— to which they are bonded. An alkylene group or an alkyleneoxy group which may be substituted with an acyloxy group having 1 to 10 carbon atoms which may have a substituent is shown.

R ²² and R ²⁵ when the heterocycle B is formed, and R ²¹ and R ²³ when the heterocycle C is formed are the divalent groups -X ^1- Y ^1- and-when they are bonded, respectively. As X ^2- Y ^2- (the side that binds to nitrogen is X ¹ and X ² ), X ¹ and X ² are the groups represented by the following formulas (1x) or (2x), respectively, and Y ¹ and Y ² are respectively. It is a group represented by any of the following formulas (1y) to (5y). When X ¹ and X ² are groups represented by the following formulas (2x), Y ¹ and Y ² may be single bonds, respectively, and in that case, oxygen atoms may be provided between carbon atoms. ..

In the formula (1x), the four Zs are independently hydrogen atoms, hydroxyl groups, alkyl or alkoxy groups having 1 to 6 carbon atoms, or -NR ³⁸ R ³⁹ (R ³⁸ and R ³⁹ are independent, respectively. Indicates a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). R ³¹ to R ³⁶ are independent hydrogen atoms, alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 10 carbon atoms, and R ³⁷ is an alkyl group having 1 to 6 carbon atoms or 6 to 10 carbon atoms. Indicates an aryl group.

R ²⁷ , R ²⁸ , R ²⁹ , R ³¹ to R ³⁷ , R ²¹ to R ²³ when not forming a heterocycle, and R ²⁵ are 5-membered rings coupled with any other of these. Alternatively, a 6-membered ring may be formed. R ³¹ and R ³⁶ and R ³¹ and R ³⁷ may be directly coupled.

When the hetero ring is not formed, R ²¹ , R ²² , R ²³ and R ²⁵ independently have a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms or an alkoxy group, and a carbon number of carbon atoms. It represents an acyloxy group of 1 to 10, an aryl group having 6 to 11 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms which may have a substituent or an oxygen atom between carbon atoms. ..

In the formula (I), unless otherwise specified, the hydrocarbon group is an alkyl group, an aryl group, or an aralkyl group. Unless otherwise specified, the alkyl group and the alkyl moiety in the alkoxy group, aryl group or aralkyl group may be linear, branched chain, cyclic or a combination of these structures.

The same applies to the alkyl group, alkoxy group, aryl group, and aralkyl group in the other formulas below. In the formula (I), examples of the substituent in R ²⁹ include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, and an acyloxy group having 1 to 6 carbon atoms. Examples of the substituent in the case of "may have a substituent" except for R ²⁹ include a halogen atom or an alkoxy group having 1 to 15 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom and a chlorine atom are preferable.

However, the symbols in the formula (II) are as follows.
Ring Z is a 5-membered ring or a 6-membered ring each independently having 0 to 3 heteroatoms in the ring, and the hydrogen atom contained in the ring Z may be substituted. When the hydrogen atom is substituted, the substituent includes a halogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.

R ¹ and ^R 2, ^{R 2} and ^{R 3,} and the carbon atoms or heteroatoms constituting ^{R 1} and ring Z is, respectively form a heterocyclic ring A1, heterocycle B1 and heterocyclic C1 together with the nitrogen atom linked to each other In that case, the hydrogen atoms contained in the heterocycle A1, the heterocycle B1 and the heterocycle C1 may be substituted. When the hydrogen atom is substituted, the substituent includes a halogen atom or an alkyl group having 1 to 15 carbon atoms which may have a substituent.

When not forming a hetero ring, R ¹ and R ² each independently contain an unsaturated bond, a hetero atom, a saturated or unsaturated ring structure between hydrogen atoms, halogen atoms, or carbon atoms. Well, it shows a hydrocarbon group which may have a substituent. R ⁴ and R ³ in the case of not forming a hetero ring may independently contain a hetero atom between a hydrogen atom, a halogen atom, or a carbon atom, and may have a substituent or an alkyl group or a substituent. Indicates an alkoxy group.

In the formula (II), the number of carbon atoms of the hydrocarbon group is 1 to 15. The number of carbon atoms of the alkyl group or the alkoxy group may be 1 to 10. In the formula (II), as the substituent in the case of "may have a substituent", a halogen atom or an alkoxy group having 1 to 10 carbon atoms can be exemplified. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom and a chlorine atom are preferable.

Examples of the compound (I) include compounds represented by any of the formulas (I-1) to (I-4).

However, the symbols in the formulas (I-1) to (I-4) are the same as the respective provisions of the same symbols in the formula (I), and the preferred embodiments are also the same.

Among the compounds (I-1) to (I-4), the NIR dye (C) contains the compounds (I-1) to (I-) from the viewpoint of increasing the visible light transmittance of the resin layer containing the NIR dye (C). 3) is preferable, and compound (I-1) is particularly preferable.

In compound (I-1), X ¹ is preferably a group (2x), and Y ¹ is preferably a single bond or a group (1y). In this case, as R ³¹ to R ³⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. Specific examples of -Y ^1- X ^1- include divalent organic groups represented by the formulas (11-1) to (12-3).

-C (CH ₃ ) _2- CH (CH ₃ ) -... (11-1)
-C (CH ₃ ) _2- CH _2- ... (11-2)
-C (CH ₃ ) _2- CH (C ₂ H ₅ ) -... (11-3)
-C (CH ₃ ) _2- C (CH ₃ ) (nC ₃ H ₇ ) -... (11-4)
-C (CH ₃ ) _2- CH _2- CH _2- ... (12-1)
-C (CH ₃ ) _2- CH _2- CH (CH ₃ ) -... (12-2)
-C (CH ₃ ) _2- CH (CH ₃ ) -CH _2- ... (12-3)

Further, in compound (I-1), R ²¹ is independently formulated (1) from the viewpoint of solubility, heat resistance, and steepness of change near the boundary between the visible region and the near infrared region in the spectral transmittance curve. The group represented by 4-1) or the formula (4-2) is more preferable.

In formulas (4-1) and (4-2), R ⁸¹ to R ⁸⁵ independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

In compound (I-1), R ²⁴ is preferably -NR ²⁷ R ²⁸ . -NR ²⁷ R ²⁸ is -NH-C (= O) -R ²⁹ from the viewpoint of solubility in the resin to be combined with the NIR dye (C) and the solvent used when forming the resin layer on the substrate. Is preferable. In compound (I-1), a compound in which R ²⁴ is -NH-C (= O) -R ²⁹ is represented by the formula (I-11).

In the compound (I-11), R ²³ and R ²⁶ are independently preferable to be a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and all of them are more preferably a hydrogen atom.

In the compound (I-11), as R ²⁹ , an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, or An aralkyl group having 7 to 18 carbon atoms, which may have a substituent and may have an oxygen atom between carbon atoms, is preferable. As the substituent, a halogen atom such as a fluorine atom, a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms , Acyloxy group having 1 to 6 carbon atoms and the like.

The R ²⁹ has a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, or a substituent. Alkoxy groups having 7 to 18 carbon atoms, which may have oxygen atoms between carbon atoms, are preferable.

R ²⁹ may be a linear, branched, cyclic alkyl group having 1 to 17 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms and / or 1 to 6 carbon atoms which may be substituted with a fluorine atom. A phenyl group that may be substituted with an alkoxy group, and an alkyl that may have an oxygen atom between carbon atoms and may be substituted with a fluorine atom having 7 to 18 carbon atoms and having 1 to 6 carbon atoms at the terminal. A group selected from an aralkyl group having a phenyl group which may be substituted with a group and / or an alkoxy group having 1 to 6 carbon atoms is preferable.

As R ²⁹ , one or more hydrogen atoms may be independently substituted with a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, or a cyano group, and unsaturated bonds, oxygen atoms, saturation, or A group that is a hydrocarbon group having at least one or more branches and having 5 to 25 carbon atoms, which may contain an unsaturated ring structure, can also be preferably used. Examples of such R ²⁹ include groups represented by the following formulas (11a), (11b), (12a) to (12e), and (13a) to (13e).

More specifically, the compound (I-11) includes the compounds shown in Table 9 below. In Table 9, the group (11-1) is shown as (11-1). The same applies to other groups. The display of groups is the same in the other tables below. In addition, the compounds shown in Table 9 have the same meaning of each symbol on the left and right sides of the squarylium skeleton. The same applies to the squarylium dyes shown in the other tables below.

In compound (I-1), R ²⁴ is preferably -NH-SO _2- R ³⁰ from the viewpoint of increasing the transmittance of visible light, particularly the transmittance of light having a wavelength of 430 to 550 nm. In compound (I-1), a compound in which R ²⁴ is -NH-SO _2- R ³⁰ is represented by the formula (I-12).

In the compound (I-12), R ²³ and R ²⁶ are independently preferable to be a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and all of them are more preferably a hydrogen atom.

In compound (I-12), R ³⁰ has an alkyl or alkoxy group having 1 to 12 carbon atoms which may have a branch independently from the viewpoint of light resistance, or an unsaturated ring structure. 6 to 16 hydrocarbon groups are preferred. Examples of the unsaturated ring structure include benzene, toluene, xylene, furan, and benzofuran. R ³⁰ is more preferably an alkyl group or an alkoxy group having 1 to 12 carbon atoms which may independently have a branch. In each group showing R ³⁰ , a part or all of hydrogen atoms may be substituted with halogen atoms, particularly fluorine atoms. The hydrogen atom is replaced with a fluorine atom so that the adhesion between the resin layer containing the dye (I-12) and, for example, the transparent substrate is not deteriorated.

Specific examples of the R ³⁰ having an unsaturated ring structure include groups represented by the following formulas (P2), (P3), (P7), (P8), (P10) to (P13).

More specifically, the compound (I-12) includes the compounds shown in Table 10 below.

Examples of the compound (II) include compounds represented by any of the formulas (II-1) to (II-3).

However, in the formulas (II-1) and (II-2), R ¹ and R ² are alkyl having 1 to 15 carbon atoms which may independently have a hydrogen atom, a halogen atom, or a substituent. The groups are shown, and R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent.

However, in formula (II-3), R ¹ , R ⁴ , and R ⁹ to R ¹² are alkyl having 1 to 15 carbon atoms which may independently have a hydrogen atom, a halogen atom, or a substituent. The groups are shown, and R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent.

R ¹ and R ² in compound (II-1) and compound (II-2) are preferably alkyl groups having 1 to 15 carbon atoms independently from the viewpoint of solubility in a resin, visible light transmission, and the like. , An alkyl group having 7 to 15 carbon atoms is more preferable, an alkyl group having at least one of R ¹ and R ² having a branched chain having 7 to 15 carbon atoms is more preferable, and both R ¹ and R ² have 8 carbon atoms. Alkyl groups having up to 15 branched chains are particularly preferred.

