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, the optical filter having an absorption layer and a reflection layer, the absorption layer containing a near-infrared absorption pigment and a transparent resin, wherein the near-infrared absorption pigment has a maximum absorption wavelength of 760nm to 900nm in the transparent resin, and an average transmittance T of 435nm to 480nm 435‑480平均TR , average transmittance T at 480nm to 590nm 480‑590平均TR The near infrared absorbing pigment has a maximum absorption wavelength of 760 nm to 900 nm in dichloromethane and an average transmittance T of 435 nm to 480 nm. 435‑480平均DCM The average transmittance T of 95% or more at 480nm to 590nm 480‑590平均DCM More than 97%, T 435‑480平均DCM With T 435‑480平均TR The difference between 480‑590平均DCM With T 480‑590平均TR The difference is 10.5% or less, and the incident angle of the filter is 60 degrees, and the average transmittance of 800nm ​​to 900nm is 5% or less.

Description

[0001] This application is a divisional application of the Chinese patent application with application date of January 30, 2019 and application number 201980011456.9. 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, as imaging devices have become smaller and higher quality, it is required to suppress the angle of incidence dependency on light incident at a higher angle. For example, it is required to increase the transmittance of near-infrared light that should have a high reflectivity in the wavelength range of 800nm ​​to 900nm at a high incident angle and suppress the occurrence of light leakage.

[0005] In the past, many technologies using absorbents that show absorption in the wavelength range of 800nm ​​to 900nm have been known for near-infrared cutoff filters. Specifically, inorganic absorbents such as copper particles (e.g., Patent Document 1), cyanine pigments (e.g., Patent Documents 2 to 4), diimmonium pigments (e.g., Patent Document 5), phthalocyanine pigments (e.g., Patent Documents 6 and 7), and squarylium pigments are known. Salt pigments (e.g., Patent Document 8) and other pigments. In addition, it is known that, for example, Near infrared cut-off filters such as combinations of salt-based pigments with cyanine-based pigments, phthalocyanine-based pigments, etc. (for example, Patent Documents 9 and 10); combinations of porphyrazine-based pigments with diimonium-based pigments (for example, Patent Document 11).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2011 / 071052

[0009] Patent Document 2: Japanese Patent Application Publication No. 2007-163644

[0010] Patent Document 3: Japanese Patent Application Publication No. 2015-172102

[0011] Patent Document 4: International Publication No. 2015 / 172004

[0012] Patent Document 5: Japanese Patent Application Publication No. 2010-266870

[0013] Patent Document 6: Japanese Patent No. 605651

[0014] Patent Document 7: International Publication No. 2015 / 025779

[0015] Patent Document 8: Japanese Patent Application Publication No. 2016-142891

[0016] Patent Document 9: International Publication No. 2013 / 054864

[0017] Patent Document 10: International Publication No. 2016 / 158461

[0018] Patent Document 11: Japanese Patent Application Publication No. 2015-1649 Summary of the invention

[0019] Problems to be solved by the invention

[0020] However, any of the above-mentioned near infrared cut filters cannot achieve both high transmittance of visible light and suppression of light leakage in the wavelength range of 800 nm to 900 nm of light at a high incident angle at a high level.

[0021] An object of the present invention is to provide an optical filter which suppresses the reduction of near-infrared light shielding, especially near-infrared light shielding at high incident angles, while maintaining good transmittance of visible light, and an imaging device having excellent color reproducibility using the optical filter.

[0022] Means used to solve problems

[0023] An optical filter according to one embodiment of the present invention has the following characteristics: 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 near-infrared absorption pigment (A) satisfies the following (i-1) to (i-5), and the optical filter satisfies the following (ii-1):

[0024] (i-1) In the spectral transmittance curve at a wavelength of 400 nm to 1100 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 760nm to 900nm,

[0025] (i-2) at a wavelength λ of maximum absorption 最大(A)TR In the spectral transmittance curve at a wavelength of 400 nm to 1100 nm measured by including the near infrared absorbing dye (A) in the transparent resin so that the transmittance at the position is 10%, the average transmittance T of light in the wavelength range of 435 nm to 480 nm is 435-480平均(A)TR The average transmittance T of light in the wavelength range of 480nm to 590nm 480-590平均(A)TR All are above 90%,

[0026] (i-3) In the spectral transmittance curve at wavelengths of 400 nm to 1100 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 760nm to 900nm,

[0027] (i-4) at a wavelength λ of maximum absorption 最大(A)DCM In the spectral transmittance curve at a wavelength of 400 nm to 1100 nm measured by including the near infrared absorbing dye (A) in dichloromethane so that the transmittance at 10% is 10%, the average transmittance T of light in the wavelength range of 435 nm to 480 nm is 435-480平均(A)DCM The average transmittance T of light in the wavelength range of 480nm to 590nm is 95% or more. 480-590平均(A)DCM More than 97%,

[0028] (i-5) Average transmittance T 435-480平均(A)DCM With the average transmittance T 435-480平均(A)TR The difference and average transmittance T 480-590平均(A)DCM With the average transmittance T 480-590平均(A)TR The difference is less than 10.5%.

[0029] (ii-1) The average transmittance of light in the wavelength range of 800 nm to 900 nm is 5% or less when the incident angle is 60 degrees.

[0030] The present invention also provides an imaging device having the optical filter of the present invention.

[0031] Effects of the Invention

[0032] According to the present invention, a filter can be obtained that suppresses the reduction of near-infrared light blocking property, especially near-infrared light blocking property at high incident angles, while maintaining good transmittance of visible light. In addition, according to the present invention, an imaging device with excellent color reproducibility using the filter can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1This is a cross-sectional view schematically showing an example of an optical filter according to an embodiment.

[0034] Figure 2 This is a cross-sectional view schematically showing another example of the optical filter according to one embodiment.

[0035] Figure 3 This is a cross-sectional view schematically showing another example of the optical filter according to one embodiment.

[0036] Figure 4 This is a cross-sectional view schematically showing another example of the optical filter according to one embodiment.

[0037] Figure 5 This is a cross-sectional view schematically showing another example of the optical filter according to one embodiment.

[0038] Figure 6 This is a cross-sectional view schematically showing another example of the optical filter according to one embodiment. DETAILED DESCRIPTION

[0039] Hereinafter, embodiments of the present invention will be described.

[0040] 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”.

[0041] In this specification, the compound represented by formula (I) is referred to as compound (I). The same is true for compounds represented by other formulas. The pigment comprising compound (I) is referred to as pigment (I), and the same is true for other pigments. For example, the compound represented by formula (A1) described later is referred to as compound (A1), and the pigment comprising the compound is referred to as pigment (A1). In addition, for example, the group represented by formula (1x) is referred to as group (1x), and the same is true for groups represented by other formulas.

[0042] 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.

[0043] In the present specification, "to" indicating a numerical range includes the upper limit and the lower limit.

[0044] 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.

