Optical filter and image capturing device

Abstract

To provide an optical filter which offers superior near-infrared shielding capability, in particular, long-wavelength near-infrared shielding capability, while maintaining good visible light transmissivity.SOLUTION: An optical filter comprises an absorptive layer containing a near-infrared absorbing dye (A) and a transparent resin, and a reflective layer consisting of a dielectric multilayer film, where the near-infrared absorbing dye satisfies specific characteristics (i-1) to (i-3) and contains at least one of a specific cyanine compound and a squarylium dye, and the transparent resin satisfies the specific characteristics (i-3) in relation to the near-infrared absorbing dye (A).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an optical filter that transmits light in the visible wavelength region and blocks light in the near-infrared wavelength region, and an imaging device including the optical filter.

Background Art

[0002] In an imaging device using a solid-state imaging device, an optical filter that transmits light in the visible region (hereinafter also referred to as "visible light") and blocks light in the near-infrared region (hereinafter also referred to as "near-infrared light") is used in order to reproduce good color tones and obtain a clear image. As such an optical filter, a near-infrared cut filter including an absorption layer containing a near-infrared absorber and a reflection layer composed of a dielectric multilayer film that blocks near-infrared light is known. That is, since the spectral transmittance curve of the dielectric multilayer film itself changes depending on the incident angle, a near-infrared cut filter including both a reflection layer and an absorption layer can obtain a spectral transmittance curve in which the incident angle dependence is suppressed by the absorption characteristics of the absorption layer.

[0003] In recent years, in various devices equipped with such imaging devices, optical components using laser light having a wavelength of 850 to 1100 nm are often mounted together. Therefore, in the near-infrared cut filter, there is a demand for a characteristic of sufficiently cutting long-wavelength near-infrared light having a wavelength of 850 to 1100 nm while suppressing a decrease in the transmittance of visible light.

[0004] In near-infrared cut filters, conventionally, many techniques using absorbers that exhibit absorption in a relatively long wavelength region are known. Specifically, techniques such as combining squarylium dyes with cyanine dyes, phthalocyanine dyes, etc. (see, for example, Patent Documents 1 and 2), using diimonium dyes, metal dithiolate complexes, inorganic fine particles, etc. (see, for example, Patent Documents 3, 4, and 5) are known.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

[0006] However, none of the above near-infrared cut filters can achieve both high visible light transmittance and high shielding property in the long wavelength region of 850 to 1100 nm in wavelength.

[0007] An object of the present invention is to provide an optical filter that maintains good visible light transmittance and is excellent in shielding property of near-infrared light, particularly long-wavelength near-infrared light, and an imaging device having excellent color reproducibility using the optical filter. [Means for Solving the Problems]

[0008] An optical filter according to an aspect of the present invention includes an absorption layer containing a near-infrared absorbing dye (A) and a transparent resin, and a reflection layer made of a dielectric multilayer film, wherein the near-infrared absorbing dye (A) satisfies all of the following (i-1) to (i-3), and includes at least one of a cyanine compound represented by any of the following formulas (ACi1) to (ACii2) and a squarylium dye represented by the following formula (ASi), and the transparent resin satisfies the following (i-3) in relation to the near-infrared absorbing dye (A). (i-1) In an absorbance curve at wavelengths of 350 to 1200 nm measured by dissolving in dichloromethane, the maximum absorption wavelength λ max(A)DCM is in the wavelength range of 850 to 1100 nm. In the absorbance curve measured by dissolving in dichloromethane and having a wavelength range of 350 to 1200 nm, the maximum absorption wavelength is λ max(A)DCM The absorbance at is ABS λmax(A)DCM The absorbance at a wavelength of 400 nm is ABS 400(A)DCM The absorbance at a wavelength of 550 nm is ABS 550(A)DCM When this is the case, the following formulas (1) and (2) are satisfied. ABS 400(A)DCM / ABS λmax(A)DCM <0.10 …(1) ABS 550(A)DCM / ABS λmax(A)DCM <0.04 …(2) (i-3) In the absorbance curve measured by incorporating into the transparent resin and having a wavelength range of 350 to 1200 nm, the maximum absorption wavelength λ max(A)TR is in the wavelength range of 850 to 1100 nm, and the maximum absorption wavelength λ max(A)TR The absorbance at is ABS λmax(A)TR The absorbance at a wavelength of 400 nm is ABS 400(A)TR The absorbance at a wavelength of 550 nm is ABS 550(A)TR When this is the case, the following formulas (3) and (4) are satisfied. ABS 400(A)TR / ABS λmax(A)TR <0.15 …(3) ABS 550(A)TR / ABS λmax(A)TR <0.10 …(4)

[0009]

Chemical formula

[0010] However, the symbols in formulas (ACi1) to (ACii2) are as follows. R 101 ~R 107 、R 121 ~R 127 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR 112 R 113 group, -NHSO2R 114 group, -NHCOR 115Group, -SR 116 Group, -SO2R 117 Group, -OSO2R 118 Group, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. R 102 ~R 107 and R 122 ~R 127 Two adjacent ones of them may be linked to each other to form a 5-membered ring, a 6-membered ring, or a 7-membered ring. R 130a is a hydrogen atom, a methyl group, or a phenyl group. R 130b is a hydrogen atom, a methyl group, a phenyl group, or a diphenylamino group. R 112 ~R 118 are each independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. A plurality of R's contained in each formula 101 ~R 107 , R 121 ~R 127 may be the same as or different from each other. X - represents a monovalent anion.

[0011]

Chemical formula

[0012] However, the symbols in formula (ASi) are as follows. R 161 is a branched alkyl group having 3 to 20 carbon atoms, or a straight-chain alkyl group having 13 to 20 carbon atoms. R 162 ~R 167 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR112 R 113 group, -NHSO2R 114 group, -NHCOR 115 group, -SR 116 group, -SO2R 117 group, -OSO2R 118 group, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. R 112 ~R 118 each independently represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. Multiple Rs included in each formula 161 ~R 167 may be the same as or different from each other.

[0013] The present invention also provides an imaging device including the optical filter of the present invention.

Advantages of the Invention

[0014] According to the present invention, while maintaining good visible light transmittance, in terms of the shielding property of near-infrared light, an optical filter excellent in the shielding property of particularly long-wavelength near-infrared light can be obtained. Furthermore, according to the present invention, an imaging device excellent in color reproducibility using the optical filter can be provided.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] 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 formula (I) is referred to as compound (I). The same applies to compounds represented by other formulas. The dye composed of compound (I) is also referred to as dye (I), and the same applies to other dyes. For example, the compound represented by formula (ACi) described later is referred to as compound (ACi), and the dye composed of the compound is also referred to as dye (ACi). Further, for example, the group represented by formula (1x) is also referred to as group (1x), and the same applies to groups represented by other formulas.

[0017] In the present specification, for a specific wavelength range, a transmittance of, for example, 90% or more means that the transmittance does not fall below 90% over the entire wavelength range. Similarly, a transmittance of, for example, 1% or less means that the transmittance does not exceed 1% over the entire wavelength range. The average transmittance in a specific wavelength range is the weighted average of the transmittances every 1 nm in the wavelength range. In the present specification, "~" representing a numerical range includes the upper and lower limits. In the present specification, when there are a plurality of substituents represented by the same symbol in a general formula, the plurality of substituents may be the same as or different from each other.

[0018] <Optical Filter> The optical filter according to an embodiment of the present invention (hereinafter, also referred to as "this filter") has an absorption layer containing a dye (A) which is an NIR dye satisfying the following (i-1) to (i-3) and a transparent resin, and a reflective layer.

[0019] (i-1) The maximum absorption wavelength λ of the pigment (A) in the absorbance curve measured in dichloromethane in the wavelength range of 350 to 1200 nm max(A)DCM is in the wavelength range of 850 to 1100 nm.

[0020] (i-2) When the absorbance at the maximum absorption wavelength λ of the pigment (A) in the absorbance curve measured in dichloromethane in the wavelength range of 350 to 1200 nm is ABS max(A)DCM , the absorbance at a wavelength of 400 nm is ABS λmax(A)DCM , and the absorbance at a wavelength of 550 nm is ABS 400(A)DCM , the following formulas (1) and (2) are satisfied. 550(A)DCM ABS / ABS 400(A)DCM / ABS λmax(A)DCM <0.10 …(1) ABS 550(A)DCM / ABS λmax(A)DCM <0.04 …(2)

[0021] (i-3) The maximum absorption wavelength λ of the pigment (A) in the absorbance curve measured after being incorporated into the above transparent resin in the wavelength range of 350 to 1200 nm is in the wavelength range of 850 to 1100 nm, and when the absorbance at the maximum absorption wavelength λ is ABS max(A)TR , the absorbance at a wavelength of 400 nm is ABS max(A)TR , and the absorbance at a wavelength of 550 nm is ABS λmax(A)TR , the following formulas (3) and (4) are satisfied. 400(A)TR ABS 550(A)TR / ABS / ABS 400(A)TR / ABS λmax(A)TR <0.15 …(3) ABS 550(A)TR / ABS λmax(A)TR <0.10 …(4)

[0022] This filter contains the pigment (A) having the characteristics of (i-1) to (i-3) in the absorption layer and a transparent resin, so that it has excellent light-shielding properties in the long wavelength region of near-infrared light and high transmittance of visible light.

[0023] The coloring agent (A) preferably further has the following property (i-4). (i-4) The coloring agent (A) satisfies the following formulas (5) and (6). ABS 400(A)TR / ABS λmax(A)TR -ABS 400(A)DCM / ABS λmax(A)DCM <0.10 …(5) ABS 550(A)TR / ABS λmax(A)TR -ABS 550(A)DCM / ABS λmax(A)DCM <0.08 …(6)

[0024] Note that the absorbance curve of the coloring agent (A) at wavelengths of 350 to 1200 nm measured by dissolving the coloring agent (A) in dichloromethane is the absorbance curve when the addition amount of the coloring agent (A) is adjusted so that the absorbance at the maximum absorption wavelength λ max(A)DCM is 1, that is, the light transmittance is 10%. Similarly, the absorbance curve of the coloring agent (A) at wavelengths of 350 to 1200 nm measured by containing the coloring agent (A) in the transparent resin is the absorbance curve when the addition amount of the coloring agent (A) is adjusted so that the absorbance at the maximum absorption wavelength λ max(A)TR is 1, that is, the light transmittance is 10%.

[0025] The coloring agent (A) preferably further has the following property (i-5). (i-5) When the coloring agent (A) is contained in the above transparent resin, the mass absorption coefficient is 1000 / (cm·mass%) or more. Note that the mass absorption coefficient is calculated by calculating the internal light transmittance T [%] (= measured transmittance [%] / (100 - measured reflectance [%]) × 100 [%]) at the maximum absorption wavelength in the wavelength range of 350 to 1200 nm, and -log 10 (T / 100). Hereinafter, unless otherwise specified, the "mass absorption coefficient" of the coloring agent is the mass absorption coefficient calculated by the above method.

[0026] 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. This filter may have the absorption layer and the reflection layer on the same main surface of the transparent substrate, or on different main surfaces. When having the absorption layer and the reflection layer on the same main surface, the lamination order thereof is not particularly limited.

[0027] This filter may also have other functional layers. Examples of the other functional layers include an antireflection layer that suppresses the transmittance loss of visible light. In particular, when the absorption layer has the outermost surface configuration, since visible light transmittance loss due to reflection occurs at the interface between the absorption layer and air, it is preferable to provide an antireflection layer on the absorption layer.

[0028] Next, a configuration example of this filter will be described with reference to the drawings. FIG. 1 is a configuration example of an optical filter 10A having a reflection layer 12 on one main surface of an absorption layer 11. In the optical filter 10A, the absorption layer 11 can be composed of a layer containing a dye (A) and a transparent resin. Note that "having a reflection layer 12 on one main surface (upper surface) of the absorption layer 11" is not limited to the case where the reflection layer 12 is provided in contact with the absorption layer 11, and also includes the case where another functional layer is provided between the absorption layer 11 and the reflection layer 12, and the same applies to the following configurations.

[0029] FIG. 2 is a cross-sectional view schematically showing an example of an optical filter according to an embodiment having a transparent substrate, an absorption layer, and a reflection layer. The optical filter 10B has a transparent substrate 13, an absorption layer 11 disposed on one main surface of 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 be composed of a layer containing a dye (A) and a transparent resin.

[0030] FIG. 3 is a configuration example of an optical filter 10C having an absorption layer 11 and reflection layers 12a and 12b on both main surfaces of the absorption layer 11, respectively. FIG. 4 is a configuration example of an optical filter 10D having an absorption layer 11 on one main surface of a 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. FIG. 5 is a configuration example of an optical filter 10E including absorption layers 11a and 11b on both main surfaces of a transparent substrate 13, and further including reflection layers 12a and 12b on the main surfaces of the absorption layers 11a and 11b.