R ³ is preferably an alkyl group having a hydrogen atom, a halogen atom, or 1 to 3 carbon atoms, and more preferably a hydrogen atom, a halogen atom, or a methyl group, independently from the viewpoint of solubility in a resin, visible light transmission, and the like. preferable. R ⁴ is preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom, from the viewpoint of steepness of change near the boundary between the visible region and the near infrared region. R ⁵ in compound (II-1) and R ⁶ in compound (II-2) are preferably alkyl groups having 1 to 5 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom, or a halogen atom. , Hydrogen atom, halogen atom, methyl group are more preferable.

Specific examples of the compound (II-1) and the compound (II-2) include the compounds shown in Tables 11 and 12, respectively. In Tables 11 and 12, -C ₈ H ₁₇ , -C ₄ H ₉ , and -C ₆ H ₁₃ represent linear octyl, butyl, and hexyl groups, respectively.

R ¹ in compound (II-3) is preferably an alkyl group having 1 to 15 carbon atoms, and an alkyl group having 1 to 10 carbon atoms independently from the viewpoint of solubility in a resin, visible light transmission, and the like. More preferably, an ethyl group and an isopropyl group are particularly preferable.

From the viewpoint of visible light transmission and ease of synthesis, R ⁴ is preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom. R ⁷ and R ⁸ are preferably an alkyl group having 1 to 5 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom or a halogen atom, and more preferably a hydrogen atom, a halogen atom or a methyl group.

R ⁹ to R ¹² are preferably alkyl groups having 1 to 5 carbon atoms which may be independently substituted with a hydrogen atom, a halogen atom, or a halogen atom. ^{^{^{^{-CR 9 R 10 -CR 11 R 12}}}} - as, the base (11-1) to (11-3) or, divalent organic groups represented by the following formulas (11-5).
-C (CH ₃ ) (CH _2- CH (CH ₃ ) ₂ ) -CH (CH ₃ ) -... (11-5)

More specifically, the compound (II-3) includes the compounds shown in Table 13 below.

Among these, as the NIR dye (C), the dye (I-11) and the dye (I-12) are preferable from the viewpoint of solubility in a resin or a solvent and visible permeability, and the dye (I) shown in Table 9 is preferable. -11) and the dye (I-12) shown in Table 10 are more preferable. Furthermore, among these, dye (I-11-7), dye (I-12-2), dye (I-12-9), dye (I-12-15), dye (I-12-23) , Dye (I-12-24) and the like are preferable.

The NIR dye (C) may consist of one kind of compound or two or more kinds of compounds. When composed of two or more kinds of compounds, each compound does not necessarily have the property of NIR dye (C), and may have the property of NIR dye (C) as a mixture.

Compound (I) and compound (II) can each be produced by known methods. For compound (I), compound (I-11) can be prepared, for example, by the method described in US Pat. No. 5,543,086. Compound (I-12) can be produced, for example, by the methods described in US Patent Application Publication No. 2014/0061505 and International Publication No. 2014/088063. Compound (II) can be produced by the method described in WO 2017/135359.

Specific examples of the UV dye optionally contained in the absorption layer include oxazole-based, merocyanine-based, cyanine-based, naphthalimide-based, oxadiazole-based, oxazine-based, oxazolidine-based, naphthalic acid-based, and styryl-based. Examples thereof include dyes such as anthracene type, cyclic carbonyl type and triazole type. Of these, oxazole-based and merocyanine-based pigments are preferable. In addition, one type of UV dye may be used alone for the absorption layer, or two or more types may be used in combination.

[Transparent resin (P)]
The transparent resin (P) is a resin having a Tg of 130 ° C. or higher and satisfying the above (1-1) to (1 to 6) in relation to the NIR dye (A). The transparent resin (P) preferably further satisfies one or more selected from the above (1-7) to (1-9) in relation to the NIR dye (A).

Tg is determined by DSC measurement (Differential Scanning Calorimetry). When the Tg of the transparent resin (P) is 130 ° C. or higher, the absorbing layer is excellent in heat resistance for maintaining the optical characteristics of the NIR dye (A) in high temperature use. Further, in a preferred embodiment, deformation due to heat or stress is unlikely to occur, and the adhesion of the dielectric multilayer film is excellent in this filter. The Tg is preferably 200 ° C. or higher, more preferably 250 ° C. or higher. Although there is no particular upper limit on Tg, the Tg of the transparent resin (P) is preferably 400 ° C. or lower from the viewpoint of molding processability and the like.

As the transparent resin (P), the type is particularly limited as long as the Tg is 130 ° C. or higher and the above requirements (1-1) to (1 to 6) are satisfied in relation to the NIR dye (A). For example, acrylic resin, epoxy resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyparaphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin. , Polyimideimide resin, polyolefin resin, cycloolefin resin, polyester resin and the like can be used.

Among these, at least one selected from polyimide resin, polyester resin, polycarbonate resin, cycloolefin resin and epoxy resin is preferable. From the viewpoint of adhesion to the dielectric multilayer film, a polyimide resin is preferable, and a polyimide resin having a Tg of 200 ° C. or higher is particularly preferable.

The transparent resin (P) may be made of one kind of resin or two or more kinds of resins. When it is composed of two or more kinds of resins, the properties of the individual resins do not necessarily satisfy the requirements of the transparent resin (P), and the mixture may satisfy the requirements of the transparent resin (P).

As the transparent resin (P), a commercially available product may be used. Examples of commercially available products include OKP4HT, B-OKP-2, and OKP-850 (all of which are manufactured by Osaka Gas Chemical Co., Ltd., trade names) as polyester resins.

As commercially available polycarbonate resins that can be used as transparent resin (P), FPC-0220 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Panlite (registered trademark) SP3810 (manufactured by Teijin Limited, trade name), Examples thereof include PURE-ACE (registered trademark) M5 (manufactured by Teijin Limited, product name) and S5 (manufactured by Teijin Limited, product name).

Neoprim (registered trademark) C-3650 (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name) and C-3G30 (Mitsubishi Gas) obtained in the form of varnish as commercially available polyimide resins that can be used as transparent resin (P). Chemical Co., Ltd., product name), C-3450 (Mitsubishi Gas Chemical Company, product name), P500 (Mitsubishi Gas Chemical Company, product name), JL-20 (New Japan Chemical Co., Ltd.) , Trade name) (The varnishes of these polyimide resins may contain silica) and the like.

As commercially available cycloolefin resins that can be used as transparent resin (P), ARTON (registered trademark) F4520 (manufactured by JSR, trade name), ZEONEX (registered trademark) K26R, F52R, T62R, APEL (registered trademark) APL5014DP, APL6015T (Both are manufactured by Mitsui Chemicals, Inc., trade name) and the like.

From the viewpoint of maintaining sufficiently high transparency of visible light, especially green and red light, the absorption layer includes the above-mentioned essential dye NIR dye (A), any dye NIR dye (B), and NIR. It is preferable that it is composed only of a dye (C), a dye such as a UV dye, and a transparent resin (P).

However, as long as the absorption layer does not impair the effects of the present invention, the adhesive layer, a color tone correcting dye, a leveling agent, an antistatic agent, a heat stabilizer, a light stabilizer, an antioxidant, a dispersant, a flame retardant, etc. It may have an optional component such as a lubricant or a plasticizer.

The absorption layer satisfies the following (2-1) and (2-2) when the average OD value is 1 in the wavelength region of the maximum absorption wavelength λ _{max (A) TR} ± 10 nm of the NIR dye (A). It is more preferable to satisfy one or more selected from (2-3) and (2-4), and it is particularly preferable to satisfy all of (2-1) to (2-4). ..

(2-1) The average internal transmittance _{TAVE490-560 (AL)} in the wavelength region of 490 to 560 nm is 88% or more. T _{AVE 490-560 (AL)} is preferably 90% or more, more preferably 92% or more.

(2-2) The average internal transmittance _{TAVE590-630 (AL)} in the wavelength region of 590 to 630 nm is 70% or more. T _{AVE590-630 (AL)} is preferably 72% or more, more preferably 75% or more.

(2-3) It has a wavelength λ _50% at which the internal transmittance is 50% in the wavelength region of 600 to 700 nm. The wavelength λ _50% is more preferably in the wavelength region of 610 to 640 nm.

(2-4) In the wavelength region of 600 to 1200 nm, the total width of the wavelength region in which the internal transmittance is 30% or less is 250 nm or more. In the wavelength region of 600 to 1200 nm, there may be one or a plurality of wavelength regions in which the internal transmittance is 30% or less. The total width of the wavelength range in which the internal transmittance is 30% or less is preferably 250 nm or more, more preferably 300 nm or more. It can be said that the larger the total width is, the higher the NIR absorption capacity in the absorption layer is.

The content of the NIR dye (A) in the absorption layer is appropriately set so that the effect of the filter can be exhibited according to the design of the filter. The content of the NIR dye (A) in the absorption layer is from the viewpoint of blocking near-infrared light, particularly near-infrared light in a long wavelength region, while ensuring the transmittance of visible light, particularly the transmittance of green and red. Therefore, 1 to 15 parts by mass is preferable with respect to 100 parts by mass of the transparent resin (P), and 1 to 10 parts by mass is more preferable from the viewpoint of solubility.

When the absorption layer contains one or more selected from NIR dye (A), NIR dye (B) and NIR dye (C), the content of each NIR dye depends on the design of this filter. As appropriate so that the absorption layer satisfies the properties of (2-1) and (2-2), preferably one or more properties further selected from (2-3) and (2-4). Be selected.

In this case, the content of the NIR dye (A) in the absorption layer is the same as above, and the content of one or more selected from the NIR dye (B) and the NIR dye (C) ensures the transmittance of visible light. However, from the viewpoint that the characteristics of the NIR dye (B) and the NIR dye (C) can be exhibited, the NIR dye (B) and the NIR dye (C) are each about 1 to 15 with respect to 100 parts by mass of the transparent resin (P). By mass is preferable, and from the viewpoint of solubility, 3 to 10 parts by mass is more preferable. Further, the total content of one or more selected from the NIR dye (A), the NIR dye (B) and the NIR dye (C) is preferably 2 to 30 parts by mass with respect to 100 parts by mass of the transparent resin (P). From the viewpoint of solubility, 5 to 27 parts by mass is more preferable.

In this filter, the thickness of the absorption layer is preferably 0.1 to 100 μm. When the absorption layer is composed of a plurality of layers, the total thickness of each layer is preferably 0.1 to 100 μm. If the thickness is less than 0.1 μm, the desired optical characteristics may not be sufficiently exhibited, and if the thickness is more than 100 μm, the flatness of the layer may be lowered and the absorption rate may vary in the plane. The thickness of the absorption layer is more preferably 0.3 to 50 μm. Further, when another functional layer such as a reflective layer or an antireflection layer is provided, cracks or the like may occur if the absorbing layer is too thick depending on the material thereof. Therefore, the thickness of the absorption layer is more preferably 0.3 to 10 μm.

