Near infrared absorbing composition, film, filter and image sensor

Abstract

The object of the present invention is to provide a near infrared absorbing composition which has both transmittance in the visible light region and absorptivity in the near infrared region, and which is excellent in heat resistance over time and light resistance. The near infrared absorbing composition of the present invention is a near infrared absorbing composition containing an organic pigment and a metal compound, characterized in that it contains at least one of a squarylium pigment (A) or a cyanine pigment (B) having an absorption maximum wavelength in the range of 680 to 740 nm, contains a cyanine pigment (C) having an absorption maximum wavelength of 760 nm or more, and further contains at least phosphonic acid and copper ions, or a copper phosphonate complex formed of phosphonic acid and copper ions.

Description

Technical Field

[0001] The present invention relates to a near infrared absorbing composition, a near infrared absorbing film, a near infrared absorbing filter and an image sensor for a solid-state imaging element using the same. More specifically, the present invention relates to a near infrared absorbing composition which has both transmittance in the visible light region and absorptivity in the near infrared region and has excellent heat resistance over time and excellent light resistance. Background Art

[0002] CCD and CMOS image sensors are used as solid-state imaging elements for color images in camcorders, digital still cameras, mobile phones with camera functions, etc. These solid-state imaging elements use silicon photodiodes that are sensitive to light in the near-infrared wavelength region in their light-receiving parts, so visual sensitivity correction and the use of near-infrared absorption filters are required.

[0003] Portable devices are required to be further lightweight, and near-infrared absorption filters are also required to be lightweight.

[0004] In recent years, near-infrared absorption filters made by adding pigments or metal compounds to resins, which are lightweight and easy to manufacture and process, have attracted attention and are being developed.

[0005] Patent Documents 1 and 2 disclose techniques for using squarylium dyes and cyanine dyes as dyes.

[0006] The squarylium dye used in Patent Document 1 has a triple fused ring structure and shows a steep absorption peak in the region of 630 to 700 nm, and therefore shows absorption in a specific range in the near infrared region while maintaining transmittance in the visible light region.

[0007] In addition, Patent Document 2 discloses an optical filter using a squarylium compound having a maximum absorption in a specific region and a cyanine compound having a maximum absorption in a region of less than 760 nm on the longer wavelength side. Squarylium compounds generally have fluorescence in their molecular structure, but by using them together with a cyanine compound having a specific structure, the generation of fluorescence can be suppressed.

[0008] However, although the near-infrared absorption filters based on these technologies have good spectral absorption waveforms, the absorption rate of light with wavelengths above 850nm is low, and they need to be combined with technologies such as blue plate glass and dielectric laminated films, which cannot yet meet the light resistance and heat resistance requirements of the filters.

[0009] On the other hand, research has been conducted on optical materials that utilize the unique absorption characteristics of copper ions. In Patent Document 3, phosphonic acid and copper ions are used as optical materials to provide absorption characteristics, and molding processability, more specifically, chemical stability during thermoforming, is improved. Although the near-infrared absorption filter based on this technology has a high absorption rate for light with a wavelength of 800 nm or more, the problem is that the function of absorbing near-infrared rays with a wavelength shorter than that is low.

[0010] Therefore, an infrared cut filter including two absorption layers, namely, an organic pigment containing layer and a copper phosphate containing layer, is disclosed in Patent Document 4. However, there are few specific examples of organic pigments used, and the transmittance of the spectral absorption waveform recorded in the examples is low at visible light below 500 nm, leaving room for further improvement.

[0011] Prior art literature

[0012] Patent Literature

[0013] Patent Document 1: Japanese Patent No. 6183041

[0014] Patent Document 2: Japanese Patent No. 6331392

[0015] Patent Document 3: Japanese Patent No. 4684393

[0016] Patent Document 4: Japanese Patent No. 6281023 Summary of the invention

[0017] Problems to be solved by the invention

[0018] The present invention has been made in view of the above problems and circumstances, and aims to provide a near-infrared absorbing composition which has both transmittance in the visible light region and absorptivity in the near-infrared region, and has excellent heat resistance over time and excellent light resistance. In addition, the present invention aims to provide a near-infrared absorbing film, a near-infrared absorbing filter, and an image sensor for a solid-state imaging element using the same.

[0019] Means for solving problems

[0020] The present inventors have conducted various studies on the causes of the above problems from the viewpoints of transmittance in the visible light region and absorptivity in the near infrared region in order to solve the above problems. As a result, they have found that the above problems can be solved by using a composition containing a squarylium compound or a cyanine compound having a specific structure and further containing at least phosphonic acid and copper ions, or a copper phosphonate complex formed of phosphonic acid and copper ions, thereby completing the present invention.

[0021] That is, the above-mentioned problems according to the present invention are solved by the following means.

[0022] 1. A near-infrared absorbing composition comprising an organic pigment and a metal compound, characterized in that the composition comprises at least one of a squarylium pigment (A) or a cyanine pigment (B) having an absorption maximum wavelength in the range of 680 to 740 nm, and a cyanine pigment (C) having an absorption maximum wavelength of 760 nm or more.

[0023] The squarylium dye (A) is a compound having a structure represented by any one of the following general formulas (A1) to (A4) (hereinafter referred to as "dye A1", "dye A2", "dye A3" and "dye A4"),

[0024] The cyanine pigment (B) is a compound having a structure represented by the following general formula (B1) (hereinafter referred to as "pigment B1"),

[0025] The cyanine pigment (C) is a compound having a structure represented by any one of the following general formulas (C1) or (C2) (hereinafter referred to as "pigment C1" and "pigment C2"),

[0026] It also contains at least phosphonic acid and copper ions, or a phosphonate-copper complex formed by phosphonic acid and copper ions.

[0027] Squarylium pigment (A)

[0028] [Chemistry 1]

[0029]

[0030] (In the formula, R1 represents an alkyl group, an aryl group or a heterocyclic group. R2 and R3 each independently represent a hydrogen atom, a halogen atom or a substituent. R4 represents an alkyl group, an alkoxy group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms. Z1 represents an atomic group required to form a 5- to 6-membered ring.)

[0031] [Chemistry 2]

[0032]

[0033] (Where R 11 and R 12 Each independently represents a hydrogen atom, a hydroxyl group, -NHCOR 16 or -NHSO2R 17 , cannot be a hydrogen atom at the same time. 13 and R 14 Each independently represents a hydrogen atom, a halogen atom or a substituent. 15 represents a substituent. n1 represents an integer of 0 to 5. 16 and R 17 Each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms.

[0034] [Chemistry 3]

[0035]

[0036] (Where R 21 and R 22 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. 23 Each independently represents a hydroxyl group, -NHCOR 26 or -NHSO2R 27 . R 24 Each independently represents a hydrogen atom or a substituent. 25 Each independently represents a substituent. n2 each represents an integer of 0 to 4. 26 and R 27 Each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms.

[0037] [Chemistry 4]

[0038]

[0039] (Where R 31 and R 32 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. 33 Represents hydroxyl group, -NHCOR 38 or -NHSO2R 39 . R 34 and R 36 Each independently represents a halogen atom or a substituent. 35 represents an alkyl group, an aryl group or a heterocyclic group. n3 represents an integer of 0 to 3. m3 represents an integer of 0 to 6. 37 represents a hydrogen atom, a halogen atom or an alkyl group. 38 and R 39 Each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms.

[0040] Anthocyanin (B)

[0041] [Chemistry 5]

[0042]

[0043] (Where R 41 Each independently represents an alkyl group, an aryl group or a heterocyclic group. 42 Each independently represents a halogen atom or a substituent. 43 ~R 45 Each of n4 independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. Each of n4 independently represents an integer of 0 to 6. 41represents a halogen ion or anion radical. )

[0044] Cyanine pigment (C)

[0045] [Chemistry 6]

[0046]

[0047] (Where R 51 and R 52 Each independently represents a halogen atom or a substituent, and adjacent substituents may form a 5- or 6-membered ring. 51 and n 52 represents integers of 0 to 4 and 0 to 5, respectively. 53 and R 54 Each independently represents an alkyl group, an aryl group or a heterocyclic group. 55 ~R 59 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. 55 With R 57 , R 56 With R 58 or R 57 With R 59 Can be bonded to form a 5- or 6-membered ring. 51 Indicates -S- or -CR 511 R 512 -.Y 51 Represents an anionic atom or an anionic atom group. 511 and R 512 Each independently represents a hydrogen atom, an alkyl group or an aryl group. )

[0048] [Chemistry 7]

[0049]

[0050] (Where R 61 and R 62 Each independently represents a halogen atom or a substituent, and adjacent substituents may form a 5- or 6-membered ring. 61 and n 62 Each independently represents an integer of 0 to 4. 63 and R 64 Each independently represents an alkyl group, an aryl group or a heterocyclic group. 65 ~R 71 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. 65 With R 67 , R 66 With R 68 , R 67 With R 69 , R 68 With R70 or R 69 With R 71 Can be bonded to form a 5- or 6-membered ring. 61 and X 62 Each independently represents -O-, -S-, or -CR 611 R 612 -.Y 61 Represents an anionic atom or an anionic atom group. 611 and R 612 Each independently represents a hydrogen atom or an alkyl group. )

[0051] 2. The near-infrared absorbing composition according to item 1, characterized in that the organic dye is contained as at least a combination of the dye A1 and the dye C2, or a combination of the dye A4 and the dye C2.

[0052] 3. The near-infrared absorbing composition according to item 1, characterized in that the organic dye is contained as a combination of at least the dye B1 and the dye C2.

[0053] 4. The near infrared absorbing composition according to any one of items 1 to 3, wherein the phosphonic acid is an alkylphosphonic acid,

[0054] The present invention also contains a compound having a structure represented by the following general formula (I) and a copper ion, or a copper complex formed of a compound having a structure represented by the following general formula (I) and a copper ion.

[0055] [Chemistry 8]

[0056]

[0057] (In the general formula (I), R 125 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. 125 It may further have a substituent. Z represents a structural unit selected from the following formulae (Z-1) and (Z-2).

[0058] [Chemistry 9]

[0059]

[0060] The * in the above formulae (Z-1) and (Z-2) represents a bonding site, and is bonded to O in the above general formula (I).

[0061] R 121 ~R 124 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0062] The compounds having a structure represented by the general formula (I) each have at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the following condition (ii) at the same time.

[0063] Condition (i): R 121 ~R 124 All are hydrogen atoms.

[0064] Condition (ii): R 121 ~R 124 At least one of them is an alkyl group having 1 to 4 carbon atoms.

[0065] In the general formula (I), j represents the number of partial structures satisfying the condition (i), which is a number from 1 to 10. k represents the number of partial structures satisfying the condition (ii), which is a number from 1 to 10.

[0066] 5. The near-infrared absorbing composition according to any one of items 1 to 4, further comprising a compound having a structure represented by the following general formula (D1).

[0067] [Chemistry 10]

[0068]

[0069] (Where R 111 and R 113 Each independently represents an alkyl group, an alkoxy group, an amino group, an aryl group or a heterocyclic group. 112 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a carbonyl group, or a cyano group, each of which may have a substituent. )

[0070] 6. A near-infrared absorbing film, characterized in that the near-infrared absorbing composition according to any one of items 1 to 5 is used.

[0071] 7. A near infrared absorbing film, characterized in that it comprises:

[0072] An organic pigment-containing layer containing an organic pigment, and

[0073] a copper phosphonate-containing layer containing phosphonic acid and copper ions, or a copper phosphonate complex formed of phosphonic acid and copper ions,

[0074] The organic pigment contains

[0075] At least one of the squarylium dye (A) and the cyanine dye (B) having an absorption maximum wavelength in the range of 680 to 740 nm,

[0076] The anthocyanin pigment (C) also contains an anthocyanin pigment (C) having an absorption maximum wavelength above 760 nm.

[0077] 8. A near infrared absorption filter comprising the near infrared absorption film according to item 6 or 7,

[0078] The film thickness is within the range of 30 to 120 μm, and

[0079] The light transmittance satisfies all of the following conditions (1) to (4),

[0080] (1) Average light transmittance within a wavelength range of 450 nm to 600 nm: 85% or more

[0081] (2) Average light transmittance in the wavelength range of 700 nm to less than 1000 nm: less than 2%

[0082] (3) Average light transmittance within a wavelength range of 1000 nm to 1200 nm: less than 5%

[0083] (4) The cutoff wavelength at which the transmittance shows 50% at a wavelength of 600 to 700 nm is in the range of 620 to 660 nm.

[0084] 9. An image sensor for a solid-state imaging device, comprising the near infrared absorption filter according to item 8.

[0085] Effects of the Invention

[0086] By adopting the above means of the present invention, a near-infrared absorbing composition having both transmittance in the visible light region and absorptivity in the near-infrared region and excellent heat resistance over time and light resistance is provided. In addition, a near-infrared absorbing film, a near-infrared absorbing filter, and an image sensor for a solid-state imaging element using the same can be provided.

[0087] The manifestation mechanism and action mechanism of the effects of the present invention are not yet clear, but are presumed as follows.

[0088] The near infrared absorbing composition of the present invention is characterized in that it contains at least one of a squarylium dye (A) or a cyanine dye (B) having an absorption maximum wavelength in the range of 680 to 740 nm, a cyanine dye (C) having an absorption maximum wavelength of 760 nm or longer, and at least a phosphonate copper complex formed of phosphonic acid and copper ions or of phosphonic acid and copper ions.

[0089] The squarylium dye (A) and cyanine dye (B) used in the present invention have a maximum absorption wavelength in the range of 680 to 740 nm, and thus can improve transmittance because they do not have secondary absorption in the visible light region. In addition, by using a cyanine dye (C) having a maximum absorption wavelength of 760 nm or more, the absorbency in the near infrared region is improved.

[0090] Squarylium dyes generally have fluorescence in their molecular structure, and by using them together with squarylium dyes and anthocyanine dyes with certain specific structures, the generation of fluorescence can be suppressed. Among all the dyes, it has excellent heat resistance because of its simple three-dimensional structure and small steric hindrance.

[0091] Copper ions form a copper complex with phosphonic acid, thereby showing excellent transmittance in the visible light region and absorption in the near infrared region. In addition, phosphonic acid has high thermal stability, and the near infrared absorbing composition of the present invention containing phosphonic acid also obtains thermal stability.

[0092] By including at least one of the combination of dye A1 and dye C2, the combination of dye A4 and dye C2, or the combination of dye B1 and dye C2 as the combination of organic dyes used, the average light transmittance in the near infrared region can be further reduced.