[0045] <Filter>

[0046] A filter according to one embodiment of the present invention (hereinafter also referred to as “the present filter”) has an absorption layer and a reflection layer, wherein the absorption layer contains a pigment (A) and a transparent resin, wherein the pigment (A) satisfies the following (i-1) to (i-5) and is a NIR pigment, and the filter satisfies the following (ii-1).

[0047] (i-1) In the spectral transmittance curve at a wavelength of 400 nm to 1100 nm measured by containing the dye (A) in the transparent resin, the maximum absorption wavelength λ 最大(A)TR In the wavelength range of 760nm ~ 900nm.

[0048] (i-2) at a wavelength λ of maximum absorption 最大(A)TR In the spectral transmittance curve at a wavelength of 400 nm to 1100 nm measured by including the dye (A) in the transparent resin so that the transmittance at the transparent resin is 10%, the average transmittance T of light in the wavelength range of 435 nm to 480 nm is 435-480平均(A)TR The average transmittance T of light in the wavelength range of 480nm to 590nm 480-590平均(A)TR All are above 90%.

[0049] (i-3) In the spectral transmittance curve at wavelengths of 400 nm to 1100 nm measured by dissolving the dye (A) in dichloromethane, the maximum absorption wavelength λ 最大(A)DCM In the wavelength range of 760nm ~ 900nm.

[0050] (i-4) at a wavelength λ of maximum absorption 最大(A)DCM In the spectral transmittance curve at a wavelength of 400 nm to 1100 nm measured by including the dye (A) in dichloromethane so that the transmittance at 10% is 10%, the average transmittance T of light in the wavelength range of 435 nm to 480 nm is 435-480平均(A)DCM The average transmittance T of light in the wavelength range of 480nm to 590nm is 95% or more. 480-590平均(A)DCM It is more than 97%.

[0051] (i-5) Average transmittance T of dye (A) 435-480平均(A)DCM With the average transmittance T 435-480平均(A)TR The difference and average transmittance T 480-590平均(A)DCM With the average transmittance T 480-590平均(A)TR The difference is less than 10.5%.

[0052] (ii-1) The average transmittance of the filter for light in the wavelength range of 800 nm to 900 nm at an incident angle of 60 degrees is 5% or less.

[0053] Since the absorption layer contains a pigment (A) having the characteristics of (i-1) to (i-5) and a transparent resin, the present filter has excellent near-infrared light shielding properties and high visible light transmittance. In addition, the present filter can suppress the characteristic (ii-1), that is, the incident angle dependence of light incident at a high angle caused by the presence of a reflective layer. In other words, the reduction in the barrier properties of near-infrared light at high incident angles can be suppressed.

[0054] The dye (A) preferably further has the following property (i-6): (i-6) When the dye (A) is contained in the transparent resin, the mass extinction coefficient is 1900 / (cm·mass %) or more.

[0055] 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.

[0056] The optical filter may further include a transparent substrate. In this case, the absorption layer and the reflection layer are provided 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 provided on the same main surface of the transparent substrate, there is no particular restriction on the stacking order of the absorption layer and the reflection layer.

[0057] The optical filter may also have other functional layers. As other functional layers, for example, an anti-reflection layer that suppresses the loss of visible light transmittance can be cited. In particular, in the case of a structure where 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 air, an anti-reflection layer can be provided on the absorption layer.

[0058] Next, a configuration example of the present optical filter will be described using the drawings. Figure 1 This 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.

[0059] Figure 21 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.

[0060] 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 .

[0061] 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 .

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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 where 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.

[0066] Hereinafter, the absorption layer, the reflection layer, the transparent substrate and the anti-reflection layer will be described.

[0067] (Absorbent layer)

[0068] The absorbing layer contains a dye (A) and a transparent resin, wherein the dye (A) has the properties of (i-1) to (i-5) above, and preferably further has the property of (i-6) above.

[0069] The absorbing layer is typically a layer or (resin) substrate in which the pigment (A) is uniformly dissolved or dispersed in a transparent resin. The absorbing layer may contain other NIR pigments other than the pigment (A) without damaging the effect of the present invention. In addition, the absorbing layer may contain pigments other than the NIR pigment, particularly UV pigments, without damaging the effect of the present invention.

[0070] As other NIR dyes, it is preferred to contain a dye (D) satisfying the following condition (iii-1).

[0071] (iii-1) In the spectral transmittance curve at a wavelength of 400 nm to 1100 nm measured by containing the dye (D) in the above-mentioned transparent resin, the maximum absorption wavelength λ 最大(D)TR In the wavelength range of 680nm ~ 750nm.

[0072] Furthermore, the dye (D) preferably satisfies the following condition (iii-2). (iii-2) At a maximum absorption wavelength λ 最大(D)TR In the spectral transmittance curve at a wavelength of 400 nm to 1100 nm measured by containing 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.

[0073] 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)TR The 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.

[0074] [Pigment (A)]

[0075] For pigment (A), in (i-1), the maximum absorption wavelength λ 最大(A)TR In the wavelength range of 760nm~900nm. Maximum absorption wavelength λ 最大(A)TR Preferably, the wavelength is within the range of 760 nm to 860 nm.

[0076] For the dye (A), in (i-2), the average transmittance T 435-480平均(A)TR and the average transmittance T 480-590平均(A)TR The average transmittance is above 90%. 435-480平均(A)TR Preferably 91% or more, the average transmittance T 480-590平均(A)TR Preferably, it is 92% or more.

[0077] For pigment (A), in (i-3), the maximum absorption wavelength λ 最大(A)DCM In the wavelength range of 760nm~900nm. Maximum absorption wavelength λ 最大(A)DCM Preferably, the wavelength is within the range of 760 nm to 860 nm.

[0078] For the pigment (A), in (i-4), the average transmittance T 435-480平均(A)DCM is above 95%, and the average transmittance T 480-590平均(A)DCM The average transmittance T 435-480平均(A)DCM Preferably 97% or more, average transmittance T 480-590平均(A)DCM It is preferably 99% or more.

[0079] For the dye (A), in (i-5), the average transmittance T 435-480平均(A)DCM With the average transmittance T 435-480平均(A)TR The difference and average transmittance T 480-590平均(A)DCM With the average transmittance T 480-590平均(A)TR The difference is less than 10.5%. The average transmittance T 435-480平均(A)DCM With the average transmittance T 435-480平均(A)TR The difference is preferably 7% or less, and the average transmittance T 480-590平均(A)DCM With the average transmittance T 480-590平均(A)TR The difference is preferably 5% or less.

[0080] The fact that the pigment (A) satisfies (i-5) means that the visible light transmittance in dichloromethane can be maintained in a transparent resin even when used in the form of a filter. In general, it is known that pigments with a large maximum absorption wavelength are difficult to reproduce the sharp spectrum in dichloromethane in a transparent resin due to the effect of association. The pigment (A) satisfies the above (i-1) to (i-5), showing the following characteristics: while having a large maximum absorption wavelength and a high visible light transmittance in dichloromethane, the light absorption characteristics can also be maintained in a transparent resin.

