Filters and imaging devices

Abstract

The present invention relates to an optical filter and an imaging device. The present invention relates to an optical filter, comprising an absorption layer and a reflection layer, wherein the absorption layer contains a near-infrared absorption pigment (A) and a transparent resin, wherein the near-infrared absorption pigment (A) has a maximum absorption wavelength in dichloromethane within a wavelength range of 850 nm to 1100 nm, wherein the reflection layer comprises a dielectric multilayer film, wherein the value of the ratio of the absorbance of the near-infrared absorption pigment (A) in dichloromethane at a wavelength of 400 nm to the absorbance of the maximum absorption wavelength is less than 0.10, and the value of the ratio of the absorbance at a wavelength of 550 nm to the absorbance of the maximum absorption wavelength is less than 0.04, and the value of the ratio of the absorbance of the near-infrared absorption pigment (A) in the transparent resin at a wavelength of 400 nm to the absorbance of the maximum absorption wavelength is less than 0.15, and the value of the ratio of the absorbance at a wavelength of 550 nm to the absorbance of the maximum absorption wavelength is less than 0.10.

Description

[0001] This application is a divisional application of the Chinese patent application with application date of January 30, 2019 and application number 201980011470.9. Technical Field

[0002] The present invention relates to an optical filter which transmits light in a visible wavelength range and blocks light in a near-infrared wavelength range, and an imaging device having the optical filter. Background Art

[0003] In an imaging device using a solid-state imaging element, in order to reproduce the color tone well and obtain a clear image, a filter that transmits light in the visible light 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. As such a filter, a near infrared cutoff filter having an absorption layer containing a near infrared absorber and a reflection layer including 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 according to the incident angle, the near infrared cutoff filter including both the reflection layer and the absorption layer can obtain a spectral transmittance curve in which the incidence angle dependency is suppressed by the absorption characteristics of the absorption layer.

[0004] In recent years, in various devices equipped with such imaging devices, optical components using lasers with wavelengths of 850nm to 1100nm are increasingly being installed together. Therefore, near-infrared cutoff filters are required to suppress the reduction of visible light transmittance and fully cut off long-wavelength near-infrared light with wavelengths of 850nm to 1100nm.

[0005] In the past, many technologies using absorbers that show absorption in a relatively long wavelength range have been known for near infrared cut filters. Specifically, it is known that Combination of salt pigments with cyanine pigments, phthalocyanine pigments, etc. (see, for example, Patent Documents 1 and 2); technologies using diimmonium pigments, metal dithiol complexes, inorganic fine particles, etc. (see, for example, Patent Documents 3, 4, and 5).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2013 / 054864

[0009] Patent Document 2: International Publication No. 2016 / 158461

[0010] Patent Document 3: International Publication No. 2017 / 094672

[0011] Patent Document 4: International Publication No. 2014 / 168189

[0012] Patent Document 5: International Publication No. 2014 / 168190 Summary of the invention

[0013] Problems to be solved by the invention

[0014] However, any of the above-mentioned near-infrared cut filters cannot have both high transmittance of visible light and high barrier properties in the long wavelength range of 850 nm to 1100 nm.

[0015] An object of the present invention is to provide an optical filter having excellent near-infrared light shielding properties, particularly long-wavelength near-infrared light shielding properties, while maintaining good visible light transmittance, and an imaging device having excellent color reproducibility using the optical filter.

[0016] Means used to solve problems

[0017] The optical filter according to one embodiment of the present invention is characterized in that the optical filter has an absorption layer and a reflection layer, the absorption layer contains a near-infrared absorption pigment (A) and a transparent resin, the reflection layer contains a dielectric multilayer film, and the near-infrared absorption pigment (A) satisfies the following (i-1) to (i-3):

[0018] (i-1) In the absorbance curve at wavelengths of 350 nm to 1200 nm measured by dissolving the near infrared absorbing dye (A) in dichloromethane, the maximum absorption wavelength λ 最大(A)DCM In the wavelength range of 850nm to 1100nm;

[0019] (i-2) In the absorbance curve at wavelengths of 350 nm to 1200 nm measured by dissolving the near infrared absorbing dye (A) in dichloromethane, the maximum absorption wavelength λ 最大(A)DCM The absorbance at λ最大(A)DCM , Set the absorbance at a wavelength of 400nm as ABS 400(A)DCM , and set the absorbance at a wavelength of 550nm as ABS 550(A)DCM When , the following equations (1) and (2) are satisfied:

[0020] ABS 400(A)DCM / ABS λ最大(A)DCM <0.10 (1)

[0021] ABS 550(A)DCM / ABS λ最大(A)DCM <0.04 (2);

[0022] (i-3) In the absorbance curve at a wavelength of 350 nm to 1200 nm measured by containing the near infrared absorbing dye (A) in the transparent resin, the maximum absorption wavelength λ 最大(A)TR In the wavelength range of 850nm to 1100nm, and at the maximum absorption wavelength λ 最大(A)TR The absorbance at λ最大(A)TR , Set the absorbance at a wavelength of 400nm as ABS 400(A)TR , and set the absorbance at a wavelength of 550nm as ABS 550(A)TR When , the following equations (3) and (4) are satisfied:

[0023] ABS 400(A)TR / ABS λ最大(A)TR <0.15 (3)

[0024] ABS 550(A)TR / ABS λ最大(A)TR <0.10 (4).

[0025] The present invention also provides an imaging device having the optical filter of the present invention.

[0026] Effects of the Invention

[0027] According to the present invention, a filter having excellent near-infrared light blocking property, especially long-wavelength near-infrared light blocking property, can be obtained while maintaining good visible light transmittance. In addition, according to the present invention, an imaging device having excellent color reproducibility using the filter can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a cross-sectional view schematically showing an example of an optical filter according to an embodiment.

[0029] Figure 2 This is a cross-sectional view schematically showing another example of the optical filter according to one embodiment.

[0030] Figure 3 This is a cross-sectional view schematically showing another example of the optical filter according to one embodiment.

[0031] Figure 4 This is a cross-sectional view schematically showing another example of the optical filter according to one embodiment.

[0032] Figure 5 This is a cross-sectional view schematically showing another example of the optical filter according to one embodiment.

[0033] Figure 6 This is a cross-sectional view schematically showing another example of the optical filter according to one embodiment. DETAILED DESCRIPTION

[0034] Hereinafter, embodiments of the present invention will be described.

[0035] In this specification, a near infrared absorbing dye may be simply referred to as a “NIR dye”, and an ultraviolet absorbing dye may be simply referred to as a “UV dye”.

[0036] In this specification, the compound represented by formula (I) is referred to as compound (I). The same applies to compounds represented by other formulas. A pigment containing compound (I) is referred to as pigment (I), and the same applies to other pigments. For example, a compound represented by formula (ACi) described later is referred to as compound (ACi), and a pigment containing the compound is referred to as pigment (ACi). In addition, for example, a group represented by formula (1x) is referred to as group (1x), and the same applies to groups represented by other formulas.

[0037] In this specification, for a specific wavelength range, a transmittance of, for example, 90% or more means that the transmittance is not less than 90% in the entire wavelength range, and similarly, a transmittance of, for example, 1% or less means that the transmittance is not greater than 1% in the entire wavelength range. The average transmittance in a specific wavelength range is the arithmetic mean of the transmittance per 1 nm in the wavelength range.

[0038] In the present specification, "to" indicating a numerical range includes the upper limit and the lower limit.

[0039] In the present specification, when a plurality of substituents represented by the same symbol exist in a certain general formula, these plurality of substituents may be the same as or different from each other.

[0040] <Filter>

[0041] An optical filter according to one embodiment of the present invention (hereinafter also referred to as "the present optical filter") comprises an absorption layer and a reflection layer, wherein the absorption layer contains a pigment (A) and a transparent resin, and the pigment (A) is a NIR pigment satisfying the following (i-1) to (i-3).

[0042] (i-1) In the absorbance curve at wavelengths of 350 nm to 1200 nm measured by dissolving the dye (A) in dichloromethane, the maximum absorption wavelength λ 最大(A)DCM In the wavelength range of 850nm ~ 1100nm.

[0043] (i-2) In the absorbance curve at wavelengths of 350 nm to 1200 nm measured by dissolving the dye (A) in dichloromethane, when the maximum absorption wavelength λ 最大(A)DCM The absorbance at λ最大(A)DCM , Set the absorbance at a wavelength of 400nm as ABS 400(A)DCM , and set the absorbance at a wavelength of 550nm as ABS 550(A)DCMWhen , the following equations (1) and (2) are satisfied:

[0044] ABS 400(A)DCM / ABS λ最大(A)DCM <0.10 (1)

[0045] ABS 550(A)DCM / ABS λ最大(A)DCM <0.04 (2).

[0046] (i-3) In the absorbance curve at a wavelength of 350 nm to 1200 nm measured by making the dye (A) contained in the transparent resin, the maximum absorption wavelength λ 最大(A)TR In the wavelength range of 850nm to 1100nm, and at the maximum absorption wavelength λ 最大(A)TR The absorbance at λ最大(A)TR , Set the absorbance at a wavelength of 400nm as ABS 400(A)TR , and set the absorbance at a wavelength of 550nm as ABS 550(A)TR When , the following equations (3) and (4) are satisfied:

[0047] ABS 400(A)TR / ABS λ最大(A)TR <0.15 (3)

[0048] ABS 550(A)TR / ABS λ最大(A)TR <0.10 (4).

[0049] Since the absorption layer contains the dye (A) having the characteristics of (i-1) to (i-3) and a transparent resin, the present optical filter has excellent light shielding properties in the long wavelength range of near-infrared light and high transmittance of visible light.

[0050] The dye (A) preferably further has the following property (i-4).

[0051] (i-4) The dye (A) satisfies the following formulas (5) and (6).

[0052] ABS 400(A)TR / ABS λ最大(A)TR -ABS 400(A)DCM / ABS λ最大(A)DCM <0.10 (5)

[0053] ABS 550(A)TR / ABS λ最大(A)TR -ABS 550(A)DCM / ABS λ最大(A)DCM <0.08 (6)

[0054] The absorbance curve at wavelengths of 350 nm to 1200 nm measured by dissolving the dye (A) in dichloromethane is obtained by adjusting the amount of the dye (A) added so that the maximum absorption wavelength λ 最大(A)DCM The absorbance curve is the absorbance curve when the absorbance at the wavelength of 350nm to 1200nm measured by including the pigment (A) in a transparent resin. The amount of pigment (A) added is adjusted so that the maximum absorption wavelength λ 最大(A)TR The absorbance curve when the absorbance at is 1, that is, the light transmittance is 10%.

[0055] The dye (A) preferably further has the following property (i-5).

[0056] (i-5) When the dye (A) is contained in the transparent resin, the mass extinction coefficient is 1000 / (cm·mass %) or more.

[0057] It should be noted that the mass extinction coefficient can be obtained by calculating the internal transmittance T[%] (= measured transmittance [%] / (100-measured reflectance [%]) × 100[%]) of light at the maximum absorption wavelength in the wavelength range of 350nm to 1200nm and by -log 10 Hereinafter, unless otherwise specified, the "mass extinction coefficient" of a pigment is the mass extinction coefficient calculated by the above method.

[0058] The optical filter may further include a transparent substrate. In this case, the absorption layer and the reflection layer are arranged on the main surface of the transparent substrate. The optical filter may include the absorption layer and the reflection layer on the same main surface of the transparent substrate, or may include the absorption layer and the reflection layer on different main surfaces of the transparent substrate. In the case where the absorption layer and the reflection layer are included on the same main surface of the transparent substrate, there is no particular restriction on their stacking order.

[0059] The optical filter may also have other functional layers. As other functional layers, for example, an anti-reflection layer that suppresses the transmittance loss of visible light can be cited. In particular, in the case of a structure in which the absorption layer is the outermost surface, since the visible light transmittance loss caused by reflection occurs at the interface between the absorption layer and the air, an anti-reflection layer may be provided on the absorption layer.

[0060] Next, a configuration example of the present optical filter will be described using the drawings. Figure 1This is a structural example of an optical filter 10A having a reflective layer 12 on one main surface of an absorption layer 11. In the optical filter 10A, the absorption layer 11 may be composed of a layer containing a pigment (A) and a transparent resin. It should be noted that "having a reflective layer 12 on one main surface (on) the absorption layer 11" is not limited to the case where the reflective layer 12 is in contact with the absorption layer 11, but also includes the case where another functional layer is between the absorption layer 11 and the reflective layer 12, and the same applies to the following structures.

