Near-infrared absorbing composition, near-infrared absorbing film, near-infrared absorbing filter, and image sensor for solid-state imaging device

Abstract

The present invention addresses the problem of providing a near-infrared absorbing composition which achieves a good balance between transmissivity in the visible light region and absorption in the near-infrared region, while exhibiting excellent heat resistance over time and excellent light resistance.　A near-infrared absorbing composition according to the present invention contains an organic dye and a metal compound, and is characterized by containing: at least one of a squarylium dye (A) and a cyanine dye (B), each of which has a maximum absorption wavelength within the range of from 680 nm to 740 nm; a cyanine dye (C) which has a maximum absorption wavelength at 760 nm or more; and at least a phosphonic acid and a copper ion, or a copper phosphonate complex that is formed of a phosphonic acid and a copper ion.

Description

[Technical Field]

[0001] The present invention relates to a near-infrared absorbing composition, and a near-infrared absorbing film, a near-infrared absorbing filter, and an image sensor for a solid-state imaging device, each of which uses the composition. More specifically, the present invention relates to a near-infrared absorbing composition that has both transmittance in the visible light region and absorbance in the near-infrared region, and that also has excellent heat resistance and light resistance over time. [Background technology]

[0002] Video cameras, digital still cameras, and mobile phones with camera functions use CCD and CMOS image sensors, which are solid-state image sensors for capturing color images. However, these solid-state image sensors use silicon photodiodes in their light receiving section that are sensitive to light in the near-infrared wavelength region, so visibility correction is required, and a near-infrared absorbing filter is used.

[0003] There is a demand for further weight reduction in portable devices, and there is also a demand for weight reduction in near-infrared absorbing filters. In recent years, near-infrared absorbing filters in which a dye or a metal compound is added to a resin have attracted attention and are being developed, because they are lightweight and easy to manufacture and process.

[0004] As for dyes, Patent Documents 1 and 2 disclose techniques using squarylium dyes and cyanine dyes. The squarylium dye used in Patent Document 1 has a triple condensed ring structure and exhibits a steep absorption peak in the 630 to 700 nm region, and therefore exhibits absorption in a specific range of the near-infrared region while maintaining transparency in the visible light region.

[0005] Furthermore, Patent Document 2 discloses an optical filter that uses a squarylium compound having an absorption maximum in a specific region and a cyanine compound having an absorption maximum in a region longer than that and shorter than 760 nm. Squarylium compounds generally have fluorescent properties due to their molecular structure, but the generation of fluorescence can be suppressed by using them in combination with a cyanine compound having a certain structure.

[0006] However, while near-infrared absorbing filters based on these technologies have a good spectral absorption waveform, they have a low absorption rate for light with wavelengths of 850 nm or more, and require combination with technologies such as blue plate glass or dielectric laminated films, and the light resistance and heat resistance of the filters are not satisfactory.

[0007] Meanwhile, research is underway into optical materials that utilize the absorption properties unique to copper ions. In Patent Document 3, phosphonic acid and copper ions are used as optical materials to improve moldability, more specifically chemical stability during thermoforming, while retaining absorption properties. However, near-infrared absorbing filters based on this technology have a high absorption rate for light with wavelengths of 800 nm or more, but have a problem in that they have a low ability to absorb near-infrared light with shorter wavelengths.

[0008] Therefore, Patent Document 4 discloses an infrared cut filter consisting of two absorption layers, an organic dye-containing layer and a copper phosphonate-containing layer. However, there are few specific examples of the organic dyes used, and the spectral absorption waveform described in the examples has low transmittance in visible light of 500 nm or less, leaving room for further improvement. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Patent No. 6183041 [Patent Document 2] Patent No. 6331392 [Patent Document 3] Patent No. 4684393 [Patent Document 4] Patent No. 6281023 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been made in view of the above-mentioned problems and circumstances, and aims to provide a near-infrared absorbing composition that has both transparency in the visible light region and absorption in the near-infrared region, and that has excellent heat resistance over time and also excellent light resistance. The present invention also aims to provide a near-infrared absorbing film, a near-infrared absorbing filter, and an image sensor for a solid-state imaging device that use the near-infrared absorbing composition. [Means for solving the problem]

[0011] In order to solve the above-mentioned problems, the present inventors have conducted extensive research into the causes of the above-mentioned problems from the viewpoints of transmittance in the visible light region and absorbance in the near-infrared region, and as a result, have found that the above-mentioned problems can be solved by using a squarylium compound or cyanine compound having a specific structure, and further a composition containing at least phosphonic acid and copper ions, or a phosphonate copper complex formed from phosphonic acid and copper ions, and have arrived at the present invention.

[0012] That is, the above-mentioned problems of the present invention are solved by the following means.

[0013] 1. A near-infrared absorbing composition containing an organic dye and a metal compound, 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 a cyanine dye (C) having an absorption maximum wavelength of 760 nm or more, the squarylium dye (A) is a compound having a structure represented by any one of the following general formulas (A1) to (A4) (hereinafter simply referred to as "dye A1," "dye A2," "dye A3," and "dye A4"), The cyanine dye (B) is a compound having a structure represented by the following general formula (B1) (hereinafter simply referred to as "dye B1"), The cyanine dye (C) is a compound having a structure represented by either of the following general formulas (C1) and (C2) (hereinafter simply referred to as "dye C1" and "dye C2"), Furthermore, it contains at least a phosphonic acid and a copper ion, or a phosphonic acid copper complex formed from a phosphonic acid and a copper ion. death, the phosphonic acid is an alkylphosphonic acid, Furthermore, the present invention contains a copper complex formed from a compound having a structure represented by the following general formula (I) and copper ions, or a compound having a structure represented by the following general formula (I) and copper ions. A near-infrared absorbing composition comprising:

[0014] Squarylium dye (A) [ka]

[0015] (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, alkoxy group, aryl group, or heterocyclic group having 1 to 4 carbon atoms. Z1 represents an atomic group necessary to form a 5- or 6-membered ring.)

[0016] [ka]

[0017] (In the formula, R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or -NHCOR 16 or -NHSO2R 17 and cannot be a hydrogen atom at the same time. 13 and R 14 R each independently represents a hydrogen atom, a halogen atom or a substituent. 15 represents a substituent. n1 represents an integer of 0 to 5. R 16 and R 17each independently represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a heterocyclic group.

[0018] [ka]

[0019] (In the formula, R 21 and R 22 R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. 23 are each independently a hydroxy group, -NHCOR 26 or -NHSO2R 27 Represents R 24 R each independently represents a hydrogen atom or a substituent. 25 each independently represents a substituent. n2 represents an integer of 0 to 4. R 26 and R 27 each independently represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a heterocyclic group.