[0081] Regarding the dye (A), in (i-6), the mass extinction coefficient is 1900 / (cm·mass %) or more. The mass extinction coefficient is preferably 2000 / (cm·mass %) or more.

[0082] As the pigment (A), there is no particular limitation on the molecular structure as long as the requirements (i-1) to (i-5) are satisfied. Specifically, cyanine pigments can be cited. As the pigment (A), more specifically, cyanine pigments represented by the following formula (A1) or the following formula (A2) are preferred.

[0083]

[0084] The symbols in formula (A1) and formula (A2) are as follows.

[0085] R 101 ~R 109 and R 121 ~R 131 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, or an aryl group having 5 to 20 carbon atoms which may have a substituent. 110～114 and R 132～136 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms.

[0086] Multiple Rs included in various formulas 101 ~R 109 and multiple R 121 ~R 131 They can be the same as or different from each other.

[0087] X - Represents a monovalent anion.

[0088] n1 and n2 are 0 or 1. 2 ) n1 -Carbocyclic rings and containing -(CH 2 ) n2 The hydrogen atoms on the carbon ring of - may be substituted with a halogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or an aryl group having 5 to 20 carbon atoms which may have a substituent.

[0089] In the above, the alkyl group (including the alkyl group contained 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 through a carbon atom constituting an aromatic ring contained in an aromatic compound, such as a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a thiophene ring, a pyrrole ring, etc. As a substituent in an alkyl group having 1 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, or an aryl group having 5 to 20 carbon atoms which may have a substituent, halogen atoms and alkoxy groups having 1 to 10 carbon atoms may be cited.

[0090] In formula (A1) and formula (A2), R102 ~R 105 , R 108 , R 109 , R 122 ~R 127 , R 130 and R 131 Each independently is preferably a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms, or an aryl group having 5 to 20 carbon atoms, and is more preferably a hydrogen atom from the viewpoint of obtaining a high visible light transmittance.

[0091] In formula (A1) and formula (A2), R 110 ~R 114 and R 132 ~R 136 Each independently is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and is more preferably a hydrogen atom from the viewpoint of obtaining a high visible light transmittance.

[0092] R 106 , R 107 , R 128 and R 129 Each independently is preferably a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 5 to 20 carbon atoms (which may include a linear, cyclic, or branched alkyl group), and more preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. 106 and R 107 , R 128 and R 129 The same groups are preferred.

[0093] R 101 and R 121 An alkyl group having 1 to 15 carbon atoms or an aryl group having 5 to 20 carbon atoms is preferred, and an alkyl group having 1 to 15 carbon atoms having a branch is more preferred from the viewpoint of maintaining a high visible light transmittance in a transparent resin as in a solution.

[0094] As X - , we can list I - , BF 4 - PF 6 - , ClO 4 - , an anion represented by formula (X1) and an anion represented by formula (X2), preferably BF 4 - or PF 6 - .

[0095]

[0096] In the following description, the pigment (A1) except R 101 ~R 114 The portion other than the above is also referred to as the skeleton (A1). The same is true for other pigments.

[0097] The following formula (A11) shows a compound in which n1 is 1 in the formula (A1), and the following formula (A12) shows a compound in which n1 is 0 in the formula (A1).

[0098]

[0099] In formula (A11) and formula (A12), R 101 ~R 114 and X - The same as in the case of formula (A1). 115 ~R 120 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, or an aryl group having 5 to 20 carbon atoms which may have a substituent. Preferably, it is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 5 to 20 carbon atoms (which may include a chain, cyclic, or branched alkyl group), and more preferably, it is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. In addition, R 115 ~R 120 The same groups are preferred.

[0100] The following formula (A21) shows a compound in which n2 is 1 in the formula (A2), and the following formula (A22) shows a compound in which n2 is 0 in the formula (A2).

[0101]

[0102] In formula (A21) and formula (A22), R 121 ~R 136 and X - The same as in the case of formula (A2). 137 ~R 142 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, or an aryl group having 5 to 20 carbon atoms which may have a substituent. Preferably, it is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 5 to 20 carbon atoms (which may include a chain, cyclic, or branched alkyl group), and more preferably, it is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. In addition, R 137 ~R 142 The same groups are preferred.

[0103] More specifically, the compounds represented by Formula (A11), Formula (A12), Formula (A21), and Formula (A22) include compounds in which the atoms or groups bonded to the respective skeletons are shown in Tables 1 to 4 below. In all the compounds shown in Tables 1 and 2, R 101 ~R 109 In all compounds shown in Table 3 and Table 4, R 121 ~R 131 The left and right sides of the formula are the same. It should be noted that although only left-right symmetrical compounds are listed in Tables 1 to 4, 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.

[0104] R in Table 1 and Table 2 110 ~R 114 and R in Table 3 and Table 4 132 ~R 136 Indicates an atom or group bonded to the central benzene ring in each formula, and when all five atoms are hydrogen atoms, "H" is indicated. 110 ~R 114 When any one of them is a substituent and the others are hydrogen atoms, only the symbol of the substituent and the combination of the substituents are recorded. For example, "R 112 -C(CH 3 ) 3 " indicates that R 112 -C(CH 3 ) 3 , and the rest are hydrogen atoms. 132 ~R 136 Same here.

[0105] R in Table 1 115 ~R 120 and R in Table 3 137 ~R 142 represents an atom or group bonded to the central cyclohexane ring in formula (A11) or (A21), and when all six atoms are hydrogen atoms, they are represented by "H". 115 ~R 120 When any one of them is a substituent and the others are hydrogen atoms, only the symbol of the substituent and the combination of the substituents are described. 137 ~R 142 Same here.

[0106] R in Table 2 115 ~R 118 and R in Table 4 137 ~R 140represents an atom or group bonded to the central cyclopentane ring in formula (A12) or (A22), and when all four atoms are hydrogen atoms, they are represented by "H". 115 ~R 118 When any one of them is a substituent and the others are hydrogen atoms, only the symbol of the substituent and the combination of the substituents are described. 137 ~R 140 Same here.

[0107] Although X is not shown in Tables 1 to 4 - , but in any compound X - For BF 4 - or PF 6 - . In the pigment (A11-1) - For BF 4 - The case is represented as pigment (A11-1B), and X in pigment (A11-1) - PF 6 - The case of -C is indicated as pigment (A11-1P). The same applies to the other pigments shown in Tables 1 to 4. 3 H 7 and -C 4 H 9 They represent straight-chain propyl and butyl groups respectively.

[0108]

[0109] As the pigment (A11), from the viewpoint of solubility in a transparent resin, solubility in a solvent used when forming an absorption layer on a transparent substrate (hereinafter also referred to as "main solvent"), and visible light transmittance, preferred pigments include pigments (A11-1B), pigments (A11-1P), pigments (A11-2B), pigments (A11-2P), pigments (A11-3B), pigments (A11-3P), pigments (A11-4B), pigments (A11-4P), pigments (A11-5B), pigments (A11-5P), and the like.