The absorption layer is, for example, NIR dye (A), preferably one or more selected from NIR dye (A), NIR dye (B), and NIR dye (C), and particularly preferably NIR dye (A). NIR dye (B), NIR dye (C), raw material components of transparent resin (P) or transparent resin (P), and each component to be blended as needed are dissolved or dispersed in a solvent for coating. A liquid can be prepared, coated on a substrate, dried, and further cured if necessary to form. The base material may be a transparent substrate included in the present filter, or may be a peelable base material used only when forming an absorption layer. The solvent may be a dispersion medium that can be stably dispersed or a solvent that can be dissolved.

Further, the coating liquid may contain a surfactant for improving voids due to minute bubbles, dents due to adhesion of foreign substances, repelling in the drying process, and the like. Further, for coating the coating liquid, for example, a dip coating method, a cast coating method, a spin coating method or the like can be used. An absorbent layer is formed by applying the above coating liquid on a substrate and then drying it. When the coating liquid contains the raw material component of the transparent resin (P), further curing treatments such as thermosetting and photocuring are performed.

Further, the absorption layer can be manufactured in the form of a film by extrusion molding, and this film may be laminated on another member and integrated by thermocompression bonding or the like. For example, when the filter includes a transparent substrate, this film may be attached onto the transparent substrate.

The absorption layer may have one layer or two or more layers in the present filter. When having two or more layers, each layer may have the same configuration or different layers. Further, the absorption layer may be composed of a single layer or may have a structure in which a plurality of layers are laminated. Further, the absorption layer itself may function as a substrate (resin substrate).

(Transparent board)
When a transparent substrate is used for this filter, the transparent substrate is not particularly limited as long as it transmits visible light of about 400 to 700 nm, and may be a material that absorbs near-infrared light or near-ultraviolet light. Examples thereof include inorganic materials such as glass and crystals, and organic materials such as transparent resins.

Glasses that can be used for transparent substrates include absorbent glass (near-infrared absorbing glass) containing copper ions in fluoride-based glass, phosphate-based glass, etc., soda lime glass, borosilicate glass, non-alkali glass, and quartz. Examples include glass. The "phosphate-based glass" also includes silicate glass in which a part of the skeleton of the glass is composed of SiO ₂ .

As for glass, alkali metal ions (for example, Li ion and Na ion) having a small ionic radius existing on the main surface of the glass plate can be converted into alkali ions having a larger ionic radius (for example) by ion exchange at a temperature below the glass transition point. , Li ion is Na ion or K ion, and Na ion is K ion.) You may use the chemically strengthened glass obtained by exchanging with the ion.

Examples of the transparent resin material that can be used as a transparent substrate include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene and ethylene vinyl acetate copolymers, and acrylic resins such as norbornene resin, polyacrylate and polymethylmethacrylate. , Urethane resin, vinyl chloride resin, fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, polyimide resin and the like.

Further, examples of the crystal material that can be used for the transparent substrate include birefringent crystals such as quartz, lithium niobate, and sapphire. The optical characteristics of the transparent substrate may have the above-mentioned optical characteristics as an optical filter obtained by laminating the absorption layer, the reflection layer, and the like. Sapphire is preferable as the crystal material.

The transparent substrate is preferably an inorganic material, and particularly preferably glass or sapphire, from the viewpoint of shape stability related to long-term reliability such as optical characteristics as an optical filter and mechanical characteristics, and handleability during filter manufacturing.

The shape of the transparent substrate is not particularly limited, and may be block-shaped, plate-shaped, or film-shaped, and the thickness thereof is preferably, for example, 0.03 to 5 mm, and from the viewpoint of thinning, 0.03 to 0.5 mm. Is more preferable. From the viewpoint of workability, a transparent substrate made of glass and having a plate thickness of 0.05 to 0.5 mm is preferable.

(Reflective layer)
The reflective layer is made of a dielectric multilayer film and has a function of shielding light in a specific wavelength range. Examples of the reflective layer include those having wavelength selectivity that transmits visible light and mainly reflects light having a wavelength other than the light-shielding region of the absorption layer. The reflective layer preferably has a reflective region that reflects near-infrared light. In this case, the reflection region of the reflection layer may include a light-shielding region in the near-infrared region of the absorption layer. The reflective layer is not limited to the above characteristics, and may be appropriately designed to have specifications that further block light in a predetermined wavelength range, for example, the near-ultraviolet region.

When the reflective layer has a reflective region that reflects near-infrared light, the reflective layer specifically preferably satisfies the following (iii-1).
(Iii-1) In the spectral transmittance curve with an incident angle of 0 degrees, the average transmittance T _{RE850-1100ave 0 °} of light having a wavelength of 850 to 1100 nm is 0.2% or less.
The average transmittance T _{RE850-1100ave 0 °} is preferably 0.15% or less, more preferably 0.05% or less.

When the reflective layer has a reflective region that reflects near-infrared light, it is preferable that the absorbing layer and the reflective layer have the following relationship.

When the wavelength λ _{ABSHT20-0 °} on the short wavelength side showing a transmittance of 20% with respect to light having an incident angle of 0 ° in the absorption layer satisfies 650 nm ≦ λ _{ABSHT20-0 °} ≦ 800 nm, the wavelength λ _ABSHT20-0 The relationship between _° and the wavelength λ _{RESHT 20-0 °} on the short wavelength side, which shows a transmittance of 20% in the wavelength range of 650 nm or more with respect to light having an incident angle of 0 _° in the reflective layer, satisfies (iii-2). Is preferable.
(Iii-2) λ _{ABSHT 20-0 °} + 30 nm ≤ λ _{RESHT 20-0 °} ≤ 790 nm

The reflective layer preferably further satisfies (iii-3).
(Iii-3) The average transmittance of light in the wavelength region from λ _RESHT _{20-0 °} to λ _{RESHT 20-0 °} + 300 nm is 10% or less.

The reflective layer is composed of a dielectric multilayer film in which a low refractive index dielectric film (low refractive index film) and a high refractive index dielectric film (high refractive index film) are alternately laminated. The high refractive index film preferably has a refractive index of 1.6 or more, more preferably 2.2 to 2.5. Examples of the material of the high refractive index film include Ta ₂ O ₅ , TiO ₂ , and Nb ₂ O ₅ . Of these, TiO ₂ is preferable from the viewpoints of film formation property, reproducibility in refractive index and the like, stability and the like.

On the other hand, the low refractive index film preferably has a refractive index of less than 1.6, and more preferably 1.45 or more and less than 1.55. Examples of the material of the low refractive index film include SiO ₂ , SiO _x N _{y and the} like. SiO ₂ is preferable from the viewpoint of reproducibility, stability, economy, etc. in film formation.

Further, it is preferable that the transmittance of the reflective layer changes sharply in the boundary wavelength region between the transmissive region and the light-shielding region. For this purpose, the total number of laminated dielectric multilayer films constituting the reflective layer is preferably 15 layers or more, more preferably 25 layers or more, and even more preferably 30 layers or more. However, when the total number of layers increases, warpage and the like occur and the film thickness increases. Therefore, the total number of layers is preferably 100 layers or less, more preferably 75 layers or less, and even more preferably 60 layers or less. The film thickness of the dielectric multilayer film is preferably 2 to 10 μm.

If the total number of laminated dielectric multilayer films and the film thickness are within the above ranges, the reflective layer can satisfy the requirements for miniaturization, and can suppress the dependence on the incident angle while maintaining high productivity. Further, for forming the dielectric multilayer film, for example, a vacuum film forming process such as a CVD method, a sputtering method or a vacuum vapor deposition method, a wet film forming process such as a spray method or a dip method can be used.

As the reflective layer, one layer (one group of dielectric multilayer films) may give a predetermined optical characteristic, or two layers may give a predetermined optical characteristic. When having two or more layers, each reflective layer may have the same configuration or a different configuration. When two or more reflective layers are provided, they are usually composed of a plurality of reflective layers having different reflection bands.

As an example, when two reflective layers are provided, one is a near-infrared reflective layer that blocks light in a short wavelength band in the near infrared region, and the other is a long wavelength band and a near ultraviolet region in the near infrared region. It may be a near-infrared / near-ultraviolet reflective layer that blocks light in both regions. Further, for example, when the present filter has a transparent substrate and two or more reflective layers are provided, all of them may be provided on one main surface of the transparent substrate, and each reflective layer may be provided on the transparent substrate. It may be sandwiched and provided on both main surfaces.

(Anti-reflective layer)
Examples of the antireflection layer include a dielectric multilayer film, an intermediate refractive index medium, and a moth-eye structure in which the refractive index gradually changes. Of these, a dielectric multilayer film is preferable from the viewpoint of optical efficiency and productivity. The antireflection layer is obtained by alternately laminating dielectric films like the reflection layer.

This filter may include, for example, a component (layer) that provides absorption by inorganic fine particles or the like that controls the transmission and absorption of light in a specific wavelength range, as other components. Specific examples of the inorganic fine particles include ITO (Indium Tin Oxides), ATO (Antimony-doped Tin Oxides), cesium tungstate, and lanthanum boride. The ITO fine particles and the cesium tungstate fine particles have high visible light transmittance and have light absorption over a wide range in the infrared wavelength region exceeding 1200 nm, and thus can be used when such infrared light shielding property is required. ..

By having a reflective layer and an absorbing layer containing a NIR dye (A) and a transparent resin (P), this filter provides near-infrared light while maintaining good transparency of visible light, especially green and red. In particular, it is excellent in shielding long-wavelength near-infrared light.

It is preferable that this filter satisfies all of the following requirements (3-1) to (3-3) regarding the optical characteristics measured at an incident angle of 0 degrees. In addition to these, the present filter more preferably satisfies all the requirements (3-4) to (3-9).

(3-1) The minimum OD value of the NIR dye (A) in the wavelength region of the maximum absorption wavelength λ _{max (A) TR} ± 10 nm is 4 or more. The minimum OD value at an incident angle of 0 degree is more preferably 5 or more.

(3-2) The average transmittance _{TAVE490-560 (0 °)} in the wavelength region of 490 to 560 nm is 82% or more. The average transmittance T _{AVE490-560 (0 °)} is more preferably 83.0% or more, further preferably 83.5% or more.

(3-3) The average transmittance _{TAVE590-630 (0 °)} in the wavelength region of 590 to 630 nm is 50% or more. The average transmittance T _{AVE590-630 (0 °)} is more preferably 55% or more, further preferably 60% or more.