[0031] In FIGS. 3, 4, and 5, the two reflection layers 12a and 12b to be combined may be the same or different. For example, the reflection layers 12a and 12b reflect ultraviolet light and near-infrared light, and have the property of transmitting visible light, and the reflection layer 12a reflects ultraviolet light and light in the first near-infrared region, and the reflection layer 12b may be configured to reflect ultraviolet light and light in the second near-infrared region.

[0032] Also, in FIG. 4, the two 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 each be a combination of a near-infrared absorption layer and an ultraviolet absorption layer, or a combination of an ultraviolet absorption layer and a near-infrared absorption layer.

[0033] FIG. 6 is a configuration example of an optical filter 10F including an antireflection layer 14 on the main surface of the absorption layer 11 of the optical filter 10B shown in FIG. 2. When there is no reflection layer provided and the absorption layer forms the outermost surface configuration, it is preferable to provide an antireflection layer on the absorption layer. Note that the antireflection layer may be configured to 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.

[0034] Hereinafter, the absorption layer, reflection layer, transparent substrate, and antireflection layer will be described. (Absorption layer) The absorption layer contains a dye (A) having the characteristics of (i-1) to (i-3) above, and preferably further having the characteristic of (i-4) above, and a transparent resin.

[0035] Typically, the absorption layer is a layer in which the dye (A) is uniformly dissolved or dispersed in a transparent resin, or It is a (resin) substrate. The absorption layer may contain other NIR dyes in addition to the dye (A) as long as the effects of the present invention are not impaired. Further, the absorption layer may contain dyes other than NIR dyes, particularly UV dyes, as long as the effects of the present invention are not impaired.

[0036] As the other NIR dyes, it is preferable to contain a dye (D) that satisfies the following requirements (v-1) and (v-2). (v-1) In the absorbance curve at wavelengths of 350 to 1200 nm measured by incorporating the dye (D) into the above transparent resin, the maximum absorption wavelength λ max(D)TR is in the wavelength range of 650 to 750 nm. (v-2) The dye (D) is represented by any of the following formulas (I) to (III).

[0037] Furthermore, it is preferable that the dye (D) satisfies the following requirement (v-3). (v-3) In the spectral transmittance curve measured by incorporating the dye (D) into the above transparent resin at a concentration at which the transmittance at the maximum absorption wavelength λ max(D)TR is 10%, the average transmittance of light in the wavelength range of 400 to 500 nm is 85% or more.

[0038] Also, in the spectral transmittance curve of the internal transmittance at wavelengths of 350 to 1200 nm measured by incorporating the dye (D) into the above transparent resin, the absorption peak having the absorption peak at λ max(D)TR (hereinafter referred to as the "absorption peak of λ max(D)TR ) has a steep slope on the visible light side, that is, the wavelength from a transmittance of 70% to a transmittance of 20% in the slope on the visible light side is preferably 60 nm or less, more preferably 50 nm or less.

[0039] [Dye (A)] In (i-1), the dye (A) has a maximum absorption wavelength λ max(A)DCM in the wavelength range of 850 to 1100 nm. The maximum absorption wavelength λ max(A)DCM is preferably in the wavelength range of 860 to 1000 nm.

[0040] The coloring agent (A) satisfies the formula (1) and the formula (2) in (i-2). In the formula (1), " 400(A)DCM / λmax(A)DCM " indicates the value of the ratio of λmax(A)DCM to 400(A)DCM . That is, it indicates the value of λmax(A)DCM when 400(A)DCM is set to 1. The same applies to the following formulas (2) to (4). According to the formula (1), 400(A)DCM / λmax(A)DCM is less than 0.10. 400(A)DCM / λmax(A)DCM is preferably 0.08 or less, and more preferably 0.04 or less.

[0041] According to the formula (2), 550(A)DCM / λmax(A)DCM is less than 0.04. 550(A)DCM / λmax(A)DCM is preferably 0.03 or less, and more preferably 0.02 or less.

[0042] The coloring agent (A) has a maximum absorption wavelength λ max(A)TR in the wavelength range of 850 to 1100 nm in (i-3). The maximum absorption wavelength λ max(A)TR is preferably in the wavelength range of 860 to 1000 nm. Further, the coloring agent (A) satisfies the formula (3) and the formula (4) in (i-3). According to the formula (3), 400(A)TR / λmax (A)TR is less than 0.15. 400(A)TR / λmax(A)TR is preferably 0.12 or less, and more preferably 0.09 or less.

[0043] According to the formula (4), 550(A)TR / λmax(A)TR is less than 0.10. 550(A)TR / λmax(A)TR is preferably 0.08 or less, and more preferably 0.06 or less.

[0044] The dye (A) preferably satisfies the formulas (5) and (6) in (i-4). According to formula (5), ABS 400(A)TR / ABS λmax(A)TR -ABS 400(A)DCM / ABS λmax(A)DCM is less than 0.10, preferably 0.08 or less, and more preferably 0.06 or less. According to formula (6), ABS 550(A)TR / ABS λmax(A)TR -ABS 550(A)DCM / ABS λmax(A)DCM is less than 0.08, preferably 0.06 or less, and more preferably 0.04 or less.

[0045] By satisfying the above (i-1) to (i-3) in the dye (A), it can be said that the dye (A) has sharp spectral characteristics with a large maximum absorption wavelength and a high visible light transmittance both in dichloromethane and in a transparent resin. Generally, for dyes with a large maximum absorption wavelength, there is also a contribution from aggregation, and it is known that it is difficult to reproduce a high visible light transmittance and sharp spectrum in dichloromethane in a transparent resin. By satisfying the above (i-1) to (i-3), the dye (A) exhibits the characteristic that it can maintain the light absorption characteristics with a large maximum absorption wavelength and a high visible light transmittance in dichloromethane even in a transparent resin. By satisfying the above (i-1) to (i-3) in the dye (A), it can be said that the dye (A) has sharp spectral characteristics with a large maximum absorption wavelength and a high visible light transmittance both in dichloromethane and in a transparent resin. Generally, for dyes with a large maximum absorption wavelength, there is also a contribution from aggregation, and it is known that it is difficult to reproduce a high visible light transmittance and sharp spectrum in dichloromethane in a transparent resin. By satisfying the above (i-1) to (i-3), the dye (A) exhibits the characteristic that it can maintain the light absorption characteristics with a large maximum absorption wavelength and a high visible light transmittance in dichloromethane even in a transparent resin.

[0046] Furthermore, by satisfying (i-4), the dye (A) can maintain the light absorption characteristics of the dye (A) in dichloromethane with better reproducibility in a transparent resin when used in an optical filter.

[0047] The dye (A) has a mass extinction coefficient of 1000 / (cm·mass%) or more in (i-5). The mass extinction coefficient is preferably 1500 / (cm·mass%) or more.

[0048] As the pigment (A), the molecular structure is not particularly limited as long as the requirements (i-1) to (i-3) are satisfied. Specifically, at least one pigment selected from the group consisting of cyanine pigments, croconium pigments, phthalocyanine pigments, squarylium pigments, diimonium pigments, and diketopyrrolopyrrole pigments can be mentioned. From the viewpoint of high visible light transmittance, cyanine pigments and squarylium pigments are particularly preferred.

[0049] As the cyanine pigment which is the pigment (A), the cyanine pigment represented by any of the following formulas (ACi) to (ACiv) is preferred.

[0050]

Chemical formula

[0051]

Chemical formula

[0052] However, the symbols in the formulas (ACi) to (ACiv) are as follows. R 101 ~R 107 、R 121 ~R 127 、R 141 and R 151 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR 112 R 113 group, -NHSO2R 114 group, -NHCOR 115 group, -SR 116 group, -SO2R 117 group, -OSO2R 118 group, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members.

[0053] R 102 ~R 107 and R122 ~R 127 Two adjacent ones may be connected to each other to form a 5-membered ring, 6-membered ring, or 7-membered ring. For formula (ACi), in particular, R 105 and R 106 are preferably connected to form an aromatic ring together with a part (C=C) of the benzene ring of the skeleton. For formula (ACii), in particular, R 125 and R 126 are preferably connected to form an aromatic ring together with a part (C=C) of the benzene ring of the skeleton.

[0054] R 142 and R 143 may be a hydrogen atom or may be bonded to each other to form an aromatic ring D having 6 members. R 145 and R 144 may be a hydrogen atom or may be bonded to each other to form an aromatic ring E having 6 members. However, both the aromatic ring D and the aromatic ring E are not formed.

[0055] R 109 ~R 111 、R 129 ~R 131 、R 146 ~R 148 、and R 152 ~R 154 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a -NR 112 R 113 group, a cycloalkyl group having 3 to 14 carbon atoms, or an aryl group having 6 to 14 carbon atoms.

[0056] R 109 and R 111 、R 129 and R 131 、R 146 and R 148 、and R 152 and R 154 may be bonded to each other to form a 5-membered ring or 6-membered ring. When forming a ring, the hydrogen atom bonded to the ring may be substituted with an alkyl group having 1 to 6 carbon atoms, and two of the constituent atoms of the ring may be bridged with a methylene group.

[0057] R112 ~R 118 is, independently, a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. A plurality of R contained in each formula 101 ~R 107 、R 121 ~R 127 、R 141 ~R 145 、R 151 、D, and E may be the same as or different from each other. X - represents a monovalent anion.

[0058] In the above, the alkyl group of the alkyl group and the alkoxy group may be linear, and may include a branched structure or a saturated ring structure. The aryl group refers to a group bonded through carbon atoms constituting an aromatic ring of an aromatic compound, for example, a benzene ring, a naphthalene ring, a biphenyl, a furan ring, a thiophene ring, a pyrrole ring, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom and a chlorine atom are preferred.

[0059] X - Examples of - include I - 、BF4 - 、PF6 - 、ClO4 - 、anions represented by formula (X1), and (X2), etc., and preferably, BF4 - 、PF6

[0060]

Chemical formula

[0061] Examples of the pigment (ACi) include those represented by the following formula (ACi1), and R in formula (ACi) 109 ~R 111A compound having a hydrogen atom is preferred from the viewpoint of maintaining high visible light transmittance in a transparent resin.

[0062]

Chemical formula

[0063] R in formula (ACi1) 101 ~R 107 and X - are the same as those described in the above formulas (ACi) to (ACiv), including preferred embodiments. R 101 is preferably an alkyl group having 1 to 20 carbon atoms with a linear or branched structure, and more preferably an alkyl group having 4 to 20 carbon atoms with a linear or branched structure, from the viewpoint of solubility in a transparent resin or a solvent (hereinafter also referred to as "host solvent") used when forming an absorption layer on a transparent substrate. R 102 ~R 107 are each independently a hydrogen atom, -NR 112 R 113 group, -NHSO2R 114 group, -NHCOR 115 group, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, or a heterocyclic group having 3 to 14 members, and a hydrogen atom, or an alkyl group or an alkoxy group having 1 to 20 carbon atoms are more preferred. In this case, R 112 ~R 115 can be the same as those described in the above formulas (ACi) to (ACiv).

[0064] As the dye (ACii), a compound in which R 129 and R 131 in formula (ACii) are bonded to form a 6-membered ring, and a compound in which R 129 and R 131 in formula (ACii) are bonded to form a 5-membered ring are preferred from the viewpoint of maintaining high visible light transmittance in a transparent resin.

[0065]

Chemical formula

[0066] R in Formulas (ACii1) and (ACii2) 121 ~R 127 and X - are the same as those described in Formulas (ACi) to (ACiv) above, including preferred embodiments. In Formula (ACii1), R 130a is a hydrogen atom, a phenyl group, or a methyl group, preferably a phenyl group. In Formula (ACii2), R 130b is a hydrogen atom, a phenyl group, a methyl group, or a diphenylamino group, preferably a phenyl group or a diphenylamino group.

[0067] R 121 is preferably an alkyl group having a linear or branched structure and 1 to 20 carbon atoms, and more preferably an alkyl group having a linear or branched structure and 4 to 20 carbon atoms, from the viewpoint of solubility in the transparent resin and the host solvent. R 122 ~R 127 are each independently a hydrogen atom, a dimethylamino group, a -NHSO2R 114 group, a -NHCOR 115 group, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, or a heterocyclic group having 3 to 14 members, and more preferably a hydrogen atom or an alkyl group or an alkoxy group having 1 to 20 carbon atoms. In this case, R 112 ~R 115 can be the same as those described in Formulas (ACi) to (ACiv) above.

[0068] As the dye (ACiii), specifically, compounds having neither aromatic ring D nor aromatic ring E in Formula (ACiii) represented by the following Formula (ACiii1), compounds having only aromatic ring E in Formula (ACiii) represented by the following Formula (ACiii2), and compounds having only aromatic ring D in Formula (ACiii) represented by the following Formula (ACiii3) can be mentioned.