[0110]

[0111] As the pigment (A12), from the viewpoint of solubility in a transparent resin, solubility in a solvent used when forming an absorption layer on a transparent substrate (hereinafter also referred to as "main solvent"), and visible light transmittance, preferred pigments include pigment (A12-1B), pigment (A12-1P), pigment (A12-2B), pigment (A12-2P), pigment (A12-3B), pigment (A12-3P), pigment (A12-4B), pigment (A12-4P), pigment (A12-5B), pigment (A12-5P), and the like.

[0112]

[0113] As the pigment (A21), from the viewpoint of solubility in a transparent resin, solubility in a solvent used when forming an absorption layer on a transparent substrate (hereinafter also referred to as "main solvent"), and visible light transmittance, preferred pigments include pigment (A21-1B), pigment (A21-1P), pigment (A21-2B), pigment (A21-2P), pigment (A21-3B), pigment (A21-3P), pigment (A21-4B), pigment (A21-4P), pigment (A21-5B), pigment (A21-5P), and the like.

[0114]

[0115] As the pigment (A22), from the viewpoint of solubility in a transparent resin, solubility in a solvent used when forming an absorption layer on a transparent substrate (hereinafter also referred to as "main solvent"), and visible light transmittance, preferred pigments include pigment (A22-1B), pigment (A22-1P), pigment (A22-2B), pigment (A22-2P), pigment (A22-3B), pigment (A22-3P), pigment (A22-4B), pigment (A22-4P), pigment (A22-5B), pigment (A22-5P), and the like.

[0116] Since the pigment (A1) and the pigment (A2) have different skeletons as described above, the maximum absorption wavelength λ 最大(A)TR For the pigment (A1), although it depends on the type or combination of atoms or groups bonded to the skeleton (A1), the maximum absorption wavelength λ 最大(A1)TR In the wavelength range of about 760nm to about 830nm. For the pigment (A2), although it depends on the type or combination of atoms or groups bonded to the skeleton (A2), the maximum absorption wavelength λ 最大(A2)TR In the wavelength range of about 800nm ​​to about 900nm.

[0117] In addition, for the dye (A1), when n1 of the skeleton (A1) is 1 and when n1 is 0, the maximum absorption wavelength λ 最大(A1)TR For the pigment (A11), although it depends on the type or combination of atoms or groups bonded to the skeleton (A11), the maximum absorption wavelength λ 最大(A11)TR In the wavelength range of about 760nm to about 800nm. In addition, for the pigment (A12), although it depends on the type or combination of atoms or groups bonded to the skeleton (A12), the maximum absorption wavelength λ 最大(A12)TR In the wavelength range of about 800nm ​​to about 830nm.

[0118] Similarly, for the dye (A2), when n2 is 1 and when n2 is 0, the maximum absorption wavelength λ 最大(A2)TR For the pigment (A21), although it depends on the type or combination of atoms or groups bonded to the skeleton (A21), the maximum absorption wavelength λ 最大(A21)TR In the wavelength range of about 800 nm to about 830 nm. In addition, for the pigment (A22), although it depends on the type or combination of atoms or groups bonded to the skeleton (A22), the maximum absorption wavelength λ 最大(A22)TR In the wavelength range of about 830nm to about 900nm.

[0119] 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 20 nm to 60 nm, more preferably 30 nm to 50 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).

[0120] As a preferred combination of two or more pigments (A), the pigment (A11) having a maximum absorption wavelength on the shorter wavelength side among the pigments (A) is referred to as pigment S, the pigment (A22) having a maximum absorption wavelength on the longer wavelength side is referred to as pigment L, and the pigment (A12) or pigment (A21) having a maximum absorption wavelength between the maximum absorption wavelengths of pigment S and pigment L is referred to as pigment M. It is preferred to select two or more from pigment S, pigment M and pigment L for combination.

[0121] 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 within the wavelength range of 765 nm to 785 nm, and more preferably within the wavelength range of 770 nm to 780 nm. 最大(A)TR The maximum absorption wavelength λ of the pigment L is preferably within the wavelength range of 795 nm to 815 nm, and more preferably within the wavelength range of 800 nm to 810 nm. 最大(A)TR The wavelength range is preferably 820 nm to 850 nm, and more preferably 830 nm to 850 nm.

[0122] It should be noted that pigment (A1), pigment (A2) can for example be manufactured by the method described in Dyes and Pigments 73 (2007) 344-352 or J. Heterocyclic Chem., 42, 959 (2005). In addition, pigment (A11-5P), pigment (A21-5P) can be manufactured by the trade name S2138 and S2139 of Few Chemicals company as a commercially available product.

[0123] [Pigment (D)]

[0124] Examples of the pigment (D) include anthocyanin pigments, phthalocyanine pigments, naphthalocyanine pigments, dithiol metal complex pigments, diimmonium pigments, polymethine pigments, phthalide pigments, naphthoquinone pigments, anthraquinone pigments, indophenol pigments, squarylium pigments, and phthalic acid pigments that satisfy the requirement (iii-1) and preferably further satisfy the requirement (iii-2). At least one pigment selected from the group consisting of salt pigments.

[0125] Among them, the squaric acid that satisfies the requirement (iii-1) and preferably satisfies the requirement (iii-2) is particularly preferred. Salt pigment. Contains squaric acid The pigment (D) of the salt pigment has little absorption of visible light in the above absorption spectrum, and 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.

[0126] As a The pigment (D) of the salt pigment is preferably λ 最大(D)TRA compound represented by any one of formula (I) to formula (III) within a wavelength range of 680 nm to 750 nm. In addition, the mass extinction coefficient when the pigment (D) is contained in a transparent resin is preferably 1000 / (cm·mass %) or more, more preferably 1500 / (cm·mass %) or more.

[0127]

[0128] The symbols in formula (I) are as follows.

[0129] 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 -SO 2 -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.

[0130]

[0131] 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 five-membered or six-membered heterocyclic ring A, heterocyclic ring B and heterocyclic ring C, respectively.

[0132] 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.

[0133] 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). 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.

[0134]

[0135] 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 37It represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0136] 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.

[0137] 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.

[0138]

[0139] The symbols in formula (II) are as follows.

[0140] 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.

[0141] R 1 and R 2 , R 2 and R 3 and R 1 and the carbon atoms or heteroatoms constituting the ring Z may be connected to each other and together with the nitrogen atom form a heterocycle A1, a heterocycle B1 and a 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 4Each 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.

[0142]

[0143] The symbols in formula (III) are as follows.

[0144] R 51 each independently represents a halogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent,

[0145] 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.

[0146] 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,

[0147] 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.

[0148] Examples of compound (I) include compounds represented by any one of formula (I-1) to formula (I-4).

[0149]

[0150] 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.

[0151] 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.