[0020] [ka]

[0021] (In the formula, R 31 and R 32 R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. 33 is a hydroxy group, -NHCOR 38 or -NHSO2R 39 Represents R 34 and R 36 R 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. R 37 represents a hydrogen atom, a halogen atom, or an alkyl group. 38 and R 39 each independently represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a heterocyclic group.

[0022] Cyanine dye (B) [ka]

[0023] (In the formula, R 41 R each independently represents an alkyl group, an aryl group, or a heterocyclic group. 42 R each independently represents a halogen atom or a substituent. 43 ~R 45 each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Each n4 independently represents an integer of 0 to 6. Y 41 represents a halogen ion or an anion atomic group.

[0024] Cyanine dye (C) [ka]

[0025] (In the formula, R 51 and R 52 each independently represents a halogen atom or a substituent, and adjacent substituents may be joined together to form a 5- or 6-membered ring. 51 and n 52 R represents an integer of 0 to 4 and 0 to 5, respectively. 53 and R 54 R each independently represents an alkyl group, an aryl group, or a heterocyclic group. 55 ~R 59 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. 55 and R 57 , R 56 and R 58 or R 57 and R 59 and may be bonded to form a 5- or 6-membered ring. 51 -S- or -CR 511 R 512 - represents Y 51 represents an anionic atom or an anionic atomic group. 511 and R 512 each independently represents a hydrogen atom, an alkyl group, or an aryl group.

[0026] [ka]

[0027] (In the formula, R 61 and R 62 each independently represents a halogen atom or a substituent, and adjacent substituents may be joined together to form a 5- or 6-membered ring. 61 and n 62 R each independently represents an integer of 0 to 4. 63 and R 64 R each independently represents an alkyl group, an aryl group, or a heterocyclic group. 65 ~R 71 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. 65 and R 67 , R 66 and R 68 , R 67 and R 69 , R 68 and R 70 or R 69 and R 71 and may be bonded to form a 5- or 6-membered ring. 61 and X 62 each independently represents -O-, -S-, or -CR 611 R 612 - represents Y 61 represents an anionic atom or an anionic atomic group. 611 and R 612 each independently represents a hydrogen atom or an alkyl group.

[0031] [ka]

[0032] (In the above 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 may further have a substituent. Z represents a structural unit selected from the following formulae (Z-1) and (Z-2).

[0033] [ka]

[0034] * in the above formulas (Z-1) and (Z-2) represents a bonding site, which bonds to O in the above general formula (I). R 121 ~R 124 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, the compound having the structure represented by the general formula (I) above simultaneously has at least one partial structure that satisfies the following condition (i) and at least one partial structure that satisfies the following condition (ii). Condition (i): R 121 ~R 124 are 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 above general formula (I), j represents the number of partial structures that satisfy the above condition (i) and is a number from 1 to 10. k represents the number of partial structures that satisfy the above condition (ii) and is a number from 1 to 10.

[0035] 2. The organic dyes are contained as a combination of at least the dye A1 and the dye C2, or a combination of the dye A4 and the dye C2. 2. The near-infrared absorbing composition according to claim 1, 3. The organic dye is contained as a combination of at least the dye B1 and the dye C2. 2. The near-infrared absorbing composition according to claim 1, 4 Furthermore, the composition contains a compound having a structure represented by the following general formula (D1): The first to second items are characterized by the following: 3 The near-infrared absorbing composition according to any one of claims 1 to 5.

[0036] [ka]

[0037] (In the formula, R 111 and R 113R 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.

[0038] 5 .Items 1 to 5 4 The near infrared absorbing composition according to any one of the preceding items is used. A near-infrared absorbing film characterized by:

[0039] 6 An organic dye-containing layer containing an organic dye; a copper phosphonate-containing layer containing phosphonic acid and copper ions or a copper phosphonate complex formed from phosphonic acid and copper ions; The organic dye is Absorption maximum wavelength in the range of 680 to 740 nm ,vinegar Qualium dye (A) or Is and at least one of an anine dye (B), Absorption maximum wavelength is 760nm or more Rusi Contains anine pigment (C) death, the phosphonic acid is an alkylphosphonic acid, The copper phosphonate-containing layer further contains a compound having a structure represented by the following general formula (I) and copper ions, or a copper complex formed from a compound having a structure represented by the following general formula (I) and copper ions: A near-infrared absorbing film characterized by:

[0040] 7 .No. 5 Section or Article 6 The near-infrared absorbing film according to item 1 is provided. 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): A near-infrared absorbing filter. (1) Average light transmittance within the wavelength range of 450 nm to 600 nm: 85% or more (2) Average light transmittance in the wavelength range of 700 nm or more but less than 1000 nm: less than 2% (3) Average light transmittance within the wavelength range of 1000 nm to 1200 nm: less than 5% (4) A cutoff wavelength in the range of 620 to 660 nm, which shows a light transmittance of 50% at wavelengths of 600 to 700 nm.

[0041] 8 .No. 7 The near-infrared absorbing filter according to item 1. An image sensor for a solid-state imaging device, comprising: [Effects of the Invention]

[0042] The above-mentioned means of the present invention provide a near-infrared absorbing composition that has both transmittance in the visible light region and absorbance in the near-infrared region, and that has excellent heat resistance over time and also excellent light resistance.Furthermore, it is possible to provide a near-infrared absorbing film, a near-infrared absorbing filter, and an image sensor for a solid-state imaging device using the near-infrared absorbing composition.

[0043] The mechanism by which the effects of the present invention are manifested or the mechanism of action is not clear, but is speculated as follows.

[0044] 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, and a cyanine dye (C) having an absorption maximum wavelength of 760 nm or more, and further containing at least a phosphonic acid and a copper ion, or a phosphonate copper complex formed from a phosphonic acid and a copper ion.

[0045] The squarylium dye (A) and cyanine dye (B) used in the present invention have an absorption maximum wavelength in the range of 680 to 740 nm, and therefore have no side absorption in the visible light region, thereby improving transmittance. Furthermore, by using them in combination with a cyanine dye (C) having an absorption maximum wavelength of 760 nm or more, the absorbance in the near-infrared region is improved.

[0046] Although squarylium dyes generally have fluorescent properties due to their molecular structure, the emission of fluorescence can be suppressed by using squarylium dyes and cyanine dyes with specific structures in combination. Both dyes have simple steric structures and little steric hindrance, and therefore have excellent heat resistance.

[0047] Copper ions form a copper complex with phosphonic acid, thereby exhibiting excellent transmittance in the visible light region and excellent absorbency 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 exhibits high thermal stability.

[0048] The average light transmittance in the near-infrared region can be further reduced by using at least one of the following combinations of organic dyes: dye A1 and dye C2, dye A4 and dye C2, or dye B1 and dye C2.