[0069] [Chemical formula]

[0070] R in formulas (ACiii1), (ACiii2), and (ACiii3) 141 , R 146 ~R 148 and X - are the same as those described in the above formulas (ACi) to (ACiv) including preferred embodiments. R 141 is preferably an alkyl group having a linear or branched structure and 1 to 20 carbon atoms from the viewpoint of solubility in a transparent resin or a host solvent, and more preferably an alkyl group having a linear or branched structure and 2 to 5 carbon atoms from the viewpoint of ease of synthesis. R 147 is preferably a hydrogen atom, a methyl group, or a phenyl group, and more preferably a hydrogen atom or a phenyl group.

[0071] R 146 and R 148 are both preferably hydrogen atoms, or R 146 and R 148 are preferably bonded to form a 5-membered or 6-membered ring together with the main chain (methine chain) to which they are bonded. When forming a ring, the hydrogen atom bonded to the ring may be substituted with an alkyl group having 1 to 6 carbon atoms, or two of the constituent atoms of the ring may be bridged with a methylene group. R 146 and R 148 are preferably bonded to form a 6-membered ring together with the main chain, and the structure represented by -(CH2)3- described below is more preferable.

[0072] In the dye (ACiv), R 151 is preferably an alkyl group having a linear or branched structure and 1 to 20 carbon atoms from the viewpoint of solubility in a transparent resin or a host solvent, and more preferably an alkyl group having a linear or branched structure and 2 to 5 carbon atoms from the viewpoint of ease of synthesis. R 153 is preferably a hydrogen atom, a methyl group, or a phenyl group, and more preferably a hydrogen atom or a phenyl group.

[0073] R152 and R 154 are each a hydrogen atom, or R 152 and R 154 are preferably bonded to form a 5- or 6-membered ring together with the main chain (methine chain) to which they are bonded. When forming a ring, the hydrogen atom bonded to the ring may be substituted with an alkyl group having 1 to 6 carbon atoms, and two of the constituent atoms of the ring may be bridged with a methylene group. R 152 and R 154 are bonded to form a 6-membered ring together with the main chain, and the structure represented by -(CH2)3- described later is more preferable.

[0074] As the compounds represented by Formula (ACi1), Formula (ACii1), Formula (ACii2), Formula (ACiii1), Formula (ACiii2), Formula (ACiii3), and Formula (ACiv), more specifically, the atoms or groups bonded to each skeleton include the compounds shown in Tables 1 to 7 below. In all the compounds shown in Table 1, R 101 to R 107 are the same on both the left and right sides of the formula. In all the compounds shown in Tables 2 and 3, R 121 to R 127 are the same on both the left and right sides of the formula. In all the compounds shown in Tables 4 to 6, R 141 is the same on both the left and right sides of the formula. In all the compounds shown in Table 7, R 151 is the same on both the left and right sides of the formula. In Tables 1 to 7, the alkyl group represented by -C n H 2n+1 (n is an integer of 3 or more) represents a straight-chain alkyl group, and -Ph represents a phenyl group. Although only symmetric compounds are listed in Tables 1 to 7, the present invention is not limited thereto, and asymmetric compounds may also be used. Asymmetric compounds have the advantage of improving solubility in resins.

[0075] In Tables 4 to 6, when R 146 and R 148 are bonded to form a 6-membered ring together with three carbon atoms (C-C=C) of the methine chain, R 146 and R 148is represented as -(CH2)3-. For other rings and cases where the hydrogen atoms of the ring are substituted, they shall be described according to the above description. R in Table 7 152 and R 154 are the same. In Tables 4 to 7, R 146 and R 148 and R 152 and R 154 The "NOR" described in the column indicates the following divalent group.

[0076]

Chemical formula

[0077] In Tables 1 to 7, X - is not shown, but in any compound, X - is BF4 - , PF6 - or anion X1. In the dye (ACi1-1), when X - is BF4 - the case is designated as dye (ACi1-1B), when PF6 - the case is designated as dye (ACi1-1P), and when it is anion (X1) the case is designated as dye (ACi1-1X1). The same applies to other dyes shown in Tables 1 to 7.

[0078]

Table 1

[0079] Among these, as the dye (ACi1), dyes (ACi1-1B), (ACi1-1P), (ACi1-1X1), (ACi1-2B), (ACi1-2P), (ACi1-14B), (ACi1-15B), etc. are preferable.

[0080]

Table 2

[0081] As the pigment (ACii1), among these, pigments such as pigment (ACii1-1B), pigment (ACii1-1P), pigment (ACii1-7B), pigment (ACii1-7P) are preferable.

[0082]

Table 3

[0083] As the pigment (ACii2), among these, pigments such as pigment (ACii2-1B), pigment (ACii2-1P), pigment (ACii2-2B), pigment (ACii2-2P), pigment (ACii2-11B), pigment (ACii2-11P), pigment (ACii2-12B), pigment (ACii2-12P) are preferable.

[0084]

Table 4

[0085] As the pigment (ACiii1), among these, pigments such as pigment (ACiii1-1B), pigment (ACiii1-1P), pigment (ACiii1-2B), pigment (ACiii1-2P), pigment (ACiii1-3B), pigment (ACiii1-3P), pigment (ACiii1-7B), pigment (ACiii1-7P), pigment (ACiii1-9B), pigment (ACiii1-9P), pigment (ACiii1-12B), pigment (ACiii1-12P), pigment (ACiii1-17B), pigment (ACiii1-17P), pigment (ACiii1-19B), pigment (ACiii1-19P) etc. are preferable.

[0086]

Table 5

[0087] As the pigment (ACiii2), among these, pigments such as pigment (ACiii2-1B), pigment (ACiii2-1P), pigment (ACiii2-2B), pigment (ACiii2-2P), pigment (ACiii2-3B), pigment (ACiii2-3P), pigment (ACiii2-7B), pigment (ACiii2-7P), pigment (ACiii2-9B), pigment (ACiii2-9P), pigment (ACiii2-12B), pigment (ACiii2-12P), pigment (ACiii2-17B), pigment (ACiii2-17P), pigment (ACiii2-19B), pigment (ACiii2-19P) etc. are preferred.

[0088]

Table 6

[0089] As the pigment (ACiii3), among these, pigment (ACiii3-1B), pigment (ACiii3-1P), pigment (ACiii3-2B), pigment (ACiii3-2P), pigment (ACiii3-3B), pigment (ACiii3-3P), pigment (ACiii3-7B), pigment (ACiii3-7P), pigment (ACiii3-9B), pigment (ACiii3-9P), pigment (ACiii3-12B), pigment (ACiii3-12P), pigment (ACiii3-17B), pigment (ACiii3-17P), pigment (ACiii3-19B), pigment (ACiii3-19P) etc. are preferred.

[0090]

Table 7

[0091] As the pigment (ACiv), among these, pigment (ACiv-1B), pigment (ACiv-1P), pigment (ACiv-2B), pigment (ACiv-2P), pigment (ACiv-3B), pigment (ACiv-3P), pigment (ACiv-7B), pigment (ACiv-7P), pigment (ACiv-9B), pigment (ACiv-9P), pigment (ACiv-12B), pigment (ACiv-12P), pigment (ACiv-17B), pigment (ACiv-17P), pigment (ACiv-19B), pigment (ACiv-19P), pigment (ACiv-26B), pigment (ACiv-26P), etc. are preferred.

[0092] Note that pigment (ACi), pigment (ACii), and pigment (ACiv) can be produced, for example, by the method described in J. Heterocyclic Chem., 42(2005), 959. Pigment (ACiii) can be produced by the method described in UKRAINSKII KHIMICHESKII ZHURNAL, 44(8), 838, (1978).

[0093] Also, as the pigments (ACi1-1B), pigment (ACi1-2B), and pigment (ACii2-2B), the product names S0772, S2437, and S2007 manufactured by Few Chemicals, which are commercially available products, can be used respectively. As the pigments (ACiii1-9B), pigment (ACiii2-9B), and pigment (ACiii3-9B), the product names S1379, S1984, and S1985 manufactured by Spectrum Info., which are commercially available products, can be used respectively.

[0094] As the squarylium pigment which is pigment (A), the squarylium pigment represented by the following formula (ASi) or (ASii) is preferred.

[0095]

Chemical formula

[0096] However, the symbols in the formulas (ASi) and (ASii) are as follows. R 161 is a branched alkyl group having 3 to 20 carbon atoms, or a linear alkyl group having 13 to 20 carbon atoms. R 161 is preferably a branched alkyl group having 8 to 20 carbon atoms, and more preferably a linear alkyl group having 16 to 20 carbon atoms, from the viewpoint of solubility in a transparent resin or a host solvent. R161 From the viewpoint of maintaining high transmittance in the transparent resin, a branched alkyl group having 8 to 20 carbon atoms is more preferable.

[0097] Y 3 is C-R 179 or N. R 162 ~R 167 and R 171 ~R 179 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, -NR 112 R 113 group, -NHSO2R 114 group, -NHCOR 115 group, -SR 116 group, -SO2R 117 group, -OSO2R 118 group, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members.

[0098] Examples of the heterocyclic group having 3 to 14 members include heterocyclic groups containing at least one selected from N, O, and S as heteroatoms. R 171 is preferably a linear alkyl group having 8 to 20 carbon atoms and a branched alkyl group having 8 to 20 carbon atoms from the viewpoint of solubility in the transparent resin and the host solvent. R 171 is more preferably a branched alkyl group having 16 to 20 carbon atoms from the viewpoint of maintaining high transmittance in the transparent resin. R 162 ~R 167 and R 172 ~R 178 are each independently preferably a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, -NHSO2R 114 group, or -NHCOR 115 group, and more preferably a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, or -NHCOR 115 group. R 179is preferably an alkyl group or an alkoxy group having 1 to 20 carbon atoms, more preferably an alkyl group or an alkoxy group having 1 to 8 carbon atoms. The plurality of Rs contained in each formula 161 ~R 167 , R 171 ~R 178 and Y 3 may be the same as or different from each other.

[0099] R 112 ~R 118 are each independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom and a chlorine atom are preferred.

[0100] R 112 ~R 118 are each independently preferably an alkyl group or an alkoxy group having 1 to 20 carbon atoms, more preferably an alkyl group or an alkoxy group having 1 to 16 carbon atoms.

[0101] In the above, unless otherwise specified, the alkyl group of the alkyl group and the alkoxy group may be linear, or may contain a branched structure or a saturated ring structure. The aryl group refers to a group bonded through carbon atoms constituting an aromatic ring of an aromatic compound, for example, a benzene ring, a naphthalene ring, biphenyl, a furan ring, a thiophene ring, a pyrrole ring, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom and a chlorine atom are preferred.

[0102] More specifically, examples of the compounds represented by formula (ASi) and formula (ASii) include the compounds shown in Tables 8 and 9 below, in which the atoms or groups bonded to each skeleton are as follows. In all the compounds shown in Table 8, R 161 ~R 167is the same on both the left and right sides of the formula. In all the compounds shown in Table 9, R 171 ~R 178 and Y 3 are the same on both the left and right sides of the formula. In Tables 8 and 9, alkyl groups such as -C4H9 are all straight-chain alkyl groups. Although only symmetric compounds are listed in Tables 8 and 9, the present invention is not limited thereto, and asymmetric compounds may also be used. Asymmetric compounds have the advantage of improved solubility in resins.

[0103]

Table 8

[0104] As the pigment (ASi), pigment (ASi-1), pigment (ASi-2), pigment (ASi-3), pigment (ASi-19), pigment (ASi-22), pigment (ASi-24), pigment (ASi-25), pigment (ASi-28), pigment (ASi-31), etc. are preferable, and pigment (ASi-1), pigment (ASi-19), pigment (ASi-22), pigment (ASi-25), pigment (ASi-31), etc. are more preferable. As the asymmetric pigment (ASi), pigments in which the left and right combinations are any combination of ASi-19 and any of ASi-24, ASi-25, and ASi-28, pigments that are any combination of ASi-22 and any of ASi-24 and ASi-31, pigments that are any combination of ASi-24 and any of ASi-25 and ASi-28, etc. are preferable.

[0105]

Table 9

[0106] Among these, as the pigment (ASii), pigment (ASii-1) to pigment (ASii-8), pigment (ASii-10), pigment (ASii-15) to pigment (ASii-17), etc. are preferable, and pigment (ASii-8), pigment (ASii-15) to pigment (ASii-17), etc. are more preferable.

[0107] Note that the dye (ASi) and the dye (ASii) can be produced, for example, by the method described in European Journal of Medical Chemistry, 54 647, (2012), and for the dye (ASii), it can be produced by introducing the compound described in Org. Lett. 18, 5232 (2016) on both sides of the squarylium ring, and the compound can be introduced at two diagonal positions of squaric acid by the method described in, for example, Organic Letters, 8, 111, (2006).

[0108] The absorption layer may contain one kind of the dye (A) alone, or may contain two or more kinds in combination. When containing two or more kinds, the maximum absorption wavelength λ max(A)TR of each dye (A) is preferably different. The difference in the maximum absorption wavelength λ max(A)TR in two or more kinds of the dye (A) is preferably in the range of, for example, 50 to 300 nm, and more preferably 50 to 150 nm. When the dye (A) consists of two or more compounds, each compound does not necessarily have the properties of the dye (A), and it is sufficient to have the properties of the dye (A) as a mixture.