[0061] Figure 2 1 is a cross-sectional view schematically showing an example of an optical filter having an embodiment of 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 disposed 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 pigment (A) and a transparent resin.

[0062] Figure 3 This is a structural example of an optical filter 10C including an absorption layer 11 and reflection layers 12 a and 12 b on both main surfaces of the absorption layer 11 .

[0063] Figure 4 This is a structural example of an optical filter 10D having an absorption layer 11 on one principal surface of a transparent substrate 13 and reflecting layers 12 a and 12 b on the other principal surface of the transparent substrate 13 and on the principal surface of the absorption layer 11 .

[0064] Figure 5 This is a structural example of an optical filter 10E having absorption layers 11 a and 11 b on both principal surfaces of a transparent substrate 13 and reflection layers 12 a and 12 b on principal surfaces of the absorption layers 11 a and 11 b.

[0065] exist Figure 3 , Figure 4 and Figure 5 In the embodiment, the two combined reflective layers 12a and 12b may be the same or different. For example, the reflective layers 12a and 12b may have the characteristics of reflecting ultraviolet light and near-infrared light and transmitting visible light, the reflective layer 12a reflects ultraviolet light and light in the first near-infrared region, and the reflective layer 12b reflects ultraviolet light and light in the second near-infrared region.

[0066] In addition, Figure 5 In the embodiment, the two absorbing layers 11a and 11b may be the same or different. When the absorbing layers 11a and 11b are different, for example, the absorbing layers 11a and 11b may be a combination of a near infrared absorbing layer and an ultraviolet absorbing layer, or may be a combination of an ultraviolet absorbing layer and a near infrared absorbing layer.

[0067] Figure 6 For Figure 2 The structure example of the optical filter 10F shown in the figure has an anti-reflection layer 14 on the main surface of the absorption layer 11 of the optical filter 10B. In the case of a structure in which no reflection layer is provided and the absorption layer is the outermost surface, an anti-reflection layer can be provided on the absorption layer. It should be noted that the anti-reflection layer can be a structure that covers not only the outermost surface of the absorption layer but also the entire side surface of the absorption layer. In this case, the moisture-proof effect of the absorption layer can be improved.

[0068] Hereinafter, the absorption layer, the reflection layer, the transparent substrate and the anti-reflection layer will be described.

[0069] (Absorbent layer)

[0070] The absorbing layer contains a dye (A) and a transparent resin, wherein the dye (A) has the above-mentioned properties (i-1) to (i-3), and preferably further has the above-mentioned property (i-4).

[0071] The absorbing layer is typically a layer or (resin) substrate in which the pigment (A) is uniformly dissolved or dispersed in a transparent resin. In the scope of not damaging the effect of the present invention, the absorbing layer may contain other NIR pigments except the pigment (A). In addition, in the scope of not damaging the effect of the present invention, the absorbing layer may also contain pigments except the NIR pigment, particularly UV pigments.

[0072] As other NIR dyes, it is preferred to contain a dye (D) satisfying the following requirements (v-1) and (v-2).

[0073] (v-1) In the absorbance curve at a wavelength of 350 nm to 1200 nm measured by making the dye (D) contained in the above-mentioned transparent resin, the maximum absorption wavelength λ 最大(D)TR In the wavelength range of 650nm ~ 750nm.

[0074] (v-2) The dye (D) is represented by any one of the formulas (I) to (III) described below.

[0075] Furthermore, the dye (D) preferably satisfies the following requirement (v-3).

[0076] (v-3) at a wavelength λ of maximum absorption 最大(D)TR In a spectral transmittance curve measured by including the dye (D) in the transparent resin at a transmittance concentration of 10%, the average transmittance of light in the wavelength range of 400 nm to 500 nm is 85% or more.

[0077] In the spectral transmittance curve of the internal transmittance at a wavelength of 350 nm to 1200 nm measured by making the dye (D) contained in the above transparent resin, 最大(D)TRThe absorption peak with an absorption vertex at 最大(D)TR The slope of the visible light side of the absorption peak ("absorption peak") is steep, that is, for the slope on the visible light side, the wavelength from the transmittance of 70% to the transmittance of 20% is preferably below 60nm, and more preferably below 50nm.

[0078] [Pigment (A)]

[0079] For pigment (A), in (i-1), the maximum absorption wavelength λ 最大(A)DCM In the wavelength range of 850nm~1100nm. Maximum absorption wavelength λ 最大(A)DCM Preferably, the wavelength is within the range of 860 nm to 1000 nm.

[0080] For the pigment (A), in (i-2), the formula (1) and the formula (2) are satisfied. In the formula (1), “ABS 400(A)DCM / ABS λ最大(A)DCM ” means ABS 400(A)DCM Compared with ABS λ最大(A)DCM That is, when ABS λ最大(A)DCM ABS when set to 1 400(A)DCM The same is true in the following equations (2) to (4). According to equation (1), ABS 400(A)DCM / ABS λ最大(A)DCM Less than 0.10. ABS 400(A)DCM / ABS λ最大(A)DCM It is preferably 0.08 or less, and more preferably 0.04 or less.

[0081] According to formula (2), ABS 550(A)DCM / ABS λ最大(A)DCM Less than 0.04. ABS 550(A)DCM / ABS λ最大(A)DCM It is preferably 0.03 or less, and more preferably 0.02 or less.

[0082] For pigment (A), in (i-3), the maximum absorption wavelength λ 最大(A)TR In the wavelength range of 850nm~1100nm. Maximum absorption wavelength λ 最大(A)TR Preferably, the wavelength is in the range of 860 nm to 1000 nm. In addition, for the pigment (A), in (i-3), the formulas (3) and (4) are satisfied. According to the formula (3), ABS 400(A)TR / ABS λ最大(A)TR Less than 0.15. ABS 400(A)TR / ABS λ最大(A)TR It is preferably 0.12 or less, and more preferably 0.09 or less.

[0083] According to formula (4), ABS550(A)TR / ABS λ最大(A)TR Less than 0.10. ABS 550(A)TR / ABS λ最大(A)TR It is preferably 0.08 or less, and more preferably 0.06 or less.

[0084] For the pigment (A), it is preferred that the formula (5) and the formula (6) are satisfied in (i-4). According to the formula (5), ABS 400(A)TR / ABS λ最大(A)TR -ABS 400(A)DCM / ABS λ最大(A)DCM Less than 0.10, preferably less than 0.08, more preferably less than 0.06. According to formula (6), ABS 550(A)TR / ABS λ最大(A)TR -ABS 550(A)DCM / ABS λ最大(A)DCM It is less than 0.08, preferably 0.06 or less, and more preferably 0.04 or less.

[0085] By satisfying the above (i-1) to (i-3), it can be said that the pigment (A) has sharp spectral characteristics with a large maximum absorption wavelength and high visible light transmittance in both dichloromethane and transparent resin. In general, it is known that pigments with a large maximum absorption wavelength are difficult to reproduce the high visible light transmittance and sharp spectrum in dichloromethane in transparent resin due to the effect of association. By satisfying the above (i-1) to (i-3), the following characteristics are shown: while having a large maximum absorption wavelength and a high visible light transmittance in dichloromethane, the absorption characteristics can also be maintained in a transparent resin.

[0086] Furthermore, when the dye (A) satisfies (i-4), the light absorption characteristics of the dye (A) in dichloromethane can be retained with better reproducibility in the transparent resin when used in the form of an optical filter.

[0087] Regarding the dye (A), in (i-5), the mass extinction coefficient is 1000 / (cm·mass %) or more. The mass extinction coefficient is preferably 1500 / (cm·mass %) or more.

[0088] As the pigment (A), there is no particular limitation on the molecular structure as long as it satisfies the requirements (i-1) to (i-3). Specifically, it can be selected from the group consisting of anthocyanin pigments, cresol pigments, phthalocyanine pigments, squarylium pigments, and phthalocyanine pigments. At least one pigment selected from the group consisting of salt pigments, diimmonium pigments and diketopyrrolopyrrole pigments is particularly preferred from the viewpoint of high visible light transmittance. Salt pigment.

[0089] As the cyanine dye as the dye (A), a cyanine dye represented by any one of the following formulae (ACi) to (ACiv) is preferred.

[0090]

[0091] However, the symbols in formulas (ACi) to (ACiv) are as follows.

[0092] R 101 ~R 107 , R 121 ~R 127 , R 141 and R 151 each independently represents a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl 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 a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a 3- to 14-membered heterocyclic group.

[0093] R 102 ~R 107 and R 122 ~R 127 Two adjacent ones of can be connected to each other to form a five-membered ring, a six-membered ring or a seven-membered ring. For formula (ACi), it is particularly preferred that R 105 and R 106 The structure of the aromatic ring is formed together with a part of the benzene ring (C=C) of the skeleton. In addition, for the formula (ACii), it is particularly preferred that R 125 and R 126 It is connected to form an aromatic ring structure together with a part of the benzene ring of the skeleton (C=C).

[0094] R 142 and R 143 R is a hydrogen atom or may be bonded to each other to form a six-membered aromatic ring D. 145 and R 144 They are hydrogen atoms or may be bonded to each other to form a six-membered aromatic ring E. However, the case where both the aromatic ring D and the aromatic ring E are formed is excluded.

[0095] 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, -NR 112 R 113 group, a cycloalkyl group having 3 to 14 carbon atoms, or an aryl group having 6 to 14 carbon atoms.

[0096] R 109 and R 111 , R 129 and R 131 , R 146 and R 148 and R 152 and R 154 They may be bonded to each other to form a 5-membered ring or a 6-membered ring. When forming a ring, hydrogen atoms bonded to the ring may be substituted by an alkyl group having 1 to 6 carbon atoms, and two atoms constituting the ring may be bridged by a methylene group.

[0097] R 112 ~R 118 Each is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, a haloalkyl 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 3- to 14-membered heterocyclic group.

[0098] Multiple Rs included in various formulas 101 ~R 107 , multiple R 121 ~R 127 , multiple R 141 ~R 145 , multiple R 151 , multiple Ds and multiple Es may be the same as or different from each other,

[0099] X - Represents a monovalent anion.

[0100] In the above, the alkyl group and the alkyl group in the alkoxy group may be a straight chain, or may contain a branched structure or a saturated ring structure. The aryl group refers to a group bonded by carbon atoms constituting an aromatic ring such as a benzene ring, a naphthalene ring, a biphenyl, a furan ring, a thiophene ring, a pyrrole ring, etc. possessed by an aromatic compound. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. may be cited, preferably a fluorine atom and a chlorine atom.

[0101] As X - , we can list I - 、BF4 - PF6 - 、ClO4 -, an anion represented by formula (X1) and an anion represented by formula (X2), etc., preferably BF4 - PF6 - and anions (X1).

[0102]

[0103] As the pigment (ACi), from the viewpoint of maintaining high visible light transmittance in a transparent resin, a pigment represented by the following formula (ACi1) is preferred, wherein R in the formula (ACi) is: 109 ~R 111 A compound containing hydrogen atoms.

[0104]

[0105] R in formula (ACi1) 101 ~R 107 and X - And preferred embodiments thereof are the same as those described in the above formulae (ACi) to (ACiv). 101 From the viewpoint of solubility in the transparent resin and in the solvent (hereinafter also referred to as the "main solvent") used when forming the absorption layer on the transparent substrate, it is preferably an alkyl group having 1 to 20 carbon atoms in a linear or branched structure, and more preferably an alkyl group having 4 to 20 carbon atoms in a linear or branched structure. 102 ~R 107 Each is independently preferably a hydrogen atom, -NR 112 R 113 Group, -NHSO2R 114 Group, -NHCOR 115 group, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, or a 3-membered to 14-membered heterocyclic group, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. In this case, R 112 ~R 115 The same as described in the above formulas (ACi) to (ACiv) may be used.

[0106] As the pigment (ACii), from the viewpoint of maintaining high visible light transmittance in a transparent resin, a pigment represented by the following formula (ACii1) is preferred, wherein R in the formula (ACii) is: 129 With R 131 A compound in which R is bonded to form a 6-membered ring; and represented by the following formula (ACii2), wherein R in the formula (ACii) 129 With R 131 A compound in which two or more 2-hydroxy-2-nitropropene groups are bonded to form a 5-membered ring.