[0049] The squarylium dye used in the near-infrared absorbing composition of the present invention has fluorescence emission properties and there is room for improvement in lightfastness, but it is believed that the inclusion of a copper compound having a structure represented by general formula (D1) makes it possible to quench the fluorescence emitted by the squarylium dye through the heavy atom effect (the effect of the copper atom). In other words, by promoting non-radiative deactivation from the excited state of the squarylium dye to the ground state, deterioration of the squarylium dye itself and surrounding dyes due to photoexcitation can be prevented, and lightfastness can be improved.

[0050] Furthermore, the compound formed from phosphonic acid and copper ions, which is used in the near-infrared absorbing composition of the present invention, is prone to aggregation and has room for improvement in dispersibility. However, by using an alkylphosphonic acid as the phosphonic acid and containing a compound having a structure represented by general formula (I), dispersion stability can be obtained. [Brief explanation of the drawings]

[0051] [Figure 1]Cross-sectional view showing an example of a near-infrared absorbing film having a two-layer structure [Figure 2] A cross-sectional view showing an example of a near-infrared absorbing filter made of a near-infrared absorbing film having a two-layer structure. [Figure 3] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a camera module equipped with a solid-state imaging device having a near-infrared absorbing filter of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0052] The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition containing an organic dye and a metal compound, and 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, and also contains a cyanine dye (C) having an absorption maximum wavelength of 760 nm or more, wherein the squarylium dye (A) is a compound having a structure represented by any of the following general formulas (A1) to (A4), the cyanine dye (B) is a compound having a structure represented by the following general formula (B1), and the cyanine dye (C) is a compound having a structure represented by any of the following general formulas (C1) or (C2), and further contains at least a phosphonic acid and a copper ion, or a phosphonate copper complex formed from a phosphonic acid and a copper ion. This feature is a technical feature common to or corresponding to the following embodiments.

[0053] As an embodiment of the present invention, it is preferable from the viewpoint of exerting the effects of the present invention that the organic dyes are contained as a combination of at least the dye A1 and the dye C2, or a combination of the dye A4 and the dye C2.

[0054] In addition, it is also preferable from the viewpoint of exerting the effect that the organic dyes are contained as a combination of at least the dye B1 and the dye C2.

[0055] Furthermore, it is preferable to contain a compound having a structure represented by the general formula (D1) above, from the viewpoint of suppressing the generation of fluorescence caused by containing a squarylium dye and improving light resistance.

[0056] Furthermore, it is preferable that the phosphonic acid is an alkylphosphonic acid and further contains a copper complex formed from a compound having a structure represented by general formula (I) and copper ions, or a compound having a structure represented by general formula (I) and copper ions, from the viewpoint of dispersion stability of the phosphonic acid and copper ions and the phosphonate copper complex.

[0057] The present invention, its components, and embodiments for carrying out the present invention will be described in detail below. In this application, the symbol "to" is used to mean that the numerical values ​​before and after it are included as lower and upper limits.

[0058] <<Configuration of near-infrared absorbing composition>> 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, and a cyanine dye (C) having an absorption maximum wavelength of 760 nm or more, and further containing at least a phosphonic acid and a copper ion, or a phosphonate copper complex formed from a phosphonic acid and a copper ion.

[0059] The constituent materials of the near-infrared absorbing composition of the present invention will be described in detail below.

[0060] [Organic dye] The amount of the near-infrared absorbing dye added is preferably within a range of 0.01 to 0.3% by mass relative to 100% by mass of the content of the near-infrared absorber constituting the near-infrared absorbing composition. The term "near-infrared absorber" refers to phosphonic acid and copper ions, or a phosphonate copper complex formed from phosphonic acid and copper ions, contained as components constituting the near-infrared absorbing composition.

[0061] When the added amount of the near-infrared absorbing dye is 0.01% by mass or more relative to 100% by mass of the content of the near-infrared absorbent constituting the near-infrared absorbing composition, the near-infrared absorption can be sufficiently increased, and when it is 0.3% by mass or less, the visible light transmittance of the obtained near-infrared absorbing composition is not impaired.

[0062] [Squarylium dye (A)] The near-infrared absorbing composition of the present invention is characterized by containing at least one of a squarylium dye (A) and a cyanine dye (B) having an absorption maximum wavelength within the range of 680 to 740 nm.

[0063] The squarylium dye (A) is a compound having a structure represented by any one of the following general formulas (A1) to (A4), and hereinafter will be simply referred to as "dye A1," "dye A2," "dye A3," and "dye A4."

[0064] The dye A1 is represented by the following general formula (A1).

[0065] [ka]

[0066] In the 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 necessary to form a 5- or 6-membered ring.

[0067] In general formula (A1), the alkyl group represented by R1 may be linear or branched, and examples thereof include methyl, ethyl, propyl, i-propyl, t-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, and pentadecyl, and may further have a substituent.

[0068] In the general formula (A1), examples of the aryl group represented by R1 include phenyl and naphthyl, which may further have a substituent. In general formula (A1), examples of the heterocyclic group represented by R1 include furyl, thienyl, pyridyl, pyridazyl, pyrimidyl, pyrazyl, triazyl, imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, quinazolyl, phthalazyl, pyrrolidyl, imidazolidyl, morpholyl, and oxazolidyl, and each may further have a substituent.

[0069] In the general formula (A1), R1 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms.

[0070] In general formula (A1), examples of the substituents represented by R2 and R3 include alkyl groups (methyl, ethyl, propyl, i-propyl, t-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.).

[0071] Further examples include aryl groups (phenyl, naphthyl, etc.) and heterocyclic groups (furyl, thienyl, pyridyl, pyridazyl, pyrimidyl, pyrazyl, triazyl, imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, quinazolyl, phthalazyl, pyrrolidyl, imidazolidyl, morpholyl, oxazolidyl, etc.).

[0072] Further examples include alkoxy groups (such as methoxy, ethoxy, propoxy, pentyloxy, hexyloxy, octyloxy, and dodecyloxy), cycloalkoxy groups (such as cyclopentyloxy and cyclohexyloxy), and aryloxy groups (such as phenoxy and naphthyloxy).

[0073] Further examples include alkylthio groups (methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodecylthio, etc.), cycloalkylthio groups (cyclopentylthio, cyclohexylthio, etc.), and arylthio groups (phenylthio, naphthylthio, etc.).

[0074] Further examples include alkoxycarbonyl groups (such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, and dodecyloxycarbonyl) and aryloxycarbonyl groups (such as phenyloxycarbonyl and naphthyloxycarbonyl).

[0075] Further examples include sulfamoyl groups (aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl, etc.).