[0152] 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 formula (11-1) to formula (12-3) can be mentioned.

[0153] -C(CH 3 ) 2 -CH(CH 3 )- (11-1)

[0154] -C(CH 3 ) 2 -CH 2 - (11-2)

[0155] -C(CH 3 ) 2 -CH(C 2 H 5 )- (11-3)

[0156] -C(CH 3 ) 2 -C(CH 3 )(nC 3 H 7 )- (11-4)

[0157] -C(CH 3 ) 2 -CH 2 -CH 2 - (12-1)

[0158] -C(CH 3 ) 2 -CH 2 -CH(CH 3 )- (12-2)

[0159] -C(CH 3 ) 2 -CH(CH 3 )-CH 2 - (12-3)

[0160] In addition, in compound (I-1), R 21 More preferably, they are independently groups represented by formula (4-1) or formula (4-2).

[0161]

[0162] In formula (4-1) and formula (4-2), R 71 ~R 75 Each of the groups independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

[0163] 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 or transparent resin, -NH-C(=O)-R 29 Formula (I-11) shows that R 24 -NH-C(=O)-R 29 of compounds.

[0164]

[0165] R in compound (I-11) 23 and R 26 Each of them is preferably independently 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, and more preferably both of them are hydrogen atoms.

[0166] 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.

[0167] 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.

[0168] 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.

[0169]

[0170]

[0171] More specifically, the compounds shown in Table 5 below can be cited as compound (I-11). It should be noted that in Table 5, group (11-1) is represented as (11-1). The same applies to other groups. The representation of groups in the following other tables is also the same. In addition, all compounds shown in Table 5 are 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.

[0172] Table 5

[0173]

[0174] 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 Preferred is -NH-SO 2 -R 30 Formula (I-12) shows that R 24 -NH-SO 2 -R 30 of compounds.

[0175]

[0176] R in compound (I-12) 23 and R 26 Each of them is preferably independently 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, and more preferably both of them are hydrogen atoms.

[0177] 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.

[0178] As R having an unsaturated ring structure 30 Specific examples include groups represented by the following formulae (P1) to (P8).

[0179]

[0180] More specifically, the compounds shown in the following Table 6 can be cited as compound (I-12).

[0181] Table 6

[0182]

[0183] Examples of compound (II) include compounds represented by any one of formula (II-1) to formula (II-3).

[0184]

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] More specifically, the compounds (II-1) and (II-2) are shown in Table 7 and Table 8 below. In Table 7 and Table 8, -C 8 H 17 , -C 4 H 9 , -C 6 H 13 They represent a straight-chain octyl group, a straight-chain butyl group, and a straight-chain hexyl group, respectively.

[0190] Table 7

[0191]

[0192] Table 8

[0193]

[0194] From the viewpoints of solubility in transparent resins, visible light transmittance, etc., R in compound (II-3) 1Each 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.

[0195] 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.

[0196] 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) or a divalent organic group represented by the following formula (11-5).

[0197] -C(CH 3 )(CH 2 -CH(CH 3 ) 2 )-CH(CH 3 )- (11-5)

[0198] More specifically, the compounds shown in the following Table 9 can be cited as compound (II-3).

[0199] Table 9

[0200]

[0201] Examples of compound (III) include compounds represented by formula (III-1) and formula (III-2).

[0202]

[0203] 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.

[0204] In compound (III-1) and compound (III-2), R 52 , R 53R 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 , R 59 ~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 Tables 10 and 11 below.

[0205] Table 10

[0206]

[0207] Table 11

[0208]

[0209] 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).

[0210] Compounds (I) to (III) can each be manufactured using a known method. Regarding 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. Regarding compound (II), it can be manufactured using the method described in International Publication No. 2017 / 135359.

[0211] 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.

[0212] As for the transparent resin, a transparent resin that satisfies the relationships (i-1), (i-2), and (i-5) with the dye (A) is used.

[0213] 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).

[0214] Wherein, transparent resin is preferably polyester resin, polycarbonate resin, polyimide resin and acrylic imide resin.These resins can be used alone or in combination of two or more.When pigment (A) is pigment (A1) or pigment (A2), polyester resin, polycarbonate resin, polyimide resin and acrylic imide resin are particularly preferred.

[0215] 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).

[0216] 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).

[0217] Examples of the polyimide resin include Neopulim (registered trademark) C3650 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Neopulim (registered trademark) C3G30 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Neopulim (registered trademark) C3450 (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.

[0218] 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.

[0219] 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.

[0220] The absorption layer contains a dye (A) having the properties of (i-1) to (i-5) and a transparent resin, so that the present optical filter has the property of (ii-1). In other words, the dye (A) is a compound that can make the optical filter obtained by using the dye satisfy the property of (ii-1).

[0221] (ii-1) Average transmittance T of light in the wavelength range of 800 nm to 900 nm at an incident angle of 60 degrees 800-900平均60° The average transmittance T is less than 5%. 800-900平均60° It is preferably 3% or less, and more preferably 1% or less.

[0222] In the present optical filter, when the absorption layer contains a dye (D) in addition to the dye (A), the dye (D) is preferably a compound such that the optical filter obtained by using the dye (D) together with the dye (A) satisfies the following requirements (ii-2) to (ii-6).

[0223] (ii-2) Average transmittance T of the filter for light in the wavelength range of 435 nm to 480 nm at an incident angle of 0 degrees 435-480平均0° More than 70%.

[0224] (ii-3) Average transmittance T of the filter for light in the wavelength range of 490 nm to 580 nm at an incident angle of 0 degrees 490-580平均0° It is more than 84%.

[0225] (ii-4) Average transmittance T of the filter for light in the wavelength range of 800 nm to 900 nm at an incident angle of 60 degrees 800-900平均60° Less than 1%.

[0226] (ii-5) Maximum transmittance T of the filter for light in the wavelength range of 800 nm to 900 nm at an incident angle of 60 degrees 800-900最大60° Less than 10%.

[0227] (ii-6) The wavelength λ on the short wavelength side of the wavelength at which the filter shows a transmittance of 20% when the incident angle is 0 degrees SHT20-0°The wavelength λ on the short wavelength side of the wavelength that shows a transmittance of 20% at an incident angle of 30 degrees within the wavelength range of 640 nm to 690 nm SHT20-30° With wavelength λ SHT20-0° The difference is less than 10 nm.

[0228] Average transmittance T in (ii-2) 435-480平均0° The average transmittance T in (ii-3) is preferably 75% or more, and more preferably 77% or more. 490-580平均0° It is preferably 85% or more, and more preferably 87% or more. The average transmittance T in (ii-4) 800-900平均60° It is preferably 0.9% or less, and more preferably 0.5% or less. The maximum transmittance T in (ii-5) 800-900最大60° It is preferably 8.5% or less, and more preferably 5% or less. In (ii-6), the wavelength λ SHT20-30° With wavelength λ SHT20-0° The difference is preferably 5 nm or less, more preferably 3 nm or less.