[0107]

[0108] R in formula (ACii1) and formula (ACii2) 121 ~R 127 and X - And the preferred embodiments thereof are the same as those described in the above formulas (ACi) to (ACiv). In formula (ACii1), R 130a is a hydrogen atom, a phenyl group or a methyl group, preferably a phenyl group. 130b It is a hydrogen atom, a phenyl group, a methyl group or a diphenylamino group, and is preferably a phenyl group or a diphenylamino group.

[0109] As R 121 From the viewpoint of solubility in the transparent resin and the main solvent, it is preferably an alkyl group having 1 to 20 carbon atoms having a linear or branched structure, and more preferably an alkyl group having 4 to 20 carbon atoms having a linear or branched structure. 122 ~R 127 Each is independently preferably a hydrogen atom, a dimethylamino group, -NHSO2R 114 Group, -NHCOR 115 group, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, or a 3-membered to 14-membered heterocyclic group, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. In this case, R 112 ~R 115 The same as described in the above formulas (ACi) to (ACiv) may be used.

[0110] Specifically, the pigment (ACiii) includes: a compound represented by the following formula (ACiii1) which does not have either an aromatic ring D or an aromatic ring E in the formula (ACiii); a compound represented by the following formula (ACiii2) which has only an aromatic ring E in the formula (ACiii); and a compound represented by the following formula (ACiii3) which has only an aromatic ring D in the formula (ACiii).

[0111]

[0112] R in formula (ACiii1), formula (ACiii2) and formula (ACiii3) 141 , R 146 ~R 148 and X - And preferred embodiments thereof are the same as those described in the above formulae (ACi) to (ACiv). 141From the viewpoint of solubility in the transparent resin and the solubility in the main solvent, an alkyl group having 1 to 20 carbon atoms in a linear or branched structure is preferred, and from the viewpoint of ease of synthesis, an alkyl group having 2 to 5 carbon atoms in a linear or branched structure is more preferred. 147 It is preferably a hydrogen atom, a methyl group or a phenyl group, and more preferably a hydrogen atom or a phenyl group.

[0113] R 146 and R 148 Preferably, they are all hydrogen atoms, or R 146 and R 148 They are bonded to form a 5-membered ring or a 6-membered ring together with the main chain (methine chain) to which they are bonded. When forming a ring, the hydrogen atoms bonded to the ring may be substituted by an alkyl group having 1 to 6 carbon atoms, and two atoms of the constituent atoms of the ring may be bridged by a methylene group. 146 and R 148 They are bonded to form a 6-membered ring together with the main chain, and a structure represented by -(CH2)3- described later.

[0114] In the pigment (ACiv), as R 151 From the viewpoint of solubility in the transparent resin and the solubility in the main solvent, an alkyl group having 1 to 20 carbon atoms in a linear or branched structure is preferred, and from the viewpoint of ease of synthesis, an alkyl group having 2 to 5 carbon atoms in a linear or branched structure is more preferred. 153 It is preferably a hydrogen atom, a methyl group or a phenyl group, and more preferably a hydrogen atom or a phenyl group.

[0115] R 152 and R 154 Preferably, they are all hydrogen atoms, or R 152 and R 154 They are bonded to form a 5-membered ring or a 6-membered ring together with the main chain (methine chain) to which they are bonded. When forming a ring, the hydrogen atoms bonded to the ring may be substituted by an alkyl group having 1 to 6 carbon atoms, and two atoms of the constituent atoms of the ring may be bridged by a methylene group. 152 and R 154 They are bonded to form a 6-membered ring together with the main chain, and a structure represented by -(CH2)3- described later.

[0116] More specifically, the compounds represented by Formula (ACi1), Formula (ACii1), Formula (ACii2), Formula (ACiii1), Formula (ACiii2), Formula (ACiii3), and Formula (ACiv) include compounds in which the atoms or groups bonded to each skeleton are shown in Tables 1 to 7 below. In all the compounds shown in Table 1, R 101 ~R 107In all compounds shown in Table 2 and Table 3, R 121 ~R 127 In all compounds shown in Tables 4 to 6, R 141 The left and right sides of the formula are the same. In all compounds shown in Table 7, R 151 The left and right sides of the formula are the same. In Tables 1 to 7, -C n H 2n+1 (n is an integer greater than or equal to 3) represents a linear alkyl group, and -Ph represents a phenyl group. It should be noted that although only left-right symmetrical compounds are listed in Tables 1 to 7, the present invention is not limited thereto, and left-right asymmetrical compounds may also be used. Left-right asymmetrical compounds have the advantage of improved solubility in resins.

[0117] In Tables 4 to 6, R 146 and R 148 When R is bonded to form a 6-membered ring together with the three carbon atoms of the methine chain (CC=C) 146 and R 148 It is represented as -(CH2)3-. Other rings and cases where the hydrogen atoms of the rings are substituted are also described in the same manner as described above. 152 and R 154 In Tables 4 to 7, R 146 and R 148 and R 152 and R 154 "NOR" described in one column represents the following divalent group.

[0118]

[0119] Although X is not shown in Tables 1 to 7 - , but in any compound X - For BF4 - PF6 - Or anion X1. In the pigment (ACi1-1) X - For BF4 - The situation is represented as pigment (ACi1-1B), and X is added to pigment (ACi1-1). - PF6 - The situation is represented as pigment (ACi1-1P), and X is added to the pigment (ACi1-1). - When it is an anion (X1), it is expressed as a dye (ACi1-1X1). The same applies to other dyes shown in Tables 1 to 7.

[0120] Table 1

[0121]

[0122] As the pigment (ACi1), preferred are pigment (ACi1-1B), pigment (ACi1-1P), pigment (ACi1-1X1), pigment (ACi1-2B), pigment (ACi1-2P), pigment (ACi1-14B), pigment (ACi1-15B), etc.

[0123] Table 2

[0124]

[0125] Among them, the pigment (ACii1) is preferably pigment (ACii1-1B), pigment (ACii1-1P), pigment (ACii1-7B), pigment (ACii1-7P), or the like.

[0126] Table 3

[0127]

[0128] As the pigment (ACii2), preferred are pigment (ACii2-1B), pigment (ACii2-1P), pigment (ACii2-2B), pigment (ACii2-2P), pigment (ACii2-11B), pigment (ACii2-11P), pigment (ACii2-12B), pigment (ACii2-12P), etc.

[0129] Table 4

[0130]

[0131] As the pigment (ACiii1), preferred are 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.

[0132] Table 5

[0133]

[0134] As the pigment (ACiii2), preferred are 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.

[0135] Table 6

[0136]

[0137] As the pigment (ACiii3), preferred are 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.

[0138] Table 7

[0139]

[0140] As the pigment (ACiv), preferred are 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.

[0141] Pigment (ACi), pigment (ACii) and pigment (ACiv) can be produced by the method described in, for example, J. Heterocyclic Chem., 42 (2005), 959. Pigment (ACiii) can be produced by the method described in UKRAINSKII KHIMICHESKII ZHURNAL, 44 (8), 838, (1978).

[0142] In addition, the pigment (ACi1-1B), pigment (ACi1-2B) and pigment (ACii2-2B) can use the trade names S0772, S2437 and S2007 manufactured by Few Chemicals as commercial products, respectively. The pigment (ACiii1-9B), pigment (ACiii2-9B) and pigment (ACiii3-9B) can use the trade names S1379, S1984 and S1985 manufactured by Spectrum Info. as commercial products, respectively.

[0143] As a pigment (A) The salt pigment is preferably a squarylium pigment represented by the following formula (ASi) or (ASii): Salt pigment.

[0144]

[0145] The symbols in formula (ASi) and formula (ASii) are as follows.

[0146] R 161 is a branched alkyl group having 3 to 20 carbon atoms or a linear alkyl group having 13 to 20 carbon atoms. From the viewpoint of solubility in the transparent resin and the solubility in the main solvent, R 161 It 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. 161 More preferably, it is a branched alkyl group having 8 to 20 carbon atoms.

[0147] Y 3 CR 179 or N.

[0148] R 162 ~R 167 and R 171 ~R 179 are each independently a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl 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 a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a 3- to 14-membered heterocyclic group.

[0149] Examples of the 3- to 14-membered heterocyclic group include heterocyclic groups containing at least one hetero atom selected from N, O and S. From the viewpoint of solubility in the transparent resin and solubility in the main solvent, R 171 Preferably, it is a linear alkyl group having 8 to 20 carbon atoms or a branched alkyl group having 8 to 20 carbon atoms. 171 More preferably, it is a branched alkyl group having 16 to 20 carbon atoms. 162 ~R 167 and R 172 ~R 178 Each of them is independently preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, -NHSO2R 114 Group or -NHCOR 115 The group is more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or -NHCOR 115 Group. R 179 An alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is more preferred.

[0150] Multiple Rs included in various formulas 161 ~R 167 , multiple R 171 ~R 178 and multiple Y 3 They can be the same as or different from each other.

[0151] R 112 ~R 118 Each is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, a haloalkyl 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 3-membered to 14-membered heterocyclic group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferred.

[0152] R 112 ~R 118Each independently is preferably an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 16 carbon atoms or an alkoxy group having 1 to 16 carbon atoms.

[0153] In the above, unless otherwise specified, the alkyl group in the alkyl group and the alkoxy group may be a straight chain, or may contain a branched structure or a saturated ring structure. The aryl group refers to a group bonded by carbon atoms constituting an aromatic ring such as a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a thiophene ring, a pyrrole ring, etc. possessed by an aromatic compound. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. may be cited, preferably a fluorine atom and a chlorine atom.

[0154] More specifically, the compounds represented by Formula (ASi) and Formula (ASii) include compounds in which atoms or groups bonded to the respective skeletons are shown in Table 8 and Table 9 below. 161 ~R 167 In all compounds shown in Table 9, R 171 ~R 178 and Y 3 The left and right sides of the formula are the same. In Table 8 and Table 9, all alkyl groups such as -C4H9 are straight-chain alkyl groups. It should be noted that although only left-right symmetrical compounds are listed in Table 8 and Table 9, the present invention is not limited thereto, and left-right asymmetrical compounds may also be used. Left-right asymmetrical compounds have the advantage of improved solubility in resins.

[0155]

[0156] As the pigment (ASi), among them, 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 preferred, and pigment (ASi-1), pigment (ASi-19), pigment (ASi-22), pigment (ASi-25), pigment (ASi-31), etc. are more preferred. As the left-right asymmetric pigment (ASi), a pigment in which the left-right combination is a combination of ASi-19 with any one of ASi-24, ASi-25 and ASi-28; a pigment in which the left-right combination is a combination of ASi-22 with any one of ASi-24 and ASi-31; a pigment in which the left-right combination is a combination of ASi-24 with any one of ASi-25 and ASi-28, etc. are preferred.

[0157]

[0158] Among them, preferred pigments (ASii-1) to (ASii-8), pigments (ASii-10), pigments (ASii-15) to (ASii-17) and the like are preferable, and pigments (ASii-8), pigments (ASii-15) to (ASii-17) and the like are more preferable.

[0159] It should be noted that the pigment (ASi) and the pigment (ASii) can be prepared, for example, by the method described in European Journal of Medical Chemistry, 54, 647, (2012); in addition, the pigment (ASii) can be prepared by the method described in Org. Lett. 18, 5232 (2016) and introduced into the squaric acid. The compound is placed on both sides of the salt ring, and the compound is introduced into two positions on the diagonal line of the squaric acid by the method described in, for example, Organic Letters, 8, 111, (2006).

[0160] The absorption layer may contain a single pigment (A) or a combination of two or more pigments (A). When containing two or more pigments (A), the maximum absorption wavelength λ of each pigment (A) is preferably 最大(A)TR The maximum absorption wavelength λ of two or more pigments (A) is different. 最大(A)TR The difference is preferably in the range of 50 nm to 300 nm, more preferably 50 nm to 150 nm. It should be noted that when the pigment (A) comprises two or more compounds, it is not necessary for each compound to have the properties of the pigment (A), as long as the mixture has the properties of the pigment (A).

[0161] As a preferred combination of two or more pigments (A), for example, the pigment (A) having a maximum absorption wavelength on the shorter wavelength side among the pigments (A) is recorded as pigment S, the pigment (A) having a maximum absorption wavelength on the longer wavelength side is recorded as pigment L, and the pigment (A) having a maximum absorption wavelength between the maximum absorption wavelengths of the pigment S and the pigment L is recorded as pigment M. It is preferred to combine two or more selected from the group consisting of pigment S, pigment M and pigment L.