[0076] Further examples include 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.).

[0077] Further examples include 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.).

[0078] Further examples include carbamoyl groups (aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc.).

[0079] Further examples include ureido groups (methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido, naphthylureido, 2-pyridylaminoureido, etc.).

[0080] Further examples include sulfinyl groups (methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, and 2-pyridylsulfinyl groups), alkylsulfonyl groups (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, and dodecylsulfonyl groups), and arylsulfonyl groups (phenylsulfonyl, naphthylsulfonyl, and 2-pyridylsulfonyl groups).

[0081] Further examples include amino groups (amino, ethylamino, dimethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc.).

[0082] Further examples include a cyano group, a nitro group, a hydroxy group, a halogen atom (fluorine, chlorine, bromine, etc.), an alkyl halide (methyl fluoride, trifluoromethyl, chloromethyl, trichloromethyl, perfluoropropyl, etc.), etc. These substituents may further have the above-mentioned substituents.

[0083] Among the above substituents, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, a sulfonylamino group, and a hydroxy group are preferred, and a hydroxy group, an acylamino group, and a sulfonylamino group are more preferred.

[0084] R2 and R3 are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an acylamino group, or a sulfonylamino group, and more preferably a hydrogen atom, an alkyl group, a hydroxy group, an acylamino group, or a sulfonylamino group. It is also preferred that they combine with R1 to form a 5- or 6-membered ring.

[0085] In general formula (A1), R4 represents an alkyl group, alkoxy group, aryl group or heterocyclic group having 1 to 4 carbon atoms, and has the same meaning as described above for the substituent, but is preferably an alkyl group having 1 to 4 carbon atoms.

[0086] In general formula (A1), the atomic groups necessary to form the 5- or 6-membered ring represented by Z1 include combinations such as -CR5R6-, -O-, -C(=O)-, -S-, and -NR7-, with -CR5R6- and -C(=O)- being preferred, and -CR5R6- being more preferred. R5, R6, and R7 are each independently preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, with a hydrogen atom or an alkyl group being more preferred. These may be further substituted with the above-mentioned substituents.

[0087] The dye A2 is represented by the following general formula (A2).

[0088] [ka]

[0089] In the above general formula (A2), R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or -NHCOR 16 or -NHSO2R 17 and cannot be a hydrogen atom at the same time. 13 and R 14 R each independently represents a hydrogen atom, a halogen atom or a substituent. 15 represents a substituent. n1 represents an integer of 0 to 5. R 16 and R 17 each independently represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a heterocyclic group.

[0090] In general formula (A2), R 11 and R 12 is preferably a hydrogen atom, a hydroxy group, or -NHCOR 16 and is preferably not simultaneously a hydrogen atom and capable of hydrogen bonding with the oxygen atom of squaric acid. Most preferably, it is a hydroxy group.

[0091] In general formula (A2), R 13 and R 14 The substituents in R are the same as R and R in the description of the general formula (A1), 13 and R 14 is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or -NHCOR 16 or -NHSO2R 17 More preferred are a hydrogen atom, an alkyl group or an alkoxy group, and most preferred is a hydrogen atom.

[0092] In general formula (A2), R 15represents a substituent, has the same meaning as R2 and R3 in the description of general formula (A1) above, and can be bonded to each other to form a 5- or 6-membered ring. R 15 As the alkyl group, preferably, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an acylamino group, or a sulfonylamino group is mentioned, and more preferably, a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group is mentioned. In terms of the spectral absorption waveform, in order to suppress side absorption in the vicinity of 400 to 450 nm, it is preferable that a hydrogen atom be located at the ortho position relative to the N atom.

[0093] In general formula (A2), R 16 and R 17 is preferably an alkyl group having 1 to 4 carbon atoms, and may further have a substituent. In formula (A2), n1 represents 0 to 5, and preferably 0 to 2.

[0094] The dye A3 is represented by the following general formula (A3).

[0095] [ka]

[0096] In the above general formula (A3), R 21 and R 22 R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. 23 are each independently a hydroxy group, -NHCOR 26 or -NHSO2R 27 Represents R 24 R each independently represents a hydrogen atom or a substituent. 25 each independently represents a substituent. n2 represents an integer of 0 to 4. R 26 and R 27 each independently represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a heterocyclic group.

[0097] In general formula (A3), R 21and R 22 With regard to the above, preferred examples include an alkyl group and an aryl group, which may further have a substituent. In general formula (A3), R 23 is preferably a hydroxy group or -NHCOR 26 and most preferably a hydroxy group.

[0098] In general formula (A3), R 24 and R 25 The substituents represented by are the same as R2 and R3 in the description of the general formula (A1) above, and there is no problem if they can be substituted. 24 and R 25 is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or -NHCOR 26 or -NHSO2R 27 More preferred are a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

[0099] In general formula (A3), R 26 and R 27 is preferably an alkyl group having 1 to 4 carbon atoms, which may further have a substituent. In formula (A3), n2 represents 0 to 5, and preferably 0 to 2.

[0100] The dye A4 is represented by the following general formula (A4).

[0101] [ka]

[0102] In general formula (A4), R 31 and R 32 R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. 33 is a hydroxy group, -NHCOR 38 or -NHSO2R 39 Represents R 34 and R 36R 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. R 37 represents a hydrogen atom, a halogen atom, or an alkyl group. 38 and R 39 each independently represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a heterocyclic group.

[0103] In general formula (A4), R 31 and R 32 is R in the description of the general formula (A3) above. 21 and R 22 The same applies to the preferred range. In general formula (A4), R 33 is R in general formula (A3). 23 and is preferably a hydroxy group or -NHCOR 38 and most preferably a hydroxy group.

[0104] In general formula (A4), R 34 and R 36 are the same as R2 and R3 in the description of the general formula (A1) above, and there is no problem if they are substitutable. 34 and R 36 is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or -NHCOR 38 or -NHSO2R 39 More preferred are a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

[0105] In general formula (A4), R 35 is preferably an alkyl group, which may further have a substituent. R 37 is preferably a hydrogen atom or an alkyl group. R 38 and R 39 is preferably an alkyl group having 1 to 4 carbon atoms, which may further have a substituent. n3 and m3 are preferably integers of 0 to 2.

[0106] [Cyanine dye (B)] The near-infrared absorbing composition of the present invention is characterized by containing at least one of a squarylium dye (A) and a cyanine dye (B), each of which has an absorption maximum wavelength in the range of 680 to 740 nm. The cyanine dye (B) is a compound having a structure represented by general formula (B1) (hereinafter simply referred to as "dye B1").

[0107] The dye B1 is represented by the following general formula (B1).