[0093] The squarylium dye used in the near-infrared absorbing composition of the present invention has fluorescence luminescence and has room for improvement in light resistance. It is believed that by containing a copper compound having a structure represented by the general formula (D1), the fluorescence emitted by the squarylium dye can be extinguished by utilizing the heavy atom effect (the effect produced by the copper atom). That is, by promoting the radiationless inactivation of the squarylium dye from an excited state to a base state, it is possible to prevent the deterioration caused by the light excitation of the squarylium dye itself and the surrounding pigments, and thus improve the light resistance.

[0094] The compound composed of phosphonic acid and copper ions used in the near infrared absorbing composition of the present invention easily aggregates and has room for improvement in dispersibility. However, dispersion stability can be obtained by using an alkylphosphonic acid as the phosphonic acid and containing a compound having a structure represented by the general formula (I). BRIEF DESCRIPTION OF THE DRAWINGS

[0095] Figure 1 This is a cross-sectional view showing an example of a near-infrared absorbing film having a two-layer structure.

[0096] Figure 2 It is a cross-sectional view showing an example of a near-infrared absorption filter including a near-infrared absorption film having a two-layer structure.

[0097] Figure 3 It is a schematic cross-sectional view showing an example of the configuration of a camera module including a solid-state imaging element having the near infrared absorption filter of the present invention. DETAILED DESCRIPTION

[0098] The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition containing an organic pigment and a metal compound, characterized in that it contains at least one of a squarylium pigment (A) or a cyanine pigment (B) having an absorption maximum wavelength in the range of 680 to 740 nm, and contains a cyanine pigment (C) having an absorption maximum wavelength of 760 nm or more, wherein the squarylium pigment (A) is a compound having a structure represented by any one of the following general formulas (A1) to (A4), the cyanine pigment (B) is a compound having a structure represented by the following general formula (B1), and the cyanine pigment (C) is a compound having a structure represented by any one of the following general formulas (C1) or (C2), and further contains at least phosphonic acid and copper ions, or a copper phosphonate complex formed of phosphonic acid and copper ions.

[0099] This feature is a common or corresponding technical feature of the following implementation modes.

[0100] As an embodiment of the present invention, from the viewpoint of expressing the effects of the present invention, it is preferred that the organic dye is contained as at least a combination of the dye A1 and the dye C2, or a combination of the dye A4 and the dye C2.

[0101] Furthermore, from the viewpoint of the effect expression, it is also preferable to contain the organic dye as at least a combination of the dye B1 and the dye C2.

[0102] Furthermore, from the viewpoint of suppressing the generation of fluorescence generated by the inclusion of a squarylium dye and improving light resistance, it is preferred to contain a compound having a structure represented by the general formula (D1).

[0103] In addition, from the viewpoint of dispersion stability of phosphonic acid, copper ions and phosphonate copper complex, it is preferred that the phosphonic acid is an alkylphosphonic acid, and further contains a compound having a structure represented by the general formula (I) and copper ions, or a copper complex formed by a compound having a structure represented by the general formula (I) and copper ions.

[0104] The present invention and its constituent elements, and modes and solutions for implementing the present invention are described in detail below. It should be noted that in the present application, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0105] 《Composition of near infrared absorbing composition》

[0106] The near infrared absorbing composition of the present invention is characterized by containing at least one of a squarylium dye (A) or a cyanine dye (B) having an absorption maximum wavelength in the range of 680 to 740 nm, a cyanine dye (C) having an absorption maximum wavelength of 760 nm or longer, and at least a phosphonic acid and a copper ion, or a phosphonate copper complex formed of the phosphonic acid and the copper ion.

[0107] The constituent materials of the near infrared absorbing composition of the present invention will be described in detail below.

[0108] [Organic pigments]

[0109] The amount of the near infrared absorbing pigment added is preferably in the range of 0.01 to 0.3 mass % relative to 100 mass % of the near infrared absorbing agent constituting the near infrared absorbing composition. The "near infrared absorbing agent" refers to phosphonic acid and copper ions contained as components constituting the near infrared absorbing composition, or a copper phosphonate complex formed by phosphonic acid and copper ions.

[0110] When the amount of the near infrared absorbing pigment added is 0.01 mass % or more relative to 100 mass % of the near infrared absorbing agent constituting the near infrared absorbing composition, the near infrared absorption can be sufficiently improved, while when it is 0.3 mass % or less, the visible light transmittance of the obtained near infrared absorbing composition is not impaired.

[0111] [Squarylium cyanine pigment (A)]

[0112] The near infrared absorbing composition of the present invention is characterized in that it contains at least one of a squarylium dye (A) and a cyanine dye (B) having an absorption maximum wavelength in the range of 680 to 740 nm.

[0113] The squarylium dye (A) is a compound having a structure represented by any one of the following general formulas (A1) to (A4), and is hereinafter referred to as “dye A1”, “dye A2”, “dye A3”, and “dye A4”.

[0114] The dye A1 is represented by the following general formula (A1).

[0115] [Chemistry 11]

[0116]

[0117] In the above general formula (A1), R1 represents an alkyl group, an aryl group or a heterocyclic group. R2 and R3 each independently represent a hydrogen atom, a halogen atom or a substituent. R4 represents an alkyl group, an alkoxy group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms. Z1 represents an atomic group required to form a 5- to 6-membered ring.

[0118] In the general formula (A1), the alkyl group represented by R1 may be a straight chain or a branched chain, and examples thereof include methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc., and may further have a substituent.

[0119] In the general formula (A1), examples of the aryl group represented by R1 include a phenyl group and a naphthyl group, and the aryl group may further have a substituent.

[0120] In the general formula (A1), examples of the heterocyclic group represented by R1 include furanyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, quinazoline, phthalazinyl, pyrrolidinyl, imidazoline, morpholinyl and oxazoline, and may further have a substituent.

[0121] In the general formula (A1), R1 is preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0122] In the general formula (A1), examples of the substituent represented by R2 or R3 include alkyl groups (methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), alkenyl groups (vinyl, allyl, etc.) and alkynyl groups (ethynyl, propargyl, etc.).

[0123] In addition, aryl groups (phenyl, naphthyl, etc.) and heterocyclic groups (furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, quinazolinyl, phthalazinyl, pyrrolidinyl, imidazolinyl, morpholinyl and oxazolinyl, etc.) can be listed.

[0124] In addition, alkoxy groups (methoxy, ethoxy, propoxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy, etc.), cycloalkoxy groups (cyclopentyloxy, cyclohexyloxy, etc.), and aryloxy groups (phenoxy, naphthoxy, etc.) are mentioned.

[0125] In addition, there can be mentioned alkylthio groups (methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodecylthio and the like), cycloalkylthio groups (cyclopentylthio, cyclohexylthio and the like) and arylthio groups (phenylthio, naphthylthio and the like).

[0126] In addition, there can be mentioned alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl and the like) and aryloxycarbonyl groups (phenoxycarbonyl, naphthoxycarbonyl and the like).

[0127] In addition, sulfamoyl groups (aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl, etc.) are mentioned.

[0128] In addition, acyl groups (acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.) and acyloxy groups (acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, dodecylcarbonyloxy, phenylcarbonyloxy, etc.) can be listed.

[0129] In addition, there can be mentioned acylamino groups (methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, trifluoromethylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.) and sulfonylamino groups (methylsulfonylamino, ethylsulfonylamino, hexylsulfonylamino, decylsulfonylamino, phenylsulfonylamino, etc.).

[0130] In addition, carbamoyl groups (aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc.) can be mentioned.

[0131] In addition, urea groups (methyl urea group, ethyl urea group, pentyl urea group, cyclohexyl urea group, octyl urea group, dodecyl urea group, phenyl urea group, naphthyl urea group, 2-pyridyl semicarbazide group, etc.) can be mentioned.

[0132] In addition, sulfinyl groups (methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl), alkylsulfonyl groups (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl) and arylsulfonyl groups (phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.) can be listed.

[0133] In addition, amino groups (amino, ethylamino, dimethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc.) are mentioned.

[0134] Further examples include cyano, nitro, hydroxyl, halogen atoms (fluorine, chlorine, bromine, etc.), halogenated alkyl groups (fluoromethyl, trifluoromethyl, chloromethyl, trichloromethyl, perfluoropropyl, etc.), etc. These substituents may further have the above-mentioned substituents.

[0135] Among the above-mentioned substituents, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, a sulfonylamino group, a hydroxyl group and the like are preferred, and a hydroxyl group, an acylamino group and a sulfonylamino group are more preferred.

[0136] R2 and R3 are preferably hydrogen, halogen, alkyl, alkoxy, hydroxy, acylamino and sulfonylamino, more preferably hydrogen, alkyl, hydroxy, acylamino and sulfonylamino. In addition, they are preferably bonded to R1 to form a 5- to 6-membered ring.

[0137] In the general formula (A1), R4 represents an alkyl group, alkoxy group, aryl group or heterocyclic group having 1 to 4 carbon atoms, which has the same meaning as described in the description of the substituents above, and is preferably an alkyl group having 1 to 4 carbon atoms.

[0138] In the general formula (A1), as the atomic group required for forming a 5- to 6-membered ring represented by Z1, a combination of -CR5R6-, -O-, -C(=O)-, -S- and -NR7- can be listed, preferably -CR5R6- and -C(=O)-, more preferably -CR5R6-. R5, R6 and R7 are each independently preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, more preferably a hydrogen atom or an alkyl group. They may be further substituted by the above-mentioned substituents.

[0139] The dye A2 is represented by the general formula (A2) shown below.

[0140] [Chemistry 12]

[0141]

[0142] In the above general formula (A2), R 11 and R 12 Each independently represents a hydrogen atom, a hydroxyl group, -NHCOR 16 or -NHSO2R 17 , cannot be a hydrogen atom at the same time. 13 and R 14 Each independently represents a hydrogen atom, a halogen atom or a substituent. 15 represents a substituent. n1 represents an integer of 0 to 5. 16 and R 17 Each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms.

[0143] In the general formula (A2), R 11 and R 12Preferably, a hydrogen atom, a hydroxyl group, or -NHCOR 16 , which is not a hydrogen atom at the same time, and is preferably capable of hydrogen bonding with the oxygen atom of the squaric acid. The most preferred is a hydroxyl group.

[0144] In the general formula (A2), R 13 and R 14 The substituents in the formula (A1) have the same meanings as R2 and R3 in the above description. 13 and R 14 Preferably, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, -NHCOR 16 or -NHSO2R 17 , more preferably, a hydrogen atom, an alkyl group or an alkoxy group can be cited, and a hydrogen atom is most preferred.

[0145] In the general formula (A2), R 15 represents a substituent and has the same meaning as R2 and R3 in the description of the above general formula (A1), and can bond to each other to form a 5- or 6-membered ring.

[0146] As R 15 Preferably, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an acylamino group or a sulfonylamino group can be listed, and more preferably, a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group can be listed.

[0147] From the viewpoint of the spectral absorption waveform, in order to suppress the side absorption near 400 to 450 nm, it is preferred that a hydrogen atom is located at the ortho position with respect to the N atom.

[0148] In the general formula (A2), R 16 and R 17 It is preferably an alkyl group having 1 to 4 carbon atoms, and may further have a substituent.

[0149] In the general formula (A2), n1 represents 0-5, preferably 0-2.

[0150] The dye A3 is represented by the following general formula (A3).

[0151] [Chemistry 13]

[0152]

[0153] In the above general formula (A3), R 21 and R 22 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. 23 Each independently represents a hydroxyl group, -NHCOR 26 or -NHSO2R 27 . R 24 Each independently represents a hydrogen atom or a substituent. 25Each independently represents a substituent. n2 each represents an integer of 0 to 4. 26 and R 27 Each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms.

[0154] In the general formula (A3), for R 21 and R 22 Preferred examples include an alkyl group and an aryl group, which may further have a substituent.

[0155] In the general formula (A3), R 23 Preferably hydroxyl or -NHCOR 26 , most preferably hydroxyl.

[0156] In the general formula (A3), R 24 and R 25 The substituent represented by R2 and R3 has the same meaning as R2 and R3 in the description of the above general formula (A1), and there is no problem as long as it can be substituted. 24 and R 25 , preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, -NHCOR 26 or -NHSO2R 27 More preferably, a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group can be cited.

[0157] In the general formula (A3), R 26 and R 27 An alkyl group having 1 to 4 carbon atoms is preferred, and may further have a substituent.

[0158] In the general formula (A3), n2 represents 0-5, preferably 0-2.

[0159] The dye A4 is represented by the following general formula (A4).

[0160] [Chemistry 14]

[0161]

[0162] In the general formula (A4), R 31 and R 32 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. 33 Represents hydroxyl group, -NHCOR 38 or -NHSO2R 39 . R 34 and R 36 Each independently represents a halogen atom or a substituent. 35 represents an alkyl group, an aryl group or a heterocyclic group. n3 represents an integer of 0 to 3. m3 represents an integer of 0 to 6. 37 represents a hydrogen atom, a halogen atom or an alkyl group.38 and R 39 Each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms.

[0163] In the general formula (A4), R 31 and R 32 The same as R in the description of the above general formula (A3) 21 and R 22 The meanings are the same, and the preferred ranges are also the same.

[0164] In the general formula (A4), R 33 With R of general formula (A3) 23 The same meaning, preferably hydroxyl or -NHCOR 38 , most preferably hydroxyl.

[0165] In the general formula (A4), R 34 and R 36 R2 and R3 have the same meanings as in the description of the general formula (A1) above, and there is no problem as long as they can be substituted. 34 and R 36 Preferably, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, -NHCOR 38 or -NHSO2R 39 More preferably, a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group can be cited.

[0166] In the general formula (A4), R 35 An alkyl group is preferred, and may further have a substituent.

[0167] R 37 A hydrogen atom or an alkyl group is preferred.

[0168] R 38 and R 39 An alkyl group having 1 to 4 carbon atoms is preferred, and may further have a substituent.

[0169] It is preferable that n3 and m3 are integers of 0-2.

[0170] [Cyanine pigment (B)]

[0171] The near infrared absorbing composition of the present invention is characterized in that it contains at least one of a squarylium dye (A) or a cyanine dye (B) having an absorption maximum wavelength in the range of 680 to 740 nm. The cyanine dye (B) is a compound having a structure represented by the general formula (B1) (hereinafter referred to as "dye B1").

[0172] The dye B1 is represented by the following general formula (B1).

[0173] [Chemistry 15]

[0174]

[0175] In the general formula (B1), R 41 Each independently represents an alkyl group, an aryl group or a heterocyclic group. 42 Each independently represents a halogen atom or a substituent. 43 ~R 45 Each of n4 independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. Each of n4 independently represents an integer of 0 to 6. 41 Represents a halogen ion or anion radical.