[0229] The content of the pigment (A) in the absorption layer is an amount that satisfies (ii-1) according to the design of the present filter. From the viewpoint of ensuring the transmittance of visible light and blocking near-infrared light, suppressing the incident angle dependence of the reflective layer on light incident at a high angle, and especially reducing light leakage in the wavelength range of 800nm ​​to 900nm at a high incident angle, the content of the pigment (A) in the absorption layer is preferably 0.1 to 20 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 20 parts by mass.

[0230] In the pigment (A), when two or more selected from the group consisting of pigment S, pigment M and pigment L are used, the content of each pigment is preferably 0.1 to 20 parts by mass, more preferably 1 to 20 parts by mass, based on the total content of all pigments (A) being within the above range, relative to 100 parts by mass of the transparent resin.

[0231] 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 as to satisfy the characteristics (ii-2) to (ii-6).

[0232] In this case, the content of the pigment (A) in the absorbing layer is the same as above, and from the viewpoint of ensuring visible light transmittance and being able to bring into play the characteristics of the pigment (D), the content of the pigment (D) is preferably 0.1 to 20 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the transparent resin. In addition, the total content of the pigment (A) and the pigment (D) is preferably 0.1 to 20 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the transparent resin.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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).

[0238] (Transparent substrate)

[0239] 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.

[0240] Examples of glass that can be used for the transparent substrate include fluorophosphate glass, phosphate glass, etc., absorption glass containing copper ions (near infrared absorbing glass), soda-lime glass, borosilicate glass, alkali-free glass, quartz glass, etc. It should be noted that "phosphate glass" also includes glass having a part of the glass skeleton composed of SiO 2 Made of silicate phosphate glass.

[0241] 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.

[0242] 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.

[0243] 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.

[0244] 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.

[0245] 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.

[0246] (Reflective layer)

[0247] The reflective layer includes, for example, 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.

[0248] 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.

[0249] The absorption layer preferably has a wavelength λ on the shorter wavelength side of the wavelength at which the transmittance is 20% for light at an incident angle of 0 degrees. ABSHT20-0° In the wavelength range of 650nm to 720nm. ABSHT20-0° With λ RESHT20-0° The relationship satisfies (iv-1), the λ RESHT20-0° This is a wavelength on the shorter wavelength side of the wavelength at which the reflective layer of the optical filter including the reflective layer shows a transmittance of 20% for light having an incident angle of 0 degrees.

[0250] (iv-1)λ ABSHT20-0° +30nm≤λ RESHT20-0° ≤790nm

[0251] The reflective layer further preferably satisfies (iv-2).

[0252] (iv-2) The reflective layer from λRESHT20-0° to λ RESHT20-0° The average transmittance of light in the wavelength range of +300 nm is 10% or less.

[0253] In the present optical filter, since the absorption layer contains the dye (A), even when light enters the reflection layer at a high angle, the incidence angle dependency of the reflection layer can be suppressed, and in particular, leakage light in the wavelength range of 800 nm to 900 nm at high incident angles can be reduced.

[0254] 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. Examples of the material of the high refractive index film include Ta. 2 O 5 、TiO 2 , Nb 2 O 5 Among them, TiO is preferred from the viewpoints of film-forming properties, reproducibility of refractive index, stability, etc. 2 .

[0255] 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 SiO 2 、SiO x N y From the viewpoints of film-forming reproducibility, stability, economy, etc., SiO 2 .

[0256] 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.

[0257] 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.

[0258] 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.

[0259] 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 of sandwiching the transparent substrate.

[0260] (Anti-reflection layer)

[0261] 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.

[0262] In the present 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 have light absorption in a wide range of infrared wavelengths greater than 1200 nm, so they can be used when the infrared light blocking property is required.

[0263] The present optical filter has a reflective layer and an absorption layer containing a pigment (A), and thus can suppress the incident angle dependency of light incident at a high angle, and can particularly reduce light leakage in the wavelength range of 800 nm to 900 nm at high incident angles, and has a high transmittance for visible light.

[0264] When the absorption layer contains the pigment (A), the present filter satisfies the above (ii-1). When the absorption layer further contains the pigment (D), the present filter satisfies the above optical properties (ii-2) to (ii-6).

[0265] When the optical filter is used in an imaging device such as a digital camera, for example, an imaging device with excellent color reproducibility can be provided. The imaging device using the optical filter has a solid-state imaging element, an imaging lens, and the optical filter. The optical filter can be used, for example, in the following manner: arranged between the imaging lens and the solid-state imaging element, or directly attached to the solid-state imaging element, imaging lens, etc. of the imaging device via an adhesive layer.

[0266] Example

[0267] Next, the present invention will be described in more detail with reference to Examples.

[0268] [Test Examples 1 to 72: Preparation and Evaluation of Absorbent Layer]

[0269] (pigment)

[0270] As the pigment (A) used in the examples, pigment (A11-1B), pigment (A12-1B), pigment (A12-2P), pigment (A21-1B), pigment (A22-1B), pigment (A22-1P) were synthesized by the method of recording in dyes and pigments (Dyes and pigments) 73 (2007) 344-352. In addition, as pigment (D), compound (I-12-24) was synthesized by a conventional method.

[0271] In addition, as the pigments used in the comparative examples, FDN003 (manufactured by Yamada Chemical Co., Ltd., phthalocyanine pigment), ADS1065A (manufactured by American Dye Source, diimmonium pigment), and ADS-920MC (manufactured by American Dye Source, Ni dithiol complex pigment) were prepared. Salt pigments (Scf), anthocyanin pigments (Acf1)~(Acf7).

[0272]

[0273]

[0274]

[0275] Dissolve each of the above pigments in dichloromethane, measure the light absorption spectrum at wavelengths of 400nm to 1100nm, and find the maximum absorption wavelength λ 最大(A)DCM In addition, the concentration is adjusted to λ 最大(A)DCM The average transmittance T of light in the wavelength range of 435nm to 480nm when the transmittance is 10% 435-480平均(A)DCM The average transmittance T of light in the wavelength range of 480nm to 590nm 480-590平均(A)DCMThe optical properties of these pigments were evaluated using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi High-Tech Corporation). The results are shown in Table 12. In the table, “T in DCM” 435-480 ” represents the average transmittance T 435-480平均(A)DCM , "DCM in T 480-590 ” represents the average transmittance T 480-590平均(A)DCM .

[0276] Table 12

[0277]

[0278] As can be seen from Table 12, the visible light transmittance of the pigments other than the cyanine pigments is insufficient in terms of the spectral characteristics of the dichloromethane solution.

[0279] (Fabrication of the Absorbent Layer)

[0280] The above-synthesized cyanine pigment and transparent resin were used to prepare an absorption layer and the optical properties were evaluated. Test examples 1 to 6, 14 to 19, 27 to 32, 39 to 44, and 51 to 53 are test examples of the present filter, and test examples 7 to 13, 20 to 26, 33 to 38, 45 to 50, and 54 to 72 are comparative test examples. The following commercially available products were used as transparent resins.