[0162] Specifically, there can be mentioned a combination of a pigment S and a pigment M, a combination of a pigment S and a pigment L, a combination of a pigment M and a pigment L, and a combination of a pigment S, a pigment M, and a pigment L. It should be noted that the maximum absorption wavelength λ of the pigment S is 最大(A)TR The maximum absorption wavelength λ of the pigment M is preferably in the range of 850 nm to 900 nm, and more preferably in the range of 860 nm to 890 nm. 最大(A)TRThe maximum absorption wavelength λ of the pigment L is preferably in the wavelength range of 900 nm to 1000 nm, and more preferably in the wavelength range of 930 nm to 980 nm. 最大(A)TR The wavelength range is preferably 1000 nm to 1100 nm, and more preferably 1000 nm to 1050 nm.

[0163] [Pigment (D)]

[0164] The dye (D) satisfies the requirements of (v-1) and (v-2), that is, the maximum absorption wavelength λ 最大(A)TR A squaric acid selected from any one of the following formulae (I) to (III) within a wavelength range of 650 nm to 750 nm: At least one dye selected from the group consisting of salt dyes. The dye (D) preferably further satisfies the requirement of (v-3) above.

[0165] Containing the above-mentioned acid The pigment (D) of the salt pigment has little absorption of visible light in the above absorbance curve, λ 最大(D)TR The absorption peak has a steep slope on the visible light side, and has high storage stability and stability against light.

[0166] When the dye (D) is contained in a transparent resin, the mass extinction coefficient is preferably 1000 / (cm·mass %) or more, and more preferably 1500 / (cm·mass %) or more.

[0167]

[0168] The symbols in formula (I) are as follows.

[0169] R 24 and R 26 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms 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 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 which may have a substituent, or a linear or branched saturated or unsaturated hydrocarbon group or a saturated cyclic hydrocarbon group (alaryl group) having 7 to 18 carbon atoms which may have a substituent and may have an oxygen atom between carbon atoms and which is substituted with one or more aryl groups and may contain a saturated ring structure; -NHR 30 or -SO2-R 30(R 30 A hydrocarbon group having 1 to 25 carbon atoms, each of which has one or more hydrogen atoms which may be substituted with a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group or a cyano group and may contain an unsaturated bond, an oxygen atom, or a saturated or unsaturated ring structure between carbon atoms) or a group represented by the following formula (S): 41 , R 42 (k is 2 or 3) and (k is 2 or 3) independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0170]

[0171] R 21 and R 22 , R 22 and R 25 and R 21 and R 23 They may be connected to each other and together with the nitrogen atom form a 5-membered or 6-membered heterocyclic ring A, heterocyclic ring B and heterocyclic ring C, respectively.

[0172] For R in the case of forming a heterocyclic ring A 21 and R 22 As R 21 and R 22 The bonded divalent group -Q- represents an alkylene group in which the hydrogen atom may be substituted by 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 in which the hydrogen atom may be substituted by 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.

[0173] For R in the case of forming a heterocyclic ring B 22 and R 25 and R in the case of forming a heterocyclic ring C 21 and R 23 As R 22 and R 25 and R 21 and R 23 The divalent group -X to which each is bonded 1 -Y 1 -and-X 2 -Y 2 -(the side bonded to nitrogen is X 1 and X 2 ), X 1 and X 2 Each is a group represented by the following formula (1x) or (2x), Y 1 and Y 2Each is a group represented by any one selected from the following formulae (1y) to (5y). 1 and X 2 When each is a group represented by the following formula (2x), Y 1 and Y 2 Each may be a single bond, in which case an oxygen atom may be present between carbon atoms.

[0174]

[0175] In formula (1x), four Zs each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, or -NR 38 R 39 (R 38 and R 39 Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). 31 ~R 36 Each independently represents 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 It represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0176] R 27 , R 28 , R 29 , R 31 ~R 37 , R when no heterocyclic ring is formed 21 ~R 23 and R 25 They may be bonded to each other to form a 5-membered ring or a 6-membered ring. 31 and R 36 , R 31 and R 37 Direct bonding is possible.

[0177] R when no heterocyclic ring is formed 21 and R 22 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an allyl group which may have a substituent, an aryl group having 6 to 11 carbon atoms which may have a substituent, or a linear or branched saturated or unsaturated hydrocarbon group or a saturated cyclic hydrocarbon group which may have a saturated ring structure and is substituted with one or more aryl groups which may have a substituent. 23 and R 25 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

[0178]

[0179] The symbols in formula (II) are as follows.

[0180] Ring Z is independently a 5-membered or 6-membered ring having 0 to 3 hetero atoms in the ring and which may be substituted.

[0181] 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 and together with the nitrogen atom form heterocycle A1, heterocycle B1 and heterocycle C1, respectively. In the case where a heterocycle is not formed, R 1 and R 2 Each independently represents 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 may have a substituent, R 3 and R 4 Each independently represents a hydrogen atom, a halogen atom, or an alkyl group which may contain a hetero atom between carbon atoms or an alkoxy group which may contain a hetero atom between carbon atoms.

[0182]

[0183] The symbols in formula (III) are as follows.

[0184] R 51 each independently represents a halogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent,

[0185] R 52 ~R 58 Each independently represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.

[0186] 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 by an alkyl group having 1 to 10 carbon atoms,

[0187] R 54 and R 55 The alkyl groups may be linked to each other to form a benzene ring A2, and the hydrogen atoms of the benzene ring A2 may be substituted by an alkyl group having 1 to 10 carbon atoms.

[0188] Examples of compound (I) include compounds represented by any one of formulae (I-1) to (I-4).

[0189]

[0190] In addition, the symbols in formula (I-1) to formula (I-4) have the same meanings as the same symbols in formula (I), and the preferred embodiments are also the same.

[0191] Among compounds (I-1) to (I-4), as the dye (A), compounds (I-1) to (I-3) are preferred, and compound (I-1) is particularly preferred, from the viewpoint of being able to increase the visible light transmittance of the absorbing layer.

[0192] In compound (I-1), as X 1 , preferably the group (2x), as Y 1 , preferably a single bond or a group (1y). In this case, as R 31 ~R 36 , preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. 1 -X 1 -, specifically, divalent organic groups represented by formulae (11-1) to (12-3) are mentioned.

[0193] -C(CH3)2-CH(CH3)- (11-1)

[0194] -C(CH3)2-CH2- (11-2)

[0195] -C(CH3)2-CH(C2H5)- (11-3)

[0196] -C(CH3)2-C(CH3)(nC3H7)- (11-4)

[0197] -C(CH3)2-CH2-CH2- (12-1)

[0198] -C(CH3)2-CH2-CH(CH3)- (12-2)

[0199] -C(CH3)2-CH(CH3)-CH2- (12-3)

[0200] In addition, in compound (I-1), R 21 More preferably, they are independently represented by the formula (4-1) or the formula (4-2).

[0201]

[0202] In formula (4-1) and formula (4-2), R 71 ~R 75Each of the groups independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

[0203] In compound (I-1), R 24 Preferably -NR 27 R 28 As-NR 27 R 28 From the viewpoint of solubility in the main solvent and in the transparent resin, -NH-C(=O)-R 29 Formula (I-11) shows that R 24 -NH-C(=O)-R 29 of compounds.

[0204]

[0205] R in compound (I-11) 23 and R 26 Each of them is preferably independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and more preferably both of them are hydrogen atoms.

[0206] In compound (I-11), as R 29 , 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 a linear or branched saturated or unsaturated hydrocarbon group or a saturated cyclic hydrocarbon group having 7 to 18 carbon atoms which may have a substituent and may have an oxygen atom between carbon atoms and may contain a saturated ring structure and substituted with one or more aryl groups. Examples of the substituent include halogen atoms such as fluorine atoms, hydroxyl groups, carboxyl groups, sulfonic groups, cyano groups, alkyl groups having 1 to 6 carbon atoms, fluoroalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and acyloxy groups having 1 to 6 carbon atoms.

[0207] As R 29 , preferably selected from the following groups: a linear, branched or cyclic alkyl group having 1 to 17 carbon atoms which may be substituted with fluorine atoms, 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 a linear or branched saturated or unsaturated hydrocarbon group or a saturated cyclic hydrocarbon group which may contain a saturated ring structure and may have an oxygen atom between carbon atoms and a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine atoms and / or an alkoxy group having 1 to 6 carbon atoms at the terminal, and which may be substituted with one or more aryl groups.

[0208] As R 29, the following groups can be used independently and preferably: a hydrocarbon group having 5 to 25 carbon atoms, in which one or more hydrogen atoms may be substituted by 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, a saturated or unsaturated ring structure between carbon atoms and at least one branched chain. 29 For example, groups represented by the following formulae (1a), (1b), (2a) to (2e), and (3a) to (3e) are mentioned.

[0209]

[0210]

[0211] More specifically, the compounds shown in Table 10 below are listed as compound (I-11). It should be noted that in Table 10, group (11-1) is represented as (11-1). The same is true for other groups. In the following other tables, the representation of the groups is also the same. In addition, any one of the compounds shown in Table 10 is in the squaric acid The symbols on the left and right of the salt skeleton have the same meaning. The same is true for salt pigments.

[0212] Table 10

[0213]

[0214] In compound (I-1), from the viewpoint of improving the transmittance of visible light, especially the transmittance of light with a wavelength of 430 nm to 550 nm, R 24 Preferably -NH-SO2-R 30 Formula (I-12) shows that R 24 -NH-SO2-R 30 of compounds.

[0215]

[0216] R in compound (I-12) 23 and R 26 Each of them is preferably independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and more preferably both of them are hydrogen atoms.

[0217] In compound (I-12), from the viewpoint of light resistance, R 30Preferably, each of them is independently an alkyl group having 1 to 12 carbon atoms which may have a branch or an alkoxy group having 1 to 12 carbon atoms which may have a branch, or a hydrocarbon group having 6 to 16 carbon atoms which has an unsaturated ring structure. Examples of the unsaturated ring structure include benzene, toluene, xylene, furan, and benzofuran. 30 More preferably, they are independently an alkyl group having 1 to 12 carbon atoms which may have a branch or an alkoxy group having 1 to 12 carbon atoms which may have a branch. 30 In each group, part or all of the hydrogen atoms may be substituted by halogen atoms, particularly fluorine atoms. It should be noted that, in the case where the optical filter includes a structure of a transparent substrate, the extent to which the hydrogen atoms are substituted by fluorine atoms is such that the adhesion between the absorption layer containing the pigment (I-12) and the transparent substrate is not reduced.

[0218] As R having an unsaturated ring structure 30 Specific examples include groups represented by the following formulae (P1) to (P8).

[0219]

[0220] More specifically, the compounds shown in the following Table 11 can be cited as compound (I-12).

[0221] Table 11

[0222]

[0223] Examples of compound (II) include compounds represented by any one of formula (II-1) to formula (II-3).

[0224]

[0225] In formula (II-1) and formula (II-2), R 1 and R 2 Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 15 carbon atoms which may have a substituent, and R 3 ~R 6 Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent.

[0226] In formula (II-3), R 1 , R 4 and R 9 ~R 12 Each independently represents 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 8Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent.

[0227] From the viewpoint of solubility in transparent resins, visible light transmittance, etc., R in compound (II-1) and compound (II-2) 1 and R 2 Each of the above groups is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 7 to 15 carbon atoms, and further preferably R 1 and R 2 At least one of them is a branched alkyl group having 7 to 15 carbon atoms, and R is particularly preferred. 1 and R 2 Both are branched alkyl groups having 8 to 15 carbon atoms.

[0228] From the perspective of solubility in transparent resins, visible light transmittance, etc., R 3 Each of them is preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom, a halogen atom or a methyl group. 4 It is preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom. 5 and R in compound (II-2) 6 Each of the above groups is preferably independently 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.

[0229] More specifically, the compounds (II-1) and (II-2) are shown in Table 12 and Table 13 below. In Table 12 and Table 13, -C8H 17 、-C4H9、-C6H 13 They represent a straight-chain octyl group, a straight-chain butyl group, and a straight-chain hexyl group, respectively.

[0230] Table 12

[0231]

[0232] Table 13

[0233]

[0234] From the viewpoints of solubility in transparent resins, visible light transmittance, etc., R in compound (II-3) 1 Each of the above groups is preferably 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.

[0235] From the perspective of visible light transmittance and ease of synthesis, R 4 It is preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom. 7 and R 8 Each of the above groups is preferably independently 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.