(3-4) 600 in the wavelength region of ~ 800 nm, the wavelength lambda _50% of transmittance is 50% at an incident angle of 0 degrees _{(0 °)} and the transmittance at an incident angle of 30 degrees is 50% wavelength lambda _50% The absolute value of the difference _{(30 °)} | λ _{50% (30 °)} −λ _{50% (0 °)} | is 5 nm or less. | Λ _{50% (30 °)} −λ _{50% (0 °)} | is more preferably 4 nm or less, further preferably 3 nm or less.

(3-5) The average transmittance _{TAVE490-560 (30 °)} in the wavelength region of 490 to 560 nm measured at an incident angle of 30 degrees is 80% or more. The average transmittance T _{AVE490-560 (30 °)} is more preferably 81% or more, further preferably 83% or more.

(3-6) The minimum OD value in the wavelength region of the maximum absorption wavelength λ _{max (A) TR} ± 10 nm of the NIR dye (A) measured at an incident angle of 30 degrees is 3 or more. The minimum OD value at an incident angle of 30 degrees is more preferably 4 or more.

(3-7) 600 in the wavelength region of ~ 800 nm, the wavelength lambda _50% of transmittance is 50% at an incident angle of 0 degrees _{(0 °)} and the transmittance at an incident angle of 50 degrees is 50% wavelength lambda _50% The absolute value of the difference of _{(50 °)} | λ _{50% (50 °)} −λ _{50% (0 °)} | is 15 nm or less. | Λ _{50% (50 °)} −λ _{50% (0 °)} | is more preferably 13 nm or less, further preferably 10 nm or less.

(3-8) The average transmittance _{TAVE490-560 (50 °)} in the wavelength region of 490 to 560 nm measured at an incident angle of 50 degrees is 70% or more. The average transmittance T _{AVE490-560 (50 °)} is more preferably 72% or more, further preferably 74% or more.

(3-9) The minimum OD value in the wavelength region of the maximum absorption wavelength λ _{max (A) TR} ± 10 nm of the NIR dye (A) measured at an incident angle of 50 degrees is 3 or more. The minimum OD value at an incident angle of 50 degrees is more preferably 4 or more.

This filter is useful as an optical filter for an image pickup device in a device having both an image pickup device such as a digital still camera and an optical component that uses laser light. In addition, this filter is useful for applications of optical sensors such as ambient light sensors.

An image pickup device using this filter includes a solid-state image pickup element, an image pickup lens, and this filter. This filter can be used, for example, by being arranged between an image pickup lens and a solid-state image sensor, or by being directly attached to a solid-state image sensor, an image sensor, or the like of an image pickup device via an adhesive layer.

Next, the present invention will be described in more detail with reference to Examples. First, a synthesis example and characteristics of the NIR dye (A) used for the absorption layer of the example will be described. Next, an example of the optical filter will be described.

[Test Examples 1-29; Dye synthesis and evaluation]
(Dye synthesis and evaluation)
NIR dye (A), NIR dye (B), and other NIR dyes were synthesized by the following methods. Synthesis Examples 1 to 11 are examples of synthesis of NIR dye (A), Synthesis Examples 12 to 15 are examples of synthesis of NIR dye (B), and Synthesis Examples 16 and 17 are examples of synthesis of other NIR dyes. Further, as the NIR dye (A), the trade name S0772 manufactured by Few Chemicals, which is a commercial product represented by the following formula (S0772), and as another NIR dye, a commercially available product represented by the following formula (S2437), manufactured by Few Chemicals. Product name S2437 was prepared.

In addition, an ultraviolet-visible near-infrared spectrophotometer (UH4150, manufactured by Hitachi High-Tech Science Co., Ltd.) was used to evaluate the optical characteristics of these dyes, and the following optical characteristics (spectral transmittance curve) were also evaluated. Similarly, UH4150 was used.

[Synthesis Example 1]
A dye (A1a-5Sb) was synthesized according to the reaction pathway shown below.

<Step 1>
To a 1 L eggplant flask, add tris (4-nitrophenyl) amine (25 g, 66 mmol), palladium-activated carbon (palladium 10%) (6.5 g), 1,4-dioxane (350 mL), and methanol (300 mL), and add 0. The mixture was cooled and stirred at ° C., ammonium formate (65 g, 990 mmol) was added, and the mixture was stirred at room temperature for 4 hours. After filtering the reaction solution, the filtrate was extracted with dichloromethane, the solvent was removed, 300 mL of hexane was added to the remaining solid, and the mixture was stirred for 1 day and washed. When hexane was removed by filtration, 18.1 g (yield 95%) of Intermediate 1 which was a gray solid was obtained.

<Step 2>
Intermediate 1 (15 g, 52 mmol), potassium carbonate (71.4 g, 520 mmol), 1-bromo-2 methylpropane (127 g, 930 mmol), N, N-dimethylformamide (150 mL) obtained in step 1 in a 1 L eggplant flask. ) Was added, and the mixture was stirred at 115 ° C. for 24 hours. After returning to room temperature, filtration was performed, the filtrate was extracted with dichloromethane, the solvent was removed, and the mixture was washed with methanol. As a result, 18.2 g (yield) of intermediate 2 as a brown solid was obtained. Rate 56%) Obtained.

<Step 3>
Intermediate 2 (3 g, 4.8 mmol) obtained in step 2 and N, N-dimethylformamide (60 mL) were added to a 500 mL eggplant flask, and the mixture was stirred until dissolved at 60 ° C. Then, a solution prepared by dissolving silver hexafluoroantimonate (V) (3.79 g, 11 mmol) in N, N-dimethylformamide (30 mL) was added to the solution in which Intermediate 2 was dissolved, and the mixture was stirred at 60 ° C. for 3 hours. I let you. After filtering the precipitated solid, the recovered solid is isolated by column chromatography (dichloromethane: methanol = 1000:30), the solvent is removed, a small amount of the solid is dissolved in dichloromethane, and the solid is reprecipitated with ethyl acetate. 2.8 g (yield 54%) of a dye (A1a-5Sb) which is a green solid was obtained.

[Synthesis Example 2]
Intermediate 2 (3 g, 4.8 mmol) and ethyl acetate (50 mL) obtained in step 2 of Synthesis Example 1 were added to a 500 mL eggplant flask, and the mixture was stirred at 60 ° C. until dissolved. Then, a solution prepared by dissolving potassium bis (trifluoromethylsulfonyl) imide (3.8 g, 12 mmol) and ammonium peroxodisulfate (2.7 g, 12 mmol) in a mixed solvent of acetonitrile (30 mL) and water (30 mL) was added in the middle. Body 2 was added to the dissolved solution and stirred at 60 ° C. for 4 hours. After completion of the reaction, the temperature was returned to room temperature, water (100 mL) and hexane (200 mL) were added to precipitate a solid, which was filtered and washed with ethyl acetate. The recovered solid is isolated by column chromatography (dichloromethane: methanol = 1000:30), the solvent is removed, a small amount of the solid is dissolved in dichloromethane, reprecipitation is performed using ethyl acetate, and the dye is a green solid. 3.6 g (yield 63%) of (A1a-5NS) was obtained.

[Synthesis Example 3]
2.6 g of dye (A1a-5P), which is a green solid, in the same manner as in Synthesis Example 2 except that potassium bis (trifluoromethylsulfonyl) imide is changed to potassium hexafluorophosphate (2.2 g, 12 mmol). (Yield 59%) was obtained.

[Synthesis Example 4]
2.5 g (A1a-5Cl) of the dye (A1a-5Cl), which is a green solid, was added in the same manner as in Synthesis Example 2 except that potassium bis (trifluoromethylsulfonyl) imide was changed to sodium perchlorate (1.5 g, 12 mmol). Yield 63%) was obtained.

[Synthesis Example 5]
2.7 g of dye (A1a-5B) which is a green solid by the same method as in Synthesis Example 2 except that potassium bis (trifluoromethylsulfonyl) imide is changed to sodium tetrafluoroborate (1.3 g, 12 mmol). (Yield 71%) was obtained.

[Synthesis Example 6]
A dye (A1a-4P) was synthesized according to the reaction pathway shown below.

<Step 1>
The reaction was carried out using the same raw materials except that 1-bromo-2 methylpropane used in step 2 of Synthesis Example 1 was changed to 1-bromobutane (127 g, 930 mmol), an extraction operation was performed with dichloromethane, and then column chromatography was performed. Isolation was performed by chromatography (hexane: ethyl acetate = 1000: 40) to obtain 23 g (yield 71%) of Intermediate 3, which is a pale yellow oily substance.

<Step 2>
Intermediate 3 (3 g, 4.8 mmol) and ethyl acetate (50 mL) obtained in step 1 of Synthesis Example 6 were added to a 500 mL eggplant flask, and the mixture was stirred at 60 ° C. until dissolved. Then, the intermediate 3 was dissolved in a solution prepared by dissolving potassium hexafluorophosphate (2.2 g, 12 mmol) and ammonium peroxodisulfate (2.7 g, 12 mmol) in a mixed solvent of acetonitrile (30 mL) and water (30 mL). In addition to the prepared solution, the mixture was stirred at 60 ° C. for 4 hours. After completion of the reaction, the temperature was returned to room temperature, water (100 mL) and hexane (200 mL) were added to precipitate a solid, which was filtered and washed with ethyl acetate. The recovered solid is isolated by column chromatography (dichloromethane: ethyl acetate = 10: 1), the solvent is removed, a small amount of the solid is dissolved in dichloromethane, reprecipitation is performed using hexane, and the dye is a green solid. 2.8 g (yield 63%) of (A1a-4P) was obtained.

[Synthesis Example 7]
The dye (A1a-4NS) which is a green solid is prepared in the same manner as in Step 2 of Synthesis Example 6 except that potassium hexafluorophosphate is changed to potassium bis (trifluoromethylsulfonyl) imide (3.8 g, 12 mmol). 3.1 g (yield 54%) was obtained.

[Synthesis Example 8]
0.9 g (A1a-4B) of the dye (A1a-4B), which is a green solid, was added in the same manner as in step 2 of Synthesis Example 6 except that potassium hexafluorophosphate was changed to sodium tetrafluoroborate (1.3 g, 12 mmol). Yield 22%) was obtained.

[Synthesis Example 9]
A dye (A1a-7P) was synthesized according to the method shown below.

<Step 1>
Reaction was carried out using the same raw materials except that 1-bromo-2 methylpropane used in step 2 of Synthesis Example 1 was changed to 1-bromooctane (18 equal to Intermediate 1), and an extraction operation was performed with dichloromethane. After that, the mixture was isolated by column chromatography (hexane: ethyl acetate = 1000: 40) to obtain 13.4 g (yield 67%) of Intermediate 4, which is a pale yellow oily substance.