[0281] <Transparent resin>

[0282] Transparent resin (R1); OKP-850 (manufactured by Osaka Gas Chemical Co., Ltd., trade name, polyester resin)

[0283] Transparent resin (R2); SP3810 (manufactured by Teijin Limited, trade name, polycarbonate resin)

[0284] Transparent resin (R3); PLEXIMID8817 (manufactured by Daicel Corporation, trade name, acrylic imide resin)

[0285] Transparent resin (R4); Neopulim (registered trademark) C3G30 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name, polyimide resin)

[0286] Transparent resin (R5); FPC-0220 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name, polyimide resin)

[0287] Transparent resin for comparative example (Rcf); BR96 (manufactured by Mitsubishi Rayon Co., Ltd., trade name, acrylic resin)

[0288] The pigment, transparent resin (R1), and cyclohexanone were stirred thoroughly and uniformly dissolved. The resulting solution was coated on a glass plate (D263; manufactured by SCHOTT) and dried to obtain an absorption layer having a film thickness shown in Table 13. The maximum absorption wavelength λ 最大(A)TR The amount of pigment added was adjusted so that the transmittance of light at 10% was obtained. The spectral transmittance curve of the absorbing layer was obtained using the spectral transmittance curve of the glass plate with the absorbing layer and the spectral transmittance curve of the glass plate at wavelengths of 400 nm to 1100 nm.

[0289] Calculate the average transmittance T of light in the wavelength range of 435nm to 480nm from the spectral transmittance curve 435-480平均(A)TR (The table shows “T 435-480 ”) and the average transmittance T of light in the wavelength range of 480nm to 590nm 480-590平均(A)TR (The table shows “T 480-590 ”). In addition, the average transmittance T 435-480平均(A)TR With the average transmittance T 435-480平均(A)DCM The difference (in the table is "T 435-480 The difference between the two is (“) and the average transmittance T 480-590平均(A)TR With the average transmittance T 480-590平均(A)DCM The difference (in the table is "T 480-590 In addition, the mass extinction coefficient / (cm·mass %) was calculated. The results are shown in Table 13. The pigment concentration in the table is such that the above λ 最大(A)TR Parts by mass relative to 100 parts by mass of the transparent resin (R1) when the transmittance of light at 10% is adjusted.

[0290]

[0291] In the above, the transparent resin (R1) was replaced with the transparent resins (R2) to (R5) or the transparent resin for comparative example (Rcf) and the same evaluation was performed. The results for the transparent resin (R2) are shown in Table 14, the results for the transparent resin (R3) are shown in Table 15, the results for the transparent resin (R4) are shown in Table 16, the results for the transparent resin (R5) are shown in Table 17, and the results for the transparent resin for comparative example (Rcf) are shown in Table 18.

[0292]

[0293]

[0294]

[0295]

[0296]

[0297] As can be seen from Tables 13 to 18, when the dye (A1) or the dye (A2) and a transparent resin suitable for combination with these dyes are used, the requirements (i-1) to (i-5) are satisfied.

[0298] [Examples 1 to 6: Production and Evaluation of Filters]

[0299] (Manufacturing of optical filters)

[0300] TiO was alternately layered on a 0.3 mm thick glass substrate (D263; manufactured by SCHOTT) by evaporation. 2 Film and SiO 2 Film, thereby forming a reflective layer X including a dielectric multilayer film. The relationship between the incident angle of the reflective layer X and the transmittance in each wavelength range is shown in Table 19. In addition, on the main surface of the glass substrate opposite to the surface on which the reflective layer X is formed, the transparent resin shown in Table 20 is combined with the pigment (A) and the pigment (D) to form an absorption layer, thereby obtaining the optical filters (NIR filters) of Examples 1 to 6. It should be noted that the pigment content in Table 20 is the mass part of the pigment relative to 100 parts by mass of the transparent resin.

[0301] In Table 19, T RE435-480平均 It represents the average transmittance of light in the wavelength range of 435nm to 480nm, T RE490-580平均 It represents the average transmittance of light in the wavelength range of 490nm to 580nm, T RE800-900平均 It represents the average transmittance of light in the wavelength range of 800nm ​​to 900nm, T RE800-900最大 Indicates the maximum transmittance of light in the wavelength range of 800nm ​​to 900nm, λ RESHT20 It indicates the wavelength when the transmittance on the short-wavelength side of the reflection band is 20%.

[0302] Table 19

[0303]

[0304] Table 20

[0305]

[0306] (evaluate)

[0307] The relationship between the incident angle and the transmittance in each wavelength range of the optical filters of Examples 1 to 6 is shown in Tables 21 to 26. 435-480平均 It represents the average transmittance of light in the wavelength range of 435nm to 480nm, T 490-580平均It represents the average transmittance of light in the wavelength range of 490nm to 580nm, T 800-900平均 It represents the average transmittance of light in the wavelength range of 800nm ​​to 900nm, T 800-900最大 Indicates the maximum transmittance of light in the wavelength range of 800nm ​​to 900nm, λ SHT20 It indicates the wavelength when the transmittance on the short-wavelength side of the NIR cutoff band is 20%.

[0308] Table 21

[0309] Angle of incidence 0 degrees 10 degrees 20 degrees 30 degrees 40 degrees 50 degrees 60 degrees <![CDATA[T 435-480平均 [%]]]> 80.7 80.9 81.2 80.5 77.4 69.1 55.5 <![CDATA[T 490-580平均 [%]]]> 89.0 89.1 89.2 88.3 85.2 80.9 76.9 <![CDATA[T 800-900平均 [%]]]> 0.0 0.0 0.0 0.0 0.1 0.1 0.8 <![CDATA[T 800-900最大 [%]]]> 0.0 0.0 0.0 0.0 1.0 0.7 8.5 <![CDATA[λ SHT20 [nm]]]> 663 664 664 663 654 641 638

[0310] Table 22

[0311] Angle of incidence 0 degrees 10 degrees 20 degrees 30 degrees 40 degrees 50 degrees 60 degrees <![CDATA[T 435-480平均 [%]]]> 80.9 81.1 81.4 80.7 77.6 69.3 55.6 <![CDATA[T 490-580平均 [%]]]> 89.8 90.0 90.1 89.1 85.9 81.6 77.5 <![CDATA[T 800-900平均 [%]]]> 0.0 0.0 0.0 0.0 0.1 0.5 0.7 <![CDATA[T 800-900最大 [%]]]> 0.0 0.0 0.0 0.0 1.5 5.7 5.3 <![CDATA[λ SHT20 [nm]]]> 659 660 660 659 653 638 637