[0236] R 9 ~R 12 Each of -CR is preferably independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may be substituted with a halogen atom. 9 R 10 -CR 11 R 12 -, examples include the above-mentioned groups (11-1) to (11-3) and the following divalent organic groups represented by the formula (11-5).

[0237] -C(CH3)(CH2-CH(CH3)2)-CH(CH3)- (11-5)

[0238] More specifically, the compounds shown in the following Table 14 can be cited as compound (II-3).

[0239] Table 14

[0240]

[0241] Examples of compound (III) include compounds represented by formula (III-1) and formula (III-2).

[0242]

[0243] Among them, 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.

[0244] In compound (III-1) and compound (III-2), R 52 , R 53 R is independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and more preferably a hydrogen atom, a halogen atom, or a methyl group. 58 It is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and is more preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of ease of synthesis. 56 , R 57 , R59 ~R 62 Each is independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a hydrogen atom is more preferred from the viewpoint of ease of synthesis. More specifically, compounds (III-1) and (III-2) include the compounds shown in Table 15 and Table 16 below.

[0245] Table 15

[0246]

[0247] Table 16

[0248]

[0249] The pigment (D) may be composed of one compound or two or more compounds. When composed of two or more compounds, it is not necessary for each compound to have the properties of the pigment (D), as long as the mixture has the properties of the pigment (D).

[0250] Compounds (I) to (III) can each be manufactured using a known method. For compound (I), compound (I-11) can be manufactured using the method described in, for example, U.S. Patent No. 5543086. Compound (I-12) can be manufactured using the method described in, for example, U.S. Patent Application Publication No. 2014 / 0061505 and International Publication No. 2014 / 088063. Compound (II) can be manufactured using the method described in International Publication No. 2017 / 135359.

[0251] Regarding UV pigments, we can list: Azoles, merocyanines, anthocyanines, naphthalimides, Oxadiazoles, Oxazine, Specific examples include oxazolidine, naphthalene dicarboxylic acid, styryl, anthracene, cyclic carbonyl, triazole and other pigments. Azole or merocyanine pigments. In addition, in the absorption layer, one UV pigment may be used alone, or two or more UV pigments may be used in combination.

[0252] As for the transparent resin, a transparent resin that satisfies the relationship (i-3) and preferably further satisfies the relationship (i-4) with the dye (A) is used.

[0253] The transparent resin may be selected from, for example, one or more selected from acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyarylether phosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, and polyester resins, depending on the type of the pigment (A).

[0254] The transparent resin preferably contains a resin having at least one bond selected from an ester bond, a carbonate bond and an imide bond in the main chain. The transparent resin having these bonds in the main chain is advantageous in maintaining a high visible light transmittance when mixed with a pigment and in having excellent heat resistance of the resin itself.

[0255] Among them, the transparent resin is preferably a polyester resin, a polycarbonate resin, a polyimide resin and an acrylic imide resin. These resins can be used alone or in combination of two or more. When the pigment (A) is a pigment (ACi) to a pigment (ACiv), a pigment (ASi) or a pigment (ASii), a polyester resin, a polycarbonate resin, a polyimide resin and an acrylic imide resin are particularly preferred.

[0256] As the transparent resin, commercially available products can be used. Examples of commercially available polyester resins include OKP4HT, OKP4, B-OKP2, and OKP-850 (all manufactured by Osaka Gas Chemical Co., Ltd., trade names), and VYLON (registered trademark) 103 (manufactured by Toyobo Co., Ltd., trade name).

[0257] Examples of the polycarbonate resin include LeXan (registered trademark) ML9103 (trade name, manufactured by SABIC), EP5000 (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), SP3810 (trade name, manufactured by Teijin Limited), SP1516 (trade name, manufactured by Teijin Limited), TS2020 (trade name, manufactured by Teijin Limited), and Xylex (registered trademark) 7507 (trade name, manufactured by SABIC).

[0258] Examples of the polyimide resin include Neopulim (registered trademark) C-3650 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Neopulim (registered trademark) C-3G30 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Neopulim (registered trademark) C-3450 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), JL-20 (manufactured by Shin Nippon Rika, trade name), and FPC-0220 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name) (these polyimide resins may contain silica), etc. Examples of the acrylic imide resin include PLEXIMID8817 (manufactured by Daicel Corporation, trade name), etc.

[0259] From the viewpoints of transparency, solubility of the dye (A) and the dye (D), and heat resistance, the transparent resin preferably has a high glass transition temperature (Tg), for example, a resin having a Tg of 140° C. or higher.

[0260] The absorbing layer may further contain optional components such as a thickener, a color correction pigment, a leveling agent, an antistatic agent, a heat stabilizer, a light stabilizer, an antioxidant, a dispersant, a flame retardant, a lubricant, and a plasticizer within a range not impairing the effects of the present invention.

[0261] When the absorption layer contains a dye (A) and a transparent resin having the properties of (i-1) to (i-3) and further contains a dye (D), it is preferred that the following (ii-1) to (ii-3) are satisfied in the spectral transmittance curve at an incident angle of 0 degrees.

[0262] (ii-1) The wavelength λ on the short wavelength side of the wavelength at which the absorbing layer shows a transmittance of 20% ABSHT20-0° In the wavelength range of 655nm ~ 675nm.

[0263] (ii-2) Average transmittance T of the absorption layer for light with a wavelength of 435 nm to 630 nm AB435-630平均0° More than 65%.

[0264] (ii-3) Average transmittance T of the absorption layer for light with a wavelength of 850 nm to 1100 nm AB850-1100平均0° Below 70%.

[0265] The wavelength λ in (ii-1) ABSHT20-0° It is preferably in the wavelength range of 655nm to 670nm, and more preferably in the wavelength range of 655nm to 665nm. It should be noted that, for example, when the optical filter has a transparent substrate and the transparent substrate is a near-infrared absorbing glass, the wavelength λ is set to ABSHT20-0° The wavelength λ in this case is adjusted to the above preferred range + about 5 nm to about 20 nm.ABSHT20-0° The wavelength range is preferably 660 nm to 675 nm, and more preferably 665 nm to 675 nm.

[0266] Average transmittance T in (ii-2) AB435-630平均0° It is preferably 70% or more, and more preferably 80% or more. The average transmittance T in (ii-3) AB850-1100平均0° It is preferably 60% or less, and more preferably 45% or less.

[0267] The content of the pigment (A) in the absorption layer is appropriately set according to the design of the present filter so that the effect of the present filter can be exerted. From the viewpoint of ensuring visible light transmittance and blocking near-infrared light, especially near-infrared light in the long wavelength range, the content of the pigment (A) in the absorption layer is preferably 1 to 15 parts by mass relative to 100 parts by mass of the transparent resin, and from the viewpoint of solubility, the content of the pigment (A) in the absorption layer is preferably 1 to 8 parts by mass.

[0268] In the pigment (A), when two or more selected from the group consisting of the pigment S, the pigment M and the pigment L are used, the content of each pigment is preferably 1 to 15 parts by mass relative to 100 parts by mass of the transparent resin, and is more preferably 2 to 13 parts by mass from the viewpoint of solubility, provided that the total content of all the pigments (A) is within the above range.

[0269] When the absorption layer contains the dye (A) and the dye (D), the contents of the dye (A) and the dye (D) are appropriately selected according to the design of the present optical filter so that the absorption layer satisfies the characteristics (ii-1) to (ii-3).

[0270] In this case, the content of the pigment (A) in the absorption layer is the same as above, and from the viewpoint of ensuring visible light transmittance and being able to exert the characteristics of the pigment (D), relative to 100 parts by mass of the transparent resin, the content of the pigment (D) is preferably 1 part by mass to 15 parts by mass, and from the viewpoint of solubility, the content of the pigment (D) is more preferably 3 parts by mass to 14 parts by mass. In addition, relative to 100 parts by mass of the transparent resin, the total content of the pigment (A) and the pigment (D) is preferably 2 parts by mass to 30 parts by mass, and from the viewpoint of solubility, the total content of the pigment (A) and the pigment (D) is more preferably 5 parts by mass to 27 parts by mass.

[0271] In the present optical filter, the thickness of the absorption layer is preferably 0.1 μm to 100 μm. When the absorption layer includes multiple layers, the total thickness of each layer is preferably 0.1 μm to 100 μm. When the thickness is less than 0.1 μm, the desired optical properties may not be fully exhibited. When the thickness is greater than 100 μm, the flatness of the layer decreases, and in-plane deviation of the absorption rate may occur. The thickness of the absorption layer is more preferably 0.3 μm to 50 μm. In addition, in the case of having other functional layers such as a reflective layer and an anti-reflective layer, cracks may occur when the absorption layer is too thick, depending on the material. Therefore, the thickness of the absorption layer is more preferably 0.3 μm to 10 μm.

[0272] The absorption layer can be formed, for example, by dissolving or dispersing the pigment (A), preferably the pigment (A) and the pigment (D), the transparent resin or the raw material component of the transparent resin, and each component prepared as required in a solvent to prepare a coating liquid, applying the coating liquid on a substrate and drying it, and then curing it as required. The substrate can be a transparent substrate included in the present filter, or a peelable substrate used only when forming the absorption layer. In addition, the solvent can be any dispersion medium that can be stably dispersed or a solvent that can dissolve.

[0273] In addition, in order to improve the voids caused by microbubbles, the depressions caused by the attachment of foreign matter, the shrinkage cavities in the drying process, etc., the coating liquid may contain a surfactant. In addition, the coating liquid may be applied by, for example, a dip coating method, a cast coating method, or a spin coating method. The above-mentioned coating liquid is applied to the substrate and then dried to form an absorption layer. In addition, when the coating liquid contains a raw material component of a transparent resin, a curing treatment such as heat curing or photocuring is further performed.

[0274] The absorbing layer may be formed into a film by extrusion molding, or the film may be laminated on another member and integrated by thermocompression bonding, etc. For example, when the optical filter includes a transparent substrate, the film may be bonded to the transparent substrate.

[0275] The optical filter may have one absorption layer or more than two absorption layers. In the case of having more than two absorption layers, each layer may have the same structure or different structures. Taking the case where the absorption layer contains a pigment (A), a pigment (D) and a UV pigment as an example, one layer may be a near-infrared absorption layer containing a pigment (A) and a pigment (D) and a transparent resin, and the other layer may be a near-ultraviolet absorption layer containing a UV pigment and a transparent resin. As another example, one layer may be a first near-infrared absorption layer containing a pigment (D) and a transparent resin, and the other layer may be a second near-infrared absorption layer containing a pigment (A), a UV pigment and a transparent resin. In addition, the absorption layer itself may function as a substrate (resin substrate).

[0276] (Transparent substrate)

[0277] When a transparent substrate is used in the present filter, the material of the transparent substrate is not particularly limited as long as it transmits visible light of about 400 nm to about 700 nm, and may be a material that absorbs near infrared light or near ultraviolet light. Examples include inorganic materials such as glass or crystal, and organic materials such as transparent resin.

[0278] Examples of glass that can be used for the transparent substrate include fluorophosphate glass, phosphate glass, etc., which contain copper ions in absorption-type glass (near infrared absorption glass), soda-lime glass, borosilicate glass, alkali-free glass, quartz glass, etc. It should be noted that "phosphate glass" also includes silicophosphate glass in which a part of the glass skeleton is composed of SiO2.

[0279] As glass, chemically strengthened glass can be used, which is obtained by replacing alkali metal ions with a small ionic radius (such as Li ions and Na ions) present on the main surface of a glass plate with alkali metal ions with a larger ionic radius (for example, Na ions or K ions for Li ions, and K ions for Na ions) through ion exchange at a temperature below the glass transition temperature.

[0280] As transparent resin materials that can be used as transparent substrates, there are listed: polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyolefin resins such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer; acrylic resins such as norbornene resin, polyacrylate, and polymethyl methacrylate; polyurethane resins, vinyl chloride resins, fluorine-containing resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl alcohol resins, polyimide resins, etc.

[0281] In addition, as the crystal material that can be used for the transparent substrate, birefringent crystals such as crystal, lithium niobate, and sapphire can be listed. Regarding the optical properties of the transparent substrate, the filter obtained by stacking the above-mentioned absorption layer, reflection layer, etc. has the above-mentioned optical properties. As the crystal material, sapphire is preferred.

[0282] From the viewpoint of shape stability related to long-term reliability of the optical and mechanical properties of the optical filter, and the viewpoint of handleability during filter production, the transparent substrate is preferably an inorganic material, and particularly preferably glass and sapphire.