[0108] [ka]

[0109] In general formula (B1), R 41 R each independently represents an alkyl group, an aryl group, or a heterocyclic group. 42 R each independently represents a halogen atom or a substituent. 43 ~R 45 each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Each n4 independently represents an integer of 0 to 6. Y 41 represents a halogen ion or an anion atomic group.

[0110] In general formula (B1), R 41 is preferably an alkyl group, which may further have a substituent. R 42 is not particularly limited as long as it can be substituted, but has the same meaning as R2 and R3 in the description of the general formula (A1) above, 42 is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or -NHCOR 46 or -NHSO2R 47 More preferred are a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

[0111] In general formula (B1), R 43 ~R45 is preferably a hydrogen atom, a halogen atom or an alkyl group, and R 43 and R 45 They can also be bonded to form a ring. R 46 and R 47 is preferably an alkyl group having 1 to 4 carbon atoms, which may further have a substituent. n4 is preferably an integer of 0 to 2.

[0112] In general formula (B1), Y 41 Examples of anions represented by the formula (I) include halogen ions and halide ions (ions such as fluoride, chloride, bromide, and iodide), enolates (acetylacetonate, hexafluoroacetylacetonate), hydroxy ions, sulfite ions, sulfate ions, alkylsulfonate ions, arylsulfonate ions, nitrate ions, nitrite ions, carbonate ions, perchlorate ions, alkylcarboxylate ions, arylcarboxylate ions, tetraalkylborate, salicinate, benzoate, PF6 - , BF4 - and SbF6 - etc., but halogen ions, PF6 are preferred. - or BF4 - is.

[0113] [Cyanine dye (C)] The near-infrared absorbing composition of the present invention is characterized by containing a cyanine dye (C) having an absorption maximum wavelength of 760 nm or more. The cyanine dye (C) is a compound having a structure represented by either general formula (C1) or (C2) (hereinafter simply referred to as "dye C1" and "dye C2").

[0114] The dye C1 is represented by the following general formula (C1).

[0115] [ka]

[0116] In general formula (C1), R 51 and R 52 each independently represents a halogen atom or a substituent, and adjacent substituents may be joined together to form a 5- or 6-membered ring. 51 and n 52 R represents an integer of 0 to 4 and 0 to 5, respectively. 53 and R 54 R each independently represents an alkyl group, an aryl group, or a heterocyclic group. 55 ~R 59 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. 55 and R 57 , R 56 and R 58 or R 57 and R 59 and may be bonded to form a 5- or 6-membered ring. 51 -S- or -CR 511 R 512 - represents Y 51 represents an anionic atom or an anionic atomic group. 511 and R 512 each independently represents a hydrogen atom, an alkyl group, or an aryl group.

[0117] In general formula (C1), R 51 and R 52 The substituents represented by the formula (A1) are the same as R2 and R3 in the description of the formula (A1) above, and are preferably halogen atoms, alkyl groups, alkoxy groups, aryl groups, 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. Also, they may further have a substituent. n 51 and n 52 is preferably an integer of 0 to 2.

[0118] In general formula (C1), R 53 and R 54 is preferably an alkyl group, and preferably further has a substituent. R 55 ~R 59is preferably a hydrogen atom, an alkyl group or an aryl group, and particularly R 56 and R 58 Preferably, they are bonded to each other via the bond to form a 5- or 6-membered ring, which may further have a substituent.

[0119] In general formula (C1), X 51 is preferably -CR 511 R 512 - represents R 511 and R 512 is preferably a hydrogen atom or an alkyl group. 51 represents Y in general formula (B1). 41 The same applies to the preferred range.

[0120] The dye C2 is represented by the following general formula (C2).

[0121] [ka]

[0122] In general formula (C2), R 61 and R 62 each independently represents a halogen atom or a substituent, and adjacent substituents may be joined together to form a 5- or 6-membered ring. 61 and n 62 R each independently represents an integer of 0 to 4. 63 and R 64 R each independently represents an alkyl group, an aryl group, or a heterocyclic group. 65 ~R 71 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. 65 and R 67 , R 66 and R 68 , R 67 and R 69 , R 68 and R 70 or R 69 and R 71 and may be bonded to form a 5- or 6-membered ring. 61 and X 62each independently represents -O-, -S-, or -CR 611 R 612 - represents Y 61 represents an anionic atom or an anionic atomic group. 611 and R 612 each independently represents a hydrogen atom or an alkyl group.

[0123] In general formula (C2), R 61 and R 62 The substituents represented by the formula (A1) are the same as R2 and R3 in the description of the general formula (A1) above, and are preferably halogen atoms, alkyl groups, alkoxy groups, aryl groups, etc., and may further have a substituent. Adjacent substituents may be bonded to form a 5- or 6-membered ring, preferably a phenyl group. They may further have a substituent. n 61 and n 62 is preferably an integer of 0 to 2.

[0124] R 63 and R 64 is preferably an alkyl group, and preferably further has a substituent. R 65 ~R 71 is preferably a hydrogen atom, an alkyl group or an aryl group, and particularly R 66 and R 68 , R 67 and R 69 , or R 66 and R 68 and R 70 Preferably, they are bonded to each other via the bond to form one or more 5- or 6-membered rings, which may further have a substituent.

[0125] In general formula (C2), X 61 and X 62 -S- or -CR 611 R 612 - is preferred, and -CR 611 R 612 It is even more preferable that: R 611 and R 612is preferably a hydrogen atom or an alkyl group. Y 61 represents Y in the description of the general formula (B1) above. 41 The same applies to the preferred range.

[0126] The dyes of general formulae (A1) to (A4), (B1), (C1), and (C2) are necessary to form a spectral absorption band mainly within the range of 400 to 800 nm in the spectral absorption spectrum. By containing at least one of squarylium dyes (A1) to (A4) or cyanine dye (B1) having an absorption maximum wavelength within the range of 680 to 740 nm, and also containing cyanine dye (C1) or (C2) having an absorption maximum wavelength of 760 nm or more, it becomes possible to form a preferable spectral absorption waveform.

[0127] The combination of dyes A1 and C2, A4 and C2, or B1 and C2 is preferable because it can reduce the transmittance in the near-infrared region while suppressing a decrease in the transmittance in the visible region. Furthermore, by mixing multiple dyes among the above combinations, it is possible to smooth the transmission spectrum waveform.

[0128] Representative examples of the dyes of general formulae (A1) to (A4), (B1), (C1), and (C2) and their maximum absorption wavelengths in a methanol solvent are shown below, but the present invention is not limited thereto.

[0129] The maximum absorption wavelength is determined by the solubility of each dye, but is approximately 1 x 10 -5 A 200 mol / L methanol solution was prepared, and the maximum absorption wavelength was determined by measuring wavelengths of 300 to 1200 nm using a spectrophotometer V-780 manufactured by JASCO Corporation.