[0312] Table 23

[0313] Angle of incidence 0 degrees 10 degrees 20 degrees 30 degrees 40 degrees 50 degrees 60 degrees <![CDATA[T 435-480平均 [%]]]> 77.6 77.9 78.1 77.4 74.4 66.5 53.3 <![CDATA[T 490-580平均 [%]]]> 88.3 88.4 88.5 87.6 84.5 80.2 76.2 <![CDATA[T 800-900平均 [%]]]> 0.0 0.0 0.0 0.0 0.1 0.1 0.3 <![CDATA[T 800-900最大 [%]]]> 0.0 0.0 0.0 0.0 1.2 1.2 2.1 <![CDATA[λ SHT20 [nm]]]> 657 658 659 658 653 637 635

[0314] Table 24

[0315] Angle of incidence 0 degrees 10 degrees 20 degrees 30 degrees 40 degrees 50 degrees 60 degrees <![CDATA[T 435-480平均 [%]]]> 78.2 78.5 78.7 78.0 75.0 67.0 53.8 <![CDATA[T 490-580平均 [%]]]> 88.2 88.4 88.5 87.5 84.5 80.2 76.3 <![CDATA[T 800-900平均 [%]]]> 0.0 0.0 0.0 0.0 0.1 0.1 0.7 <![CDATA[T 800-900最大 [%]]]> 0.0 0.0 0.0 0.0 0.8 0.7 8.2 <![CDATA[λ SHT20 [nm]]]> 663 663 663 662 654 642 639

[0316] Table 25

[0317] Angle of incidence 0 degrees 10 degrees 20 degrees 30 degrees 40 degrees 50 degrees 60 degrees <![CDATA[T 435-480平均 [%]]]> 76.7 76.9 77.1 76.5 73.5 65.7 52.6 <![CDATA[T 490-580平均 [%]]]> 88.3 88.4 88.5 87.6 84.5 80.2 76.2 <![CDATA[T 800-900平均 [%]]]> 0.0 0.0 0.0 0.0 0.1 0.3 0.4 <![CDATA[T 800-900最大 [%]]]> 0.0 0.0 0.0 0.0 1.5 3.6 1.9 <![CDATA[λ SHT20 [nm]]]> 661 661 662 660 640 640 638

[0318] Table 26

[0319] Angle of incidence 0 degrees 10 degrees 20 degrees 30 degrees 40 degrees 50 degrees 60 degrees <![CDATA[T 435-480平均 [%]]]> 70.8 71.0 71.2 70.6 67.9 60.6 48.6 <![CDATA[T 490-580平均 [%]]]> 85.3 85.5 85.6 84.7 81.7 77.6 73.8 <![CDATA[T 800-900平均 [%]]]> 0.0 0.0 0.0 0.0 0.1 0.1 0.1 <![CDATA[T 800-900最大 [%]]]> 0.0 0.0 0.0 0.0 0.8 0.4 0.4 <![CDATA[λ SHT20 [nm]]]> 657 657 658 657 652 638 636

[0320] It can be seen from Tables 21 to 26 that in Examples 1 to 6, the incident angle is 0 degrees. SHT20 With an incident angle of 30 degrees SHT20 The differences are all less than 1 nm. The optical filters of Examples 1 to 6 are optical filters that satisfy any one of (ii-1) to (ii-6).

[0321] Industrial Applicability

[0322] The optical filter of the present invention has good visible light transmittance, and particularly has good near-infrared light shielding properties that suppress a decrease in shielding properties of near-infrared light at high incident angles. Therefore, it is useful in applications such as imaging devices such as digital cameras, which have been advancing in performance in recent years.

[0323] 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.

[0324] This application is based on Japanese Patent Application No. 2018-018607 filed on February 5, 2018, the contents of which are incorporated herein by reference.

[0325] Description of symbols

[0326] 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 has an absorption layer and a reflection layer, wherein the absorption layer contains a transparent resin, a near-infrared absorption pigment A and a near-infrared absorption pigment D, and the thickness of the absorption layer is 0.3 μm to 10 μm, and The filter satisfies the following (1) to (5): (1) The average transmittance of light in the wavelength range of 435nm to 480nm is 70% or more when the incident angle is 0 degrees. (2) The average transmittance of light in the wavelength range of 490nm to 580nm is 84% ​​or more when the incident angle is 0 degrees. (3) The average transmittance of light in the wavelength range of 800 nm to 900 nm at an incident angle of 60 degrees is 0.1% or less, (4) The maximum transmittance of light in the wavelength range of 800nm ​​to 900nm at an incident angle of 60 degrees is 2.1% or less, (5) The wavelength λ on the shorter wavelength side of the wavelength showing a transmittance of 20% when the incident angle is 0 degrees SHT20-0° The wavelength λ on the short wavelength side of the wavelength that shows a transmittance of 20% at an incident angle of 30 degrees within the wavelength range of 640 nm to 690 nm SHT20-30° With wavelength λ SHT20-0° The difference is less than 10nm. The near infrared absorbing pigment A is a compound represented by the following formula (A1) or the following formula (A2), The symbols in formula (A1) and formula (A2) are as follows: R 101 ~R 109 and R 121 ~R 131 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, or an aryl group having 5 to 20 carbon atoms which may have a substituent; R 110 ~ 114 and R 132 ~ 136 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms, Multiple Rs included in various formulas 101 ~R 109 and multiple R 121 ~R 131 They can be the same or different from each other. X - represents a monovalent anion, n1 and n2 are 0 or 1; bonded to -(CH2) n1 -Carbocyclic rings and containing -(CH2) n2 -The hydrogen atoms on the carbon ring may be substituted by halogen atoms, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or an aryl group having 5 to 20 carbon atoms which may have a substituent; 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), wherein 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 may be substituted with one or more aryl groups; R 30 Each of the hydrocarbon groups has 1 to 25 carbon atoms, wherein 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 may contain an unsaturated bond, an oxygen atom or a saturated or unsaturated ring structure between carbon atoms; R 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 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) The maximum transmittance of light in the wavelength range of 800 nm to 900 nm at an incident angle of 60 degrees is 1.9% or less.

3. The optical filter according to claim 2, wherein: The filter also satisfies the following (10): (10) The maximum transmittance of light in the wavelength range of 800 nm to 900 nm is 0.4% or less when the incident angle is 60 degrees.

4. The optical filter according to claim 1, wherein: The optical filter also has one or more absorption layers containing a transparent resin.

5. The optical filter according to claim 1, wherein: The optical filter also has glass or transparent resin as a substrate.

6. The optical filter according to claim 1, wherein: The optical filter further includes a substrate made of any one of phosphate glass, borosilicate glass, alkali-free glass, and a transparent resin.

7. The optical filter according to claim 1, wherein: The reflective layer has a thickness of 2 μm to 10 μm.

8. The optical filter according to claim 1, wherein: The optical filter also has an anti-reflection layer.

9. The optical filter according to claim 1, wherein: The absorption layer contains a transparent resin having a Tg of 140° C. or higher, and the absorption layer itself functions as a resin substrate.

10. An imaging device, wherein: The imaging device comprises the optical filter according to any one of claims 1 to 9.

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