[0283] The shape of the transparent substrate is not particularly limited, and may be block, plate or film-shaped, and its thickness is preferably 0.03 mm to 5 mm, and more preferably 0.03 mm to 0.5 mm from the viewpoint of thinning. From the viewpoint of processability, a transparent substrate made of glass and having a thickness of 0.05 mm to 0.5 mm is preferred.

[0284] (Reflective layer)

[0285] The reflective layer includes a dielectric multilayer film and has a function of blocking light in a specific wavelength range. As the reflective layer, for example, a layer having wavelength selectivity that transmits visible light and mainly reflects light of wavelengths other than the light-shielding region of the absorption layer can be cited. The reflective layer preferably has a reflective region that reflects near-infrared light. In this case, the reflective region of the reflective layer can include a light-shielding region in the near-infrared region of the absorption layer. The reflective layer is not limited to the above-mentioned characteristics, and can also be appropriately designed to further block light in a specified wavelength range, such as light in the near-ultraviolet region.

[0286] When the reflective layer has a reflective region that reflects near-infrared light, specifically, the reflective layer preferably satisfies the following (iii-1).

[0287] (iii-1) For the reflective layer, in the spectral transmittance curve at an incident angle of 0 degrees, the average transmittance T of light with a wavelength of 850 nm to 1100 nm is RE850-1100平均0° The average transmittance T is less than 0.2%. RE850-1100平均0° It is preferably 0.15% or less, and more preferably 0.05% or less.

[0288] In the case where the reflective layer has a reflective region that reflects near-infrared light, the absorption layer and the reflective layer preferably have the following relationship.

[0289] The wavelength λ on the short wavelength side at which the absorption layer shows a transmittance of 20% for light at an incident angle of 0 degrees is ABSHT20-0° The wavelength λ on the short wavelength side at which the reflective layer shows a transmittance of 20% for light with an incident angle of 0 degrees is RESHT20-0° The relationship preferably satisfies (iii-2).

[0290] (iii-2)λ ABSHT20-0° +30nm≤λ RESHT20-0° ≤790nm

[0291] The reflective layer further preferably satisfies (iii-3).

[0292] (iii-3) The reflective layer from λ RESHT20-0° to λ RESHT20-0° The average transmittance of light in the wavelength range of +300 nm is 10% or less.

[0293] The reflective layer is composed of a dielectric multilayer film obtained by alternately stacking a dielectric film with a low refractive index (low refractive index film) and a dielectric film with a high refractive index (high refractive index film). The refractive index of the high refractive index film is preferably 1.6 or more, more preferably 2.2 to 2.5. As materials for the high refractive index film, for example, Ta2O5, TiO2, and Nb2O5 can be cited. Among them, TiO2 is preferred from the viewpoints of film forming properties, reproducibility of the refractive index, stability, etc.

[0294] On the other hand, the refractive index of the low refractive index film is preferably less than 1.6, more preferably greater than or equal to 1.45 and less than 1.55. Examples of the material of the low refractive index film include SiO2, SiO x N y From the viewpoints of reproducibility, stability, economy, etc. of film-forming properties, SiO2 is preferred.

[0295] In addition, it is preferred that the transmittance of the reflective layer changes steeply within the boundary wavelength range of the transmission region and the light-shielding region. For this purpose, the total number of stacked dielectric multilayer films constituting the reflective layer is preferably 15 layers or more, more preferably 25 layers or more, and further preferably 30 layers or more. However, when the total number of stacked layers increases, warping or the film thickness increases, so the total number of stacked layers is preferably 100 layers or less, more preferably 75 layers or less, and further preferably 60 layers or less. In addition, the film thickness of the dielectric multilayer film is preferably 2 μm to 10 μm.

[0296] If the total number of layers and the film thickness of the dielectric multilayer film are within the above range, the reflective layer satisfies the requirements for miniaturization and can suppress the incidence angle dependency while maintaining high productivity. In addition, in the formation of the dielectric multilayer film, for example, vacuum film forming processes such as CVD, sputtering, and vacuum evaporation; wet film forming processes such as spraying and dipping can be used.

[0297] The prescribed optical properties may be imparted to a single reflective layer (a set of dielectric multilayer films), or may be imparted to a prescribed optical property by two or more reflective layers. In the case of having two or more reflective layers, each reflective layer may have the same structure or different structures. In the case of having two or more reflective layers, it is usually composed of a plurality of reflective layers with different reflection bands.

[0298] As an example, when two reflective layers are provided, one layer may be a near-infrared reflective layer that blocks light in the short-wavelength band of the near-infrared region, and the other layer may be a near-infrared / near-ultraviolet reflective layer that blocks light in both the long-wavelength band of the near-infrared region and the near-ultraviolet region. In addition, for example, when the present optical filter has a transparent substrate, when two or more reflective layers are provided, all the reflective layers may be provided on one main surface of the transparent substrate, or each reflective layer may be provided on both main surfaces of the transparent substrate in a manner that the transparent substrate is sandwiched therebetween.

[0299] (Anti-reflection layer)

[0300] As the anti-reflection layer, dielectric multilayer films, intermediate refractive index media, moth-eye structures with gradually changing refractive indexes, etc. can be cited. Among them, dielectric multilayer films are preferred from the viewpoints of optical efficiency and productivity. The anti-reflection layer is obtained by alternately stacking dielectric films like the reflective layer.

[0301] In the present optical filter, as other components, for example, components (layers) that impart absorption by inorganic particles that control the transmission and absorption of light in a specific wavelength range may be included. Specific examples of inorganic particles include ITO (indium tin oxide), ATO (antimony-doped tin oxide), cesium tungstate, and lanthanum boride. ITO particles and cesium tungstate particles have high visible light transmittance and light absorption in a wide range of infrared wavelengths greater than 1200 nm, and therefore can be used when the infrared light blocking property is required.

[0302] The present optical filter has a reflective layer and an absorption layer containing a dye (A), thereby achieving excellent near-infrared light shielding properties, particularly long-wavelength infrared light shielding properties, while maintaining good visible light transmittance.

[0303] In the present optical filter, when the absorption layer contains the dye (A), it is preferred that the following (iv-2) to (iv-5) are satisfied.

[0304] (iv-2) For this filter, the average transmittance T of light with a wavelength of 850nm to 1100nm at an incident angle of 0 degrees is 850-1100平均0° It is 0.2% or less, preferably 0.15% or less, and more preferably 0.10% or less.

[0305] (iv-3) For this filter, the average transmittance T of light with a wavelength of 435nm to 630nm at an incident angle of 0 degrees is 435-630平均0° It is 65% or more, preferably 70% or more, and more preferably 75% or more.

[0306] (iv-4) For this filter, the average transmittance T of light with a wavelength of 850nm to 1100nm at an incident angle of 30 degrees is 850-1100平均30° It is 2% or less, preferably 1% or less, and more preferably 0.05% or less.

[0307] (iv-5) For this filter, the maximum transmittance T of light with a wavelength of 850nm to 1100nm at an incident angle of 30 degrees is 850-1100最大30° It is 5% or less, preferably 3% or less, and more preferably 2% or less.

[0308] In the present optical filter, when the absorption layer further contains a dye (D), it is preferred that the optical property (iv-1) below is satisfied.

[0309] (iv-1) For the present optical filter, within the wavelength range of 615 nm to 725 nm, the value obtained by averaging the absolute value of the difference between the transmittance in the spectral transmittance curve at an incident angle of 0 degrees and the transmittance in the spectral transmittance curve at an incident angle of 30 degrees is 2% / nm or less, preferably 1.5% / nm or less, and more preferably 1.0% / nm or less.

[0310] The present filter has good visible light transmittance and excellent near-infrared light blocking properties, especially long-wavelength near-infrared light blocking properties. The present filter is useful, for example, in the use of a filter for an imaging device in a device that has both an imaging device such as a digital camera and an optical component using a laser. An imaging device using the present filter has a solid-state imaging element, an imaging lens, and the present filter. The present filter can be used, for example, in the following manner: arranged between an imaging lens and a solid-state imaging element; or directly attached to a solid-state imaging element, an imaging lens, etc. of an imaging device via an adhesive layer.

[0311] Example

[0312] Next, the present invention will be described in more detail by way of examples. First, the synthesis examples and properties of the dye (A) and the dye (D) used in the absorption layer of the examples will be described. Next, examples of the optical filter will be described.

[0313] [Test Examples 1 to 54: Synthesis and Evaluation of Dyes and Preparation and Evaluation of Absorbing Layers]

[0314] (Synthesis and evaluation of pigments)

[0315] Regarding the pigment (ACi1-1B), pigment (ACi1-2B), pigment (ACii2-2B), pigment (ACiii2-9B) and pigment (ACiii3-9B) in the pigment (A) used in the example, commercially available products manufactured by Few Chemicals under the trade names S0772, S2437 and S2007 and commercial products manufactured by Spectrum info under the trade names S1984 and S1985 were prepared respectively.

[0316] In addition, pigment (ACii1-1P), pigment (ACii1-1B), pigment (ACii2-1P), pigment (ACii2-1B), pigment (ACiii1-2P), pigment (ACiii2-2P), pigment (ACiv-2P), pigment (ACiv-26P), pigment (ASi-1), pigment (ASi-2) and pigment (ASii-2) were synthesized as pigment (A) using the following method.

[0317] Furthermore, a dye (I-12-24) was synthesized as the dye (D) by a conventional method.

[0318] In addition, as the pigment used in comparative example, TXEX910B (manufactured by Nippon Catalyst Co., Ltd., phthalocyanine pigment) and Dim01 (diimmonium pigment) shown in the following formula synthesized by the method of recording in Japanese Patent Publication No. 2014-25016 were prepared. It should be noted that, in the evaluation of the optical properties of these pigments, an ultraviolet visible spectrophotometer (manufactured by Hitachi High-Tech Co., Ltd., U-4150 type) was used, and U-4150 was also used in the evaluation of the following optical properties (spectral transmittance curve).

[0319]

[0320] (1) Production of pigment (ACii1-1P)

[0321] The pigment (ACii1-1P) was synthesized according to the reaction pathway shown below.

[0322]

[0323] <Step 1>

[0324] Benzo[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 to a 1 L eggplant flask, dissolved in sulfolane (250 mL), and stirred at 70°C for 2 hours. 1-Bromobutane (35 g, 255 mmol) and potassium hydroxide (15 g, 260 mmol) were added to the suspension, and stirred at 70°C for 19 hours. After the reaction was completed, an extraction operation was performed using an organic solvent obtained by mixing hexane:ethyl acetate = 4:1, and the solvent was removed. Then, a yellow oily substance was separated as the product (1) (20.3 g, yield 96%) by flash column chromatography (hexane:ethyl acetate = 8:2).

[0325] <Step 2>

[0326] The product (1) (5 g, 22 mmol) obtained in step 1 was added to a 300 mL eggplant-shaped flask and dissolved in 50 mL of tetrahydrofuran. Under a nitrogen atmosphere, 100 mL of 1 M methylmagnesium bromide was added dropwise at 0 ° C, warmed to room temperature, and then stirred for 12 hours. After confirming the disappearance of the raw material using thin layer chromatography (TLC), the reaction solution was slowly poured into a beaker to which 200 mL of ice water was added, and then 50 g of 60% hexafluorophosphoric acid aqueous solution was added and stirred at room temperature for 1 hour. Extraction was performed using dichloromethane, and then the water solvent was removed using anhydrous magnesium sulfate to remove the organic solvent. Then, a small amount was dissolved in dichloromethane and reprecipitated using ethyl acetate to obtain a yellow-green solid as product (2) (6.85 g, yield 86%).

[0327] <Step 3>

[0328] The product (2) (3 g, 8.3 mmol) obtained in step 2 and the cyanine intermediate 1 (1.59 g, 4 mmol) synthesized with reference to J. Heterocyclic Chem., 42, 959, (2005) were added to a 300 mL eggplant flask, dissolved in 90 mL of pyridine, and stirred at 150° C. for 3 hours. After the reaction was completed, pyridine was removed while azeotroping in toluene, and the obtained solid was washed with hexane. Then, it was separated by flash column chromatography (dichloromethane: ethyl acetate = 10: 1), the solvent was removed, a small amount was dissolved in dichloromethane, and a reprecipitation operation was performed several times with hexane, thereby obtaining a pigment (ACii1-1P) as a black solid (1.0 g, yield 34%).