[0130] <Specific examples of dye A1> The following (A1-1) to (A1-20) are typical examples of the dye A1.

[0131] [ka]

[0132] [ka]

[0133] <Specific examples of dye A2> The following (A2-1) to (A2-14) are typical examples of the dye A2.

[0134] [ka]

[0135] [ka]

[0136] <Example of dye A3> The following (A3-1) to (A3-18) are typical examples of the dye A3.

[0137] [ka]

[0138] [ka]

[0139] <Example of dye A4> The following (A4-1) to (A4-20) are typical examples of the dye A4.

[0140] [ka]

[0141] [ka]

[0142] <Specific examples of dye B1> The following (B1-1) to (B1-14) are typical examples of the dye B1.

[0143] [ka]

[0144] [ka]

[0145] <Specific example of dye C1> The following (C1-1) to (C1-10) are typical examples of the dye C1.

[0146] [ka]

[0147] <Specific examples of dye C2> The following (C2-1) to (C2-30) are typical examples of the dye C2. However, TsO - represents a p-toluenesulfonate ion (also called a tosylate ion or a tosylate anion).

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] Next, representative methods for synthesizing the dyes of general formulae A1 to A4, B1, and C1 and C2 will be described.

[0152] Squarylium dyes can be easily synthesized with reference to the following literature: JP 2004-319309 A, JP 2008-209462 A, JP 2009-36811 A, JP 2009-180875 A, and JP 2017-197437 A

[0153] Cyanine dyes can be easily synthesized with reference to the following literature. 1) F.M. Harmer, "Heterocyclic Compounds Cyanine Dyes and Related Compounds," John Wiley & Sons, New York, London, 1964

[0154] 2) D.M. Sturmer, "Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry," Chapter 18, Section 14, pp. 482-515, John Wiley & Sons, New York, London, 1977

[0155] 3) "Rodd's Chemistry of Carbon Compounds," 2nd Ed., vol. IV, part B, Chapter 15, pp. 369-422, Elsevier Science Publishing Company Inc., New York, 1977.

[0156] 4) JP 6-313939 A, JP 5-88293 A, JP 2006-16564 A, JP 2000-321704 A, JP 2006-63171 A, and JP 2018-177830 A

[0157] Examples of synthesis of the dyes of general formulae A1 to A4, B1, C1 and C2 are shown below.

[0158] <Synthesis Example 1> (Synthesis of A1-1)

[0159] [ka]

[0160] To 0.6 g of intermediate 1 and 0.12 g of squaric acid, 15 mL of toluene and 15 mL of 1-butanol were added, and the mixture was heated under reflux for 5 hours while dehydrating using an esterification tube. After cooling, the solvent was removed under reduced pressure, and toluene was added for further concentration. The residue was dissolved in toluene, and 0.47 g of the target product was isolated by column chromatography (developing solvent: a mixture of ethyl acetate and n-heptane). Identification by MASS, 1H-NMR, and IR spectroscopy confirmed that it was the target product (A1-1).

[0161] <Synthesis Example 2> (Synthesis of A2-2)

[0162] [ka]

[0163] To 1.50 g of intermediate 2 and 0.22 g of squaric acid, 20 mL of toluene and 20 mL of 1-butanol were added, and the mixture was heated under reflux for 4 hours while dehydrating with an esterification tube attached. After cooling, the solvent was removed under reduced pressure, and toluene was added for further concentration. The residue was dissolved in toluene, and 1.26 g of the target product was isolated by column chromatography (developing solvent: a mixture of ethyl acetate and n-heptane). Identification by MASS, 1H-NMR, and IR spectroscopy confirmed that it was the target product (A2-2).

[0164] <Synthesis Example 3> (Synthesis of A3-1)

[0165] [ka]

[0166] To 1.15 g of intermediate 3 and 0.22 g of squaric acid, 20 mL of toluene and 20 mL of 1-butanol were added, and the mixture was heated under reflux for 8 hours while dehydrating with an esterification tube attached. After cooling, the solvent was removed under reduced pressure, and toluene was added for further concentration. The residue was dissolved in toluene, and 0.78 g of the target product was isolated by column chromatography (developing solvent: a mixture of ethyl acetate and n-heptane). Identification by MASS, 1H-NMR, and IR spectroscopy confirmed that it was the target product (A3-1).

[0167] <Synthesis Example 4> (Synthesis of A4-1)

[0168] [ka]

[0169] To 1.35 g of intermediate 4 and 1.06 g of intermediate 5, 20 mL of toluene and 20 mL of 1-butanol were added, and the mixture was heated under reflux for 3 hours while dehydrating with an esterification tube attached. After cooling, the solvent was removed under reduced pressure, and toluene was added for further concentration. The residue was dissolved in toluene, and 1.22 g of the target product was isolated by column chromatography (developing solvent: a mixture of ethyl acetate and n-heptane). Identification by MASS, 1H-NMR, and IR spectroscopy confirmed that it was the target product (A4-1).

[0170] <Synthesis Example 5> (Synthesis of B1-3)

[0171] [ka]

[0172] 1.60 g of intermediate 6 and 0.97 g of intermediate 7 were added to 40 mL of methanol and 0.36 g of triethylamine, and the mixture was heated under reflux for 6 hours. After cooling, the precipitated crystals were filtered and washed with methanol to isolate 0.76 g of the target product. Identification by MASS, 1H-NMR, and IR spectroscopy confirmed that this was the target product (B1-3).

[0173] <Synthesis Example 6> (Synthesis of C1-7)

[0174] [ka]

[0175] To 1.26 g of intermediate 8 and 0.65 g of intermediate 9, 40 mL of methanol and 0.22 g of triethylamine were added and the mixture was heated under reflux for 6 hours. After cooling, the solvent was removed under reduced pressure, the mixture was extracted with ethyl acetate, neutralized, washed with water, and the ethyl acetate was concentrated. The residue was dissolved in methylene chloride and subjected to column chromatography (eluent: a mixture of ethyl acetate and methanol) to isolate 0.83 g of the target product. Identification by MASS, 1H-NMR, and IR spectroscopy confirmed that it was the target product (C1-7).

[0176] <Synthesis Example 7> (Synthesis of C2-18)

[0177] [ka]

[0178] 4.09 g of intermediate 10 was dissolved in 2.5 mL of meta-cresol, and 2.0 g of intermediate 11 was added. The mixture was heated and stirred in a 120°C oil bath for 10 minutes. Next, 50 mL of ethanol and 0.5 g of triethylamine were added, and the mixture was heated and stirred in a 70°C water bath for 30 minutes. 0.5 g of sodium tetrafluoride was added to the reaction solution, and the mixture was stirred and cooled to precipitate. The crystals were collected by filtration and recrystallized from a mixed solvent of fluorinated alcohol and methanol to isolate 0.58 g of the target product. Identification by MASS, 1H-NMR, and IR spectroscopy confirmed that it was the target product (C2-18).