[0109] As a preferable combination of two or more kinds of the dye (A), for example, the dye (A) having the maximum absorption wavelength on the relatively short wavelength side among the dyes (A) is defined as the dye S, the dye (A) having the maximum absorption wavelength on the relatively long wavelength side is defined as the dye L, and the dye (A) having the maximum absorption wavelength between the maximum absorption wavelengths of the dye S and the dye L is defined as the dye M. It is preferable to select and combine two or more kinds from the dye S, the dye M, and the dye L.

[0110] Specifically, the combination of the dye S and the dye M, the combination of the dye S and the dye L, the combination of the dye M and the dye L, and the combination of the dye S, the dye M, and the dye L can be mentioned. The maximum absorption wavelength λ max(A)TR of the dye S is preferably in the wavelength range of 850 to 900 nm, and more preferably in the wavelength range of 860 to 890 nm. The maximum absorption wavelength λ max(A)TRis preferably in the wavelength range of 900 to 1000 nm, more preferably in the wavelength range of 930 to 980 nm. The maximum absorption wavelength λ of the dye L max(A)TR is preferably in the wavelength range of 1000 to 1100 nm, more preferably in the wavelength range of 1000 to 1050 nm.

[0111] [Dye (D)] Dye (D) satisfies the requirements of (v-1) and (v-2), that is, the maximum absorption wavelength λ max(D)TR is in the wavelength range of 650 to 750 nm, and is at least one dye selected from the group consisting of squarylium dyes represented by any of the following formulas (I) to (III). Dye (D) preferably further satisfies the requirement of (v-3) above.

[0112] The dye (D) composed of the above squarylium dye has little absorption of visible light in the above absorbance curve, and the absorption peak of λ max(D)TR has a steep slope on the visible light side, and has high storage stability and stability to light.

[0113] Also, the mass extinction coefficient of the dye (D) when contained in the transparent resin is preferably 1000 / (cm·mass%) or more, more preferably 1500 / (cm·mass%) or more.

[0114] [Chemical formula]

[0115] However, the symbols in formula (I) are as follows. R 24 and R 26 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, -NR 27 R 28 (R 27 and R 28 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, -C(=O)-R 29(R 29 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 11 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), -NHR 30 or -SO2-R 30 (R 30 is a hydrocarbon group having 1 to 25 carbon atoms in which one or more hydrogen atoms may be substituted with a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, or a cyano group, and which may contain an unsaturated bond, an oxygen atom, or a saturated or unsaturated ring structure between carbon atoms).), or a group represented by the following formula (S) (R 41 , R 42 independently represents a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 10 carbon atoms. k is 2 or 3.).

[0116]

Chemical formula

[0117] R 21 and R 22 , R 22 and R 25 , and R 21 and R 23 may be linked to each other to form heterocyclic rings A, B, and C each having 5 or 6 members together with the nitrogen atom. When heterocyclic ring A is formed, R 21 and R 22 as a divalent group -Q- to which they are bonded, the hydrogen atom may be an alkylene group substituted with an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyloxy group having 1 to 10 carbon atoms which may have a substituent, or an alkyleneoxy group.

[0118] When heterocyclic ring B is formed, R 22 and R 25 , and when heterocyclic ring C is formed, R 21 and R 23are each a divalent group -X formed by combining these 1 -Y 1 - and -X 2 -Y 2 - (where the side bonded to nitrogen is X 1 and X 2 ), X 1 and X 2 are each a group represented by the following formula (1x) or (2x), and Y 1 and Y 2 are each a group represented by any one selected from the following formulas (1y) to (5y). When X 1 and X 2 are each a group represented by the following formula (2x), Y 1 and Y 2 may each be a single bond, and in that case, it may have an oxygen atom between carbon atoms.

[0119]

Chemical formula

[0120] In formula (1x), the four Zs are each independently a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, or -NR 38 R 39 (R 38 and R 39 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). R 31 ~R 36 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 37 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0121] R 27 、R 28 、R 29 、R 31 ~R 37 、when not forming a heterocyclic ring, R 21 ~R 23 、and R 25may combine with any of the others among these to form a 5-membered or 6-membered ring. R 31 and R 36 、R 31 and R 37 may be directly bonded. When no heterocyclic ring is formed, R 21 and R 22 each independently represent a hydrogen atom, an alkyl group or allyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group or aralkyl group having 6 to 11 carbon atoms which may have a substituent. When no heterocyclic ring is formed, R 23 and R 25 each independently represent a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having 1 to 6 carbon atoms.

[0122]

Chemical formula

[0123] However, the symbols in formula (II) are as follows. Ring Z is each independently a 5-membered or 6-membered ring having 0 to 3 heteroatoms in the ring and which may be substituted, R 1 and R 2 、R 2 and R 3 、and R 1 and the carbon atoms or heteroatoms constituting ring Z may be connected to each other to form heterocyclic rings A1, B1 and C1 together with a nitrogen atom respectively. When no heterocyclic ring is formed, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain an unsaturated bond, a heteroatom, a saturated or unsaturated ring structure between carbon atoms and which may have a substituent. R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group which may contain a heteroatom between carbon atoms.

[0124] [Chemical formula]

[0125] However, the symbols in formula (III) are as follows. R 51 each independently represents a halogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, R 52 ~R 58 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent. R 52 and R 53 may be linked to each other to form a saturated or unsaturated hydrocarbon ring B2 having 5 to 15 carbon atoms, and the hydrogen atoms of the hydrocarbon ring B2 may be substituted with an alkyl group having 1 to 10 carbon atoms, R 54 and R 55 may be linked to each other to form a benzene ring A2, and the hydrogen atoms of the benzene ring A2 may be substituted with an alkyl group having 1 to 10 carbon atoms.

[0126] Examples of the compound (I) include compounds represented by any of formulas (I-1) to (I-4).

[0127] [Chemical formula]

[0128] However, the symbols in formulas (I-1) to (I-4) are the same as the respective definitions of the same symbols in formula (I), and the preferred embodiments are also the same.

[0129] Among the compounds (I-1) to (I-4), as the dye (A), compounds (I-1) to (I-3) are preferred from the viewpoint of increasing the visible light transmittance of the absorption layer, and compound (I-1) is particularly preferred.

[0130] In compound (I-1), X1 Preferably, the group is (2x), and Y 1 Preferably, it is a single bond or the group (1y). In this case, R 31 ~R 36 Preferably, it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. Note that -Y 1 -X 1 - Specifically, examples of the divalent organic group represented by the formulas (11-1) to (12-3) can be given.

[0131] -C(CH3)2-CH(CH3)- …(11-1) -C(CH3)2-CH2- …(11-2) -C(CH3)2-CH(C2H5)- …(11-3) -C(CH3)2-C(CH3)(nC3H7)- …(11-4) -C(CH3)2-CH2-CH2- …(12-1) -C(CH3)2-CH2-CH(CH3)- …(12-2) -C(CH3)2-CH(CH3)-CH2- …(12-3)

[0132] Also, in the compound (I-1), R 21 is more preferably a group represented by the formula (4-1) or (4-2) independently from the viewpoints of solubility, heat resistance, and the steepness of the change near the boundary between the visible region and the near-infrared region in the spectral transmittance curve.

[0133]

Chemical formula

[0134] In the formulas (4-1) and (4-2), R 71 ~R 75 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

[0135] In the compound (I-1), R 24 is -NR 27 R28 is preferred. -NR 27 R 28 As, from the viewpoint of solubility in a host solvent or a transparent resin, -NH-C(=O)-R 29 is preferred. In compound (I-1), R 24 is -NH-C(=O)-R 29 The compound is shown in formula (I-11).

[0136]

Chemical formula

[0137] In compound (I-11), R 23 and R 26 are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and more preferably a hydrogen atom in each case.

[0138] In compound (I-11), R 29 is preferably 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. Examples of the substituent include a halogen atom such as a fluorine atom, a hydroxyl group, a carboxy 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, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, and the like.

[0139] R 29 is preferably a group selected from a linear, branched or cyclic alkyl group having 1 to 17 carbon atoms which may be substituted with a fluorine atom, a phenyl group which may be substituted with a fluoroalkyl group having 1 to 6 carbon atoms and / or an alkoxy group having 1 to 6 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms which may have an oxygen atom between carbon atoms and may have a phenyl group substituted with a fluorine atom having 1 to 6 carbon atoms at the terminal and / or an alkoxy group having 1 to 6 carbon atoms.

[0140] R 29 As R, a hydrocarbon group having at least one branch and having 5 to 25 carbon atoms, in which 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 which may contain an unsaturated bond, an oxygen atom, or a saturated or unsaturated ring structure between carbon atoms, can also be preferably used. Such R 29 Examples thereof include groups represented by the following formulas (1a), (1b), (2a) to (2e), and (3a) to (3e).

[0141]

Chemical formula

[0142]

Chemical formula

[0143] More specifically, examples of the compound (I-11) include the compounds shown in Table 10 below. In Table 10, the group (11-1) is shown as (11-1). The same applies to other groups. The group display is the same in the following other tables. Also, for the compounds shown in Table 10, the meanings of the symbols are the same on the left and right of the squarylium skeleton. The same applies to the squarylium dyes shown in the following other tables.

[0144]

Table 10

[0145] In the compound (I-1), R 24 is preferably -NH-SO2-R from the viewpoint of increasing the transmittance of visible light, particularly light having a wavelength of 430 to 550 nm. 30 In the compound (I-1), a compound in which R 24 is -NH-SO2-R 30 is shown by the formula (I-12).

[0146] [Chemical formula]

[0147] In compound (I-12), R 23 and R 26 are independently preferably a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 6 carbon atoms, and more preferably a hydrogen atom in each case.

[0148] In compound (I-12), R 30 is preferably, from the viewpoint of light resistance, an alkyl or alkoxy group having 1 to 12 carbon atoms which may have a branch, or a hydrocarbon group having 6 to 16 carbon atoms having an unsaturated ring structure. Examples of the unsaturated ring structure include benzene, toluene, xylene, furan, benzofuran, etc. R 30 is more preferably an alkyl or alkoxy group having 1 to 12 carbon atoms which may have a branch. In each group representing R 30 , part or all of the hydrogen atoms may be substituted with a halogen atom, particularly a fluorine atom. When this filter has a configuration including a transparent substrate, the substitution of hydrogen atoms with fluorine atoms should be such that the adhesion between the absorption layer containing the dye (I-12) and the transparent substrate does not deteriorate.

[0149] Specific examples of R 30 having an unsaturated ring structure include the groups represented by the following formulas (P1) to (P8).

[0150] [Chemical formula]

[0151] More specifically, examples of compound (I-12) include the compounds shown in Table 11 below.

[0152] [Table 11]

[0153] Examples of the compound (II) include compounds represented by any of formulae (II-1) to (II-3).

[0154]

Chemical formula

[0155] However, in formula (II-1) and formula (II-2), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 15 carbon atoms which may have a substituent, 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.

[0156] However, in formula (II-3), R 1 , R 4 , and R 9 to R 12 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 15 carbon atoms which may have a substituent, 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.

[0157] In compounds (II-1) and (II-2), R 1 and R 2 are independently preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 7 to 15 carbon atoms, from the viewpoints of solubility in a transparent resin, visible light transmittance, etc. At least one of R 1 and R 2 is more preferably an alkyl group having a branched chain of 7 to 15 carbon atoms, and both of R 1 and R 2 being an alkyl group having a branched chain of 8 to 15 carbon atoms is particularly preferred.

[0158] R 3From the viewpoints of solubility in a transparent resin, visible light transmittance, etc., independently, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom, a halogen atom, or a methyl group is more preferable. R 4 From the viewpoint of the sharpness of the change near the boundary between the visible region and the near-infrared region, a hydrogen atom or a halogen atom is preferable, and a hydrogen atom is particularly preferable. R in compound (II-1) 5 and R in compound (II-2) 6 are independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may be substituted with a halogen atom, and more preferably a hydrogen atom, a halogen atom, or a methyl group.

[0159] More specifically, examples of compound (II-1) and compound (II-2) include the compounds shown in Table 12 and Table 13 below. In Table 12 and Table 13, -C8H 17 , -C4H9, -C6H 13 represent a linear octyl group, a butyl group, and a hexyl group, respectively.

[0160]

Table 12

[0161]

Table 13

[0162] R in compound (II-3) 1 is preferably, from the viewpoints of solubility in a transparent resin, visible light transmittance, etc., independently, an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an ethyl group or an isopropyl group.

[0163] R 4 is preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom, from the viewpoints of visible light transmittance and ease of synthesis. R 7 and R 8is preferably, independently, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may be substituted by a halogen atom, more preferably a hydrogen atom, a halogen atom, or a methyl group.