<Step 2>
1.0 g (yield 20%) of a green solid dye (A1a-7P) was obtained in the same manner except that the intermediate 3 described in step 2 of Synthesis Example 6 was changed to intermediate 4.

[Synthesis Example 10]
2.4 g (A1a-7NS) of a green solid dye (A1a-7NS) was added in the same manner except that potassium hexafluorophosphate used in step 2 of Synthesis Example 9 was changed to potassium bis (trifluoromethylsulfonyl) imide. Yield 37%) was obtained.

[Synthesis Example 11]
A dye (A1a-1NS) was synthesized according to the method shown below.

<Step 1>
The reaction was carried out using the same raw materials except that 1-bromo-2 methylpropane used in step 2 of Synthesis Example 1 was changed to bromoethane (18 equal to Intermediate 1), and the extraction operation was carried out with dichloromethane. Then, it was isolated by column chromatography (hexane: ethyl acetate = 8: 2) to obtain 1.7 g (yield 12%) of Intermediate 5, which is a pale yellow oily substance.

<Step 2>
It is a green solid in the same manner except that the intermediate 3 described in step 2 of Synthesis Example 6 was changed to intermediate 5 and potassium hexafluorophosphate was changed to potassium bis (trifluoromethylsulfonyl) imide. 0.8 g (yield 22%) of the dye (A1a-1NS) was obtained.

[Synthesis Example 12]
A dye (B1-5Sb) was synthesized according to the reaction pathway shown below.

<Step 1>
4-Bromoaniline (25.4 g, 148 mmol) and N, N-dimethylformamide (80 mL) were added to a 1 L eggplant flask, and the mixture was stirred at 110 ° C. until dissolution. Then, 1-bromo-2-methylpropane (54.7 g, 399 mmol) and N-ethyldiisopropylamine (57.3 g, 444 mmol) were added, and the mixture was reacted at 130 ° C. for 15 hours. After returning to room temperature, an extraction operation was carried out with a mixed solvent of ethyl acetate: hexane = 1: 4, and after removing the solvent, isolation by column chromatography (hexane: ethyl acetate = 1000: 50) revealed a white solid. The intermediate 6 was obtained in an amount of 15 g (yield 36%).

<Step 2>
Intermediate 6 (12 g, 42 mmol) obtained in step 1 in a 1 L eggplant flask, 1,4-phenylenediamine (1.1 g, 9.8 mmol), sodium tert-butoxide (8 g, 83 mmol), tris (dibenzylidene). Add acetone) dipalladium (0) (1 g, 1.1 mmol), 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (2 g, 4 mmol), 1,4-dioxane (80 mL), and add. The reaction was carried out at 100 ° C. for 20 hours. After returning to room temperature and removing the residual solid of the catalyst by Celite filtration, an extraction operation was carried out with a saturated aqueous solution of dichloromethane and ammonium chloride, and after removing the solvent, the precipitated solid was washed with methanol to form an intermediate 7 which is a brown solid. Was obtained in 17.5 g (yield 97%).

<Step 3>
Intermediate 7 (2 g, 2 mmol) obtained in step 2 and N, N-dimethylformamide (20 mL) were added to a 500 mL eggplant flask, and the mixture was stirred until dissolved at 60 ° C. Then, a solution of silver hexafluoroantimonate (V) (1.6 g, 4.5 mmol) in N, N-dimethylformamide (20 mL) was added to the solution of intermediate 7 and at 60 ° C. It was stirred for 2 hours. After filtering the precipitated solid, wash it with N, N-dimethylformamide, slowly add about 150 mL of water to the filtrate, filter the precipitated solid again, wash it with water and hexane, and then perform column chromatography (dichloromethane). : Isolate with ethyl acetate = 7: 3), remove the solvent, dissolve a small amount of the solid in dichloromethane, perform reprecipitation work with ethyl acetate, and add 1 dye (B1-5Sb), which is a reddish brown solid. .3 g (43% yield) was obtained.

[Synthesis Example 13]
Intermediate 7 (5 g, 5.4 mmol) obtained in step 2 of Synthesis Example 12 and ethyl acetate (50 mL) were added to a 500 mL eggplant flask, and the mixture was stirred at 60 ° C. until dissolved. Then, potassium bis (trifluoromethylsulfonyl) imide (4.4 g, 13.8 mmol) and ammonium peroxodisulfate (3.1 g, 13.5 mmol) were dissolved in a mixed solvent of acetonitrile (30 mL) and water (30 mL). The solution was added to the solution in which the intermediate 7 was dissolved, and the mixture was stirred at 60 ° C. for 4 hours. After completion of the reaction, the temperature was returned to room temperature, water (100 mL) and hexane (200 mL) were added to precipitate a solid, which was filtered and washed with ethyl acetate. The recovered solid is isolated by column chromatography (dichloromethane: methanol = 1000:30), the solvent is removed, a small amount of the solid is dissolved in dichloromethane, reprecipitation is performed using hexane, and the dye is a reddish brown solid. 6.0 g (yield 75%) of (B1-5NS) was obtained.

[Synthesis Example 14]
A reddish brown solid dye (B1-5P) was obtained in a yield of 36% by the same method as in Synthesis Example 2 except that potassium bis (trifluoromethylsulfonyl) imide was changed to potassium hexafluorophosphate.

[Synthesis Example 15]
An n-butyl-modified intermediate was synthesized (yield) in the same manner except that 1-bromo-2 methylpropane used in step 1 of Synthesis Example 12 was changed to 1-bromobutane (54.7 g, 399 mmol). The rate was 89%), and a dye (B1-4Sb) which was a reddish brown solid was obtained in a yield of 72% by using the same method as in steps 2 and 3 of Synthesis Example 12.

[Synthesis Example 16]
The dye (S1) was synthesized according to the reaction pathway shown below. That is, the products (10) (6.5 mmol) and squaric acid (3.4 mmol) prepared with reference to European Journal of Medical Chemistry, 54, 647, (2012) were placed in a 500 mL eggplant flask, and toluene (330 mL) was added. And 1-butanol (110 mL) were dissolved, quinoline (8 mmol) was added, and the mixture was stirred at 150 ° C. for 4 hours. The product (10) is an iodine salt of a compound in which the hydrogen at the 1-position of 2-methyl-benzo [c, d] indole is replaced with R, and R is -CH _2- CH (C ₆ H _13). ) (C ₈ H ₁₇ ).

After completion of the reaction, the solvent was removed, isolated by column chromatography (hexane: ethyl acetate = 8: 2), the solvent was removed, and after washing with hexane, the dye (S1) (0.5 g, yield) which was a reddish brown solid. 25%) was obtained.

[Synthesis Example 16]
The dye (S2) was synthesized according to the reaction pathway shown below.

<Step 1>
Benzo [cd] indole-2 (1H) -one (30 g, 177 mmol) and chloroform (500 mL) were placed in a 1 L three-necked flask, and the mixture was heated and stirred at 65 ° C. to dissolve the raw materials, then cooled to 0 ° C. and bromine. (28.3 g, 177 mmol) was slowly added dropwise. After completion of the dropping, the temperature was returned to room temperature, and after stirring for 24 hours, hexane was added to the reaction solution for dilution, and the precipitate was collected by filtration. The solid on the filter paper was washed with hexane a plurality of times and vacuum dried to obtain 60 g (yield 100% or more) of Intermediate 8 which is an ocher solid.

<Step 2>
To a 1 L eggplant flask, add intermediate 8 (30 g, 121 mmol) synthesized in step 1, 4-Dimethylaminopyridine (2.0 g, 16 mmol), potassium iodide (4.0 g, 24 mmol) and sulfolane (300 mL), and add 70. The mixture was stirred at ° C. for 1 h. Potassium hydroxide (21 g, 374 mmol) and 7- (Bromomethyl) pentadecane (111 g, 363 mmol) were added to the reaction solution, and the reaction was carried out at 70 ° C. for 19 hours. After completion of the reaction, the temperature was returned to room temperature, and an extraction operation was carried out using an organic solvent in which hexane and ethyl acetate were mixed at a ratio of 4: 1 and water to remove the solvent. Then, it was isolated by column chromatography (hexane: ethyl acetate = 1000:10) to obtain 45 g (yield 78%) of Intermediate 9, which is a yellow oily substance.

<Step 3>
Intermediate 9 (33 g, 70 mmol) and ethyl acetate (2.5 g, 28 mmol) synthesized in step 2, copper (I) iodide (1.9 g, 10 mmol), 28% sodium methoxide / in a 1 L eggplant flask. A methanol solution (42 g) was added, and the mixture was stirred and reacted at 90 ° C. for 6 hours. Further, copper (I) iodide (1 g, 5 mmol) and a 28% sodium methoxide / methanol solution (20 g) were added, and the mixture was further stirred at 90 ° C. for 15 hours. After completion of the reaction, the temperature was returned to room temperature, Celite filtration was performed, and then an extraction operation was performed with dichloromethane and water to remove the solvent. Then, it was isolated by column chromatography (hexane: ethyl acetate = 1000: 30) to obtain 26 g (yield 88%) of Intermediate 10, which is a yellow oily substance.

<Step 4>
Intermediate 10 (26 g, 61 mmol) synthesized in step 3 and dichloromethane (500 mL) were placed in a 2 L three-necked flask and cooled to −78 ° C. Then, 1 M boron tribromide dichloromethane solution (200 mL) was slowly added dropwise, and after completion of the addition, the reaction solution was returned to room temperature and stirred for 2 hours. After completion of the reaction, the mixture was cooled to 0 ° C., 200 mL of water was slowly added, and boron tribromide was quenched. The precipitated solid was filtered, and the filtrate was extracted with dichloromethane and an aqueous solution of sodium hydrogen carbonate to remove the solvent. Together with the solid recovered during filtration, the mixture was washed with hexane multiple times to obtain 24 g (yield 95%) of Intermediate 11, which is a yellow solid.

<Step 5>
Intermediate 11 (10 g, 24 mmol) synthesized in step 4, potassium carbonate (16.9 g, 120 mmol) and DMF (120 mL) were added to a 1 L three-necked flask, and the mixture was stirred at 70 ° C. Then, 7- (Bromomethyl) pentadecane (8.95 g, 29 mmol) was added dropwise, and the mixture was stirred at 70 ° C. for 2 hours. After completion of the reaction, an extraction operation was carried out with water and an organic solvent in which hexane and ethyl acetate were mixed at a ratio of 1: 1 to remove the solvent. Then, it was isolated by column chromatography (hexane: ethyl acetate = 10: 1) to obtain 14 g (yield 91%) of Intermediate 12, which is a yellow oily substance.