[0179] [Metal compounds] [Phosphonic acid copper complex] The near-infrared absorbing composition of the present invention is characterized by containing phosphonic acid and copper ions, or a phosphonate copper complex formed from phosphonic acid and copper ions. By containing the phosphonate copper complex, it is possible to reduce the light transmittance in the region from around 800 nm to longer wavelengths.

[0180] Phosphonic acid has a structure represented by the following general formula (H1).

[0181] [ka]

[0182] In the above general formula (H1), R 131 R represents a branched, linear or cyclic alkyl group, alkenyl group, alkynyl group, aryl group or allyl group having 1 to 30 carbon atoms, and at least one hydrogen atom may or may not be substituted with a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde group, a carboxy group, a hydroxy group or a group having an aromatic ring. 131 is preferably an alkyl group having 1 to 20 carbon atoms in terms of good resistance to humidity and heat and near-infrared absorption. 131 However, an alkyl group having 1 to 4 carbon atoms is more preferred in that it can achieve both near-infrared absorption and visible light transmittance.

[0183] Examples of the phosphonic acid compound having a structure represented by 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, benzenephosphonic acid, and 4-methoxyphenylphosphonic acid, some examples of which are exemplified as the following compounds (H-1) to (H-8).

[0184] [ka]

[0185] In the present invention, the phosphonic acid constituting the phosphonate copper complex is preferably at least one alkylphosphonic acid selected from the following group of phosphonic acids.

[0186] 1: Methylphosphonic acid 2: Ethylphosphonic acid 3: Propylphosphonic acid 4: Butylphosphonic acid 5: Pentylphosphonic acid 6: Hexylphosphonic acid 7: Octylphosphonic acid 8: 2-Ethylhexylphosphonic acid 9: 2-Chloroethylphosphonic acid 10: 3-Bromopropylphosphonic acid 11: 3-Methoxybutylphosphonic acid 12:1,1-dimethylpropylphosphonic acid 13: 1,1-Dimethylethylphosphonic acid 14: 1-Methylpropylphosphonic acid

[0187] The copper phosphonate complex applicable to the present invention will be described below. The copper phosphonate complex has a structure represented by the following general formula (H2).

[0188] [ka]

[0189] In general formula (H2), R 132 represents an alkyl group, a phenyl group, or a benzyl group.

[0190] The copper salt used to form the phosphonic acid copper complex having the structure represented by general formula (H2) is a copper salt capable of supplying divalent copper ions. Examples include 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, and anhydrous copper citrate, as well as hydrates or hydrates of the copper salts of these organic acids; copper salts of inorganic acids such as copper oxide, copper chloride, copper sulfate, copper nitrate, copper phosphate, basic copper sulfate, and basic copper carbonate, as well as hydrates or hydrates of the copper salts of these inorganic acids; and copper hydroxide.

[0191] In the present invention, the phosphonic acid constituting the phosphonate copper complex is preferably an alkylphosphonic acid, and examples thereof include an ethylphosphonic acid copper complex, a propylphosphonic acid copper complex, a butylphosphonic acid copper complex, a pentylphosphonic acid copper complex, a hexylphosphonic acid copper complex, an octylphosphonic acid copper complex, a 2-ethylhexylphosphonic acid copper complex, a 2-chloroethylphosphonic acid copper complex, a 3-bromopropylphosphonic acid copper complex, a 3-methoxybutylphosphonic acid copper complex, a 1,1-dimethylpropylphosphonic acid copper complex, a 1,1-dimethylethylphosphonic acid copper complex, and a 1-methylpropylphosphonic acid copper complex.

[0192] In the near-infrared absorbing composition of the present invention, it is preferable that the copper complex fine particles are uniformly dispersed when a near-infrared absorbing film described later is formed, from the viewpoint of spectroscopic characteristics, and for this purpose, it is preferable that the particle size of the copper complex fine particles in the near-infrared absorbing dispersion liquid is small.

[0193] 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.

[0194] The average particle size of the copper complex fine particles in the near-infrared absorbing dispersion can be measured by dynamic light scattering using a zeta potential / particle size measuring system ELSZ-1000ZS manufactured by Otsuka Electronics Co., Ltd.

[0195] [Compound having a structure represented by general formula (I)] In the near-infrared absorbing composition of the present invention, it is preferable, from the viewpoint of improving dispersion stability, that the phosphonic acid is an alkylphosphonic acid and further contains a compound having a structure represented by the following general formula (I) and copper ions, or a copper complex formed from a compound having a structure represented by the following general formula (I) and copper ions:

[0196] [ka]

[0197] The compound having the structure represented by general formula (I) may react with copper ions to form a copper complex.

[0198] In 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 may further have a substituent, and there is no particular limitation on the substituent as long as it does not impair the effects of the present invention.

[0199] R 125The alkyl group having 1 to 20 carbon atoms represented by the formula (I) may be linear 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 dispersibility and moisture resistance of the metal complex, an alkyl group having 6 to 16 carbon atoms is preferred.

[0200] Also, R 125 Examples of the aryl group having 6 to 20 carbon atoms represented by the formula (I) include a phenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, and a biphenylyl group, and preferred are a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a biphenylyl group, and a fluorenonyl group. Each aryl group may further have a substituent, which is not particularly limited as long as it does not impair the effects of the present invention.

[0201] R 125 Examples of the substituent that may be substituted include alkyl groups (e.g., methyl, ethyl, trifluoromethyl, isopropyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, etc.), halogen atoms (e.g., fluorine, 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.), and heteroaryl groups (e.g., pyridyl, carbazolyl, etc.). Examples of the fused ring include, but are not limited to, 9,9′-dimethylfluorene, carbazole, and dibenzofuran.

[0202] In general formula (I), R 121 ~R 124represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, with a methyl group being particularly preferred from the viewpoint of dispersibility of the metal complex.

[0203] Also, R 121 ~R 124 The compound is characterized in that it simultaneously has, within its molecular structure, at least one partial structure that satisfies the following condition (i) and at least one partial structure that satisfies the following condition (ii):

[0204] Condition (i): R 121 ~R 124 are all hydrogen atoms. Condition (ii):R 121 ~R 124 At least one of them is an alkyl group having 1 to 4 carbon atoms.