[0164] R 9 ~R 12 is preferably, independently, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may be substituted by a halogen atom. -CR 9 R 10 -CR 11 R 12 As -CR -C(CH3)(CH2-CH(CH3)2)-CH(CH3)-…(11-5)

[0165] More specifically, examples of the compound (II-3) include the compounds shown in Table 14 below.

[0166]

Table 14

[0167] Examples of the compound (III) include compounds represented by either formula (III-1) or formula (III-2).

[0168]

Chemical formula

[0169] However, in (III-1) and (III-2), R 52 ~R 62 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent.

[0170] In compound (III-1) and compound (III-2), R 52 and R 53is independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, more preferably a hydrogen atom, a halogen atom, or a methyl group. R 58 is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, and from the viewpoint of ease of synthesis, more preferably an alkyl group having 1 to 3 carbon atoms. R 56 , R 57 , R 59 ~R 62 are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and from the viewpoint of ease of synthesis more preferably a hydrogen atom. More specifically, examples of the compound (III-1) and the compound (III-2) include the compounds shown in Table 15 and Table 16 below, respectively.

[0171]

Table 15

[0172]

Table 16

[0173] The pigment (D) may consist of one kind of compound or may consist of two or more kinds of compounds. When it consists of two or more kinds of compounds, each individual compound does not necessarily have the properties of the pigment (D), and it may have the properties of the pigment (D) as a mixture.

[0174] Compounds (I) to (III) can each be produced by a known method. For compound (I), compound (I-11) can be produced, for example, by the method described in U.S. Patent No. 5,543,086. Compound (I-12) can be produced, for example, by the methods described in U.S. Patent Application Publication No. 2014 / 0061505 and International Publication No. 2014 / 088063. For compound (II), it can be produced by the method described in International Publication No. 2017 / 135359.

[0175] Examples of UV dyes include dyes such as oxazole-based, merocyanine-based, cyanine-based, naphthalimide-based, oxadiazole-based, oxazine-based, oxazolidine-based, naphthalic acid-based, styryl-based, anthracene-based, cyclic carbonyl-based, and triazole-based dyes. Among these, oxazole-based or merocyanine-based dyes are preferred. Also, the UV dye may be used alone or in combination of two or more in the absorption layer.

[0176] As the transparent resin, a transparent resin that satisfies (i-3) and preferably further satisfies (i-4) in relation to the dye (A) is used.

[0177] Depending on the type of the dye (A), the transparent resin is selected from, for example, one or more of acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, and polyester resin.

[0178] The transparent resin preferably includes a resin having at least one bond selected from ester bond, carbonate bond, and imide bond in the main chain. The transparent resin having these bonds in the main chain is advantageous in terms of maintaining high visible light transmittance when mixed with the dye and excellent heat resistance of the resin itself.

[0179] Among these, polyester resins, polycarbonate resins, polyimide resins, and acrylic imide resins are preferred as the transparent resin. These resins may be used alone or in combination of two or more. When the dye (A) is the dye (ACi) to the dye (ACiv), the dye (ASi), or the dye (ASii), in particular, polyester resins, polycarbonate resins, polyimide resins, and acrylic imide resins are preferred.

[0180] As the transparent resin, commercially available products may be used. Examples of commercially available products include, as polyester resins, OKP4HT, OKP4, B-OKP2, OKP-850 (all manufactured by Osaka Gas Chemical Co., Ltd., trade names), Baylon (registered trademark) 103 (manufactured by Toyobo Co., Ltd., trade name), and the like.

[0181] Examples of polycarbonate resins include LeXan (registered trademark) ML9103 (manufactured by Sabic, trade name), EP5000 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), SP3810 (manufactured by Teijin Limited, trade name), SP1516 (manufactured by Teijin Limited, trade name), TS2020 (manufactured by Teijin Limited, trade name), xylex (registered trademark) 7507 (manufactured by Sabic, trade name), and the like.

[0182] Examples of polyimide resins include Neoprim (registered trademark) C-3650 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), C-3G30 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), C-3450 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), JL-20 (manufactured by Shin Nippon Rika Co., Ltd., trade name), FPC-0220 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name) (these polyimide resins may contain silica) and the like. Examples of acrylic imide resins include PLEXIMID8817 (manufactured by Daicel Evonik Co., Ltd., trade name) and the like.

[0183] From the viewpoints of transparency, solubility of the dye (A) and further the dye (D), and heat resistance, a resin having a high glass transition point (Tg), for example, a resin having a Tg of 140°C or higher is preferred as the transparent resin.

[0184] The absorption layer may further contain an adhesion promoter, a color tone correcting dye, a leveling agent, an antistatic agent, a heat stabilizer, a light stabilizer, an antioxidant, a dispersant, a flame retardant, a lubricant, a plasticizer, or other optional components as long as the effects of the present invention are not impaired.

[0185] When the absorption layer contains a dye (A) having the characteristics of (i-1) to (i-3) and a transparent resin, and further contains a dye (D), it preferably satisfies the following (ii-1) to (ii-3) in the spectral transmittance curve at an incident angle of 0 degrees.

[0186] (ii-1) In the absorption layer, the wavelength λ on the short wavelength side of the wavelength at which the transmittance is 20% ABSHT20-0° is in the wavelength range of 655 to 675 nm. (ii-2) The average transmittance T of light with wavelengths from 435 to 630 nm in the absorption layer AB435-630ave0° is 65% or more. (ii-3) The average transmittance T of light with wavelengths from 850 to 1100 nm in the absorption layer AB850-1100ave0° is 70% or less.

[0187] The wavelength λ in (ii-1) ABSHT20-0° is preferably in the wavelength range of 655 to 670 nm, and more preferably in the wavelength range of 655 to 665 nm. For example, when this filter has a transparent substrate and the transparent substrate is a near-infrared absorbing glass, in accordance with the absorption of the near-infrared absorbing glass, the wavelength λ ABSHT20-0° is adjusted by about +5 to 20 nm from the above preferred range. That is, in this case, the wavelength λ ABSHT20-0° is preferably in the wavelength range of 660 to 675 nm, and more preferably in the wavelength range of 665 to 675 nm.

[0188] The average transmittance T in (ii-2) AB435-630ave0° is preferably 70% or more, and more preferably 80% or more. The average transmittance T in (ii-3) AB850-1100ave0° is preferably 60% or less, and more preferably 45% or less.

[0189] In the absorption layer, the content of the dye (A) is appropriately set according to the design of this filter so that the effect of this filter can be exerted. From the viewpoint of ensuring the transmittance of visible light and blocking near-infrared light, particularly near-infrared light in the long-wavelength region, the content of the dye (A) in the absorption layer is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the transparent resin, and more preferably 1 to 8 parts by mass from the viewpoint of solubility.

[0190] In the case of using two or more selected from the dye S, the dye M, and the dye L in the dye (A), the content of each dye is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the transparent resin after setting the total content of the whole dye (A) within the above range, and more preferably 2 to 13 parts by mass from the viewpoint of solubility.

[0191] When the absorption layer contains the dye (A) and the dye (D), their contents are appropriately selected according to the design of this filter so that the absorption layer satisfies the characteristics of (ii-1) to (ii-3).

[0192] In this case, the content of the dye (A) in the absorption layer is the same as above, and the content of the dye (D) is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the transparent resin from the viewpoint of ensuring the transmittance of visible light and exerting the characteristics of the dye (D), and more preferably 3 to 14 parts by mass from the viewpoint of solubility. Further, the total content of the dye (A) and the dye (D) is preferably 2 to 30 parts by mass with respect to 100 parts by mass of the transparent resin, and more preferably 5 to 27 parts by mass from the viewpoint of solubility.

[0193] In this filter, the thickness of the absorption layer is preferably 0.1 to 100 μm. When the absorption layer is composed of multiple layers, the total thickness of each layer is preferably 0.1 to 100 μm. If the thickness is less than 0.1 μm, there is a possibility that the desired optical characteristics cannot be fully exhibited. If the thickness exceeds 100 μm, the flatness of the layer may decrease, and in-plane variation in the absorption rate may occur. The thickness of the absorption layer is more preferably 0.3 to 50 μm. Further, when other functional layers such as a reflective layer and an antireflection layer are provided, depending on the material, if the absorption layer is too thick, there is a possibility of cracking or the like. Therefore, the thickness of the absorption layer is more preferably 0.3 to 10 μm.

[0194] The absorption layer can be formed, for example, by dissolving or dispersing a dye (A), preferably the dye (A) and the dye (D), a transparent resin or a raw material component of the transparent resin, and each component optionally blended in a solvent to prepare a coating solution, applying this to a substrate, drying it, and further curing it if necessary. The above substrate may be the transparent substrate included in this filter, or may be a peelable substrate used only when forming the absorption layer. Also, the solvent may be a dispersion medium that can be stably dispersed or a solvent that can be dissolved.

[0195] Also, the coating solution may contain a surfactant for improving voids due to minute bubbles, dents due to adhesion of foreign substances, etc., and repelling in the drying process. Further, for coating the coating solution, for example, a dipping coating method, a cast coating method, a spin coating method, or the like can be used. After applying the above coating solution onto the substrate and drying it, an absorption layer is formed. Also, when the coating solution contains a raw material component of a transparent resin, a curing treatment such as heat curing or light curing is further performed.

[0196] Also, the absorption layer can be manufactured in film form by extrusion molding, and this film may be laminated on another member and integrated by thermocompression bonding or the like. For example, when this filter includes a transparent substrate, this film may be adhered onto the transparent substrate.

[0197] The absorption layer may have one layer or two or more layers in this filter. When having two or more layers, each layer may have the same configuration or different configurations. Taking the case where the absorption layer contains the dye (A), the dye (D), and a UV dye as an example, one layer may be a near-infrared absorption layer containing the dye (A) and the dye (D) and a transparent resin, and the other layer may be a near-ultraviolet absorption layer containing the UV dye and a transparent resin. As another example, one layer may be a first near-infrared absorption layer containing the dye (D) and a transparent resin, and the other layer may be a second near-infrared absorption layer containing the dye (A), the UV dye, and a transparent resin. Also, the absorption layer itself may function as a substrate (resin substrate).

[0198] (Transparent Substrate) When a transparent substrate is used for this filter, if the transparent substrate transmits visible light of approximately 400 to 700 nm, the materials constituting it are not particularly limited, and materials that absorb near-infrared light or near-ultraviolet light may also be used. For example, inorganic materials such as glass and crystal, and organic materials such as transparent resin can be mentioned.

[0199] Examples of the glass that can be used for the transparent substrate include absorption-type glass (near-infrared absorbing glass) containing copper ions such as fluorophosphate glass and phosphate glass, soda-lime glass, borosilicate glass, non-alkali glass, fused silica glass, etc. Note that "phosphate glass" also includes calcium silicate glass in which part of the glass skeleton is composed of SiO2.

[0200] As the glass, at a temperature below the glass transition point, by ion exchange, alkali metal ions with a small ionic radius (for example, Li ions, Na ions) present on the main surface of the glass plate are exchanged with alkali ions with a larger ionic radius (for example, for Li ions, they are Na ions or K ions, and for Na ions, they are K ions). Chemically strengthened glass obtained by such exchange may be used.

[0201] Examples of the transparent resin material that can be used for the transparent substrate include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, norbornene resin, polyacrylate, acrylic resins such as polymethyl methacrylate, urethane resin, vinyl chloride resin, fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, polyimide resin, etc.

[0202] In addition, 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 properties of the transparent substrate are preferably those described above as an optical filter obtained by laminating with the above absorption layer, reflection layer, etc. Sapphire is preferred as the crystal material.

[0203] The transparent substrate is preferably an inorganic material, particularly glass and sapphire, from the viewpoints of long-term reliability such as optical characteristics as an optical filter, shape stability related to mechanical characteristics, and handleability during filter manufacturing.

[0204] The shape of the transparent substrate is not particularly limited and may be in the form of a block, plate, or film. Its thickness is preferably, for example, 0.03 to 5 mm, and more preferably 0.03 to 0.5 mm from the viewpoint of thinning. From the viewpoint of processability, a transparent substrate made of glass with a plate thickness of 0.05 to 0.5 mm is preferred.

[0205] (Reflection layer) The reflection layer is composed of a dielectric multilayer film and has a function of shielding light in a specific wavelength range. Examples of the reflection layer include those having wavelength selectivity that transmits visible light and mainly reflects light with wavelengths outside the light-shielding region of the absorption layer. The reflection layer preferably has a reflection region that reflects near-infrared light. In this case, the reflection region of the reflection layer may include the light-shielding region in the near-infrared region of the absorption layer. The reflection layer is not limited to the above characteristics and may be appropriately designed according to specifications that further block light in a predetermined wavelength range, for example, the near-ultraviolet region.

[0206] When the reflection layer has a reflection region that reflects near-infrared light, specifically, the reflection layer preferably satisfies the following (iii-1). (iii-1) In the spectral transmittance curve at an incident angle of 0 degrees, the average transmittance T of light with wavelengths from 850 to 1100 nm RE850-1100ave0° is 0.2% or less. The average transmittance T RE850-1100ave0° is preferably 0.15% or less, and more preferably 0.05% or less.