[0176] In the general formula (B1), R 41 An alkyl group is preferred, and may further have a substituent.

[0177] R 42 There are no particular restrictions as long as they are substitutable groups, and R2 and R3 have the same meanings as in the description of the general formula (A1). 42 Preferably, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, -NHCOR 46 or -NHSO2R 47 More preferably, a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group can be cited.

[0178] In the general formula (B1), R 43 ~R 45 Preferably, a hydrogen atom, a halogen atom or an alkyl group, R 43 With R 45 They can also be bonded to form a ring.

[0179] R 46 and R 47 It is preferably an alkyl group having 1 to 4 carbon atoms, and may further have a substituent. n4 is preferably an integer of 0-2.

[0180] In the general formula (B1), as Y 41 Examples of the anions include halogen ions and halide ions (fluoride, chloride, bromide, iodide, etc.), enolate anions (acetylacetonate anion, hexafluoroacetylacetonate anion), hydroxyl ions, sulfite ions, sulfate ions, alkylsulfonate ions, arylsulfonate ions, nitrate ions, nitrite ions, carbonate ions, perchlorate ions, alkylcarboxylate ions, arylcarboxylate ions, tetraalkylborate, salicylate, benzoate, PF6 - 、BF4 - and SbF6 - etc., preferably halogen ions, PF6 - or BF4 - .

[0181] [Cyanine pigment (C)]

[0182] The near infrared absorbing composition of the present invention is characterized in that it contains a cyanine pigment (C) having an absorption maximum wavelength of 760 nm or more. The cyanine pigment (C) is a compound having a structure represented by any one of the general formulas (C1) or (C2) (hereinafter referred to as "pigment C1" and "pigment C2").

[0183] The dye C1 is represented by the following general formula (C1).

[0184] [Chemistry 16]

[0185]

[0186] In the general formula (C1), R 51 and R 52 Each independently represents a halogen atom or a substituent, and adjacent substituents may form a 5- or 6-membered ring. 51 and n 52 represents integers of 0 to 4 and 0 to 5, respectively. 53 and R 54 Each independently represents an alkyl group, an aryl group or a heterocyclic group. 55 ~R 59 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. 55 With R 57 , R 56 With R 58 or R 57 With R 59 Can be bonded to form a 5- or 6-membered ring. 51 Indicates -S- or -CR 511 R 512 -.Y 51 Represents an anionic atom or an anionic atom group. 511 and R 512 Each independently represents a hydrogen atom, an alkyl group or an aryl group.

[0187] In the general formula (C1), R 51 and R 52 The substituent represented has the same meaning as R2 and R3 in the description of the general formula (A1), and is preferably a halogen atom, an alkyl group, an alkoxy group, or an aryl group, etc., and may further have a substituent, and adjacent substituents may be bonded to form a 5- or 6-membered ring, preferably a phenyl group. In addition, it may further have a substituent.

[0188] n 51 and n 52 An integer of 0-2 is preferable.

[0189] In the general formula (C1), R53 and R 54 An alkyl group is preferred, and it is also preferred that the group further has a substituent.

[0190] R 55 ~R 59 Preferably, it is a hydrogen atom, an alkyl group or an aryl group, and R 56 With R 58 They are bonded to form a 5- or 6-membered ring, which may further have a substituent.

[0191] In the general formula (C1), X 51 Preferred representation -CR 511 R 512 -. R 511 and R 512 Preferably, it is a hydrogen atom or an alkyl group. 51 With Y in the general formula (B1) 41 The meanings are the same, and the preferred ranges are also the same.

[0192] The dye C2 is represented by the general formula (C2) shown below.

[0193] [Chemistry 17]

[0194]

[0195] In the general formula (C2), R 61 and R 62 Each independently represents a halogen atom or a substituent, and adjacent substituents may form a 5- or 6-membered ring. 61 and n 62 Each independently represents an integer of 0 to 4. 63 and R 64 Each independently represents an alkyl group, an aryl group or a heterocyclic group. 65 ~R 71 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. 65 With R 67 , R 66 With R 68 , R 67 With R 69 , R 68 With R 70 or R 69 With R 71 Can be bonded to form a 5- or 6-membered ring. 61 and X 62 Each independently represents -O-, -S-, or -CR 611 R 612 -.Y 61 Represents an anionic atom or an anionic atom group. 611 and R 612Each independently represents a hydrogen atom or an alkyl group.

[0196] In the general formula (C2), R 61 and R 62 The substituent represented has the same meaning as R2 and R3 in the description of the above general formula (A1), and is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, etc., and may further have a substituent. In addition, adjacent substituents may be bonded to form a 5- or 6-membered ring, preferably a phenyl group. In addition, it may further have a substituent.

[0197] n 61 and n 62 An integer of 0-2 is preferable.

[0198] R 63 and R 64 An alkyl group is preferred, and it is also preferred that the group further has a substituent.

[0199] R 65 ~R 71 Preferably, it is a hydrogen atom, an alkyl group or an aryl group, and R 66 With R 68 , R 67 With R 69 , or R 66 and R 68 and R 70 They are bonded to form one or more 5- or 6-membered rings, which may further have a substituent.

[0200] In the general formula (C2), X 61 and X 62 Preferably -S- or -CR 611 R 612 -, more preferably -CR 611 R 612 -.

[0201] R 611 and R 612 A hydrogen atom or an alkyl group is preferred.

[0202] Y 61 The same as Y in the description of the above general formula (B1) 41 The meanings are the same, and the preferred ranges are also the same.

[0203] The pigments of the general formulae (A1) to (A4), (B1), (C1) and (C2) are required to form a spectral absorption band mainly in the range of 400 to 800 nm in the spectral absorption spectrum. By containing at least any one of the squarylium pigments (A1) to (A4) or the cyanine pigment (B1) having an absorption maximum wavelength in the range of 680 to 740 nm, and containing a cyanine pigment (C1) or (C2) having an absorption maximum wavelength above 760 nm, a preferred spectral absorption waveform can be formed.

[0204] Preferably, in terms of being able to reduce the transmittance in the near infrared region while suppressing the decrease in the transmittance in the visible light region, a combination of pigments A1 and C2, a combination of A4 and C2, or a combination of B1 and C2 is preferred. In addition, in the above-mentioned combination, by mixing a plurality of pigments, the transmission spectrum waveform can also be smoothed.

[0205] Representative specific examples of the dyes of general formulae (A1) to (A4), (B1), (C1), and (C2) and their maximum absorption wavelengths in methanol solvent are shown below, but the present invention is not limited thereto.

[0206] The maximum absorption wavelength is determined according to the solubility of each pigment. -5 A mol / L methanol solution was measured at a wavelength of 300 to 1200 nm using a spectrophotometer V-780 manufactured by JASCO Corporation to determine its maximum absorption wavelength.

[0207] <Specific examples of pigment A1>

[0208] The following (A1-1) to (A1-20) are representative specific examples of the dye A1.

[0209] [Chemistry 18]

[0210]

[0211] [Chemistry 19]

[0212]

[0213] <Specific examples of pigment A2>

[0214] The following (A2-1) to (A2-14) are representative specific examples of the dye A2.

[0215] [Chemistry 20]

[0216]

[0217] [Chemistry 21]

[0218]

[0219] <Specific examples of pigment A3>

[0220] The following (A3-1) to (A3-18) are representative specific examples of the dye A3.

[0221] [Chemistry 22]

[0222]

[0223] [Chemistry 23]

[0224]

[0225] <Specific examples of pigment A4>

[0226] The following (A4-1) to (A4-20) are representative specific examples of the dye A4.

[0227] [Chemistry 24]

[0228]

[0229] [Chemistry 25]

[0230]

[0231] <Specific examples of pigment B1>

[0232] The following (B1-1) to (B1-14) are representative specific examples of the dye B1.

[0233] [Chemistry 26]

[0234]

[0235] [Chemistry 27]

[0236]

[0237] <Specific example of pigment C1>

[0238] The following (C1-1) to (C1-10) are representative specific examples of the dye C1.

[0239] [Chemistry 28]

[0240]

[0241] <Specific example of dye C2>

[0242] The following (C2-1) to (C2-30) are representative specific examples of the dye C2.

[0243] Among them, TsO recorded in the chemical structure formula - represents the p-toluenesulfonate ion (also called the toluenesulfonate ion or the toluenesulfonate anion).

[0244] [Chemistry 29]

[0245]

[0246] [Chemistry 30]

[0247]

[0248] [Chemistry 31]

[0249]

[0250] Next, a representative synthesis method of the dyes of the general formulae A1 to A4, B1, and C1 to C2 will be described.

[0251] The squarylium dye can be easily synthesized with reference to the following documents.

[0252] Japanese Patent Application Publication No. 2004-319309, Japanese Patent Application Publication No. 2008-209462, Japanese Patent Application Publication No. 2009-36811, Japanese Patent Application Publication No. 2009-180875, and Japanese Patent Application Publication No. 2017-197437

[0253] Cyanine pigments can be easily synthesized with reference to the following literature.

[0254] 1) "ヘテロサイクリック·コンパウン" written by EF Harmer Heterocyclic CompoundsCyanine Dyes and Related Compounds)", John Wiley & Sons, New York, London, 1964 Annual

[0255] 2) "ヘ" written by DMSturmerテロサイクリック·コンパウンズースペシャル·トッピクス· Heterocyclic Compounds-Specialtopics in heterocyclic chmistry)", Chapter 18, Section 14, Pages 482-515, John Wiley & Sons, New York, London, 1977 Annual

[0256] 3) "ロッズ·ケミストリー·オブ·カーボン·コンパウンズ

[0257] (Rodd's Chemistry of Carbon Compounds)" 2nd Edition, Volume IV, Part B, Chapter 15, Pages 369~422, エルセビア·サイエンス·パブリック·カンパニー·インク (Elsevier SciencePublishing Company Inc., New York, 1977 Annual

[0258] 4) Japanese Patent Application Publication No. 6-313939, Japanese Patent Application Publication No. 5-88293, Japanese Patent Application Publication No. 2006-16564, Japanese Patent Application Publication No. 2000-321704, Japanese Patent Application Publication No. 2006-63171, and Japanese Patent Application Publication No. 2018-177830

[0259] Synthesis examples of dyes of general formulae A1 to A4, B1, and C1 to C2 are shown below.

[0260] <Synthesis example 1>

[0261] (Synthesis of A1-1)

[0262] [Chemistry 32]

[0263]

[0264] Toluene: 15mL and 1-butanol: 15mL were added to intermediate 1: 0.6g and squaric acid: 0.12g, and an ester tube was installed. The mixture was heated under reflux for 5 hours while dehydrating. After cooling, the solvent was distilled off under reduced pressure, and toluene was added and concentrated. The residue was dissolved in toluene, and the target product: 0.47g was separated by column chromatography (eluting solvent was a mixture of ethyl acetate and n-heptane). MASS, 1H-NMR, and IR spectra were used to identify the target product (A1-1).

[0265] <Synthesis example 2>

[0266] (Synthesis of A2-2)

[0267] [Chemistry 33]

[0268]

[0269] Add toluene: 20mL and 1-butanol: 20mL to intermediate 2: 1.50g, squaric acid: 0.22g, install an ester tube, and heat under reflux for 4 hours while dehydrating. After cooling, remove the solvent under reduced pressure, add toluene, and concentrate. Dissolve the residue in toluene, and separate the target product: 1.26g by column chromatography (eluting solvent is a mixture of ethyl acetate and n-heptane). Identify it by MASS, 1H-NMR, and IR spectra, and confirm it is the target product (A2-2).

[0270] <Synthesis example 3>

[0271] (Synthesis of A3-1)

[0272] [Chemistry 34]

[0273]

[0274] Add toluene: 20mL and 1-butanol: 20mL to intermediate 3: 1.15g, squaric acid: 0.22g, install an ester tube, and heat under reflux for 8 hours while dehydrating. After cooling, remove the solvent under reduced pressure, add toluene, and concentrate. Dissolve the residue in toluene, and separate the target product: 0.78g by column chromatography (eluting solvent is a mixture of ethyl acetate and n-heptane). Identify it by MASS, 1H-NMR, and IR spectra, and confirm it is the target product (A3-1).

[0275] <Synthesis Example 4>

[0276] (Synthesis of A4-1)

[0277] [Chemistry 35]

[0278]

[0279] Add 20 mL of toluene and 20 mL of 1-butanol to 1.35 g of intermediate 4 and 1.06 g of intermediate 5, install an ester tube, and heat under reflux for 3 hours while dehydrating. After cooling, remove the solvent under reduced pressure, add toluene, and concentrate. Dissolve the residue in toluene, and separate the target product (1.22 g) by column chromatography (eluting solvent is a mixture of ethyl acetate and n-heptane). Identify by MASS, 1H-NMR, and IR spectra, and confirm that it is the target product (A4-1).

[0280] <Synthesis Example 5>

[0281] (Synthesis of B1-3)

[0282] [Chemistry 36]

[0283]

[0284] Methanol: 40 mL and triethylamine: 0.36 g were added to intermediate 6: 1.60 g and intermediate 7: 0.97 g, and the mixture was heated under reflux for 6 hours. After cooling, the precipitated crystals were filtered and washed with methanol to separate the target product: 0.76 g. MASS, 1H-NMR, and IR spectra were used to identify the target product (B1-3).

[0285] <Synthesis Example 6>

[0286] (Synthesis of C1-7)

[0287] [Chemistry 37]

[0288]

[0289] Add methanol: 40 mL and triethylamine: 0.22 g to intermediate 8: 1.26 g and intermediate 9: 0.65 g, and heat under reflux for 6 hours. After cooling, remove the solvent under reduced pressure, extract with ethyl acetate, neutralize, wash with water, and concentrate the ethyl acetate. Dissolve the residue in dichloromethane, and separate the target product: 0.83 g by column chromatography (eluting solvent is a mixture of ethyl acetate and methanol). Identify by MASS, 1H-NMR, and IR spectra, and confirm that it is the target product (C1-7).

[0290] <Synthesis Example 7>

[0291] (Synthesis of C2-18)

[0292] [Chemistry 38]

[0293]

[0294] Dissolve 4.09 g of intermediate 10 in 2.5 mL of m-cresol, add 2.0 g of intermediate 11, and heat with stirring in a 120°C oil bath for 10 minutes. Then, add 50 mL of ethanol and 0.5 g of triethylamine, and heat with stirring in a 70°C water bath for 30 minutes. Add 0.5 g of sodium boron tetrafluoride to the reaction solution, and stir and cool to precipitate it. Filter the crystals, recrystallize from a mixed solvent of fluorinated alcohol and methanol, and separate the target product: 0.58 g. Identification by MASS, 1H-NMR, and IR spectra confirmed that it was the target product (C2-18).