[0329] (2) Production of pigment (ACii1-1B)

[0330] In the production of dye (ACii1-1P), dye (ACii1-1B) was obtained in the same manner as dye (ACii1-1P) except that 42% tetrafluoroboric acid aqueous solution was used in step 2 instead of 60% hexafluorophosphoric acid aqueous solution.

[0331] (3) Production of pigment (ACii2-1P)

[0332] In the production of the dye (ACii1-1P), a dye (ACii2-1P) was obtained according to the reaction pathway shown below in the same manner as the dye (ACii1-1P) except that the cyanine intermediate 2 was used instead of the cyanine intermediate 1 in step 3.

[0333]

[0334] (4) Production of pigment (ACii2-1B)

[0335] In the production of the pigment (ACii1-1B), a pigment (ACii2-1B) was obtained by the same method as that of the pigment (ACii1-1B), except that the cyanine intermediate 2 was used instead of the cyanine intermediate 1 in step 3.

[0336] (5) Production of pigment (ACiii1-2P)

[0337] The dye (ACiii1-2P) was synthesized according to the reaction pathway shown below.

[0338]

[0339] <Step 1 (Chlorination)>

[0340] 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 tetrahydrofuran solution to obtain a solid product (3) (70 g, yield 70%).

[0341] <Step 2 (Salt Exchange)>

[0342] The product (3) (20 g, 64 mmol) obtained in step 1, methanol (100 mL), and acetone (100 mL) were added to a 1 L eggplant flask, and stirred at 80°C. Potassium hexafluorophosphate (16 g, 87 mmol), water (100 mL), and acetone (100 mL) were added to a separately prepared 500 mL eggplant flask, and stirred at room temperature for about 2 hours until the potassium hexafluorophosphate was dissolved. The dissolved potassium hexafluorophosphate solution was poured into the eggplant flask containing the product (3), and stirred at 80°C for 14 hours. After confirming the disappearance of the raw materials by TLC, the methanol and acetone solvents were removed, and extraction was performed with dichloromethane. Separation was performed by flash column chromatography (dichloromethane: methanol = 1000: 40), the solvent was removed, and washing was performed with hexane, and then a white solid product (4) (21 g, yield 96%) was obtained.

[0343] <Step 3>

[0344] With reference to Chem. A European Journal, 22 (4), 1266, (2016) and J. Org. Chem., 70 (21), 8575, (2005), UKRAINSKII KHIMICHESKII ZHURNAL, 44 (8), 838, (1978), cyanine intermediate 3 (11 g, yield of 13% after 5 steps of reaction) was obtained.

[0345] <Step 4>

[0346] The product (4) obtained in step 2 (5.12 g, 15 mmol) 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 the reaction was completed, pyridine was removed while azeotroping in toluene. Then, it was separated by flash column chromatography (dichloromethane: ethyl acetate = 10: 1), the solvent was removed, a small amount was dissolved in dichloromethane, and a reprecipitation operation was performed several times using hexane to obtain a pigment (ACiii1-2P) as a reddish brown solid (0.18 g, yield 4%).

[0347] (6) Production of pigment (ACiii2-2P)

[0348] Dye (ACiii2-2P) was obtained in the same manner as the synthesis method of dye (ACiii1-2P) except that 2,3,3-trimethyl-4,5-benzo-3H-indole was used as a raw material instead of 2,3,3-trimethylindole.

[0349] (7) Production of pigment (ACiv-2P)

[0350] The dye (ACiv-2P) was synthesized according to the reaction pathway shown below.

[0351]

[0352] <Step 1>

[0353] Lupicrine (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 a solid product (5) (100 g, yield 90%).

[0354] <Step 2>

[0355] The product (5) (20 g, 66.8 mmol), methanol (100 mL), and acetone (100 mL) obtained in step 1 were added to a 1 L eggplant flask, and stirred at 80°C. Potassium hexafluorophosphate (16 g, 87 mmol), water (100 mL), and acetone (100 mL) were added to a separately prepared 500 mL eggplant flask, and stirred at room temperature for about 2 hours until the potassium hexafluorophosphate was dissolved. The dissolved potassium hexafluorophosphate solution was poured into the eggplant flask containing the product (5) and stirred at 80°C for 14 hours. After confirming the disappearance of the raw material by TLC, the methanol and acetone solvents were removed and extracted with dichloromethane. The product was separated by flash column chromatography (dichloromethane: methanol = 1000: 40), the solvent was removed, and the product was washed with hexane to obtain a white solid product (6) (20 g, yield 94%).

[0356] <Step 3>

[0357] Using the product (6) obtained in step 2, a dye (ACiv-2P) was obtained in the same manner as in step 3 described in the method for synthesizing the dye (ACii1-1P).

[0358] (8) Production of pigment (ACiv-26P)

[0359] A dye (ACiv-26P) was obtained in the same manner as the synthesis method of the dye (ACiv-2P) except that the cyanine intermediate 2 was used instead of the cyanine intermediate 1 in the production of the dye (ACiv-2P).

[0360] (9) Production of pigment (ASi-1)

[0361] The pigment (ASi-1) was synthesized according to the reaction path 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 added to a 500 mL eggplant flask, dissolved in toluene (330 mL) and 1-butanol (110 mL), quinoline (8 mmol) was added, and stirred at 150° C. for 4 hours. It should be noted that the product (10) is an iodine salt of a compound obtained by replacing the hydrogen at the 1-position of 2-methyl-benzo[c,d]indole with R, and R is -CH2-CH(C2H5)(C4H9).

[0362] After the reaction, the solvent was removed, and the mixture was separated by flash column chromatography (hexane:ethyl acetate=8:2). The solvent was removed, and the mixture was washed with hexane to obtain a reddish brown solid (ASi-1) (0.5 g, yield 25%).

[0363]

[0364] (10) Production of pigment (ASi-2)

[0365] In addition to changing the product (10) to the product (10) in the preparation of the dye (ASi-1), R is replaced by -CH2-CH(C8H 17 )(C6H 13 ) was used, except for the iodonium salt of the benz[c,d]indole compound of EMI15.1. The dye (ASi-2) was obtained in the same manner as the synthesis method of the dye (ASi-1).

[0366] (11) Production of pigment (ASii-2)

[0367] The dye (ASii-2) was synthesized according to the reaction pathway shown below.

[0368]

[0369] <Step 1>

[0370] 5-Methyl isatin (25 g, 155 mmol) and 1-butanol (180 mL) were added to a 1 L eggplant flask, and hydrazine monohydrate (9.3 g, 186 mmol) was added dropwise at 0°C. Then, the mixture was stirred at 35°C for 30 minutes, and then the temperature was raised to 80°C and stirred for 4 hours. Triethylamine (15.7 g, 155 mmol) was slowly added, and the mixture was stirred at 100°C for 11 hours. Concentrated sulfuric acid was added until the pH reached about 6, and the mixture was cooled to room temperature, the solvent was removed, and then an extraction operation was performed. The obtained solid was washed with hexane to obtain the product (7) (22 g, yield 96%) as a dark brown solid.

[0371] <Step 2>

[0372] Referring to Org. Lett., 18, 5232, (2016), the product (7) obtained in step 1 (22 g, 149 mmol), 2-bromobenzaldehyde (16 g, 90 mmol), cesium carbonate (86 g, 26 mmol), and dimethyl sulfoxide (700 mL) were added to a 1L three-necked flask. Vacuum degassing and nitrogen replacement were performed multiple times, and then stirred at 120°C for 7 hours, and then cooled to room temperature. Then, an extraction operation was performed, and separation was performed using flash column chromatography (hexane: ethyl acetate = 2: 8), and the solvent was removed, and then a yellow solid product (8) (8 g, yield 38%) was obtained.

[0373] <Step 3>

[0374] The product (9) was obtained from the product (8) obtained in step 2 by referring to the method described in European Journal of Medical Chemistry, 54, 647, (2012). It should be noted that R in the product (9) is -CH2-CH(C8H 17 )(C6H 13 Dye (ASii-2) was obtained in the same manner as the synthesis method of dye (ASi-2) except that the iodonium salt of 1-dodecyl-2-methyl-benzo[c,d]indole was replaced with product (9) in the production of dye (ASi-2).

[0375] Each of the above pigments was dissolved in dichloromethane, and the light absorption spectrum at wavelengths of 350nm to 1200nm was measured, and the maximum absorption wavelength λ was obtained from the absorbance curve. 最大(A)DCM In addition, according to the maximum absorption wavelength λ 最大(A)DCM The ABS is obtained by adjusting the dye concentration in dichloromethane so that the transmittance of the light at 10% 400(A)DCM / ABS λ最大(A)DCM and ABS 550(A)DCM / ABS λ最大(A)DCM The results are shown in Table 17. In the table, "ABS in DCM 400 / λ最大 ” means ABS 400(A)DCM / ABS λ最大(A)DCM ABS in DCM 550 / λ最大 ” means ABS 550(A)DCM / ABS λ最大(A)DCM In addition, "ASi-xx / ASi-yy" refers to the R on the left side of the above formula (ASi). 161 ~R 167 Same as the compound with the color code ASi-xx, R on the right 161 ~R 167 The same compound as the compound with the pigment code ASi-yy.

[0376] Table 17

[0377]

[0378] (Fabrication of the Absorbent Layer)

[0379] The absorption layer was prepared using the pigment and 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 the present optical filter, and test examples 13, 14, 25, 26, 35, 36, 45 to 54 are comparative test examples. As the transparent resin, the following commercially available products were used.

[0380] <Transparent resin>

[0381] Transparent resin (R1); Neopulim (registered trademark) C-3G30 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name, polyimide resin)

[0382] Transparent resin (R2); OKP-850 (manufactured by Osaka Gas Chemical Co., Ltd., trade name, polyester resin)

[0383] Transparent resin (R3); SP3810 (manufactured by Teijin Limited, trade name, polycarbonate resin)

[0384] Transparent resin (R4); PLEXIMID8817 (manufactured by Daicel Corporation, trade name, acrylic imide resin)

[0385] Transparent resin for comparative example (Rcf); BR1122 (manufactured by Mitsubishi Rayon Co., Ltd., trade name, acrylic resin)

[0386] The pigment, transparent resin (R1), and cyclohexanone were stirred thoroughly and uniformly dissolved. The obtained solution was coated on a glass plate (D263; manufactured by SCHOTT, trade name) and dried to obtain an absorption layer with a film thickness of 1 μm. The amount of pigment added (pigment concentration) was adjusted so that the maximum absorption wavelength λ when the film thickness was 1 μm 最大(A)TR The transmittance of light at 10% is 10%. The absorbance curve of the absorbing layer is obtained by using the absorbance curve of the glass plate with the absorbing layer and the absorbance curve of the glass plate at wavelengths of 350nm to 1200nm.

[0387] The maximum absorption wavelength λ was obtained based on the absorbance curve of the absorption layer. 最大 (A)TR, ABS 400(A)TR / ABS λ最大(A)TR (The table shows "ABS in resin 400 / λ最大 ”) and ABS 550(A)TR / ABS λ最大(A)TR (The table shows "ABS in resin 550 / λ最大 ”). In addition, ABS was obtained 400(A)TR / ABS λ最大(A)TR -ABS 400(A)DCM / ABS λ最大(A)DCM (“ABS” in the table 400 / λ最大 Difference”) and ABS 550(A)TR / ABS λ最大(A)TR –ABS 550(A)DCM / ABS λ最大(A)DCM (“ABS” in the table 550 / λ最大 In addition, the mass extinction coefficient / (cm·mass%) was calculated. The results are shown in Table 18. The pigment concentration in the table is adjusted so that the above λ最大(A)TR The mass parts of the pigment relative to 100 mass parts of the transparent resin (R1) when the transmittance of light at 10% is 10%.

[0388]

[0389] In the above, the transparent resin (R1) was replaced with the transparent resins (R2) to (R5) or the transparent resin (Rcf) for comparative examples and the same evaluation was performed. The results for the transparent resin (R2) are shown in Table 19, the results for the transparent resin (R3) are shown in Table 20, the results for the transparent resin (R4) are shown in Table 21, and the results for the transparent resin (Rcf) for comparative examples are shown in Table 22.

[0390]

[0391]

[0392] As can be seen from Tables 18 to 22, if pigments (ACi) to (ACiv), pigments (ASi) or pigments (ASii) and transparent resins suitable for combining with these pigments are used, the requirements of (i-1) to (i-3) are satisfied. In addition, it can be seen that the preferred combination among these satisfies the requirement of (i-4).