[0207] When the reflection layer has a reflection region that reflects near-infrared light, the absorption layer and the reflection layer preferably have the following relationship.

[0208] The wavelength λ on the short-wavelength side where the transmittance of light at an incident angle of 0 degrees in the absorption layer is 20% ABSHT20-0° and the wavelength λ on the short-wavelength side where the transmittance of light at an incident angle of 0 degrees in the reflection layer is 20%RESHT20-0° It is preferable that the relationship with satisfies (iii-2). (iii-2) λ ABSHT20-0° +30 nm ≤ λ RESHT20-0° ≤ 790 nm

[0209] The reflective layer preferably further satisfies (iii-3). (iii-3) The reflective layer has an average transmittance of 10% or less for light in the wavelength range from λ RESHT20-0° to λ RESHT20-0° + 300 nm.

[0210] 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 for the high refractive index film include Ta2O5, TiO2, and Nb2O5. Among these, TiO2 is preferable in terms of film forming property, reproducibility in refractive index, stability, etc.

[0211] On the other hand, the low refractive index film preferably has a refractive index of less than 1.6, more preferably 1.45 or more and less than 1.55. Examples of the material for the low refractive index film include SiO2, SiO x N y etc. SiO2 is preferable in terms of reproducibility, stability, economy, etc. in film forming property.

[0212] Furthermore, it is preferable that the transmittance of the reflective layer changes steeply in the boundary wavelength region between the transmission region and the light shielding region. For this purpose, the total number of laminated layers of the dielectric multilayer film 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 laminated layers increases, warping or the like may occur, or the film thickness may increase. Therefore, the total number of laminated layers is preferably 100 layers or less, more preferably 75 layers or less, and even more preferably 60 layers or less. Also, the film thickness of the dielectric multilayer film is preferably 2 to 10 μm.

[0213] If the total number of stacked layers and the film thickness of the dielectric multilayer film are within the above ranges, the reflective layer can meet the requirements of miniaturization and suppress the incident angle dependence while maintaining high productivity. Further, for forming the dielectric multilayer film, for example, vacuum film forming processes such as CVD method, sputtering method, vacuum evaporation method, etc., and wet film forming processes such as spray method, dip method, etc. can be used.

[0214] The reflective layer may provide predetermined optical characteristics with one layer (one group of dielectric multilayer films) or with two layers. When there are two or more layers, each reflective layer may have the same configuration or different configurations. When there are two or more reflective layers, it is usually composed of a plurality of reflective layers having different reflection bands.

[0215] As an example, when providing two reflective layers, one may be a near-infrared reflective layer that shields light in the short-wavelength band of the near-infrared region, and the other may be a near-infrared / near-ultraviolet reflective layer that shields light in both the long-wavelength band of the near-infrared region and the near-ultraviolet region. Further, for example, when this filter has a transparent substrate, when providing two or more reflective layers, all of them may be provided on one main surface of the transparent substrate, or each reflective layer may be provided on both main surfaces with the transparent substrate interposed therebetween.

[0216] (Anti-reflection layer) Examples of the anti-reflection layer include a dielectric multilayer film, an intermediate refractive index medium, a moth-eye structure in which the refractive index gradually changes, etc. Among them, a dielectric multilayer film is preferable from the viewpoints of optical efficiency and productivity. The anti-reflection layer is obtained by alternately laminating dielectric films in the same manner as the reflective layer.

[0217] This filter may include, as other components, for example, a component (layer) that provides absorption by inorganic fine particles or the like that control the transmission and absorption of light in a specific wavelength range. Specific examples of the inorganic fine particles include ITO (Indium TIN Oxides), ATO (Antimony-doped TIN Oxides), cesium tungstate, lanthanum boride, and the like. ITO fine particles and cesium tungstate fine particles have a high transmittance of visible light and light absorptivity in a wide range of infrared wavelength regions exceeding 1200 nm, and thus can be used when such infrared light shielding properties are required.

[0218] By having a reflective layer and an absorption layer containing the dye (A), this filter maintains good visible light transmittance and is excellent in the shielding property of near-infrared light, particularly in the shielding property of long-wavelength near-infrared light.

[0219] When the absorption layer contains the dye (A), it is preferable that this filter satisfies the following (iv-2) to (iv-5). (iv-2) For this filter, the average transmittance T of light with wavelengths of 850 to 1100 nm at an incident angle of 0 degrees 850-1100ave0° is 0.2% or less. Preferably it is 0.15% or less, more preferably 0.10% or less. (iv-3) For this filter, the average transmittance T of light with wavelengths of 435 to 630 nm at an incident angle of 0 degrees 435-630ave0° is 65% or more. Preferably it is 70% or more, more preferably 75% or more.

[0220] (iv-4) For this filter, the average transmittance T of light with wavelengths of 850 to 1100 nm at an incident angle of 30 degrees 850-1100ave30° is 2% or less. Preferably it is 1% or less, more preferably 0.05% or less. (iv-5) For this filter, the maximum transmittance T of light with wavelengths of 850 to 1100 nm at an incident angle of 30 degrees 850-1100max30° is 5% or less. Preferably it is 3% or less, more preferably 2% or less.

[0221] When the absorption layer of this filter further contains a dye (D), it preferably satisfies the following optical property (iv-1). (iv-1) For this filter, in the wavelength range of 615 to 725 nm, the average value of the absolute value of the difference in transmittance between the spectral transmittance curves at an incident angle of 0 degree and an incident angle of 30 degrees is 2% / nm or less. Preferably it is 1.5% / nm or less, more preferably 1.0% / nm or less.

[0222] This filter has good visible light transmittance and is excellent in the shielding property of near-infrared light, particularly in the shielding property of long-wavelength near-infrared light. This filter is useful, for example, for the application of an optical filter for an imaging device in a device having both an imaging device such as a digital still camera and an optical component using a laser beam. An imaging device using this filter includes a solid-state imaging device, an imaging lens, and this filter. This filter can be used, for example, by being disposed between an imaging lens and a solid-state imaging device, or by being directly adhered to the solid-state imaging device, imaging lens, etc. of the imaging device via an adhesive layer.

Examples

[0223] Next, the present invention will be described more specifically by way of examples. First, synthesis examples and characteristics of the dyes (A) and (D) used in the absorption layer of the examples will be described. Next, examples of the optical filter will be described.

[0224] [Test Examples 1 to 54: Synthesis, Evaluation of Dyes, Preparation and Evaluation of Absorption Layers] (Synthesis and Evaluation of Dyes) Among the dyes (A) for the examples, for the dyes (ACi1-1B), (ACi1-2B), (ACii2-2B), (ACiii2-9B), and (ACiii3-9B), the product names S0772, S2437, and S2007 manufactured by Few Chemicals, and the product names S1984 and S1985 manufactured by Spectrum info, which are commercially available products, were prepared respectively.

[0225] Also, as the dye (A), the dyes (ACii1-1P), (ACii1-1B), (ACii2-1P), (ACii2-1B), (ACiii1-2P), (ACiii2-2P), (ACiv-2P), (ACiv-26P), and the dye (ASi-1), (ASi-2), and (ASii-2) were synthesized by the following method.

[0226] Furthermore, as the dye (D), the dye (I-12-24) was synthesized by a conventional method. Also, as the dyes for comparative examples, TXEX910B (manufactured by Nippon Shokubai Co., Ltd., phthalocyanine dye) and Dim01 (diimonium dye) shown in the following formula, synthesized by the method described in JP-A-2014-25016, were prepared. For the evaluation of the optical properties of these dyes, a UV-visible spectrophotometer (U-4150 type, manufactured by Hitachi High-Technologies Corporation) was used, and similarly, U-4150 was used for the evaluation of the following optical properties (spectroscopic transmittance curve).

[0227] [Chemical formula]

[0228] (1) Production of the dye (ACii1-1P) The dye (ACii1-1P) was synthesized according to the reaction route shown below.

[0229] [Chemical formula]

[0230] <Step 1> Into a 1 L eggplant flask, benz[cd]indol-2(1H)-one (16 g, 94 mmol), potassium iodide (4 g, 24 mmol), and N,N-dimethyl-4-aminopyridine (2 g, 16 mmol) were added and dissolved in sulfolane (250 mL), and the mixture was stirred at 70 °C for 2 hours. To the above suspension, 1-bromobutane (35 g, 255 mmol) and potassium hydroxide (15 g, 260 mmol) were added, and the mixture was stirred at 70 °C for 19 hours. After completion of the reaction, extraction was performed with an organic solvent mixture of hexane:ethyl acetate = 4:1. After removing the solvent, a yellow oily substance was isolated as product (1) (20.3 g, yield 96%) by flash column chromatography (hexane:ethyl acetate = 8:2).

[0231] <Step 2> The product (1) (5 g, 22 mmol) obtained in Step 1 was placed in a 300 mL eggplant flask and dissolved in 50 mL of tetrahydrofuran. Under a nitrogen atmosphere and at 0 °C, 100 mL of 1 M methylmagnesium bromide was added dropwise. After warming to room temperature, the mixture was stirred for 12 hours. After confirming the disappearance of the starting material using thin-layer chromatography (TLC), the reaction solution was slowly poured into a beaker containing 200 mL of ice water, and then 50 g of 60% aqueous hexafluorophosphoric acid solution was added, and the mixture was stirred at room temperature for 1 hour. After extraction with dichloromethane, the aqueous solvent was removed with anhydrous magnesium sulfate, and the organic solvent was removed. Then, it was dissolved in a small amount of dichloromethane, and reprecipitation was performed using ethyl acetate to obtain a yellow-green solid as product (2) (6.85 g, yield 86%).

[0232] <Step 3> Into a 300 mL eggplant flask, the product (2) (3 g, 8.3 mmol) obtained in Step 2 and cyanine intermediate 1 (1.59 g, 4 mmol) synthesized with reference to J. Heterocyclic Chem., 42, 959, (2005) were added, dissolved in 90 mL of pyridine, and stirred at 150 °C for 3 hours. After completion of the reaction, pyridine was removed while azeotroping with toluene, and the obtained solid was washed with hexane. Then, it was isolated by flash column chromatography (dichloromethane:ethyl acetate = 10:1), the solvent was removed, dissolved in a small amount of dichloromethane, and reprecipitation was performed multiple times using hexane to obtain a black solid (1.0 g, yield 34%), and the dye (ACii1-1P) was obtained.

[0233] (2) Production of Dye (ACii1-1B) In the production of the dye (ACii1-1B), the dye (ACii1-1B) was obtained in the same manner as the dye (ACii1-1P), except that an aqueous solution of 42% tetrafluoroboric acid was used instead of the aqueous solution of 60% hexafluorophosphoric acid in Step 2.

[0234] (3) Production of Dye (ACii2-1P) In the production of the dye (ACii1-1P), the dye (ACii2-1P) was obtained according to the following reaction pathway in the same manner as the dye (ACii1-1P), except that cyanine intermediate 2 was used instead of cyanine intermediate 1 in Step 3.

[0235] [Chemical formula]

[0236] (4) Production of Dye (ACii2-1B) In the production of the dye (ACii1-1B), the dye (ACii2-1B) was obtained in the same manner as the dye (ACii1-1B), except that cyanine intermediate 2 was used instead of cyanine intermediate 1 in Step 3.

[0237] (5) Production of Dye (ACiii1-2P) The dye (ACiii1-2P) was synthesized according to the reaction pathway shown below.

[0238] [Chemical formula]

[0239] <Step 1 (Chlorination)> 2,3,3-Trimethylindoline (50 g, 314 mmol) and iodoethane (100 g, 993 mmol) were added to a 1 L eggplant flask and stirred at 95 °C for 48 hours. The obtained pink solid was washed with a tetrahydrofuran solution to obtain a solid product (3) (70 g, yield 70%).

[0240] <Step 2 (Salt Exchange)> The product (3) (20 g, 64 mmol) obtained in Step 1, methanol (100 mL), and acetone (100 mL) were placed in a 1 L eggplant flask and stirred at 80 °C. Potassium hexafluorophosphate (16 g, 87 mmol), water (100 mL), and acetone (100 mL) were placed in a separately prepared 500 mL eggplant flask and stirred at room temperature for about 2 hours until potassium hexafluorophosphate dissolved. The dissolved potassium hexafluorophosphate solution was poured into the flask containing the product (3), and the mixture was stirred at 80 °C for 14 hours. After confirming the disappearance of the raw material by TLC, the solvents of methanol and acetone were removed, and extraction was performed with dichloromethane. Isolation was carried out by flash column chromatography (dichloromethane:methanol = 1000:40), the solvent was removed, and after washing with hexane, a white solid product (4) (21 g, yield 96%) was obtained.

[0241] <Step 3> Chem. A European Journal, 22(4), 1266, (2016) and J. Org. Chem., 70(21), 8575, (2005), UKRAINSKII KHIMICHESKII ZHURNAL, 44 Reference was made to (8), 838, (1978) to obtain cyanine intermediate 3 (11g, 5 steps, 13%).