[0295] [Metal compounds]

[0296] [Copper Phosphate Complex]

[0297] The near infrared absorbing composition of the present invention is characterized in that it contains phosphonic acid and copper ions, or a copper phosphonate complex formed of phosphonic acid and copper ions. By containing the copper phosphonate complex, the transmittance in the region from about 800 nm to long wavelengths can be reduced.

[0298] Phosphonic acid has a structure represented by the following general formula (H1).

[0299] [Chemistry 39]

[0300]

[0301] In the above general formula (H1), R 131 represents a branched, linear or cyclic alkyl, alkenyl, alkynyl, aryl or allyl group having 1 to 30 carbon atoms, at least one hydrogen atom of which may be substituted by a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde group, a carboxyl group, a hydroxyl group or a group having an aromatic ring, or may be unsubstituted. In terms of good moisture-heat resistance and near-infrared absorption, R 131 Preferably, it is an alkyl group having 1 to 20 carbon atoms. Furthermore, in terms of being able to have both near infrared absorption and visible light transmittance, R 131 It is an alkyl group having 1 to 4 carbon atoms.

[0302] Examples of phosphonic acid compounds having a structure represented by the general formula (H1) include ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, 2-ethylhexylphosphonic acid, 2-chloroethylphosphonic acid, 3-bromopropylphosphonic acid, 3-methoxybutylphosphonic acid, 1,1-dimethylpropylphosphonic acid, 1,1-dimethylethylphosphonic acid, 1-methylpropylphosphonic acid, phenylphosphonic acid, and 4-methoxyphenylphosphonic acid, and one example thereof is shown as the following compounds (H-1) to (H-8).

[0303] [Chemistry 40]

[0304]

[0305] In the present invention, the phosphonic acid constituting the copper phosphonate complex is preferably at least one alkylphosphonic acid selected from the following phosphonic acid group.

[0306] 1: Methylphosphonic acid

[0307] 2: Ethylphosphonic acid

[0308] 3: Propylphosphonic acid

[0309] 4: Butylphosphonic acid

[0310] 5: Pentylphosphonic acid

[0311] 6: Hexylphosphonic acid

[0312] 7: Octylphosphonic acid

[0313] 8: 2-Ethylhexylphosphonic acid

[0314] 9: 2-Chloroethylphosphonic acid

[0315] 10: 3-Bromopropylphosphonic acid

[0316] 11: 3-Methoxybutylphosphonic acid

[0317] 12: 1,1-Dimethylpropylphosphonic acid

[0318] 13: 1,1-Dimethylethylphosphonic acid

[0319] 14: 1-Methylpropylphosphonic acid

[0320] The copper phosphonate complex applicable to the present invention is described below. The copper phosphonate complex has a structure represented by the following general formula (H2).

[0321] [Chemistry 41]

[0322]

[0323] In the general formula (H2), R 132 represents an alkyl group, a phenyl group, or a benzyl group.

[0324] As the copper salt used in the formation of the copper phosphonate complex having a structure represented by the general formula (H2), a copper salt capable of supplying divalent copper ions is used. For example, copper salts of organic acids such as anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous copper acetoacetate, anhydrous copper ethylacetoacetate, anhydrous copper methacrylate, anhydrous copper pyrophosphate, anhydrous copper naphthenate, anhydrous copper citrate, and hydrates or hydrates of the copper salts of the organic acids; copper salts of inorganic acids such as copper oxide, copper chloride, copper sulfate, copper nitrate, copper phosphate, basic copper sulfate, basic copper carbonate, and hydrates or hydrates of the copper salts of the inorganic acids; and copper hydroxide.

[0325] In the present invention, the phosphonic acid constituting the copper phosphonate complex is preferably an alkylphosphonic acid, and examples thereof include ethyl copper phosphonate complex, propyl copper phosphonate complex, butyl copper phosphonate complex, pentyl copper phosphonate complex, hexyl copper phosphonate complex, octyl copper phosphonate complex, 2-ethylhexyl copper phosphonate complex, 2-chloroethyl copper phosphonate complex, 3-bromopropyl copper phosphonate complex, 3-methoxybutyl copper phosphonate complex, 1,1-dimethylpropyl copper phosphonate complex, 1,1-dimethylethyl copper phosphonate complex, and 1-methylpropyl copper phosphonate complex.

[0326] In the near infrared absorbing composition of the present invention, the copper complex microparticles are preferably uniformly dispersed when forming a near infrared absorbing film described later from the viewpoint of spectral characteristics. Therefore, the particle size of the copper complex microparticles in the near infrared absorbing dispersion is preferably small.

[0327] The average particle size of the copper complex fine particles in the near-infrared absorbing dispersion is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 80 nm or less.

[0328] The average particle size of the copper complex fine particles in the near-infrared absorbing dispersion can be measured by a dynamic light scattering method using a zeta potential-particle size measurement system ELSZ-1000ZS manufactured by Otsuka Electronics Co., Ltd.

[0329] [Compound having a structure represented by general formula (I)]

[0330] In the near infrared absorbing composition of the present invention, from the viewpoint of improving dispersion stability, the phosphonic acid is preferably an alkylphosphonic acid, and the composition further contains a compound having a structure represented by the following general formula (I) and copper ions, or a copper complex formed of a compound having a structure represented by the following general formula (I) and copper ions.

[0331] [Chemistry 42]

[0332]

[0333] The compound having a structure represented by the general formula (I) may react with copper ions to form a copper complex.

[0334] In the general formula (I), R 125 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. 125 It may further have a substituent, and the substituent is not particularly limited as long as the effects of the present invention are not inhibited.

[0335] As R 125 The alkyl group having 1 to 20 carbon atoms may be straight chain or branched, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, n-octyl, 2-butyloctyl, 2-hexyloctyl, n-decyl, 2-hexyldecyl, n-dodecyl, and n-stearyl. Each alkyl group may further have a substituent, and is not particularly limited. From the viewpoint of the dispersibility and moisture resistance of the metal complex, an alkyl group having 6 to 16 carbon atoms is preferred.

[0336] In addition, as R 125 The aryl group having 6 to 20 carbon atoms represented by the present invention includes, for example, phenyl, mesityl, tolyl, xylyl, naphthyl, anthracenyl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenyl, etc., preferably phenyl, naphthyl, fluorenyl, phenanthryl, biphenyl, fluorenonyl. Each aryl group may further have a substituent, and there is no particular limitation as long as the effect of the present invention is not impaired.

[0337] As R125 Possible substituents include, for example, alkyl groups (e.g., methyl, ethyl, trifluoromethyl, isopropyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, etc.), halogen atoms (e.g., fluorine atoms, etc.), cyano groups, nitro groups, dialkylamino groups (e.g., dimethylamino, etc.), trialkylsilyl groups (e.g., trimethylsilyl, etc.), triarylsilyl groups (e.g., triphenylsilyl, etc.), triheteroarylsilyl groups (e.g., tripyridylsilyl, etc.), benzyl groups, aryl groups (e.g., phenyl, etc.), heteroaryl groups (e.g., pyridyl, carbazolyl, etc.), and condensed rings include, without particular limitation, 9,9′-dimethylfluorene, carbazole, dibenzofuran, etc.

[0338] In the general formula (I), R 121 ~R 124 Each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. From the viewpoint of the dispersibility of the metal complex, a methyl group is particularly preferred.

[0339] In addition, it is characterized in that in R 121 ~R 124 In the embodiment, at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the following condition (ii) are simultaneously present in the molecular structure.

[0340] Condition (i): R 121 ~R 124 All are hydrogen atoms.

[0341] Condition (ii): R 121 ~R 124 At least one of them is an alkyl group having 1 to 4 carbon atoms.

[0342] For some structures that satisfy condition (ii), R 121 ~R 124 At least one of the groups is an alkyl group having 1 to 4 carbon atoms, and further includes a structure in which two groups are such alkyl groups, three groups are such alkyl groups, and all four groups are such alkyl groups. From the viewpoint of the dispersibility of the metal complex, it is preferred that only one group is an alkyl group having 1 to 4 carbon atoms.

[0343] The partial structure that satisfies condition (i) is R 121 ~R 124 The ethylene oxide structure composed entirely of hydrogen atoms has a high ability to form a complex with metals, which helps improve dispersibility. On the other hand, the ethylene oxide structure substituted with an alkyl group under condition (ii) has a large number of components and, by utilizing the entropy effect, helps improve dispersion stability when water is mixed.

[0344] In the general formula (I), j represents R specified in the above condition (i). 121 ~R124 The number of partial structures consisting entirely of hydrogen atoms is in the range of 1 to 10, preferably in the range of 1 to 3. k represents R specified in the above condition (ii) 121 ~R 124 The number of the partial structure in which at least one of the structures is an alkyl group having 1 to 4 carbon atoms is in the range of 1 to 10, preferably in the range of 1 to 3.

[0345] j and k represent the average added mole numbers of ethylene oxide structures and alkyl-substituted ethylene oxide structures, respectively.

[0346] It should be noted that in the present application, "ethylene oxide structure" refers to a repeating unit structure of polyethylene oxide, that is, a structure of ethylene oxide ring opening as a three-membered ring cyclic ether. In addition, "propylene oxide structure" refers to a repeating unit structure of polypropylene oxide, that is, a structure of propylene oxide ring opening as a three-membered ring cyclic ether.

[0347] In the above general formula (I), Z represents a structural unit selected from the following formulae (Z-1) and (Z-2).

[0348] [Chemistry 43]

[0349]

[0350] The * in the above formulae (Z-1) and (Z-2) represents a bonding site, and is bonded to O in the above general formula (I).

[0351] In the above general formula (I), when Z is the formula (Z-1), it is a diester, and when Z is the formula (Z-2), it is a monoester. From the viewpoint of the dispersibility of the metal complex, it is preferred that the diester and the monoester are a mixture, and among the monoester and the diester, the molar ratio of the monoester is preferably in the range of 20 to 95%.

[0352] The compound having a structure represented by the general formula (I) can be synthesized by referring to known methods described in, for example, JP-A-2005-255608, JP-A-2015-000396, JP-A-2015-000970, JP-A-2015-178072, JP-A-2015-178073, and Japanese Patent No. 4422866.

[0353] The content of phosphorus atoms in the near-infrared absorbing film is preferably 1.5 or less, and further preferably 0.3 to 1.3, relative to 1 mol of copper ions. That is, if the content ratio of phosphorus atoms to copper ions (hereinafter referred to as "P / Cu") is 0.3 to 1.3 in terms of molar ratio, it is confirmed that it is very suitable from the viewpoint of moisture resistance of the near-infrared absorbing film and dispersibility of copper ions in the near-infrared absorbing layer.

[0354] If the P / Cu ratio is less than 0.3 in molar ratio, the copper ions coordinated to the compound represented by the general formula (i) become excessive, and the copper ions tend to be difficult to disperse uniformly in the near-infrared absorbing film. On the other hand, if the P / Cu ratio exceeds 1.3 in molar ratio, when the thickness of the near-infrared absorbing film is thinned and the content of copper ions is increased, devitrification tends to occur easily, and this tendency becomes particularly significant in a high temperature and humid environment. Furthermore, it is more preferred that the P / Cu ratio is 0.8 to 1.3 moles. If the molar ratio is 0.8 or more, the dispersibility of copper ions in the resin can be reliably and sufficiently improved.

[0355] An example of the structure of a representative exemplary compound is described below.

[0356] <Illustrated compound 1>

[0357] As shown in Table 1 below, Exemplary Compound 1 has:

[0358] R 125 :methyl,

[0359] Condition (i): R 121 ~R 124 =H

[0360] Condition (ii): R 121 =H, R 122 =Methyl, R 123 =Methyl, R 124 =H

[0361] Z: Z-1, Z-2

[0362] j:1.0

[0363] k:8.0

[0364] The structure of is represented by the structures of the exemplary compound (1-1) in which Z is Z-2 and the exemplary compound (1-2) in which Z is Z-1.

[0365] [Chemistry 44]

[0366]

[0367] In the case of Exemplary Compound 1, the monoester ratio is 55%, and it contains 55% of the Exemplary Compound (1-1) and 45% of the Exemplary Compound (1-2).

[0368] In the present invention, the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure is not particularly limited, and compounds in which the structures are randomly arranged are also included in the compounds defined in the present invention. The following exemplary compounds (1-3) and (1-4) are also included in exemplary compound 1.

[0369] [Chemistry 45]

[0370]

[0371] In the present invention, the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure is not particularly limited, and compounds in which the structures are randomly arranged are also included in the compounds defined in the present invention.

[0372] <Exemplary compound 2>

[0373] As shown in Table 1 below, Example Compound 2 has:

[0374] R 125 :methyl,

[0375] Condition (i): R 121 ~R 124 =H

[0376] Condition (ii): R 121 =H, R 122 =H, R 123 =H, R 124 =Methyl

[0377] Z: Z-1, Z-2

[0378] j:2.0

[0379] k: 3.0

[0380] The structure of is represented by the structures of the exemplary compound (2-1) in which Z is Z-2 and the exemplary compound (2-2) in which Z is Z-1.

[0381] [Chemistry 46]

[0382]

[0383] In the case of the exemplary compound 2, the monoester ratio is 50%, and the same molar amounts of the exemplary compound (2-1) and the exemplary compound (2-2) are contained.

[0384] Similar to the above-mentioned Exemplary Compound 1, the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure in Exemplary Compound 2 can also be arbitrarily changed according to the synthesis method. Exemplary Compound 2 also includes the following Exemplary Compounds (2-3) and (2-4).

[0385] [Chemistry 47]

[0386]

[0387] In the present invention, the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure is not particularly limited, and compounds in which the structures are randomly arranged are also included in the compounds defined in the present invention.

[0388] Next, specific examples of the compound having a structure represented by the general formula (I) are listed in the following Tables I to IV, but the present invention is not limited to these exemplified compounds.

[0389] [Table 1]

[0390]

[0391] [Table 2]

[0392]

[0393] [Table 3]

[0394]

[0395] [Table 4]

[0396]

[0397] The compound having a structure represented by the general formula (I) according to the present invention can be synthesized by referring to known methods described in, for example, JP-A-2005-255608, JP-A-2015-000396, JP-A-2015-000970, JP-A-2015-178072, JP-A-2015-178073, and Japanese Patent No. 4422866.

[0398] <Synthesis of Exemplary Compounds>

[0399] Next, representative examples of the synthesis of the compound having a structure represented by the general formula (I) according to the present invention are listed, but the present invention is not limited to these synthesis methods.