[0393] [Examples 1 to 12: Production and Evaluation of Filters]

[0394] (Manufacturing of optical filters)

[0395] The following method was used to produce Figure 6 A filter with the same structure as the filter 10F shown in FIG.

[0396] In each example, as shown in Tables 23 and 24, a glass substrate with a thickness of 0.21 mm containing fluorophosphate glass (manufactured by Asahi Glass Co., Ltd., trade name: NF-50GX) containing CuO or a glass substrate with a thickness of 0.2 mm (D263; manufactured by SCHOTT, trade name) was used as a transparent substrate.

[0397] As a reflective layer, a dielectric multilayer film formed as follows was used in each example. The dielectric multilayer film was formed by alternately stacking a total of 42 layers of TiO2 film and SiO2 film on one main surface of a glass substrate by vapor deposition. The structure of the reflective layer was designed as follows: the number of stacked dielectric multilayer films, the film thickness of the TiO2 film, and the film thickness of the SiO2 film were used as parameters for simulation, and in the spectral transmittance curve at an incident angle of 0 degrees, the average transmittance of light with a wavelength of 850nm to 1100nm was 0.03%.

[0398] In addition, on the main surface of the glass substrate on the opposite side of the surface on which the reflective layer is formed, a transparent resin shown in Table 23 and Table 24, one or two of the pigments (A) (the first pigment (A) and the second pigment (A) in the table), and a pigment (D) (pigment (I-12-24)) are combined to form an absorption layer with a thickness of about 1.0 μm. It should be noted that the pigment content in Table 23 and Table 24 is the mass part of the pigment relative to 100 mass parts of the transparent resin.

[0399] Then, 7 layers of TiO2 film and SiO2 film were alternately stacked on the surface of the absorption layer by vapor deposition to form an antireflection layer, thereby obtaining filters (NIR filters) of Examples 1 to 12. Examples 1 to 11 are examples, and Example 12 is a comparative example.

[0400] (evaluate)

[0401] For the absorption layers of the optical filters obtained in Examples 1 to 12, spectral transmittance curves at an incident angle of 0 degrees were obtained. Tables 23 and 24 show the wavelengths λ on the short wavelength side of the wavelengths showing a transmittance of 20% obtained from the spectral transmittance curves. ABSHT20-0° , Average transmittance T of light with wavelength 435nm~630nm AB435-630平均0° And the average transmittance T of light with a wavelength of 850nm to 1100nm AB850-1100平均0° .

[0402] In addition, for the filters obtained in Examples 1 to 12, the spectral transmittance curves at incident angles of 0 degrees and 30 degrees were obtained. Tables 23 and 24 show the average value of the absolute value of the difference between the transmittance of the spectral transmittance curve at an incident angle of 0 degrees and the transmittance of the spectral transmittance curve at an incident angle of 30 degrees in the wavelength range of 615nm to 725nm ("Difference in wavelengths 615nm to 725nm" in the table). In addition, the average transmittance T of light with a wavelength of 850nm to 1100nm when the incident angle is 0 degrees is shown. 850-1100平均0° , Average transmittance T of light with wavelength 435nm~630nm 435-630平均0° , the average transmittance T of light with a wavelength of 850nm to 1100nm when the incident angle is 30 degrees 850-1100平均30° 、Maximum transmittance T of light with wavelength of 850nm to 1100nm 850-1100最大30° .

[0403]

[0404]

[0405] It can be seen from Table 23 and Table 24 that for the optical filters of Examples 1 to 11, the absorption layer satisfies (ii-1) to (ii-3), and the optical filter satisfies (iv-1) to (iv-5).

[0406] Industrial Applicability

[0407] The optical filter of the present invention has good transmittance of visible light and excellent shielding property of near-infrared light, especially long-wavelength near-infrared light. Therefore, it is useful for use as an optical filter for an imaging device in a device having both an imaging device and an optical component using a laser.

[0408] While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the present invention.

[0409] This application is based on Japanese Patent Application No. 2018-018608 filed on February 5, 2018, the contents of which are incorporated herein by reference.

[0410] Description of symbols

[0411] 10A, 10B, 10C, 10D, 10E, 10F…optical filters; 11, 11a, 11b…absorption layers; 12, 12a, 12b…reflection layers; 13…transparent substrate; 14…anti-reflection layers.

Claims

1. A filter, wherein: The optical filter comprises an absorption layer, a reflection layer and an anti-reflection layer, wherein the absorption layer comprises a transparent resin, a near-infrared absorption pigment A and a near-infrared absorption pigment D, and the reflection layer comprises a dielectric multilayer film, and the optical filter satisfies the following (1) to (4) and (13): (1) Average transmittance T of light with a wavelength of 850nm to 1100nm at an incident angle of 0 degrees 850-1100平均0° Less than 0.02%; (2) Average transmittance T of light with a wavelength of 435nm to 630nm at an incident angle of 0 degrees 435-630平均0° More than 70%; (3) Average transmittance T of light with a wavelength of 850nm to 1100nm at an incident angle of 30 degrees 850-1100平均30° Less than 1%; (4) Maximum transmittance T of light with a wavelength of 850nm to 1100nm at an incident angle of 30 degrees 850-1100最大30° Less than 2%; (13) In the wavelength range of 615 nm to 725 nm, the value obtained by averaging the absolute value of the difference between the transmittance in the spectral transmittance curve at an incident angle of 0 degrees and the transmittance in the spectral transmittance curve at an incident angle of 30 degrees is 1.5% / nm or less, The near infrared absorbing pigment A is a cyanine compound represented by any one of the following formulas (ACi) to (ACiv) or a squarylium compound represented by the following formula (ASi) or (ASii). Salt pigment, The symbols in formula (ACi) to formula (ACiv) are as follows: R 101 ~R 107 , R 121 ~R 127 , R 141 and R 151 each independently represents a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl 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 a group, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, a haloalkyl 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 3-membered to 14-membered heterocyclic group, R 102 ~R 107 and R 122 ~R 127 Two adjacent ones of may be connected to each other to form a five-membered ring, a six-membered ring or a seven-membered ring, R 142 and R 143 are hydrogen atoms or can be bonded to form a six-membered aromatic ring D, R 145 and R 144 are hydrogen atoms or may be bonded to each other to form a six-membered aromatic ring E, but excluding the case where both the aromatic ring D and the aromatic ring E are formed, 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, -NR 112 R 113 a cycloalkyl group having 3 to 14 carbon atoms, or an aryl group having 6 to 14 carbon atoms, R 109 and R 111 , R 129 and R 131 , R 146 and R 148 and R 152 and R 154 They may be bonded to each other to form a five-membered ring or a six-membered ring. When forming a ring, the hydrogen atoms bonded to the ring may be replaced by an alkyl group having 1 to 6 carbon atoms, and two atoms in the constituent atoms of the ring may be bridged by a methylene group. R 112 ~R 118 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, a haloalkyl 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 3- to 14-membered heterocyclic group, Multiple Rs included in various formulas 101 ~R 107 , multiple R 121 ~R 127 , multiple R 141 ~R 145 , multiple R 151 , multiple Ds and multiple Es may be the same as or different from each other, X - represents a monovalent anion; The symbols in formula (ASi) and formula (ASii) 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, Y 3 CR 179 or N, R 162 ~R 167 and R 171 ~R 179 are each independently a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl 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 a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a 3-membered to 14-membered heterocyclic group, R 112 ~R 118 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, a haloalkyl 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 3- to 14-membered heterocyclic group, Multiple Rs included in various formulas 161 ~R 167 , multiple R 171 ~R 178 and multiple Y 3 They can be the same as each other or different from each other; The near-infrared absorbing pigment D is a compound represented by any one of the following formulae (I) to (III): Wherein, the symbols in formula (I) are as follows, R 24 and R 26 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, -NR 27 R 28 , or a group represented by the following formula (S), R 27 and R 28 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, -C(=O)-R 29 、-NHR 30 or -SO2-R 30 , 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 which may have a substituent, or a linear or branched saturated or unsaturated hydrocarbon group or a saturated cyclic hydrocarbon group having 7 to 18 carbon atoms which may have a substituent and may have an oxygen atom between carbon atoms and which may be substituted with one or more aryl groups, and may contain a saturated ring structure, R 30 Each is a hydrocarbon group having 1 to 25 carbon atoms, wherein one or more hydrogen atoms may be substituted with a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group or a cyano group and may contain an unsaturated bond, an oxygen atom or a saturated or unsaturated ring structure between carbon atoms. 41 , R 42 independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; k is 2 or 3; R 21 and R 22 , R 22 and R 25 and R 21 and R 23 may be connected to each other and together with the nitrogen atom to form a five-membered or six-membered heterocyclic ring A, heterocyclic ring B and heterocyclic ring C respectively; For R in the case of forming a heterocyclic ring A 21 and R 22 As R 21 and R 22 The bonded divalent group -Q- represents an alkylene group in which the hydrogen atom may be substituted by 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 in which the hydrogen atom may be substituted by 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; For R in the case of forming a heterocyclic ring B 22 and R 25 and R in the case of forming a heterocyclic ring C 21 and R 23 As R 22 and R 25 and R 21 and R 23 The divalent group -X to which each is bonded 1 -Y 1 -and-X 2 -Y 2 -, the side bonded to nitrogen is X 1 and X 2 , X 1 and X 2 Each is a group represented by the following formula (1x) or (2x), Y 1 and Y 2 Each is a group represented by any one selected from the following formulae (1y) to (5y); in X 1 and X 2 When each is a group represented by the following formula (2x), Y 1 and Y 2 Each may be a single bond, in which case an oxygen atom may be present between carbon atoms; In formula (1x), four Zs each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, or -NR 38 R 39 , R 38 and R 39 Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R 31 ~R 36 Each independently represents 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 , R when no heterocyclic ring is formed 21 ~R 23 and R 25 It can be bonded with any other of them to form a five-membered ring or a six-membered ring; R 31 and R 36 , R 31 and R 37 Can be directly bonded; R when no heterocyclic ring is formed 21 and R 22 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an allyl group which may have a substituent, an aryl group having 6 to 11 carbon atoms which may have a substituent, or a linear or branched saturated or unsaturated hydrocarbon group or a saturated cyclic hydrocarbon group which may have a saturated ring structure and is substituted with one or more aryl groups; R in the case of not forming a heterocyclic ring 23 and R 25 Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; Wherein, the symbols in formula (II) are as follows, Ring Z is 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 and together with the nitrogen atom form heterocycle A1, heterocycle B1 and heterocycle C1, respectively. In the case where a heterocycle is not formed, R 1 and R 2 Each independently represents 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 may have a substituent, R 3 and R 4 Each independently represents a hydrogen atom, a halogen atom, or an alkyl group which may contain a hetero atom between carbon atoms or an alkoxy group which may contain a hetero atom between carbon atoms, Wherein, 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 optionally substituted alkyl group having 1 to 10 carbon atoms, 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 by an alkyl group having 1 to 10 carbon atoms, R 54 and R 55 The alkyl groups may be linked to each other to form a benzene ring A2, and the hydrogen atoms of the benzene ring A2 may be substituted by an alkyl group having 1 to 10 carbon atoms.

2. The optical filter according to claim 1, wherein: The filter also satisfies the following (9): (9) Average transmittance T of light with a wavelength of 850nm to 1100nm at an incident angle of 30 degrees 850-1100平均30° It is less than 0.10%.

3. The optical filter according to claim 2, wherein: The filter also satisfies the following (11) to (12): (11) Average transmittance T of light with a wavelength of 850nm to 1100nm at an incident angle of 30 degrees 850-1100平均30° Less than 0.05%; (12) Maximum transmittance T of light with a wavelength of 850nm to 1100nm at an incident angle of 30 degrees 850-1100最大30° It is less than 0.35%.

4. The optical filter according to any one of claims 1 to 3, wherein The near-infrared absorbing pigment satisfies the following (14): (14) In an absorbance curve at wavelengths of 350 nm to 1200 nm measured by containing the near infrared absorbing dye in a transparent resin, the maximum absorption wavelength λ 最大(A)TR In the wavelength range of 850nm ~ 1100nm.

5. The optical filter according to any one of claims 1 to 3, wherein The optical filter further comprises a transparent substrate, and the transparent substrate is an absorption glass containing copper ions in fluorophosphate glass or phosphate glass.

6. The optical filter according to any one of claims 1 to 3, wherein The transparent resin has at least one bond selected from an ester bond, a carbonate bond, and an imide bond in a main chain.

7. An imaging device, wherein: The imaging device comprises the optical filter according to any one of claims 1 to 6.

Images