[0242] <Step 4> The product (4) (5.12 g, 15 mmol) obtained in Step 2 and the cyanine intermediate 3 (3 g, 7 mmol) obtained in Step 3 were added to a 300 mL eggplant flask, dissolved in 160 mL of pyridine, and stirred at 140 °C for 1 hour. After completion of the reaction, pyridine was removed while azeotroping with toluene. Then, it was isolated by flash column chromatography (dichloromethane:ethyl acetate = 10:1), the solvent was removed, dissolved in a small amount of dichloromethane, and reprecipitation was performed multiple times using hexane to obtain the dye (ACiii1-2P) as a reddish-brown solid (0.18 g, yield 4%).

[0243] (6) Production of dye (ACiii2-2P) In the production of the dye (ACiii1-2P), the dye (ACiii2-2P) was obtained in the same manner as the synthesis method of the dye (ACiii1-2P), except that 2,3,3-trimethyl-4,5-benzo-3H-indole was used instead of 2,3,3-trimethylindoline as the raw material.

[0244] (7) Production of dye (ACiv-2P) The dye (ACiv-2P) was synthesized according to the reaction route shown below.

[0245]

Chemical formula

[0246] <Step 1> Lepidine (53 g, 370 mmol) and iodoethane (100 g, 641 mmol) were added to a 1 L eggplant flask and stirred at 50 °C for 15 hours. The obtained solid was washed with hexane to obtain the solid product (5) (100 g, yield 90%).

[0247] <Step 2> Into a 1 L eggplant flask, the product (5) (20 g, 66.8 mmol) obtained in Step 1, methanol (100 mL), and acetone (100 mL) were added, and the mixture was stirred at 80 °C. Separately, into a 500 mL eggplant flask, potassium hexafluorophosphate (16 g, 87 mmol), water (100 mL), and acetone (100 mL) were added, and the mixture was stirred at room temperature for about 2 hours until potassium hexafluorophosphate dissolved. The dissolved potassium hexafluorophosphate solution was poured into the eggplant flask containing the product (5), and the mixture was stirred at 80 °C for 14 hours. After confirming by TLC that the raw material had disappeared, the solvents of methanol and acetone were removed, and extraction was performed with dichloromethane. Isolation was carried out by flash column chromatography (dichloromethane:methanol = 1000:40), the solvent was removed, and after washing with hexane, a white solid product (6) (20 g, yield 94%) was obtained.

[0248] <Step 3> Using the product (6) obtained in Step 2, the dye (ACiv-2P) was obtained in the same manner as Step 3 described in the synthesis method of the dye (ACii1-1P).

[0249] (8) Production of dye (ACiv-26P) In the production of the dye (ACiv-2P), the dye (ACiv-26P) was obtained in the same manner as the synthesis method of the dye (ACiv-2P), except that cyanine intermediate 2 was used instead of cyanine intermediate 1.

[0250] (9) Production of dye (ASi-1) The dye (ASi-1) was synthesized according to the reaction pathway shown below. That is, the product (10) (6.5 mmol) prepared with reference to European Journal of Medical Chemistry, 54, 647, (2012) and squaric acid (3.4 mmol) were placed in a 500 mL eggplant flask, dissolved in toluene (330 mL) and 1-butanol (110 mL), quinoline (8 mmol) was added, and the mixture was stirred at 150 °C for 4 hours. The product (10) is an iodide salt of a compound in which the hydrogen at the 1-position of 2-methyl-benzo[c,d]indole is substituted with R, and R is -CH2-CH(C2H5)(C4H9).

[0251] After completion of the reaction, the solvent was removed, and the product was isolated by flash column chromatography (hexane:ethyl acetate = 8:2). After removing the solvent and washing with hexane, a reddish-brown solid dye (ASi-1) (0.5 g, yield 25%) was obtained.

[0252]

Chemical formula

[0253] (10) Production of dye (ASi-2) In the production of the dye (ASi-1), the product (10) was changed to an iodide salt of a benzo[c,d]indole compound in which R in the product (10) was replaced with -CH2-CH(C8H 17 )(C6H 13 ), and the dye (ASi-2) was obtained in the same manner as the synthesis method of the dye (ASi-1).

[0254] (11) Production of dye (ASii-2) The dye (ASii-2) was synthesized according to the reaction pathway shown below.

[0255]

Chemical formula

[0256] <Step 1> Into a 1 L eggplant flask, add 5-methylisatin (25 g, 155 mmol) and 1-butanol (180 mL), and dropwise add hydrazine monohydrate (9.3 g, 186 mmol) at 0 °C. After stirring at 35 °C for 30 minutes, raise the temperature to 80 °C and stir for 4 hours. Then, slowly add triethylamine (15.7 g, 155 mmol), and stir at 100 °C for 11 hours. Add concentrated sulfuric acid until the pH reaches about 6, cool to room temperature, remove the solvent, perform extraction, wash the obtained solid with hexane, and obtain the product (7) (22 g, yield 96%) as a brown solid.

[0257] <Step 2> Referring to Org. Lett., 18, 5232, (2016), add the product (7) (22 g, 149 mmol) obtained in Step 1, 2-bromobenzaldehyde (16 g, 90 mmol), cesium carbonate (86 g, 26 mmol), and dimethyl sulfoxide (700 mL) to a 1 L three-necked flask. After performing vacuum degassing and nitrogen replacement multiple times, stir at 120 °C for 7 hours, and then cool to room temperature. Then, perform extraction, isolate by flash column chromatography (hexane:ethyl acetate = 2:8), remove the solvent, and obtain the product (8) (8 g, yield 38%) as a yellow solid.

[0258] <Step 3> From the product (8) obtained in Step 2, refer to the method described in European Journal of Medical Chemistry, 54, 647, (2012) to obtain the product (9). Note that in the product (9), R is -CH2-CH (C8H 17 )(C6H 13 ). In the production of the dye (ASi-2), the dye (ASii-2) was obtained in the same manner as the synthesis method of the dye (ASi-2), except that the iodine salt of 1-dodecyl-2-methyl-benzo[c,d]indole was changed to the product (9).

[0259] Each of the above pigments was dissolved in dichloromethane, and the light absorption spectrum in the wavelength range of 350 to 1200 nm was measured. From the absorbance curve, the maximum absorption wavelength λ max(A)DCM was determined. Further, from the absorbance curve adjusted so that the transmittance of light at the maximum absorption wavelength λ max(A)DCM was 10%, ABS 400(A)DCM / ABS λmax(A)DCM and ABS 550(A)DCM / ABS λmax(A)DCM were determined. The results are shown in Table 17. In the table, "ABS 400 / λmax in DCM" indicates ABS 400(A)DCM / ABS λmax(A)DCM , and "ABS 550 / λmax in DCM" indicates ABS 550(A)DCM / ABS λmax(A)DCM . Also, "ASi-xx / ASi-yy" means a compound in which, in the above formula (ASi), the left-side R 161 ~R 167 is the same as the compound with the pigment abbreviation ASi-xx, and the right-side R 161 ~R 167 is the same as the compound with the pigment abbreviation ASi-yy.

[0260]

Table 17

[0261] (Fabrication of the absorption layer) An absorption layer was fabricated using the pigment and the transparent resin obtained above, and the optical properties were evaluated. Test Examples 1 to 12, 15 to 24, 27 to 34, 37 to 44 are test examples related to this filter, and Test Examples 13, 14, 25, 26, 35, 36, 45 to 54 are comparative test examples. The following commercially available products were used as the transparent resin.

[0262] <Transparent resin> Transparent resin (R1); Neoprim (registered trademark) C-3G30 (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name, polyimide resin) Transparent resin (R2); OKP-850 (manufactured by Osaka Gas Chemical Co., Ltd., trade name, polyester resin) Transparent resin (R3); SP3810 (manufactured by Teijin Ltd., trade name, polycarbonate resin) Transparent resin (R4); PLEXIMID8817 (manufactured by Daicel Evonik Co., trade name, acrylic imide resin) Transparent resin for comparative example (Rcf); BR1122 (manufactured by Mitsubishi Rayon Co., trade name, acrylic resin)

[0263] A pigment, transparent resin (R1), and cyclohexanone were sufficiently stirred and uniformly dissolved. The resulting solution was applied onto a glass plate (D263; manufactured by SCHOTT, trade name) and dried to obtain an absorption layer with a film thickness of 1 μm. The addition amount of the pigment (pigment concentration) was adjusted such that the light transmittance at the maximum absorption wavelength λ max(A)TR was 10% at a film thickness of 1 μm. Using the absorbance curve of the glass plate with the absorption layer in the wavelength range of 350 to 1200 nm and the absorbance curve of the glass plate, the absorbance curve of the absorption layer was obtained.

[0264] From the absorbance curve of the absorption layer, the maximum absorption wavelength λ max(A)TR , ABS 400(A)TR / ABS λmax(A)TR (in the table, "ABS in resin" 400 / λmax ) and ABS 550(A)TR / ABS λmax(A)TR (in the table, "ABS in resin" 550 / λmax ) were determined. Also, ABS 400(A)TR / ABS λmax(A)TR -ABS 400 (A)DCM / ABS λmax(A)DCM (in the table, "difference in ABS" 400 / λmax ), and ABS 550(A)TR / ABS λmax(A)TR -ABS 550(A)DCM / ABS λmax(A)DCM (in the table, "difference in ABS" 550 / λmax ) were determined. Furthermore, the mass absorption coefficient / (cm·mass%) was determined. The results are shown in Table 18. The pigment concentration in the table is the number of parts by mass relative to 100 parts by mass of the transparent resin (R1) when adjusted such that the light transmittance at the above λ max(A)TR is 10% at a film thickness of 1 μm.

[0265]

Table 18

[0266] In the above, the same evaluation was performed by replacing the transparent resin (R1) with the transparent resins (R2) to (R4) or the transparent resin (Rcf) for the comparative example. The results for the transparent resin (R2) are shown in Table 19, for the transparent resin (R3) in Table 20, for the transparent resin (R4) in Table 21, and for the transparent resin (Rcf) for the comparative example in Table 22.

[0267]

Table 19

[0268]

Table 20

[0269]

Table 21

[0270]

Table 22

[0271] It is clear from Tables 18 to 22 that the requirements (i-1) to (i-3) can be satisfied by using the dyes (ACi) to (ACiv), the dye (ASi) or the dye (ASii), and a suitable transparent resin in combination with these. Furthermore, it is clear that the requirement (i-4) is satisfied in a preferred combination among these.

[0272] [Examples 1 to 12: Manufacture and Evaluation of Optical Filter] (Manufacture of Optical Filter) An optical filter having the same configuration as the optical filter 10F shown in FIG. 6 was manufactured by the following method.

[0273] In each example, as shown in Tables 23 and 24, a glass substrate with a thickness of 0.21 mm made of CuO-containing phthalate glass (manufactured by Asahi Glass Co., Ltd., trade name: NF-50GX) or a glass substrate with a thickness of 0.2 mm (D263; manufactured by SCHOTT, trade name) was used as the transparent substrate.

[0274] As the reflective layer, a dielectric multilayer film formed as follows was used in each example. The dielectric multilayer film was formed by alternately laminating a total of 42 layers of TiO2 films and SiO2 films on one main surface of the glass substrate by vapor deposition. The structure of the reflective layer was simulated with the number of layers of the dielectric multilayer film, the film thickness of the TiO2 film, and the film thickness of the SiO2 film as parameters, and the design was such that the average transmittance of light with a wavelength of 850 to 1100 nm was 0.03% in the spectral transmittance curve at an incident angle of 0 degrees.

[0275] Also, on the main surface of the glass substrate opposite to the side where the reflective layer was formed, a transparent resin shown in Tables 23 and 24, one or two types of dye (A) (the first dye (A) and the second dye (A) in the table), and a dye (D) (dye (I-12-24)) were combined to form an absorption layer with a thickness of about 1.0 μm. The dye content in Tables 23 and 24 is the mass part of the dye with respect to 100 mass parts of the transparent resin.

[0276] Thereafter, an antireflection layer was formed by alternately laminating 7 layers of TiO2 films and SiO2 films on the surface of the absorption layer by vapor deposition, and optical filters (NIR filters) of Examples 1 to 12 were obtained. Examples 1 to 11 are examples, and Example 12 is a comparative example.

[0277] (Evaluation) For the absorption layers of the obtained optical filters of Examples 1 to 12, spectral transmittance curves at an incident angle of 0 degrees were obtained. Tables 23 and 24 show the wavelength λ on the short wavelength side of the wavelength at which the transmittance is 20% obtained from the spectral transmittance curve, ABSHT20-0° the average transmittance T of light with a wavelength of 435 to 630 nm, AB435-630ave0° and the average transmittance T of light with a wavelength of 850 to 1100 nm. AB850-1100ave0° are shown.