[0400] <Synthesis of Exemplary Compound 49>

[0401] 130 g (1.0 mol) of n-octanol was placed in an autoclave, and 116 g (2.0 mol) of propylene oxide was added thereto using potassium hydroxide as a catalyst under the conditions of a pressure of 147 kPa and a temperature of 130° C., and then 88 g (2.0 mol) of ethylene oxide was added thereto.

[0402] Next, after confirming that no n-octanol remained, the above adduct was placed in a reactor, and 47 g (0.33 mol) of phosphoric anhydride was reacted in a toluene solution at 80° C. for 5 hours, followed by washing with distilled water and removing the solvent under reduced pressure, thereby obtaining the following exemplary compound 49 (R125 =Octyl, condition (i): R 121 =H, R 122 =H, R 123 =H, R 124 =H, condition (ii): R 121 =H, R 122 =H, R 123 =H, R 124 = methyl, j: 2.0, k: 2.0, Z: phosphoric acid monoester (Z-2) / phosphoric acid diester (Z-1)).

[0403] [Chemistry 48]

[0404]

[0405] <Synthesis of Exemplary Compound 56>

[0406] 130 g (1.0 mol) of 2-ethylhexanol was placed in an autoclave, and 145 g (2.5 mol) of propylene oxide was added thereto using potassium hydroxide as a catalyst under the conditions of a pressure of 147 kPa and a temperature of 130° C., and then 110 g (2.5 mol) of ethylene oxide was added thereto.

[0407] Next, after confirming that no 2-ethylhexanol remained, the above adduct was placed in a reactor, and 47 g (0.33 mol) of phosphoric anhydride was reacted in a toluene solution at 80° C. for 5 hours, followed by washing with distilled water and removing the solvent under reduced pressure, thereby obtaining the following exemplary compound 56 (R 125 =2-ethylhexyl, condition (i): R 121 =H, R 122 =H, R 123 =

[0408] H.R 124 =H, condition (ii): R 121 =H, R 122 =H, R 123 =H, R 124 = methyl, j: 2.5, k: 2.5, Z: phosphoric acid monoester (Z-2) / phosphoric acid diester (Z-1)).

[0409] [Chemistry 49]

[0410]

[0411] [Compound having a structure represented by general formula (D1)]

[0412] The near infrared absorbing composition of the present invention preferably further contains a compound having a structure represented by the following general formula (D1) from the viewpoint of improving light resistance.

[0413] [Chemistry 50]

[0414]

[0415] In the general formula (D1), R 111 and R 113 Each independently represents an alkyl group, an alkoxy group, an amino group, an aryl group or a heterocyclic group. 112 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a carbonyl group, or a cyano group, and each of them may have a substituent.

[0416] Generally, the squaraine dye has fluorescent luminescence. Due to the light emission (radiation) in the transition of the squaraine dye from the singlet excited state to the ground state, the pigment may be degraded due to the photoexcitation-induced degradation of other squaraine dyes or cyanine dyes present in the surroundings, the reaction of the squaraine dye itself in the singlet excited state with compounds present in the surroundings such as oxygen, the molecular cleavage reaction, etc.

[0417] Therefore, there is room for improving light resistance by the extinction of the fluorescence emitted. That is, it is believed that by containing a copper compound with a structure represented by the general formula (D1), the fluorescence emitted by the squarylium cyanine pigment can be extinguished by the heavy atom effect (the effect of the copper atom). That is, by promoting the radiationless inactivation of the squarylium cyanine pigment from an excited state to a base state, the deterioration caused by light excitation of the squarylium cyanine pigment itself and the pigment located around it can be prevented, and light resistance can be improved.

[0418] In addition, since scattered light is generated during fluorescence, the image quality of a camera equipped with an optical filter may be reduced. Therefore, the squarylium dye used in the present invention also has fluorescence, so by extinguishing fluorescence, the generation of scattered light can be suppressed, thereby improving the image quality of the camera.

[0419] In the present invention, the organic dye and the copper compound used are dissolved and mixed in a solution, so that the organic dye and the copper ions interact with each other to extinguish fluorescence. The copper compound is preferably a compound having a structure represented by the general formula (D1).

[0420] In the general formula (D1), R 111 and R 112 represents an electron withdrawing group having a Hammett substituent constant (σp value) of 0.1 or more and 0.9 or less, R 113 represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an amino group, and may have a substituent.

[0421] By R 111 and R 112The substituents whose σp values ​​are 0.1 or more and 0.9 or less are described. As the value of Hammett's substituent constant σp mentioned here, the value described in the report of Hansch, C. Leo et al. (e.g. J. Med. Chem. 16, 1207 (1973); ibid. 20, 304 (1977)) is preferably used.

[0422] For example, as the substituent or atom having a σp value of 0.10 or more, there can be mentioned a chlorine atom, a bromine atom, an iodine atom, a carboxyl group, a cyano group, a nitro group, a halogen-substituted alkyl group (e.g., a trichloromethyl group, a trifluoromethyl group, a chloromethyl group, a trifluoromethylthiomethyl group, a trifluoromethanesulfonylmethyl group, a perfluorobutyl group), an aliphatic, aromatic or heterocyclic acyl group (e.g., a formyl group, an acetyl group, a benzoyl group), an aliphatic, aromatic or heterocyclic sulfonyl group (e.g., a trifluoromethanesulfonyl group, a methanesulfonyl group, a benzenesulfonyl group), a carbamoyl group (e.g., a carbamoyl group, a methylcarbamoyl group, a phenylcarbamoyl group, a 2-chlorophenylcarbamoyl group), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group, a diphenylmethylcarbonyl group), a substituted aromatic group (e.g., a pentachlorophenyl group, a pentafluorophenyl group),

[0063] Examples of the present invention include phenyl, 2,4-dimethylsulfonylphenyl, 2-trifluoromethylphenyl), heterocyclic residues (e.g., 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), azo (e.g., phenylazo), di(trifluoromethyl)amino, trifluoromethoxy, alkylsulfonyloxy (e.g., methanesulfonyloxy), acyloxy (e.g., acetyloxy, benzoyloxy), arylsulfonyloxy (e.g., benzenesulfonyloxy), phosphoryl (e.g., dimethoxyphosphoryl, diphenylphosphoryl), sulfamoyl (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), and the like.

[0423] In addition, examples of the substituent having a σp value of 0.35 or more include a cyano group, a nitro group, a carboxyl group, a fluorine-substituted alkyl group (e.g., a trifluoromethyl group, a perfluorobutyl group), an aliphatic, aromatic or heterocyclic acyl group (e.g., an acetyl group, a benzoyl group, a formyl group), an aliphatic, aromatic or heterocyclic sulfonyl group (e.g., a trifluoromethanesulfonyl group, a methanesulfonyl group, a benzenesulfonyl group), a carbamoyl group (e.g., a carbamoyl group, a methylcarbamoyl group, a phenylcarbamoyl group, a 2-chlorophenylcarbamoyl group), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group, a diphenylmethylcarbonyl group), a fluorine- or sulfonyl-substituted aromatic group (e.g., a pentafluorophenyl group, a 2,4-dimethylsulfonylphenyl group), a heterocyclic residue (e.g., a 1-tetrazolyl group), an azo group (e.g., a phenylazo group), an alkylsulfonyloxy group (e.g., a methanesulfonyloxy group), a phosphoryl group (e.g., a dimethoxyphosphoryl group, a diphenylphosphoryl group), and a sulfamoyl group.

[0424] Examples of the substituent having a σp value of 0.60 or more include a cyano group, a nitro group, and an aliphatic, aromatic or heterocyclic sulfonyl group (eg, a trifluoromethanesulfonyl group, a difluoromethanesulfonyl group, a methanesulfonyl group, and a benzenesulfonyl group).

[0425] Preferably, as R 111 and R 112 , alkyl halide (particularly alkyl substituted with fluorine), carbonyl, cyano, alkoxycarbonyl, alkylsulfonyl, alkylsulfonyloxy, etc. can be mentioned. 113 Preferred substituents include alkyl groups, alkoxy groups, and amino groups, and alkyl groups or alkoxy groups are more preferred.

[0426] Specific examples of the general formula (D1) are shown below, but the invention is not limited to these.

[0427] [Chemistry 51]

[0428]

[0429] [Chemistry 52]

[0430]

[0431] [Chemistry 53]

[0432]

[0433] [Chemistry 54]

[0434]

[0435] [Chemistry 55]

[0436]

[0437] [Chemistry 56]

[0438]

[0439] [Chemistry 57]

[0440]

[0441] [Solvent]

[0442] The solvent applicable to the preparation of the near infrared absorbing composition of the present invention will be described.

[0443] The solvent that can be used in the near infrared absorption composition of the present invention is not particularly limited, and hydrocarbon solvents can be mentioned, and more preferably, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and halogen solvents can be mentioned as preferred examples.

[0444] As aliphatic hydrocarbon solvents, for example, non-cyclic aliphatic hydrocarbon solvents such as hexane and heptane, cyclic aliphatic hydrocarbon solvents such as cyclohexane, alcohol solvents such as methanol, ethanol, n-propanol, ethylene glycol, ketone solvents such as acetone, methyl ethyl ketone, diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, ether solvents such as ethylene glycol monomethyl ether, etc. can be listed. As aromatic hydrocarbon solvents, for example, toluene, xylene, mesitylene, cyclohexylbenzene, isopropylbiphenyl, etc. can be listed. As halogen solvents, for example, dichloromethane, 1,1,2-trichloroethane, chloroform, etc. can be listed. Furthermore, anisole, 2-ethylhexane, sec-butyl ether, 2-pentanol, 2-methyltetrahydrofuran, 2-propylene glycol monomethyl ether, 2,3-dimethyl-1,4-dioxane, sec-butylbenzene, 2-methylcyclohexylbenzene, etc. can be listed. Among them, toluene and tetrahydrofuran are preferred from the viewpoint of boiling point and solubility.

[0445] [Solid content concentration]

[0446] In addition, from the perspective of achieving an appropriate concentration of solids (e.g., copper complex microparticles), suppressing particle aggregation during storage, and obtaining more excellent stability over time (dispersion stability of copper complex microparticles and near-infrared absorptivity), the ratio of the solid content to the near-infrared absorbing composition is preferably in the range of 5 to 30% by mass, and more preferably in the range of 10 to 20% by mass.

[0447] [Ultraviolet light absorber]

[0448] The near infrared absorbing composition of the present invention preferably further contains an ultraviolet absorber from the viewpoint of spectral characteristics and light resistance.

[0449] The ultraviolet absorber is not particularly limited, and examples thereof include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and triazine ultraviolet absorbers.

[0450] As benzotriazole-based ultraviolet light absorbers, for example, 5-chloro-2-(3,5-di-sec-butyl-2-hydroxyphenyl)-2H-benzotriazole, (2-2H-benzotriazole-2-yl)-6-(straight chain and side chain dodecyl)-4-methylphenol, etc. can be listed. In addition, benzotriazole-based ultraviolet light absorbers can also be obtained as commercial products, for example, TINUVIN109, TINUVIN171, TINUVIN234, TINUVIN326, TINUVIN327, TINUVIN328, TINUVIN928 and other TINUVIN (registered trademark) series, all of which are commercial products manufactured by BASF.

[0451] Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, and bis(2-methoxy-4-hydroxy-5-benzoylphenylmethane).

[0452] Examples of the salicylate-based ultraviolet absorber include phenyl salicylate and p-tert-butyl salicylate.

[0453] Examples of the cyanoacrylate-based ultraviolet absorber include 2′-ethylhexyl-2-cyano-3,3-diphenylacrylate and ethyl-2-cyano-3-(3′,4′-methylenedioxyphenyl)-acrylate.

[0454] Examples of the triazine ultraviolet absorber include 2-(2′-hydroxy-4′-hexyloxyphenyl)-4,6-diphenyltriazine, etc. Examples of commercially available triazine ultraviolet absorbers include TINUVIN (registered trademark) 477 (manufactured by BASF Corporation).

[0455] The amount of the ultraviolet absorber added is preferably within a range of 0.1 to 5.0% by mass relative to 100% by mass of the near infrared absorber content constituting the near infrared absorbent composition.

[0456] The “near infrared absorber” refers to phosphonic acid and copper ions contained as components constituting the near infrared absorbing composition, or a copper phosphonate complex formed of phosphonic acid and copper ions.

[0457] When the amount of the ultraviolet absorber added is 0.1 mass % or more relative to 100 mass % of the near infrared absorber content, the light resistance can be sufficiently improved, and when it is 5.0 mass % or less, the visible light transmittance of the obtained near infrared absorbing composition is not impaired.

[0458] 《Method for producing near infrared absorbing composition》

[0459] An example of a method for producing the near infrared absorbing composition of the present invention is described below. The production method is not limited to the method exemplified here.

[0460] A copper salt such as copper acetate is added to a given solvent such as tetrahydrofuran (THF), dissolved by stirring or ultrasonic treatment, and then a phosphate is added to prepare liquid A. In addition, a phosphonic acid such as ethylphosphonic acid is added to a given solvent such as THF, stirred and dissolved, and liquid B is prepared. A solution obtained by mixing liquid A and liquid B is stirred at room temperature for more than ten hours to prepare liquid C. Then, a given solvent such as toluene is added to liquid C, and a heat treatment is performed at a given temperature to volatilize the solvent to prepare liquid D. An organic pigment is added to a given solvent such as diacetone alcohol, stirred and dissolved, and added to liquid D to prepare liquid E. By heating liquid E at a given temperature to volatilize the solvent, the solid content concentration is adjusted, and the near-infrared absorbing composition of the present invention can be obtained.

[0461] 《Near infrared absorption film》

[0462] One of the features of the present invention is that a near-infrared absorbing film is formed using the above-mentioned various organic dyes and metal compounds, or the near-infrared absorbing composition of the present invention.

[0463] The near infrared absorbing film of the present invention may be a single layer containing an organic pigment and a metal compound in the same layer, or may be a Figure 1 The two-layer structure shown, which includes the organic dye-containing layer 3 and the copper phosphate-containing layer 2, is not limited to the structure exemplified here.

[0464] The above-mentioned various organic dyes and metal compounds, as well as the near infrared absorbing composition of the present invention, can be prepared as a liquid wet coating solution, and thus a near infrared absorbing film can be easily produced by a simple process of forming a film by spin coating, for example.

[0465] The method for forming the near infrared ray absorption film will be described below. The forming method is not limited to the method exemplified here.

[0466] [Single layer structure]

[0467] The near infrared absorbing film of the present invention can be formed by a single-layer structure containing an organic dye and a metal compound in the same layer.