<Step 6>
To a 1 L three-necked flask, add intermediate 12 (14 g, 22 mmol) synthesized in step 5, epichlorohydrin (8.2 g, 88 mmol), chloroform (50 mL), and diethyl ether (20 mL), and stir at 70 ° C. .. A mixed solution of Boron Trifluoride-Ethyl Ether Complex (15.9 g, 110 mmol) and chloroform (30 mL) was added dropwise, the temperature was raised to 130 ° C., and the mixture was stirred and reacted for 15 hours. Then, the reaction solution was cooled, toluene was added, and the solvent was removed by an evaporator about twice to obtain an orange-brown oily substance (intermediate 13'). Ethanol (20 mL) and Meldrum's acid (4.6 g, 32 mmol) were added to the oily substance, triethylamine (11.4 g, 110 mmol) was added, and the mixture was stirred at room temperature for 5 hours. After completion of the reaction, toluene was added, the solvent was removed by an evaporator about twice, isolated by column chromatography (hexane: ethyl acetate = 6: 4), and 8 g (yield) of intermediate 13 which was a magenta-colored oily substance was collected. It was obtained at a rate of 47%).

<Step 7>
Intermediate 13 (8 g, 10 mmol) synthesized in step 6 and hydrochloric acid (15 mL) were added to a 1 L eggplant flask, and the mixture was heated at 130 ° C. for 1 h. Then, tetrafluoroboric acid (3 mL) was added, and the reaction was further carried out for 1 hour. After completion of the reaction, the temperature was returned to room temperature, 50 mL of water was added, and 20 mL of tetrafluoroboric acid was added. Then, an extraction operation was carried out using dichloromethane and water to remove the solvent, and an orange oily substance, Intermediate 14, was obtained in an amount of 7.1 g (yield 94%).

<Step 8>
In a 1 L eggplant flask, intermediate 14 (7.1 g, 10 mmol) synthesized in step 7, squaric acid (0.59 g, 5.2 mmol), toluene (500 mL), 1-butanol (170 mL), quinoline (1. 77 g) was added and reacted at 130 ° C. for 2 hours. Then, the solvent was removed with an evaporator, and the mixture was isolated by column chromatography (hexane: ethyl acetate = 9: 1) to obtain 3.4 g (yield 55%) of the dye (S2) as a black solid. ..

A dye-containing resin layer was prepared using the various dyes and transparent resin prepared above, and the optical characteristics were measured. In addition, various dyes were dissolved in dichloromethane, and the optical characteristics were measured and compared with the optical characteristics of the dye-containing resin layer. The following commercially available products were used as the transparent resin. The results are shown in Table 14.

(Transparent resin (P))
Resin A; Neoprim (registered trademark) C-3G30 (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name), varnish containing polyimide resin, Tg of polyimide resin contained: 320 ° C.
Resin B; ARTON (registered trademark) F4520 (manufactured by JSR Corporation, trade name), cycloolefin resin, Tg: 151 ° C.
Resin C; B-OKP-2 (manufactured by Osaka Gas Chemical Co., Ltd., trade name), polyester resin, Tg: 150 ° C.
Resin D; OKP-850 (manufactured by Osaka Gas Chemical Co., Ltd., trade name), polyester resin, Tg: 151 ° C.
Resin E; Panlite (registered trademark) SP3810 (manufactured by Teijin Limited, trade name), polycarbonate resin, Tg: 150 ° C.
(Other transparent resins)
Resin F; BR50 (manufactured by Mitsubishi Rayon Co., Ltd., trade name), acrylic resin, Tg: 100 ° C.

The dye prepared above was uniformly dissolved in a transparent resin dissolved in cyclohexanone by 10% by mass with respect to the solid content concentration of the transparent resin. The obtained solution was applied onto a glass plate (D263: manufactured by SCHOTT, trade name) and dried to obtain a dye-containing resin layer having a film thickness of about 1 μm. The spectral transmittance curve of the dye-containing resin layer was obtained by using the spectral transmittance curve of the glass plate with the dye-containing resin layer and the spectral transmittance curve of the glass plate.

For the internal transmittance spectroscopy of the produced dye-containing resin layer, the wavelength range of 350 to 1200 nm was measured using an ultraviolet-visible near-infrared spectrophotometer, and the internal transmittance T [%] (= measured transmittance [%] / It was calculated using (100-measured reflectance [%]) × 100 [%]). The amount of the dye added (dye concentration) described in the table is the mass with respect to 100 parts by mass of the transparent resin when the internal transmittance of light at the maximum absorption wavelength λ _{max TR} is adjusted to 10% at a film thickness of 2 μm. It is a department.

From the spectral transmittance curve adjusted so that the light transmittance at the maximum absorption wavelength λ _maxTR is 10%, the average internal transmittance of light with a wavelength of 435 to 480 nm is T _AVE435-480TR , and the average of light with a wavelength of 490 to 560 nm. The internal transmittance T _AVE490-560TR and the average internal transmittance T _AVE590-630TR of light _having a wavelength of 590 to 630 nm were determined. The width WT _50% between the two wavelengths in the case of having two wavelengths having an internal transmittance of 50% in the wavelength region of 650 to 1150 nm was determined. In the table, the wavelength on the short wavelength side where the internal transmittance is 50% in the wavelength region of 650 to 1150 nm is shown by λ _SH 50%, and the wavelength on the long wavelength side is shown by λ _{LG 50%} .

It was dissolved in dichloromethane and the light absorption spectrum having a wavelength of 350 to 1200 nm was measured, and the maximum absorption wavelength λ _{max DCM} was obtained from the spectral transmittance curve. Further, from the spectral transmittance curve in which the dye concentration in dichloromethane was adjusted so that the light transmittance at the maximum absorption wavelength λ _{max DCM} was 10%, the average transmittance of light having a wavelength of 435 to 480 nm T _{AVE435-480 DCM} , The average transmittance of light having a wavelength of 490 to 560 nm T _{AVE490-560 DCM} and the average transmittance of light _having a wavelength of 590 to 630 nm T _{AVE590-630 DCM} were determined, and the difference from the average internal transmittance of the dye-containing resin layer was calculated. In the table, T _AVE _435-480 _DCM -T _AVE _{435-480 TR} is shown in the column of "Difference of T _{AVE 435-480} ". Likewise the _{T AVE490-560DCM} -T _AVE490-560TR the column "difference _{T AVE490-560"} showed _{T AVE590-630DCM} -T _AVE590-630TR the column "difference _{T AVE590-630".}

Further, FIG. 7 shows the spectral transmittance curves of the dye (A1a-5NS) in Test Example 2 in the transparent resin (P; resin A) and in dichloromethane. Further, FIG. 8 shows the spectral transmittance curves of the dye (A1a-5NS) in Test Example 19 in the transparent resin (resin F) and dichloromethane. The spectral transmittance curves of the dyes measured in the transparent resin in FIGS. 7 and 9 show the range of WT _50% with double- _headed arrows.

From Table 14, it can be seen that the combination of the NIR dye (A) and the transparent resin (P) of Test Examples 1 to 18 has the characteristics of (1-1) to (1-6). It can be seen that the NIR dye (A) is preferably a tris-type imonium dye in that the range of absorption of near-infrared light indicated by WT _50% is large. Further, NIR dye (A) is in terms difference in optical characteristics between dichloromethane solution and resin is small, Xa ^- is _{_{_{^{N [SO 2 CF 3] 2}}}} -, SbF 6 - or PF ₆ ^- are preferable, N It can be seen that [SO ₂ CF ₃ ] ₂ ^- is particularly preferable. As the transparent resin (P), it can be seen that the polyimide resin is preferable from the viewpoint that the visible light transmittance can be increased.

In Test Examples 19 to 23, since either the NIR dye or the transparent resin does not satisfy the requirements of the NIR dye (A) or the transparent resin (P), the characteristics of (1-1) to (1-6) are exhibited. It can be seen that 1 or more is not satisfied. Test Examples 24 to 28 are examples in which the dye (B1) is combined with a transparent resin that does not meet the requirements of the transparent resin (P) or the transparent resin (P), and the dye (B1) is a transparent resin such as a polyimide resin (B1). It can be seen that when combined with P), it functions preferably as the NIR dye (B).

[Examples 1 to 11; Manufacturing and evaluation of optical filters]
(Manufacturing of optical filters)
An optical filter having the same configuration as the optical filter 10B shown in FIG. 2 was manufactured and evaluated by the following method. Table 15 shows the configuration and evaluation results of the optical filter. Examples 1 to 7 are examples, and examples 8 to 11 are comparative examples.

In each example, as a transparent substrate, a CuO-containing borosilicate glass substrate (manufactured by AGC Co., Ltd., thickness 0.2 mm) or a 0.08 mm thick Teijin Pure Ace WRM5-80 (manufactured by Teijin Limited, product). Name, polycarbonate resin, Tg 215 ° C.) A resin substrate was used. In the table, "absorbent glass" and "PC resin" are described, respectively.

As the reflective layer, a dielectric multilayer film formed as follows was used. The dielectric multilayer film was formed by alternately laminating a total of 42 layers of TiO ₂ film and SiO ₂ film on one main surface of a transparent substrate by a vapor deposition method. The composition of the reflective layer is simulated by using the number of laminated dielectric multilayer films, the film thickness of TiO ₂ film, and the film thickness of SiO ₂ film as parameters, and light having a wavelength of 850 to 1100 nm in a spectral transmittance curve with an incident angle of 0 degrees. The design was such that the average transmittance of was 0.03%.

Further, on the main surface opposite to the surface on which the reflective layer of the transparent substrate was formed, the transparent resin shown in the table, NIR dye (A), NIR dye (B), NIR dye (C) (dye (I-). 12-23)) and other NIR dyes were combined to form an absorption layer with a thickness of about 2.0 μm. Here, in the dye (I-12-23), the maximum absorption wavelength λ _{max (C) TR} in the spectral transmittance curve having a wavelength of 350 to 1200 nm measured by being contained in the resin A is 714 nm.
The content of the dye in the table is the mass part of the dye with respect to 100 parts by mass of the transparent resin.

The following dyes (15), dyes (16) and dyes (17) were used as other NIR dyes. Here, the dye (15) has a maximum absorption wavelength λ _{max (A) TR} of 937 nm in a spectral transmittance curve having a wavelength of 350 to 1200 nm measured by being contained in the resin A, but the characteristic of (1-4). It is a pigment that does not satisfy. In the dye (16) and the dye (17), the maximum absorption wavelengths λ _maxTR in the spectral transmittance curve of the wavelengths of 350 to 1200 nm measured by being contained in the resin F are 839 nm and 771 nm, respectively.

[Synthesis of dye (15)]
Dye (15) was synthesized according to the reaction pathway shown below.