[0278] In addition, for the obtained optical filters of Examples 1 to 12, spectral transmittance curves at incident angles of 0 degrees and 30 degrees were obtained. Tables 23 and 24 show the values obtained from the spectral transmittance curves, which are the averages of the absolute values of the differences in transmittance between the spectral transmittance curves at an incident angle of 0 degrees and an incident angle of 30 degrees at wavelengths from 615 to 725 nm (in the table, "difference at wavelengths from 615 to 725 nm"). Also shown are the average transmittance T 850-1100ave0° , of light with wavelengths from 435 to 630 nm, the average transmittance T 435-630ave0° at an incident angle of 30 degrees for light with wavelengths from 850 to 1100 nm, the average transmittance T 850-1100ave30° at an incident angle of 0 degrees for light with wavelengths from 850 to 1100 nm, and the maximum transmittance T 850-1100max30° of light with wavelengths from 850 to 1100 nm.

[0279]

Table 23

[0280]

Table 24

[0281] From Tables 23 and 24, it can be seen that the optical filters of Examples 1 to 11 satisfy (ii-1) to (ii-3) for the absorption layer and satisfy (iv-1) to (iv-5) for the optical filter.

Industrial Applicability

[0282] The optical filter of the present invention has good visible light transmittance and is excellent in shielding near-infrared light, particularly in shielding long-wavelength near-infrared light. Therefore, it is useful for applications of optical filters for imaging devices in equipment having both an imaging device and optical components using laser light.

[0283] Although the present invention has been described in detail 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 present invention. This application is based on Japanese Patent Application No. 2018-018608 filed on February 5, 2018, the content of which is incorporated herein by reference.

Explanation of Signs

[0284] 10A, 10B, 10C, 10D, 10E, 10F… optical filters, 11, 11a, 11b… absorption layers, 12, 12a, 12b… reflection layers, 13… transparent substrate, 14… antireflection layer.

Claims

1. An optical filter having an absorption layer containing a near-infrared absorbing dye (A) and a transparent resin, and a reflective layer composed of a dielectric multilayer film, wherein the near-infrared absorbing dye (A) satisfies all of the following (i-1) to (i-3) and contains at least one of a cyanine compound represented by any of the following formulas (ACi1) to (ACii2) and a squarylium dye represented by the following formula (ASi), and the transparent resin satisfies the following (i-3) in relation to the near-infrared absorbing dye (A). However, the symbols in the formulas (ACi1) to (ACii2) are as follows. In the absorbance curve measured by dissolving in (i-1) dichloromethane and having a wavelength of 350 to 1200 nm, the maximum absorption wavelength λ ｍａｘ（Ａ）ＤＣＭ is in the wavelength range of 850 to 1100 nm. In the absorbance curve at wavelengths of 350 to 1200 nm measured by dissolving in (i-2) dichloromethane, the maximum absorption wavelength is λ ｍａｘ（Ａ）ＤＣＭ The absorbance at is ABS λｍａｘ（Ａ）ＤＣＭ , the absorbance at a wavelength of 400 nm is ABS ４００（Ａ）ＤＣＭ , the absorbance at a wavelength of 550 nm is ABS ５５０（Ａ）ＤＣＭ When defined as such, the following formulas (1) and (2) are satisfied. ABS ４００（Ａ）ＤＣＭ / ABS λｍａｘ（Ａ）ＤＣＭ <0.10 …(1) ABS ５５０（Ａ）ＤＣＭ / ABS λｍａｘ（Ａ）ＤＣＭ <0.04 …(2) (i-3) In the absorbance curve of wavelengths 350 to 1200 nm measured by including it in the transparent resin, the maximum absorption wavelength λ ｍａｘ（Ａ）ＴＲ is in the wavelength range of 850 to 1100 nm, and the absorbance at the maximum absorption wavelength λ ｍａｘ（Ａ）ＴＲ is ABS λｍａｘ（Ａ）ＴＲ , the absorbance at a wavelength of 400 nm is ABS ４００（Ａ）ＴＲ , and the absorbance at a wavelength of 550 nm is ABS ５５０（Ａ）ＴＲ When it is set as, the following formulas (3) and (4) are satisfied. ABS ４００（Ａ）ＴＲ / ABS λｍａｘ（Ａ）ＴＲ <0.15 …(3) ABS ５５０（Ａ）ＴＲ / ABS λｍａｘ（Ａ）ＴＲ <0.10 …(4) 【Chemical 1】 However, the symbols in the formula (ASi) are as follows. R １０１ ~R １０７ 、R １２１ ~R １２７ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR １１２ R １１３ group, -NHSO ２ R １１４ group, -NHCOR １１５ group, -SR １１６ group, -SO ２ R １１７ group, -OSO ２ R １１８ group, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. R １０２ ~R １０７ and R １２２ ~R １２７ Two adjacent ones of them may be linked to each other to form a 5-membered ring, a 6-membered ring, or a 7-membered ring. R １３０ａ is a hydrogen atom, a methyl group or a phenyl group. R １３０ｂ is a hydrogen atom, a methyl group, a phenyl group or a diphenylamino group. R １１２ to R １１８ are each independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. A plurality of Rs included in various forms １０１ ~R １０７ 、R １２１ ~R １２７ may be the same as or different from each other. X － represents a monovalent anion. 【Chemical Formula 2】

2. R １６１ is a branched alkyl group having 3 to 20 carbon atoms or a linear alkyl group having 13 to 20 carbon atoms. R １６２ to R １６７ each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR １１２ R １１３ group, -NHSO ２ R １１４ group, -NHCOR １１５ group, -SR １１６ group, -SO ２ R １１７ group, -OSO ２ R １１８ group, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. R １１２ to R １１８ are each independently a hydrogen atom, an alkyl or alkoxy group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 members. The plurality of Rs included in each form １６１ ~R １６７ may be the same as or different from each other. The optical filter according to claim 1, wherein the near-infrared absorbing dye (A) contains a squarylium dye represented by the formula (ASi).

3. The optical filter according to claim 1, wherein the near-infrared absorbing dye (A) contains a cyanine compound represented by any of the formulas (ACi1) to (ACii2).

4. The optical filter according to claim 1, wherein the near-infrared absorbing dye (A) further satisfies the following (i-4). (i-4) Satisfies the following formulas (5) and (6).

5. ABS ４００（Ａ）ＴＲ / ABS λｍａｘ（Ａ）ＴＲ -ABS ４００（Ａ）ＤＣＭ / ABS λｍａｘ（Ａ）ＤＣＭ <0.10 …(5) ABS ５５０（Ａ）ＴＲ / ABS λｍａｘ（Ａ）ＴＲ -ABS ５５０（Ａ）ＤＣＭ / ABS λｍａｘ（Ａ）ＤＣＭ <0.08 …(6) The optical filter according to claim 1, wherein the near-infrared absorbing dye (A) further satisfies the following (i-4). (i-4) Satisfies the following formulas (5) and (6).

6. ABS ４００（Ａ）ＴＲ / ABS λｍａｘ（Ａ）ＴＲ -ABS ４００（Ａ）ＤＣＭ / ABS λｍａｘ（Ａ）ＤＣＭ <0.06 …(5) ABS ５５０（Ａ）ＴＲ / ABS λｍａｘ（Ａ）ＴＲ -ABS ５５０（Ａ）ＤＣＭ / ABS λｍａｘ（Ａ）ＤＣＭ <0.08 …(6) However, the symbols in the formula (I) are as follows. The absorption layer further has a maximum absorption wavelength λ in an absorbance curve at wavelengths of 350 to 1200 nm measured by inclusion in the transparent resin ｍａｘ（Ｄ）ＴＲ in a wavelength region of 650 to 750 nm and contains a near-infrared absorbing dye (D) represented by any one of the following formulas (I) to (III). The optical filter according to any one of claims 1 to 5 However, the symbols in the formula (II) are as follows. R ２４ and R ２６ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, -NR ２７ R ２８ (R ２７ and R ２８ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, -C(=O)-R ２９ (R ２９ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 11 carbon atoms or an aralkyl group having 7 to 18 carbon atoms which may have a substituent and may have an oxygen atom between carbon atoms), -NHR ３０ , or, -SO ２ -R ３０ (R ３０ each represents a hydrocarbon group having 1 to 25 carbon atoms in which one or more hydrogen atoms may be substituted with a halogen atom, a hydroxyl group, a carboxy group, a sulfo group or a cyano group and which may contain an unsaturated bond, an oxygen atom, a saturated or unsaturated ring structure between carbon atoms).), or, a group represented by the following formula (S) (R ４１ , R ４２ independently represent a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 10 carbon atoms. k is 2 or 3.).) [Chemical 3] R ２１ and R ２２ 、R ２２ and R ２５ 、and R ２１ and R ２３ may be connected to each other to form heterocyclic rings A, B, and C each having 5 or 6 members together with a nitrogen atom. R when the complex ring A is formed ２１ and R ２２ are, as a divalent group -Q- formed by combining them, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkylene group which may be substituted with an acyloxy group having 1 to 10 carbon atoms which may have a substituent, or an alkyleneoxy group. R when the complex ring B is formed ２２ and R ２５ and R when the complex ring C is formed ２１ and R ２３ are each a divalent group -X １ -Y １ - and -X ２ -Y ２ -(where the side bonded to nitrogen is X １ and X ２ ) and X １ and X ２ are each a group represented by the following formula (1x) or (2x), and Y １ and Y ２ are each a group represented by any one selected from the following formulas (1y) to (5y). When X １ and X ２ are each a group represented by the following formula (2x), Y １ and Y ２ may each be a single bond, and in that case, may have an oxygen atom between carbon atoms. 【Chemical 4】 In formula (1x), the four Zs are each independently a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, or -NR ３８ R ３９ (R ３８ and R ３９ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). R ３１ to R ３６ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ３７ represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. R ２７ 、R ２８ 、R ２９ 、R ３１ ~R ３７ 、 when no complex ring is formed, R ２１ ~R ２３ 、 and R ２５ may be bonded to any one of the others to form a 5-membered or 6-membered ring. R ３１ and R ３６ 、R ３１ and R ３７ may be directly bonded. R when no complex ring is formed ２１ and R ２２ each independently represents a hydrogen atom, an alkyl group or allyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group or aralkyl group having 6 to 11 carbon atoms which may have a substituent. R ２３ and R ２５ each independently represents a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having 1 to 6 carbon atoms. [Chemical Formula 5] Ring Z is each independently a 5-membered or 6-membered ring having 0 to 3 heteroatoms in the ring and may be substituted. However, the symbols in the formula (III) are as follows. R １ and R ２ 、R ２ and R ３ 、and R １ The carbon atoms or heteroatoms that form the ring Z with R, R, and R may be connected to each other to form heterocycles A1, B1, and C1 together with a nitrogen atom, respectively. When no heterocycle is formed, R １ and R ２ each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group that may contain an unsaturated bond, a heteroatom, a saturated or unsaturated ring structure between carbon atoms and may have a substituent, and R ３ and R ４ each independently represent a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group that may contain a heteroatom between carbon atoms. 【Chemical Formula 6】

7. R ５１ each independently represents a halogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, R ５２ to R ５８ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent. R ５２ and R ５３ may be connected to each other to form a saturated or unsaturated hydrocarbon ring B2 having 5 to 15 carbon atoms, and the hydrogen atoms of the hydrocarbon ring B2 may be substituted with an alkyl group having 1 to 10 carbon atoms. R ５４ and R ５５ may be connected to each other to form benzene ring A2, and the hydrogen atoms of benzene ring A2 may be substituted with an alkyl group having 1 to 10 carbon atoms. The optical filter according to claim 6, wherein the absorption layer satisfies the following (ii-1) to (ii-3) in the spectral transmittance curve at an incident angle of 0 degrees, the reflective layer satisfies the following (iii-1), and the optical filter satisfies the following (iv-1). (ii-1) The wavelength on the short-wavelength side of the wavelength at which the transmittance is 20% is in the wavelength range of 655 to 675 nm. (ii-2) The average transmittance of light with wavelengths of 435 to 630 nm is 65% or more. (ii-3) The average transmittance of light with wavelengths of 850 to 1100 nm is 70% or less. (iii-1) In the spectral transmittance curve at an incident angle of 0 degrees, the average transmittance of light with wavelengths of 850 to 1100 nm is 0.2% or less. ​ In the wavelength range of 615 to 725 nm, the average of the absolute values of the differences in transmittance in the spectral transmittance curves at an incident angle of 0 degrees and an incident angle of 30 degrees is 2% / nm or less.

8. The optical filter according to any one of claims 1 to 7, wherein the transparent resin contains at least one selected from a polyester resin, a polycarbonate resin, and a polyimide resin.

9. The optical filter according to any one of claims 1 to 8, wherein the thickness of the absorption layer is 0.3 to 10 μm.

10. The near-infrared absorbing dye (A) has a maximum absorption wavelength λ ｍａｘ（Ａ）ＴＲ The optical filter according to any one of claims 1 to 9, comprising at least two kinds having different ｍａｘ（Ａ）ＴＲ .

11. An imaging device including the optical filter according to any one of claims 1 to 10.

Images