[0468] The near-infrared absorbing film of a single layer is formed by applying a coating liquid prepared by adding a matrix resin to the near-infrared absorbing composition of the present invention onto a substrate by spin coating or wet coating using a dispenser, and then subjecting the coating film to a predetermined heat treatment to cure the coating film.

[0469] The matrix resin used in the formation of the near-infrared absorption film is a resin that is transparent to visible light and near-infrared light and can disperse metal complex and copper phosphonate complex particles. Metal complex and copper phosphonate complex are substances with low polarity and are well dispersed in hydrophobic materials. Therefore, as the matrix resin for forming the near-infrared absorption film, a resin having an acryloyl group, an epoxy group, or a phenyl group can be used.

[0470] Among them, in particular, as the base resin of the near-infrared absorbing film, a resin having a phenyl group is also preferably used. In this case, the base resin of the near-infrared absorbing film has high heat resistance. In addition, polysiloxane silicone resin is difficult to be thermally decomposed, has high transparency to visible light and near-infrared light, and has high heat resistance, so it has favorable characteristics as a material for image sensors for solid-state imaging elements. Therefore, polysiloxane is also preferably used as the base resin of the near-infrared absorbing film.

[0471] Polysiloxanes that can be used as a base resin for the near-infrared absorbing film are commercially available, and examples thereof include silicone resins KR-255, KR-300, KR-2621-1, KR-211, KR-311, KR-216, KR-212, and KR-251 manufactured by Shin-Etsu Chemical Co., Ltd.

[0472] (Other additives)

[0473] In the near-infrared absorption film of the present invention, other additives may be applied within the range that does not impair the objective effect of the present invention, for example, sensitizers, cross-linking agents, curing accelerators, fillers, thermosetting accelerators, thermal polymerization inhibitors, plasticizers, etc., and adhesion promoters for the substrate surface and other auxiliary agents (such as conductive particles, fillers, defoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc.) may be used in combination.

[0474] By appropriately incorporating these components, properties such as stability and film properties of the target near-infrared absorption film can be adjusted.

[0475] For these components, for example, the contents described in paragraphs 0183 to 0260 of Japanese Patent Application Laid-Open No. 2012-003225, paragraphs 0101 to 0102 of Japanese Patent Application Laid-Open No. 2008-250074, paragraphs 0103 to 0104 of Japanese Patent Application Laid-Open No. 2008-250074, and paragraphs 0107 to 0109 of Japanese Patent Application Laid-Open No. 2008-250074 can be referred to.

[0476] [Two-story structure]

[0477] The near infrared absorbing film 1 of the present invention can also be used Figure 1 The two-layer structure shown is formed by respectively including an organic dye-containing layer 3 and a copper phosphate-containing layer 2. Specifically, the copper phosphate-containing layer is a layer containing phosphonic acid and copper ions, or a copper phosphate complex formed of phosphonic acid and copper ions.

[0478] For example, considering the situation that the impurities contained in the copper phosphate particles have an adverse effect on the light resistance, heat resistance and other storage properties of the organic pigment, by providing a two-layer structure or further providing an intermediate layer, the diffusion of these impurities can be suppressed, and the reduction in storage properties can be suppressed. In addition, by making a two-layer structure, it can be expected that the water permeability is reduced and the heat and moisture resistance is improved.

[0479] The mass of the organic pigment contained in the organic pigment containing layer is, for example, 0.3 to 8% of the mass of the final solid content of the organic pigment containing layer. The matrix resin used in the formation of the organic pigment containing layer is a resin that is transparent to visible light and near infrared rays and can disperse the organic pigment. For example, resins such as polyester, polyacrylic acid, polyolefin, polycarbonate, polycycloolefin, and polyvinyl butyral can be used.

[0480] The thickness is 0.5 to 5 μm, and the cutoff wavelength of the near infrared absorbing film can be adjusted by changing the thickness of the organic dye-containing layer.

[0481] The base resin used in the formation of the copper phosphate-containing layer is a resin that is transparent to visible light and near infrared rays and can disperse copper phosphate particles. Copper phosphate is a substance with relatively low polarity and is well dispersed in hydrophobic materials. For example, a resin having an acryl group, an epoxy group, or a phenyl group can be used. From the viewpoint of heat resistance, a resin having a phenyl group is particularly preferably used. In addition, from the viewpoint of transparency and heat resistance to visible light and near infrared rays, polysiloxane (silicone resin) is preferably used. The mass of the copper phosphate particles contained in the copper phosphate-containing layer is, for example, 15 to 45% by mass of the total mass of the final solid content of the copper phosphate-containing layer.

[0482] The average particle size of the copper phosphonate particles is, for example, 5 to 200 nm, preferably 5 to 100 nm. If the average particle size of the copper phosphonate particles is 5 nm or more, a special process for refining the copper phosphonate particles is not required, and the structure of the copper phosphonate can be prevented from being destroyed. In addition, if the average particle size of the copper phosphonate particles is 200 nm or less, it is almost not affected by the scattering of light such as Mie scattering, and the transmittance of the light can be prevented from being reduced, and the contrast and haze of the image formed by the camera can be prevented from being reduced. In addition, if the average particle size of the copper phosphonate particles is 100 nm or less, the influence of Rayleigh scattering is reduced, so the transparency of the copper phosphonate-containing layer in the visible light region is further improved.

[0483] The thickness of the copper phosphate containing layer is, for example, 30 to 200 μm. Preferably, it is 30 to 120 μm. Thus, for example, the average light transmittance of the near-infrared absorbing film in the wavelength region of 800 to 1100 nm can be reduced to less than 5%, and the average light transmittance of the near-infrared absorbing film in the wavelength region of 450 to 600 nm can be maintained high (for example, 70% or more).

[0484] The organic pigment of the near infrared ray absorption film of two-layer formation contains layer 3 and for example can be formed as follows. The organic pigment used in the present invention and matrix resin are added to the organic pigment prepared in the solvent and contain the layer and adopt spin coating or utilize the wet coating mode of distributor to be coated on substrate with coating liquid, then, for this coating film, carry out given heat treatment, make coating film solidify.Coating mode is preferably spin coating.This is because, by regulating the rotating speed of spin coater, thereby can finely adjust the thickness of organic pigment containing layer.

[0485] The copper phosphonate containing layer 2 can be formed, for example, as follows. A copper salt such as copper acetate is added to a given solvent such as tetrahydrofuran (THF), dissolved by ultrasonic treatment, and then a phosphate is added to prepare a liquid A. In addition, a phosphonic acid such as ethylphosphonic acid is added to a given solvent such as THF and stirred to prepare a liquid B. A solution obtained by mixing liquids A and B is stirred at room temperature for more than ten hours to prepare a liquid C. A given solvent such as toluene is added to liquid C, and a heating treatment is performed at a given temperature to volatilize the solvent to prepare a liquid D.

[0486] Next, a base resin such as a silicone resin is added to the D liquid (a dispersion of copper phosphate particles) and stirred to prepare a coating liquid for a copper phosphate-containing layer. The prepared coating liquid is applied to a substrate by spin coating or wet coating using a dispenser, and then the coating film is subjected to a predetermined heat treatment to cure the coating film. In the formation of a near-infrared absorbing film with a two-layer structure, the same base resin and additives as those for a single-layer structure can be used.

[0487] 《Near infrared absorption filter》

[0488] One feature of the near infrared absorption filter of the present invention is that it is formed using the near infrared absorption film of the present invention and can be easily produced by, for example, a coating method.

[0489] The near infrared absorption film used in the near infrared absorption filter of the present invention may be a single layer structure, but preferably a two-layer structure. For the arrangement of the layers of the near infrared absorption filter having a two-layer structure, for example, the contents described in Japanese Patent No. 6619828 can be referred to.

[0490] Figure 2This is an example of a near infrared absorption filter including a near infrared absorption film having a two-layer structure. The near infrared absorption filter of the present invention is not limited to the structure exemplified here.

[0491] If the organic dye-containing layer is formed on the surface of the copper phosphate-containing layer after the copper phosphate-containing layer is formed, the characteristics of the copper phosphate-containing layer may not be fully exerted. Therefore, it is preferred to form the copper phosphate-containing layer on the surface of the organic dye-containing layer after the organic dye-containing layer is formed.

[0492] In order to fully exhibit the characteristics, it is preferred that a transparent substrate or an intermediate protective layer is interposed between the organic dye-containing layer and the copper phosphate-containing layer.

[0493] Furthermore, the near infrared absorption filter of the present invention may include an antireflection layer on the filter surface, thereby improving the light transmittance in the visible light region, and when the near infrared absorption filter is used in an imaging device such as a digital camera, a high-brightness image can be obtained.

[0494] From the viewpoint of increasing the light transmittance in the visible light region, the film thickness of the near infrared absorption filter of the present invention is preferably within a range of 30 to 120 μm.

[0495] In addition, the near-infrared absorbing film of the present invention is suitable as a near-infrared absorbing film constituting, for example, a visual sensitivity correction component for CCD, CMOS or other light-receiving elements, a photometric component, a heat radiation absorption component, a composite optical filter, a lens component (glasses, sunglasses, goggles, optical system, optical waveguide system), an optical fiber component (optical fiber), a noise elimination component, a display cover or a display filter such as a plasma display front panel, a projector front panel, a light source heat radiation cutoff component, a color tone correction component, a lighting brightness adjustment component, an optical element (a light amplifier element, a wavelength conversion element, etc.), a Faraday element, an isolator and other optical communication functional devices, an optical disk element, etc.

[0496] 《Image Sensor for Solid-State Imaging Devices》

[0497] One feature of the image sensor for a solid-state imaging element of the present invention is that it is formed using the near-infrared absorption filter of the present invention. Specifically, it is characterized in that it is applied to an image sensor for a solid-state imaging element as a near-infrared absorption filter on the light-receiving side of a solid-state imaging element substrate (for example, a near-infrared absorption filter for a wafer-level lens, etc.), a near-infrared absorption filter on the back side (opposite side to the light-receiving side) of a solid-state imaging element substrate, etc.

[0498] By applying the near infrared absorption filter of the present invention to an image sensor for a solid-state imaging element, it is possible to improve transmittance in the visible light region, heat resistance, and light resistance.

[0499] Figure 3 It is a schematic cross-sectional view showing the structure of a camera module including a solid-state imaging element having the near infrared absorption filter of the present invention.

[0500] Figure 3 The camera module 101 shown in FIG. 1 is connected to a circuit substrate 112 as a mounting substrate via solder balls 111 as connecting members.

[0501] Specifically, the camera module 101 includes a solid-state imaging element substrate 110 having an imaging element portion 113 on a first main surface of a silicone substrate, a planarization layer 108 provided on the first main surface side (light receiving side) of the solid-state imaging element substrate 110, a near infrared absorption filter 109 provided on the planarization layer 108, a glass substrate 103 (light-transmitting substrate) disposed above the near infrared absorption filter 109, a lens holder 105 disposed above the glass substrate 103 and having an imaging lens 104 in an internal space, and a light shielding and electromagnetic shield 106 disposed so as to surround the solid-state imaging element substrate 110 and the glass substrate 103. The components are bonded together using adhesives 102 and 107.

[0502] In the method for manufacturing a camera module having a solid-state imaging element substrate and an infrared absorption filter disposed on the light-receiving side of the solid-state imaging element substrate, a near-infrared absorption film can be formed by spin-coating the infrared absorption composition of the present invention on the light-receiving side of the solid-state imaging element substrate. The near-infrared absorption film may be a single-layer structure or a two-layer structure.

[0503] Therefore, in the camera module 101 , for example, the infrared absorption filter 109 is formed by spin-coating the above-mentioned various organic pigments and metal compounds or the near-infrared absorption composition of the present invention on the planarization layer 108 to form a near-infrared absorption film.

[0504] In the camera module 101 , incident light L from the outside sequentially passes through the imaging lens 104 , the glass substrate 103 , the infrared absorption filter 109 , and the planarization layer 108 , and reaches the imaging element portion of the solid-state imaging element substrate 110 .

[0505] In addition, the camera module 101 is connected to a circuit board 112 via solder balls 111 (connection material) on the second main surface side of the solid-state imaging element substrate 110 .

[0506] Example

[0507] The present invention is specifically described below with reference to the following examples, but the present invention is not limited to these examples. It should be noted that the expression "parts" or "%" used in the examples represents "parts by mass" or "mass %" unless otherwise specified.

[0508] 《Example 1》

[0509] [Preparation of near infrared absorbing composition]

[0510] <Synthesis of pigment>

[0511] With reference to the synthesis examples described above and known methods, pigments A1-1, 2, 6, 9, 12, 17, A2-2, 6, 7, 10, A3-1, 5, 11, A4-1, 2, 5, 8, 13, B1-2, 3, 4, 6, 9, C1-1, 4, 5, 7, 8, C2-9, 12, 13, 15, 18, 22, 23, 25 and 28 were synthesized.

[0512] <Synthesis of Exemplary Compounds of the Compound Having a Structure Represented by General Formula (I)>

[0513] Referring to the known methods described above, Exemplary compounds 7, 13, 19, 42, 54, 65, 72 and 77 of the compound having a structure represented by the general formula (I) were synthesized.

[0514] <Synthesis of the compound having the structure represented by the general formula (D1)>

[0515] Compounds D-3, 19 and 43 having a structure represented by the general formula (D1) were synthesized with reference to known methods described in Japanese Patent Application Laid-Open Nos. 2007-31425 and 2007-34264.

[0516] (Preparation of Near Infrared Absorbing Composition 1)

[0517] The near infrared absorbing composition 1 was prepared according to the following method.

[0518] 2.0 g of copper (II) acetate monohydrate (manufactured by Kanto Chemical Co., Ltd., hereinafter also referred to as "copper acetate") and 82 g of tetrahydrofuran (THF) as a solvent were mixed, stirred for 3 hours, and filtered to remove insoluble copper acetate to prepare a copper acetate solution.

[0519] To the copper acetate solution, a solution prepared by dissolving 1.75 g of Exemplary Compound 72, which is a compound having a structure represented by General Formula (I) in 7.0 g of tetrahydrofuran (THF) was added with stirring over 30 minutes to prepare Solution A.

[0520] Next, 0.88 g of propylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 7.0 g of tetrahydrofuran (THF) to prepare a liquid B.

[0521] After adding solution B to solution A while stirring, the mixture was stirred at room temperature for 16 hours to prepare solution C. Next, solution C and 30 g of toluene were placed in a flask, and while heating at 50 to 100° C. using an oil bath (manufactured by Tokyo Rikakki Co., Ltd., model: OSB-2100), solvent removal and deacetic acid removal were performed using a rotary evaporator (manufactured by Tokyo Rikakki Co., Ltd., model: N-1000) for 30 minutes to prepare solution D.