<Step b1>
2-Bromothiophene (9.00 g, 55.2 m mmol) and magnesium (4.03 g, 165 mmol) were placed in a flask and dissolved in anhydrous tetrahydrofuran (55 mL) under a nitrogen atmosphere. The mixed solution was stirred at 80 ° C. for 1 hour. [1,3-Bis (diphenylphosphino) propane] nickel (II) dichloride (1.20 g, 2.21 mmol) and 2,3-dibromothiophene (12.7 g, 52.5 mmol) are placed in a separate flask and anhydrous. It was dissolved in diethyl ether (110 mL). The diethyl ether mixture was cooled to 0 ° C., the tetrahydrofuran mixture was added dropwise, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, water (55 mL) was added to the mixed solution, extracted with ethyl acetate, the organic layer was washed with saturated brine, the solvent was removed, and intermediate A3-11 (hexane) was used for column chromatography (hexane). 8.93 g, yield 66%) was obtained.

<Step b2>
Intermediate A3-11 (8.09 g, 33 mmol) obtained in step b1 was placed in a flask and dissolved in anhydrous diethyl ether (230 mL) under a nitrogen atmosphere. The solution was cooled to −78 ° C., a 1.6 M solution of normal butyllithium in hexane (20 mL, 32.0 mmol) was added dropwise, and the mixture was stirred for 1 hour. Subsequently, an anhydrous diethyl ether solution (120 mL) in which benzophenone (6.56 g, 36.0 mmol) was dissolved was added dropwise. The mixed solution was stirred at room temperature for one day and night. After completion of the reaction, saturated aqueous ammonium chloride solution (200 mL) was added, and the mixture was extracted with diisoprovir ether. The obtained organic layer was washed with saturated brine, the solvent was removed, and intermediate A3-12 (8.81 g, 77% yield) was obtained by column chromatography (hexane: dichloromethane = 1: 1).

<Step b3>
Intermediate A3-12 (4.94 g, 14.4 mmol) obtained in step b2 and Amberlist 15 (2.30 g) were placed in a flask and dissolved in anhydrous toluene (300 mL) under a nitrogen atmosphere. The mixed solution was refluxed and stirred for 7 hours. After completion of the reaction, the mixture was filtered to obtain a filtrate, the solvent was removed, and intermediate A3-13 (4.29 g, 91%) was obtained by column chromatography (hexane: dichloromethane = 2: 1).

<Step b4>
Intermediate A3-13 (4.00 g, 12.1 mmol) obtained in step b3 was placed in a flask and dissolved in anhydrous dimethylformamide (120 mL) under a nitrogen atmosphere. Anhydrous dimethylformamide solution (30 mL) in which N-bromosuccinimide (2.16 g, 12.1 mmol) was dissolved was added dropwise to the solution. The mixture was stirred at room temperature for 24 hours. After completion of the reaction, the mixture was poured into ice water and extracted with diisopropyl ether. The obtained organic layer was washed with saturated brine to remove the solvent, and then intermediate A3-14 (3.67 g, yield 74%) was obtained by column chromatography (dichloromethane).

<Step b5>
Intermediate A3-14 (3.50 g, 8.55 mmol) obtained in step b4 and shaving magnesium (0.416 g, 17.1 mmol) were placed in a flask and dissolved in anhydrous tetrahydrofuran (20 ml) under a nitrogen atmosphere. .. The solution was refluxed for 3 hours and cooled to −40 ° C. In a separate flask, N-chlorosuccinimide (1.03 g, 7.70 mmol) is dissolved in anhydrous toluene (20 ml) under a nitrogen atmosphere, and bis- (2-ethylhexyl) amine (1.86 g, 7.70 mmol) is added. , Stirred for 20 minutes.

Tetraisopropyl orthotitanium (2.43 g, 8.55 mmol) was added dropwise to a mixed solution cooled to -40 ° C, and the mixture was stirred for 5 minutes, followed by mixing N-chlorosuccinimide and bis- (2-ethylhexyl) amine. The solution was added dropwise. The mixture was stirred at room temperature for 3 hours, and after completion of the reaction, a saturated aqueous potassium carbonate solution (17 ml) was added. It was subsequently diluted with ethyl acetate and filtered, and the resulting solution was extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, the solvent was removed, and intermediate A3-15 (1.34 g, yield 27.5%) was obtained by column chromatography (hexane: triethylamine = 100: 3). It was.

<Step b6>
The intermediate A3-15 (1.30 g, 2.28 mmol) obtained in step b5 and 3,4-dihydroxy-3-cyclobutene-1,2-dione (0.130 g, 1.14 mmol) were placed in a flask. It was dissolved in a mixed solution of normal butanol (6 ml) and toluene (6 ml) under a nitrogen atmosphere. The mixture was stirred under reflux for 3 hours, the solvent was removed after the reaction was completed, and the dye (15) (0.445 g, yield 32%) was obtained by column chromatography (dichloromethane: methanol: triethylamine = 100: 1: 3). It was.

[Synthesis of dye (16) and dye (17)]
J. Heterocyclic. Chem. , 42, 959, (2005), and the dye (16) and the dye (17) were synthesized by the method described in (2005).

(Evaluation)
<Optical characteristics of absorption layer>
A spectral transmittance curve with an incident angle of 0 degrees was obtained for the absorption layers of the obtained optical filters of Examples 1 to 11. In the spectral transmittance curve, when the average OD value is 1 in the wavelength region of the maximum absorption wavelength λ _{max (A) TR} ± 10 nm of the NIR dye (A), the average internal transmittance _TAVE435 in the wavelength region of 435 to 480 nm. _-480 (AL), the average internal transmittance _{T AVE490-560} in the wavelength region of 490 ~ 560nm (AL), determine the average internal transmittance _{T AVE590-630 (AL)} in the wavelength region of 590 ~ 630 nm.

Further, when the average OD value is 1 in the wavelength region of the maximum absorption wavelength λ _{max (A) TR} ± 10 nm of the NIR dye (A), the wavelength λ at which the internal transmittance is 50% in the wavelength region of 600 to 800 nm. The total width of the wavelength range in which the internal transmittance is 30% or less in the wavelength region of _50% and 600 to 1200 nm (“T _30% or less width” in the table) was determined. The table also shows the transmittance T _{500 at} a wavelength of ₅₀₀ nm and the transmittance T ₆₀₀ at a wavelength of 600 nm.

<Optical characteristics of optical filter>
Further, for the obtained optical filters of Examples 1 to 11, the spectral transmittance curves at incident angles of 0 degrees, 30 degrees and 50 degrees were obtained, and the following optical characteristics were obtained.

Maximum absorption wavelength of NIR dye (A) at 0 degree incident angle λ _{max (A)} Minimum OD value in wavelength region of _TR ± 10 nm, average transmittance _{TAVE435-480 (0 °)} in wavelength region of 435 to 480 nm, 490 average transmittance _{T AVE490-560 (0 °)} in the wavelength region of ~ 560 nm, the average transmittance _{T AVE590-630 (0 °)} in the wavelength region of 590 ~ 630 nm, the transmittance in a wavelength range of 600 ~ 800 nm 50% The wavelength λ _{50% (0 °)} to be obtained was determined.

The maximum absorption wavelength of the NIR dye (A) at an incident angle of 30 degrees, the minimum OD value in the wavelength region of λ _{max (A) TR} ± 10 nm, and the transmittance of 50% at an incident angle of 0 degrees in the wavelength region of 600 to 800 nm. Absolute value of the difference between the wavelength λ _{50% (0 °)} and the wavelength λ _{50% (30 °)} at which the transmittance is 50% at an incident angle of 30 ° | λ _{50% (30 °)} −λ _{50% (0 °) )} | | The average transmittance _{TAVE490-560 (30 °)} in the wavelength region of 490 to 560 nm was determined.

The maximum absorption wavelength of the NIR dye (A) at an incident angle of 50 degrees, the minimum OD value in the wavelength region of λ _{max (A) TR} ± 10 nm, and the transmittance of 50% at an incident angle of 0 degrees in the wavelength region of 600 to 800 nm. Absolute value of the difference between the wavelength λ _{50% (0 °)} and the wavelength λ _{50% (50 °)} at which the transmittance is 50% at an incident angle of 50 ° | λ _{50% (50 °)} -λ _{50% (0 °) )} | | The average transmittance _{TAVE490-560 (50 °)} in the wavelength region of 490 to 560 nm was determined.

Further, the spectral transmittance curves of the absorption layer and the optical filter in the optical filter of the examples of FIG. 9, FIG. 10, FIG. 11, FIG. 11, FIG. 12, Example 4, FIG. 13 and FIG. Shown. 15 and 16 show the absorption layer and the spectral transmittance curve of the optical filter in the optical filter of the comparative example of Example 8. In the figure of the spectral transmittance curve of the absorption layer of each example, the "width of T _30% or less" is indicated by W or Wa and Wb. In Examples 4, 6 and 8, the "width of T _30% or less" is the sum of Wa and Wb.

From Table 15 and FIGS. 10, 12, and 14, in the optical filters of the examples of Examples 1 to 7, the transmittance of visible light, particularly the transmittance of green and red, can be maintained sufficiently high, and the transmittance of near-infrared light can be maintained. It can be seen that the shielding property is particularly excellent in the shielding property of long-wavelength near-infrared light.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on June 20, 2019 (Japanese Patent Application No. 2019-114575), the contents of which are incorporated herein by reference.

The optical filter of the present invention can maintain a sufficiently high transmittance of visible light, particularly green and red, and is particularly excellent in shielding near-infrared light, especially long-wavelength near-infrared light. According to the present invention, it is possible to provide an image pickup device and an optical sensor having excellent color reproducibility and durability using the optical filter.

10A, 10B, 10C, 10D, 10E, 10F ... Optical filter, 11, 11a, 11b ... Absorption layer, 12, 12a, 12b ... Reflective layer, 13 ... Transparent substrate, 14 ... Antireflection layer.