[0522] Furthermore, the organic dye shown below was dissolved in 36 g of diacetone alcohol and added to the D solution to prepare the E solution.

[0523] Pigment A1-1 2.00mg

[0524] Pigment C1-1 2.20mg

[0525] Solution E was placed in a flask and heated at 55 to 90° C. in an oil bath (manufactured by Tokyo Rikakki Co., Ltd., model: OSB-2100) while being subjected to desolvation and deacetic acid treatment using a rotary evaporator (manufactured by Tokyo Rikakki Co., Ltd., model: N-1000) for 3 hours.

[0526] Then, the amount of the solvent was adjusted so that the solid content concentration of the liquid E in the flask would be 10% by mass, and this was designated as a near infrared absorbing composition 1.

[0527] (Preparation of Near Infrared Absorbing Composition 2)

[0528] In the preparation of the above-mentioned near infrared absorbing composition 1, except that S1 was used instead of the compound having a structure represented by the general formula (I) instead of the organic dye shown in Table V, a near infrared absorbing composition 2 was prepared in the same manner. The structural formula and synthesis method of S1 are shown below.

[0529] [Chemistry 58]

[0530]

[0531] 130 g (1.0 mol) of n-octanol was placed in an autoclave, and potassium hydroxide was used as a catalyst. Under the conditions of a pressure of 147 kPa and a temperature of 130° C., 116 g (2.0 mol) of propylene oxide was added, and then 88 g (2.0 mol) of ethylene oxide was added. Next, after confirming that no n-octanol remained, the above-mentioned adduct was placed in a reactor, and 117 g (1.0 mol) of chlorosulfonic acid was added dropwise to a toluene solution over a period of about 1 hour. After reacting, the mixture was washed with distilled water, and the solvent was distilled off under reduced pressure, thereby obtaining S1.

[0532] (Preparation of Near Infrared Absorbing Compositions 3 to 13)

[0533] Near infrared absorbing compositions 3 to 13 were prepared in the same manner as in the preparation of the above-mentioned near infrared absorbing composition 1, except that the organic dye and the compound having a structure represented by the general formula (I) shown in Table V were used instead.

[0534] (Preparation of Near Infrared Absorbing Compositions 14, 16 to 21)

[0535] Near infrared absorbing compositions 14 and 16 to 21 were prepared in the same manner as in the preparation of the above-mentioned near infrared absorbing composition 1, except that the organic dye and the compound having the structure represented by the general formula (I) shown in Table VI were used instead and octylphosphonic acid was used instead of propylphosphonic acid.

[0536] (Preparation of Near Infrared Absorbing Composition 15)

[0537] A near infrared absorbing composition 15 was prepared in the same manner as the above near infrared absorbing composition 1 except that the organic pigment and the compound having a structure represented by the general formula (I) shown in Table VI were used instead, octylphosphonic acid was used instead of propylphosphonic acid, and the addition amount was reduced to 80%.

[0538] (Preparation of Near Infrared Absorbing Compositions 22 and 23)

[0539] Near infrared absorbing compositions 22 and 23 were prepared in the same manner except that in the preparation of the above-mentioned near infrared absorbing composition 1, the organic pigment and the compound having a structure represented by the general formula (I) shown in Table VI were changed, octylphosphonic acid was used instead of propylphosphonic acid, and the compound having a structure represented by the general formula (D1) shown in Table VI was added.

[0540] The following is a procedure for adding a compound having a structure represented by general formula (D1).

[0541] 50 mass % of the organic dye used, namely D-3 or D-19, a compound having a structure represented by general formula (D1), was added to solution D together with the organic dye to prepare solution E. Subsequent treatments were performed in the same manner as for near infrared absorbing composition 1.

[0542] (Preparation of Near Infrared Absorbing Compositions 24 to 35)

[0543] Near infrared absorbing compositions 24 to 35 were prepared in the same manner except that the organic pigments and the compound having a structure represented by the general formula (I) shown in Tables VI and VII were replaced in the preparation of the above-mentioned near infrared absorbing composition 1, and the compound having a structure represented by the general formula (D1) shown in Tables VI and VII was added. The step of adding the compound having a structure represented by the general formula (D1) was carried out in the same manner as the above-mentioned step.

[0544] (Preparation of Near Infrared Absorbing Composition 36)

[0545] A near infrared absorbing composition 36 was prepared in the same manner as in the preparation of the above-mentioned near infrared absorbing composition 1, except that phenylphosphonic acid was used instead of propylphosphonic acid.

[0546] (Preparation of Near Infrared Absorbing Composition 37: Comparative Example)

[0547] A near infrared absorbing composition 37 was prepared in the same manner as in the preparation of the above near infrared absorbing composition 1 except that the organic dye (diaminium dye: KAYASORB IRG-022) and the compound having a structure represented by the general formula (I) shown in Table VII were used.

[0548] (Preparation of Near Infrared Absorbing Composition 38: Comparative Example)

[0549] A near infrared absorbing composition 38 was prepared in the same manner as in the preparation of the above-mentioned near infrared absorbing composition 1, except that the organic dye (diaminium dye: KAYASORB IRG-022) and the compound having a structure represented by the general formula (I) shown in Table VII were used instead, and the compound having a structure represented by the general formula (D1) shown in Table VII was added.

[0550] (Preparation of Near Infrared Absorbing Composition 39: Comparative Example)

[0551] A near infrared absorbing composition 39 was prepared in the same manner as in the preparation of the above near infrared absorbing composition 1, except that propylphosphonic acid and the compound having a structure represented by the general formula (I) were not added.

[0552] (Preparation of Near Infrared Absorbing Composition 40: Comparative Example)

[0553] A near infrared absorbing composition 40 was prepared in the same manner as in the preparation of the above-mentioned near infrared absorbing composition 1, except that the organic dyes shown in Table VII ((a-18) and (c-1) described in Japanese Patent No. 6331392) and the compound having a structure represented by the general formula (I) were used instead.

[0554] The organic pigment, phosphonic acid, compound having a structure represented by the general formula (I), and compound having a structure represented by the general formula (D1) used in the preparation of the above-mentioned near-infrared absorbing composition are shown below. In addition, in this embodiment, the addition amount is 0.76 mol of phosphonic acid and 0.28 mol of compound having a structure represented by the general formula (I) relative to 1 mol of copper acetate.

[0555] Regarding the *octylphosphonic acid in Table VI, the amount of octylphosphonic acid added was reduced to 80%.

[0556] [Table 5]

[0557]

[0558] [Table 6]

[0559]

[0560] [Table 7]

[0561]

[0562] [evaluate]

[0563] The near-infrared absorbing composition produced as described above was subjected to the following measurements and evaluations.

[0564] Each evaluation sample diluted with toluene was prepared for the near infrared absorbing compositions 1 to 40 prepared above so that the particle concentration (solid content concentration) of the metal complex as particles became 1.0 mass %.

[0565] <Light transmittance>

[0566] For the manufactured samples, the transmittance in the wavelength range of 450 to 1200 nm was measured using a spectrophotometer V-780 manufactured by JASCO Corporation, and the average transmittance in this range was calculated. The calculated average transmittance in the wavelength range of 450 to 1200 nm was evaluated according to the following standards. In addition, the wavelength at which the transmittance in the range of 600 to 700 nm in each waveform becomes 50% was measured and set as the cut-off wavelength.

[0567] In the wavelength range of 450nm to 600nm,

[0568] ◎◎: The average light transmittance in this range is 90% or more.

[0569] ◎: The average light transmittance in this range is 88% or more and less than 90%.

[0570] ○: The average light transmittance in this range is 85% or more and less than 88%.

[0571] △: The average light transmittance in this range is 80% or more and less than 85%.

[0572] ×: The average light transmittance in this range is less than 80%.

[0573] In the wavelength range of 700nm and below 1000nm,

[0574] ◎: The average light transmittance in this range is less than 2%.

[0575] ○: The average light transmittance in this range is 2% or more and less than 5%.

[0576] △: The average light transmittance in this range is 5% or more and less than 10%.

[0577] ×: The average light transmittance in this range is 10% or more.

[0578] In the wavelength range of 1000nm to 1200nm,

[0579] ◎: The average light transmittance in this range is less than 2%.

[0580] ○: The average light transmittance in this range is 2% or more and less than 5%.

[0581] △: The average light transmittance in this range is 5% or more and less than 10%.

[0582] ×: The average light transmittance in this range is 10% or more.

[0583] The evaluation results of Example 1 are summarized in the following Tables VIII to X together with the evaluation results of Example 2. The same measurements as above were performed on single films without the solvent from each of the above compositions, and it was confirmed that the same results as those in the liquid state were obtained.

[0584] 《Example 2》

[0585] [Single-layer filter]

[0586] Each of the near infrared absorbing compositions 1 to 40 prepared above and a curable resin having a polysiloxane structure (KR-311 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed so that the solid content ratio of the resin was 70% by mass to prepare a coating liquid for forming a near infrared absorbing film.

[0587] Next, each near-infrared absorbing film-forming coating liquid was applied to a glass substrate by spin coating (rotation speed: 300 rpm) to form a coating film. The coating film was pre-baked on a hot plate at 50° C. for 60 minutes. Next, the coating film was cured by heating on a hot plate at 150° C. for 2 hours to produce a near-infrared absorbing filter having a single layer structure.

[0588] The near infrared absorption filter was subjected to the following measurements and evaluations.

[0589] [evaluate]

[0590] <Lightfastness>

[0591] The produced samples were exposed for 120 hours using a xenon fading tester, and the light resistance was calculated from the ratio of the reflection spectrum concentration at the maximum absorption wavelength in the visible region before and after the exposure and evaluated based on the following criteria.

[0592] Light resistance (%) = (maximum absorption wavelength concentration of the exposed sample / maximum absorption wavelength concentration of the unexposed sample) × 100

[0593] ◎: Light resistance is more than 95%

[0594] ○: Light resistance is 90% or more and less than 95%

[0595] △: Light resistance is 80% or more and less than 90%

[0596] ×: Light resistance less than 80%

[0597] If it is ○ or more, it is considered that there is no problem in practical use.

[0598] <Heat resistance>

[0599] The produced samples were stored for 7 days at 85°C and 10% RH or less, and the heat resistance was calculated from the concentration ratio before and after the start of storage and evaluated based on the following criteria.

[0600] Heat resistance (%) = (concentration after storage / concentration before storage) × 100

[0601] ◎: Heat resistance is 95% or more

[0602] ○: Heat resistance is 80% or more and less than 95%

[0603] △: Heat resistance is 60% or more and less than 80%

[0604] ×: Heat resistance less than 60%

[0605] If it is ○ or more, it is considered that there is no problem in practical use.

[0606] The evaluation results of Examples 1 and 2 are summarized in Tables VIII to X below.

[0607] The measurement results of the average light transmittance and the cutoff wavelength shown in the tables are the results of evaluation performed according to the method and conditions described in Example 1 and converted into light transmittance corrected to eliminate reflection due to the glass interface, etc.

[0608] [Table 8]

[0609] Table V@I@

[0610]

[0611] [Table 9] Table N

[0612]

[0613] [Table 10]

[0614] Table X

[0615]

[0616] 《Example 3》

[0617] [Manufacturing and evaluation of two-layer optical filter]

[0618] The coating solution for the organic pigment containing layer was prepared as follows. 2.00 mg of A1-1 and 2.20 mg of C1-1 were added to 36 g of diacetone alcohol and stirred for 1 hour. Then, 2 g of polyvinyl butyral resin (manufactured by Sumitomo Chemical Co., Ltd., S-LECKS-10) was added and stirred for 1 hour. Then, 1 g of 2,4-diisocyanatotoluene was further added and stirred to obtain a coating solution for the organic pigment containing layer.

[0619] The organic pigment containing layer coating liquid was applied to the glass substrate by spin coating (rotation speed: 500 rpm) to form a coating film. The coating film was heat treated at 140° C. for 60 minutes to cure the coating film to form an organic pigment containing layer. The thickness of the organic pigment containing layer was about 2 μm.

[0620] The coating liquid for the intermediate protective layer was prepared as follows: 2.83 g of glycidoxypropyltrimethoxysilane, 0.11 g of epoxy resin (SR-6GL manufactured by Sakamoto Yakuin Kogyo Co., Ltd.), 5.68 g of tetraethoxysilane, 0.06 g of ethanol diluted with nitric acid (nitric acid concentration: 10 wt%) and 5.5 g of water were added in sequence to 11.5 g of ethanol, and stirred for about 1 hour to obtain the coating liquid for the intermediate protective layer.

[0621] The intermediate protective layer coating solution was applied to the surface of the organic pigment-containing layer by spin coating (rotation speed: 300 rpm) to form a coating film, and the coating film was heat-treated at 150° C. for 20 minutes to cure the coating film to form an intermediate protective layer.

[0622] As the coating liquid for the copper phosphate containing layer, the D liquid before the addition of the organic dye in the near infrared absorbing composition 1 of Example 1 was used and prepared by the same procedure. Next, the D liquid was mixed with a curable resin having a polysiloxane structure (KR-311 manufactured by Shin-Etsu Chemical Co., Ltd.) so that the solid content ratio of the resin became 70% by mass to obtain a coating liquid for the copper phosphate containing layer.

[0623] The copper phosphate-containing layer coating solution was applied to the surface of the intermediate protective layer by spin coating (rotation speed: 300 rpm) to form a coating film. The coating film was pre-baked on a hot plate at 50° C. for 60 minutes. Then, the coating film was cured by heating on a hot plate at 150° C. for 2 hours to produce a near-infrared absorption filter having a two-layer structure (excluding the intermediate layer).

[0624] The near infrared absorption filter was subjected to the same measurements and evaluations as in Examples 1 and 2, and the same results were confirmed.

[0625] As can be seen from the results of Tables VIII to X, the near infrared absorbing composition and the near infrared absorbing film of the present invention have excellent transmittance in the visible light region and absorptivity in the near infrared region, and the near infrared absorbing filter produced from the near infrared absorbing composition of the present invention has excellent heat resistance over time and also excellent light resistance.

[0626] Industrial Applicability

[0627] The near-infrared absorbing composition of the present invention has both transmittance in the visible light region and absorptivity in the near-infrared region, and is excellent in heat resistance and light resistance over time. In addition, by using the infrared absorbing composition, a near-infrared absorbing film, a near-infrared absorbing filter, and an image sensor for a solid-state imaging element that have both transmittance in the visible light region and absorptivity in the near-infrared region and are excellent in heat resistance and light resistance over time can be provided.

[0628] Description of Reference Numerals

[0629] 1 Near infrared absorption film

[0630] 2 Copper phosphate containing layer

[0631] 3 Organic pigment containing layer

[0632] 11 Near infrared absorption filter

[0633] 12 Anti-reflective film

[0634] 13 Copper phosphate containing layer

[0635] 14 Intermediate protective layer

[0636] 15 Organic pigment containing layer

[0637] 16 substrate

[0638] 101 Camera Module

[0639] 102 Adhesive

[0640] 103 Glass Substrate

[0641] 104 Camera Lens

[0642] 105 Lens bracket

[0643] 106 Light-shielding and electromagnetic shielding

[0644] 107 Adhesive

[0645] 108 planarization layer

[0646] 109 Near infrared absorption film (near infrared absorption filter)

[0647] 110 Solid-state imaging element substrate

[0648] 111 Solder Ball

[0649] 112 Circuit board

[0650] 113 Camera Components

Claims

1. A near-infrared absorbing composition comprising an organic pigment and a metal compound, characterized in that: Contains at least one of a squarylium dye (A) or a cyanine dye (B) having an absorption maximum wavelength in the range of 680 to 740 nm, and Contains anthocyanin (C) with an absorption maximum wavelength above 760nm, The squarylium dye (A) is a compound having a structure represented by any one of the following general formulas (A1) to (A4), hereinafter referred to as "dye A1", "dye A2", "Pigment A3" and "Pigment A4", The anthocyanin pigment (B) is a compound having a structure represented by the following general formula (B1), hereinafter referred to as "pigment B1". The cyanine pigment (C) is a compound having a structure represented by any one of the following general formulas (C1) or (C2), hereinafter referred to as "pigment C1" and "pigment C2". It also contains at least phosphonic acid and copper ions, or a phosphonate copper complex formed by phosphonic acid and copper ions, wherein the phosphonic acid is an alkylphosphonic acid. It also contains a compound having a structure represented by the following general formula (I) and a copper ion, or a copper complex formed by a compound having a structure represented by the following general formula (I) and a copper ion, Squarylium pigment (A) [Chemistry 1] General formula (A1) In the formula, R1 represents an alkyl group, an aryl group or a heterocyclic group, R2 and R3 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an acylamino group or a sulfonylamino group, and can be bonded with R1 to form a 5-6 membered ring, R4 represents an alkyl group, an alkoxy group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms, and Z1 represents an atomic group required to form a 5-6 membered ring, [Chemistry 2] General formula (A2) In the formula, R 11 and R 12 Each independently represents a hydrogen atom, a hydroxyl group, -NHCOR 16 or -NHSO2R 17 , will not be a hydrogen atom at the same time, R 13 and R 14 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, -NHCOR 16 or -NHSO2R 17 , R 15 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an acylamino group or a sulfonylamino group, which may be bonded to each other to form a 5- or 6-membered ring, n1 represents an integer of 0 to 5, R 16 and R 17 each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms, [Chemistry 3] General formula (A3) In the formula, R 21 and R 22 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 23 Each independently represents a hydroxyl group, -NHCOR 26 or -NHSO2R 27 , R 24 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, -NHCOR 26 or -NHSO2R 27 , R 25 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, -NHCOR 26 or -NHSO2R 27 , n2 represents an integer from 0 to 4, R 26 and R 27 each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms, [Chemistry 4] General formula (A4) In the formula, R 31 and R 32 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 33 Represents hydroxyl group, -NHCOR 38 or -NHSO2R 39 , R 34 and R 36 Each independently represents a halogen atom, an alkyl group, an alkoxy group, -NHCOR 38 or -NHSO2R 39 , R 35 represents an alkyl group, an aryl group or a heterocyclic group, n3 represents an integer of 0 to 3, m3 represents an integer of 0 to 6, R 37 represents a hydrogen atom, a halogen atom or an alkyl group, R 38 and R 39 each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms, Anthocyanin (B) [Chemistry 5] General formula (B1) In the formula, R 41 Each independently represents an alkyl group, an aryl group or a heterocyclic group, R 42 Each independently represents a halogen atom, an alkyl group, an alkoxy group, -NHCOR 46 or -NHSO2R 47 , where R 46 and R 47 is an alkyl group having 1 to 4 carbon atoms, R 43 ~R 45 Each independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, n4 each independently represents an integer of 0 to 6, Y 41 represents a halogen ion or anion radical, Cyanine pigment (C) [Chemistry 6] General formula (C1) In the formula, R 51 and R 52 Each is independently a halogen atom, an alkyl group, an alkoxy group or an aryl group. Adjacent substituents may be bonded to form a 5- or 6-membered ring. 51 and n 52 represents integers from 0 to 4 and from 0 to 5, respectively, R 53 and R 54 Each independently represents an alkyl group, an aryl group or a heterocyclic group, R 55 ~R 59 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 55 With R 57 , R 56 With R 58 or R 57 With R 59 Can be bonded to form a 5- or 6-membered ring, X 51 Indicates -S- or -CR 511 R 512 -, Y 51 represents an anionic atom or anionic group, R 511 and R 512 each independently represents a hydrogen atom, an alkyl group or an aryl group, [Chemistry 7] General formula (C2) In the formula, R 61 and R 62 Each is independently a halogen atom, an alkyl group, an alkoxy group, or an aryl group. Adjacent substituents may be bonded to form a 5- or 6-membered ring. 61 and n 62 Each independently represents an integer from 0 to 4, R 63 and R 64 Each independently represents an alkyl group, an aryl group or a heterocyclic group, R 65 ~R 71 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 65 With R 67 , R 66 With R 68 , R 67 With R 69 , R 68 With R 70 or R 69 With R 71 Can be bonded to form a 5- or 6-membered ring, X 61 and X 62 Each independently represents -O-, -S-, or -CR 611 R 612 -, Y 61 represents an anionic atom or anionic group, R 611 and R 612 each independently represents a hydrogen atom or an alkyl group, [Chemistry 8] General formula (I) In the general formula (I), R 125 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 125 It may also have at least one or more of an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a dialkylamino group, a trialkylsilyl group, a triarylsilyl group, a triheteroarylsilyl group, a benzyl group, an aryl group, a heteroaryl group, 9,9'-dimethylfluorene, carbazole, and dibenzofuran as a substituent, and Z represents a structural unit selected from the following formulas (Z-1) and (Z-2), [Chemistry 9] (Z-1) (Z-2) The * in the formula (Z-1) and (Z-2) indicates a bonding site, which is bonded to O in the general formula (I). R 121 ~R 124 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, The compound having a structure represented by the general formula (I) has at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the following condition (ii). Condition (i): R 121 ~R 124 All hydrogen atoms, Condition (ii): R 121 ~R 124 At least one of them is an alkyl group having 1 to 4 carbon atoms, In the general formula (I), j represents the number of partial structures satisfying the condition (i), which is a number from 1 to 10, and k represents the number of partial structures satisfying the condition (ii), which is a number from 1 to 10.

2. The near infrared absorbing composition according to claim 1, characterized in that The organic dye is contained as at least a combination of the dye A1 and the dye C2, or a combination of the dye A4 and the dye C2.

3. The near infrared absorbing composition according to claim 1, characterized in that The organic dye is contained as at least a combination of the dye B1 and the dye C2.

4. The near infrared absorbing composition according to any one of claims 1 to 3, characterized in that It also contains a compound having a structure represented by the following general formula (D1), [Chemistry 10] General formula (D1) In the formula, R 111 and R 113 Each independently represents an alkyl group, an alkoxy group, an amino group, an aryl group or a heterocyclic group, and R 112 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a carbonyl group or a cyano group, and each of them may be substituted by an alkyl group or an alkoxy group.

5. A near infrared absorbing film, characterized in that: The near-infrared absorbing composition according to any one of claims 1 to 4 is used.

6. A near infrared absorbing film, characterized in that: The invention comprises: an organic pigment-containing layer containing an organic pigment, and a copper phosphonate-containing layer containing phosphonic acid and copper ions, or a copper phosphonate complex formed of phosphonic acid and copper ions, The organic pigment Contains at least one of a squarylium dye (A) or a cyanine dye (B) having an absorption maximum wavelength in the range of 680 to 740 nm, and Contains anthocyanin (C) with an absorption maximum wavelength above 760nm, The squarylium dye (A) is a compound having a structure represented by any one of the following general formulas (A1) to (A4), hereinafter referred to as "dye A1", "dye A2", "Pigment A3" and "Pigment A4", The anthocyanin pigment (B) is a compound having a structure represented by the following general formula (B1), hereinafter referred to as "pigment B1". The cyanine pigment (C) is a compound having a structure represented by any one of the following general formulas (C1) or (C2), hereinafter referred to as "pigment C1" and "pigment C2". The phosphonic acid is an alkylphosphonic acid, The copper phosphate-containing layer further contains a compound having a structure represented by the following general formula (I) and copper ions, or a copper complex formed by a compound having a structure represented by the following general formula (I) and copper ions. Squarylium pigment (A) [Chemistry 11] General formula (A1) In the formula, R1 represents an alkyl group, an aryl group or a heterocyclic group, R2 and R3 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an acylamino group or a sulfonylamino group, and can be bonded with R1 to form a 5-6 membered ring, R4 represents an alkyl group, an alkoxy group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms, and Z1 represents an atomic group required to form a 5-6 membered ring, [Chemistry 12] General formula (A2) In the formula, R 11 and R 12 Each independently represents a hydrogen atom, a hydroxyl group, -NHCOR 16 or -NHSO2R 17 , will not be a hydrogen atom at the same time, R 13 and R 14 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, -NHCOR 16 or -NHSO2R 17 , R 15 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an acylamino group or a sulfonylamino group, which may be bonded to each other to form a 5- or 6-membered ring, n1 represents an integer of 0 to 5, R 16 and R 17 each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms, [Chemistry 13] General formula (A3) In the formula, R 21 and R 22 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 23 Each independently represents a hydroxyl group, -NHCOR 26 or -NHSO2R 27 , R 24 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, -NHCOR 26 or -NHSO2R 27 , R 25 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, -NHCOR 26 or -NHSO2R 27 , n2 represents an integer from 0 to 4, R 26 and R 27 each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms, [Chemistry 14] General formula (A4) In the formula, R 31 and R 32 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 33 Represents hydroxyl group, -NHCOR 38 or -NHSO2R 39 , R 34 and R 36 Each independently represents a halogen atom, an alkyl group, an alkoxy group, -NHCOR 38 or -NHSO2R 39 , R 35 represents an alkyl group, an aryl group or a heterocyclic group, n3 represents an integer of 0 to 3, m3 represents an integer of 0 to 6, R 37 represents a hydrogen atom, a halogen atom or an alkyl group, R 38 and R 39 each independently represents an alkyl group, an aryl group or a heterocyclic group having 1 to 4 carbon atoms, Anthocyanin (B) [Chemistry 15] General formula (B1) In the formula, R 41 Each independently represents an alkyl group, an aryl group or a heterocyclic group, R 42 Each independently represents a halogen atom, an alkyl group, an alkoxy group, -NHCOR 46 or -NHSO2R 47 , where R 46 and R 47 is an alkyl group having 1 to 4 carbon atoms, R 43 ~R 45 Each independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, n4 each independently represents an integer of 0 to 6, Y 41 represents a halogen ion or anion radical, Cyanine pigment (C) [Chemistry 16] General formula (C1) In the formula, R 51 and R 52 Each is independently a halogen atom, an alkyl group, an alkoxy group or an aryl group. Adjacent substituents may be bonded to form a 5- or 6-membered ring. 51 and n 52 represents integers from 0 to 4 and from 0 to 5, respectively, R 53 and R 54 Each independently represents an alkyl group, an aryl group or a heterocyclic group, R 55 ~R 59 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 55 With R 57 , R 56 With R 58 or R 57 With R 59 Can be bonded to form a 5- or 6-membered ring, X 51 Indicates -S- or -CR 511 R 512 -, Y 51 represents an anionic atom or anionic group, R 511 and R 512 each independently represents a hydrogen atom, an alkyl group or an aryl group, [Chemistry 17] General formula (C2) In the formula, R 61 and R 62 Each is independently a halogen atom, an alkyl group, an alkoxy group, or an aryl group. Adjacent substituents may be bonded to form a 5- or 6-membered ring. 61 and n 62 Each independently represents an integer from 0 to 4, R 63 and R 64 Each independently represents an alkyl group, an aryl group or a heterocyclic group, R 65 ~R 71 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and R 65 With R 67 , R 66 With R 68 , R 67 With R 69 , R 68 With R 70 or R 69 With R 71 Can be bonded to form a 5- or 6-membered ring, X 61 and X 62 Each independently represents -O-, -S-, or -CR 611 R 612 -, Y 61 represents an anionic atom or anionic group, R 611 and R 612 each independently represents a hydrogen atom or an alkyl group, [Chemistry 18] General formula (I) In the general formula (I), R 125 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 125 It may also have at least one or more of an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a dialkylamino group, a trialkylsilyl group, a triarylsilyl group, a triheteroarylsilyl group, a benzyl group, an aryl group, a heteroaryl group, 9,9'-dimethylfluorene, carbazole, and dibenzofuran as a substituent, and Z represents a structural unit selected from the following formulas (Z-1) and (Z-2), [Chemistry 19] (Z-1) (Z-2) The * in the formula (Z-1) and (Z-2) indicates a bonding site, which is bonded to O in the general formula (I). R 121 ~R 124 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, The compound having a structure represented by the general formula (I) has at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the following condition (ii). Condition (i): R 121 ~R 124 All hydrogen atoms, Condition (ii): R 121 ~R 124 At least one of them is an alkyl group having 1 to 4 carbon atoms, In the general formula (I), j represents the number of partial structures satisfying the condition (i), which is a number from 1 to 10, and k represents the number of partial structures satisfying the condition (ii), which is a number from 1 to 10.

7. A near infrared absorption filter, characterized in that A near infrared absorbing film according to claim 5 or 6, The film thickness is within the range of 30 to 120 μm, and The light transmittance satisfies all of the following conditions (1) to (4), (1) Average light transmittance within a wavelength range of 450 nm to 600 nm: 85% or more (2) Average light transmittance in the wavelength range of 700 nm to less than 1000 nm: less than 2% (3) Average light transmittance within a wavelength range of 1000 nm to 1200 nm: less than 5% (4) The cutoff wavelength at which the transmittance shows 50% at a wavelength of 600 to 700 nm is in the range of 620 to 660 nm.

8. An image sensor for a solid-state imaging device, characterized in that: A near infrared absorption filter according to claim 7 is provided.

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