Claims

It is composed of a transparent resin having a glass transition point of 130 ° C. or higher, an absorption layer containing a near-infrared absorbing dye (A) that satisfies all of the following requirements (1-1) to (1-6), and a dielectric multilayer film. An optical filter having a reflective layer.
(1-1) In the spectral transmittance curve SC TR having a wavelength of 350 to 1200 nm measured by containing the near-infrared absorbing dye (A) in the transparent resin, the maximum absorption wavelength λ max (A) TR is 850 to 1100 nm. It is in the wavelength range of.
(1-2) Average internal transmittance of light having a wavelength of 490 to 560 nm when the internal transmittance at the maximum absorption wavelength λ max (A) TR is 10% in the spectral transmittance curve SC TR T AVE490-560 (A) TR is 90% or more.
(1-3) Average internal transmittance of light having a wavelength of 590 to 630 nm when the internal transmittance at the maximum absorption wavelength λ max (A) TR is 10% in the spectral transmittance curve SC TR T AVE590-630 (A) TR is 90% or more.
(1-4) The spectral transmittance curve SC TR has an internal transmittance of 50% in a wavelength region of 650 to 1150 nm, where the internal transmittance at the maximum absorption wavelength λ max (A) TR is 10%. It has two wavelengths, and the width between the two wavelengths is 180 nm or more.
(1-5) the transmittance of light at the maximum absorption wavelength lambda max (A) DCM in the spectral transmittance curve SC DCM wavelength 350 ~ 1200 nm to be measured the near-infrared absorbing dye (A) was dissolved in dichloromethane The value obtained by subtracting the average internal transmittance T AVE490-560 (A) TR from the average transmittance T AVE490-560 (A) DCM of light having a wavelength of 490 to 560 nm at 10% is 10% or less.
(1-6) Maximum absorption wavelength λ max (A) in the spectral transmittance curve SC DCM The average transmittance of light having a wavelength of 590 to 630 nm when the transmittance of light in DCM is 10% T AVE590-630 ( A) The value obtained by subtracting the average internal transmittance T AVE590-630 (A) TR from DCM is 10% or less.
The optical filter according to claim 1, wherein the near-infrared absorbing dye (A) further satisfies one or more selected from the following (1-7) to (1-9).
(1-7) Maximum absorption wavelength λ max (A) in the spectral transmittance curve SC DCM The average transmittance of light having a wavelength of 435 to 480 nm when the transmittance of light in DCM is 10% T AVE435-480 ( A) From DCM , the average internal transmittance of light with a wavelength of 435 to 480 nm when the internal transmittance at the maximum absorption wavelength λ max (A) TR in the spectral transmittance curve SC TR is 10% T AVE435-480. (A) The value obtained by subtracting TR is 10% or less.
(1-8) The value obtained by subtracting the average internal transmittance T AVE490-560 (A) TR from the average transmittance T AVE490-560 (A) DCM is 5% or less.
(1-9) The value obtained by subtracting the average internal transmittance T AVE590-630 (A) TR from the average transmittance T AVE590-630 (A) DCM is 5% or less.
The optical filter according to claim 1 or 2, wherein the near-infrared absorbing dye (A) is at least one selected from the compound represented by the formula (A1) below and the compound represented by the formula (A2) below.

The symbols in the formulas (A1) and (A2) are as follows.
R 201 to R 206 and R 221 to R 226 have independent hydrogen atoms, halogen atoms, sulfo groups, hydroxy groups, cyano groups, nitro groups, carboxyl groups, phosphate groups, and oxygen atoms between carbon atoms. The alkyl group or alkoxy group having 1 to 20 carbon atoms which may be substituted, or the aryl group having 6 to 14 carbon atoms and the aralkyl group having 7 to 14 carbon atoms which may be substituted, may be substituted. Alternatively, it is a heterocyclic group having 3 to 14 members. However, groups in which a substituted or unsubstituted amino group is bonded to a phenyl group are excluded. Further, in R 201 to R 206 and R 221 to R 226 , two groups bonded to the same nitrogen atom may be bonded to each other to form a heterocycle having 3 to 8 members together with the nitrogen atom. The hydrogen atom bonded to the ring may be substituted with an alkyl group having 1 to 12 carbon atoms.
R 207 to R 218 and R 227 to R 238 are independently substituted with a hydrogen atom, a halogen atom, an optionally substituted amino group, an amide group, a cyano group, a nitro group, a carboxyl group, or a halogen atom. It is an alkyl group or an alkoxy group having 1 to 12 carbon atoms which may be used. In R 207 to R 218 and R 227 to R 238 , the two groups adjacent to each other may be bonded to each other to form a ring having 3 to 8 members together with the two carbon atoms of the phenyl group. The hydrogen atom to be bonded may be substituted with an alkyl group having 1 to 12 carbon atoms.
Also, R 201 and R 207 , R 202 and R 210 , R 203 and R 211 , R 204 and R 214 , R 205 and R 215 , R 206 and R 218 , R 221 and R 227 , R 222 and R 230 , R 223 and R 231 and R 224 and R 234 , R 225 and R 235 , and R 226 and R 238 are 4 members together with a nitrogen atom bonded to a phenyl group and two carbon atoms of the phenyl group. A heterocycle of to 8 may be formed, and the hydrogen atom bonded to the ring may be substituted with an alkyl group having 1 to 12 carbon atoms.
Xa - and Xb - each independently represents a monovalent anion.
The near infrared absorbing dye (A), the represented by formula (A1), wherein Xa - is N [SO 2 CF 3] 2 -, SbF 6 - or PF 6 -, compound, and the formula (A2) The optical filter according to claim 3, wherein the optical filter according to claim 3 is at least one selected from the compounds in which Xb − is N [SO 2 CF 3 ] 2 − , SbF 6 − or PF 6 − .
The optical filter according to any one of claims 1 to 4, wherein the transparent resin is at least one selected from a polyimide resin, a polyester resin, a polycarbonate resin, a cycloolefin resin, and an epoxy resin.
The optical filter according to any one of claims 1 to 5, wherein the transparent resin is a polyimide resin.
The absorption layer further contains a near-infrared absorbing dye (B) having a maximum absorption wavelength in the wavelength region of 1100 to 1200 nm in a spectral transmittance curve having a wavelength of 350 to 1200 nm measured by being contained in the transparent resin. Item 2. The optical filter according to any one of Items 1 to 6.
The optical filter according to claim 7, wherein the near-infrared absorbing dye (B) contains at least one selected from the compound represented by the formula (B1) below and the compound represented by the formula (B2) below.

The symbols in the formulas (B1) and (B2) are as follows.
R 241 to R 248 and R 261 to R 268 are independently unsaturated bonds between hydrogen atom, halogen atom, sulfo group, hydroxy group, cyano group, nitro group, carboxyl group, phosphoric acid group and carbon atom. Alternatively, an alkyl group or an alkoxy group having 1 to 20 carbon atoms which may have an oxygen atom or may be substituted, or an aryl group having 6 to 14 carbon atoms and 7 to 14 carbon atoms which may be substituted. Alkoxy group, or a heterocyclic group having 3 to 14 members. In R 241 to R 248 and R 261 to R 268 , two groups bonded to the same nitrogen atom may be bonded to each other to form a heterocycle having 3 to 8 members together with the nitrogen atom. The hydrogen atom bonded to may be substituted with an alkyl group having 1 to 12 carbon atoms.
R 249 to R 253 and R 269 to R 273 are independently hydrogen atoms, halogen atoms, optionally substituted amino groups, amide groups, cyano groups, nitro groups, carboxyl groups, or halogen atoms. It is an alkyl group or an alkoxy group having 1 to 12 carbon atoms which may be substituted. The four R 249 to R 253 and R 269 to R 273, respectively, may be the same or different.
Xc - and Xd - each independently represents a monovalent anion.
The absorption layer contains a near-infrared absorbing dye (C) which is a squarylium dye having a maximum absorption wavelength in a wavelength region of 630 to 750 nm in a spectral transmittance curve having a wavelength of 350 to 1200 nm measured by containing it in the transparent resin. The optical filter according to any one of claims 1 to 8 further contained.
The absorption layer has the following (2-1) and (2-2) when the average OD value is 1 in the wavelength region of the maximum absorption wavelength λ max (A) TR ± 10 nm of the near-infrared absorbing dye (A). The optical filter according to any one of claims 1 to 9, which satisfies).
(2-1) The average internal transmittance TAVE490-560 (AL) in the wavelength region of 490 to 560 nm is 88% or more.
(2-2) The average internal transmittance TAVE590-630 (AL) in the wavelength region of 590 to 630 nm is 70% or more.
The absorption layer has the following (2-3) and (2-4) when the average OD value is 1 in the wavelength region of the maximum absorption wavelength λ max (A) TR ± 10 nm of the near-infrared absorbing dye (A). The optical filter according to claim 10, which satisfies one or more selected from).
(2-3) It has a wavelength λ 50% at which the internal transmittance is 50% in the wavelength region of 600 to 700 nm.
(2-4) In the wavelength region of 600 to 1200 nm, the total width of the wavelength region in which the internal transmittance is 30% or less is 250 nm or more.
The optical filter according to any one of claims 1 to 11, further comprising a transparent substrate, wherein the absorption layer and the reflection layer are each provided on the main surface of the transparent substrate.
The optical filter according to claim 12, wherein the transparent substrate is made of transparent resin or glass.
The optical filter according to claim 13, wherein the glass is a fluoride-based glass to which copper ions are added, or a phosphate-based glass to which copper ions are added.
The optical filter according to any one of claims 1 to 14, which satisfies all the following requirements (3-1) to (3-3) in the optical characteristics measured at an incident angle of 0 degrees.
(3-1) The minimum OD value of the near-infrared absorbing dye (A) in the wavelength region of the maximum absorption wavelength λ max (A) TR ± 10 nm is 4 or more.
(3-2) The average transmittance TAVE490-560 (0 °) in the wavelength region of 490 to 560 nm is 82% or more.
(3-3) The average transmittance TAVE590-630 (0 °) in the wavelength region of 590 to 630 nm is 50% or more.
The optical filter according to claim 15, further satisfying all the requirements (3-4) to (3-9) below.
(3-4) 600 in the wavelength region of ~ 800 nm, the wavelength lambda 50% of transmittance is 50% at an incident angle of 0 degrees (0 °) and the transmittance at an incident angle of 30 degrees is 50% wavelength lambda 50% The absolute value of the difference (30 °) | λ 50% (30 °) −λ 50% (0 °) | is 5 nm or less.
(3-5) The average transmittance TAVE490-560 (30 °) in the wavelength region of 490 to 560 nm measured at an incident angle of 30 degrees is 80% or more.
(3-6) The minimum OD value in the wavelength region of the maximum absorption wavelength λ max (A) TR ± 10 nm of the near-infrared absorbing dye (A) measured at an incident angle of 30 degrees is 3 or more.
(3-7) 600 in the wavelength region of ~ 800 nm, the wavelength lambda 50% of transmittance is 50% at an incident angle of 0 degrees (0 °) and the transmittance at an incident angle of 50 degrees is 50% wavelength lambda 50% The absolute value of the difference of (50 °) | λ 50% (50 °) −λ 50% (0 °) | is 15 nm or less.
(3-8) The average transmittance TAVE490-560 (50 °) in the wavelength region of 490 to 560 nm measured at an incident angle of 50 degrees is 70% or more.
(3-9) The minimum OD value in the wavelength region of the maximum absorption wavelength λ max (A) TR ± 10 nm of the near-infrared absorbing dye (A) measured at an incident angle of 50 degrees is 3 or more.
An imaging device including the optical filter according to any one of claims 1 to 16.
An optical sensor including the optical filter according to any one of claims 1 to 16.