[0205] The partial structure that satisfies condition (ii) is R 121 ~R 124 In the case where at least one of the groups is an alkyl group having 1 to 4 carbon atoms and two more groups are the same alkyl group, structures in which three groups are the same alkyl group and all four groups are the same alkyl group are included. From the viewpoint of dispersibility of the metal complex, it is preferable that only one of the groups is an alkyl group having 1 to 4 carbon atoms.

[0206] The substructure that satisfies condition (i) is R 121 ~R 124 is an ethylene oxide structure in which all atoms are hydrogen atoms, which has a high ability to form complexes with metals and contributes to improving dispersibility. On the other hand, condition (ii) is an alkyl-substituted ethylene oxide structure, which has a large number of components and contributes to improving dispersion stability when water is mixed in due to the entropy effect.

[0207] In the general formula (I), j is R defined in the above condition (i). 121 ~R 124 represents the number of partial structures in which all are hydrogen atoms, and the number is in the range of 1 to 10, preferably in the range of 1 to 3. k is the number of partial structures in which all are hydrogen atoms, and the number is in the range of 1 to 3. 121~R 124 represents the number of partial structures in which at least one of the groups is an alkyl group having 1 to 4 carbon atoms, and the number is in the range of 1 to 10, and preferably in the range of 1 to 3.

[0208] j and k represent the average number of moles of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure added, respectively.

[0209] In this application, the term "ethylene oxide structure" refers to the repeating unit structure of polyethylene oxide, i.e., a structure in which ethylene oxide, a three-membered cyclic ether, is ring-opened. Also, the term "propylene oxide structure" refers to the repeating unit structure of polypropylene oxide, i.e., a structure in which propylene oxide, a three-membered cyclic ether, is ring-opened.

[0210] In the above general formula (I), Z represents a structural unit selected from the following formulae (Z-1) and (Z-2).

[0211] [ka]

[0212] * in the above formulas (Z-1) and (Z-2) represents a bonding site, which bonds to O in the above general formula (I).

[0213] In the above general formula (I), when Z is formula (Z-1), the compound is a diester, and when Z is formula (Z-2), the compound is a monoester. From the viewpoint of dispersibility of the metal complex, the diester and the monoester are preferably a mixture, and the molar ratio of the monoester to the diester is preferably within the range of 20 to 95%.

[0214] Compounds having a structure represented by the above general formula (I) can be synthesized by referring to known methods described in, for example, JP-A Nos. 2005-255608, 2015-000396, 2015-000970, 2015-178072, 2015-178073, and Japanese Patent No. 4422866.

[0215] It has been confirmed that the content of phosphorus atoms in the near-infrared absorbing film is preferably 1.5 or less per mole of copper ions, and furthermore, that a molar ratio of 0.3 to 1.3, i.e., a molar ratio of phosphorus atoms to copper ions (hereinafter referred to as "P / Cu") of 0.3 to 1.3, is very suitable from the viewpoints of moisture resistance of the near-infrared absorbing film and dispersibility of copper ions in the near-infrared absorbing layer.

[0216] If the molar ratio of P / Cu is less than 0.3, the copper ions coordinated to the compound represented by general formula (i) will be excessive, and the copper ions will tend to be less uniformly dispersed in the near-infrared absorbing film. On the other hand, if the molar ratio of P / Cu exceeds 1.3, devitrification will tend to occur more easily when the thickness of the near-infrared absorbing film is reduced to increase the copper ion content, and this tendency is particularly pronounced in high-temperature and high-humidity environments. Furthermore, a molar ratio of P / Cu of 0.8 to 1.3 is more preferable. If this molar ratio is 0.8 or more, the dispersibility of copper ions in the resin can be reliably and sufficiently improved.

[0217] An example of the structure of a typical example compound will be described below.

[0218] <Example Compound 1> Exemplary Compound 1 is as shown in Table 1 below: R 125 : methyl group, Condition (i): R 121 ~R 124 =H Condition (ii):R 121 =H, R 122 = methyl group, R 123 = methyl group, R 124 =H Z: Z-1, Z-2 j:1.0 k:8.0 However, the compound is represented by the structure of Exemplary Compound (1-1) in which Z is Z-2, and the structure of Exemplary Compound (1-2) in which Z is Z-1.

[0219] [ka]

[0220] In the case of Exemplified Compound 1, the monoester ratio is 55%, and the Exemplified Compound (1-1) is contained at 55% and the Exemplified Compound (1-2) is contained at 45%.

[0221] 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 respective 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.

[0222] [ka]

[0223] 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 respective structures are randomly arranged are also included in the compounds defined in the present invention.

[0224] <Example Compound 2> Exemplary Compound 2 is as shown in Table 1 below: R 125 : methyl group, Condition (i): R 121 ~R 124 =H Condition (ii):R 121 =H, R 122 =H, R 123 =H, R 124 = methyl group Z: Z-1, Z-2 j:2.0 k:3.0 However, the compound is represented by the structure of Exemplary Compound (2-1) in which Z is Z-2, and the structure of Exemplary Compound (2-2) in which Z is Z-1.

[0225] [ka]

[0226] In the case of Exemplified Compound 2, the monoester ratio is 50%, and the above Exemplified Compound (2-1) and Exemplified Compound (2-2) are contained in equal molar amounts.

[0227] As in the above-mentioned exemplary compound 1, in exemplary compound 2, the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure can be arbitrarily changed depending on the synthesis method, and the following exemplary compounds (2-3) and (2-4) are also included in exemplary compound 2.

[0228] [ka]

[0229] 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 respective structures are randomly arranged are also included in the compounds defined in the present invention.

[0230] Next, specific examples of compounds having a structure represented by general formula (I) are listed in the following Tables I to IV, but the present invention is not limited to these exemplary compounds.

[0231] [Table 1]

[0232] [Table 2]

[0233] [Table 3]

[0234] [Table 4]

[0235] The compound having the structure represented by general formula (I) according to the present invention can be synthesized by referring to known methods described in, for example, JP-A Nos. 2005-255608, 2015-000396, 2015-000970, 2015-178072, 2015-178073, and Japanese Patent No. 4422866.

[0236] <Synthesis of example compounds> Next, representative examples of synthesis of compounds having a structure represented by general formula (I) according to the present invention will be given, but the present invention is not limited to these synthesis methods.

[0237] <Synthesis of Exemplary Compound 49> 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 at a pressure of 147 kPa and a temperature of 130°C, followed by the addition of 88 g (2.0 mol) of ethylene oxide.

[0238] Next, after confirming that no n-octanol remains, the adduct is placed in a reactor, and the toluene solution is reacted with 47 g (0.33 mol) of phosphoric anhydride at 80° C. for 5 hours. After that, the adduct is washed with distilled water, and the solvent is distilled off under reduced pressure to obtain the following exemplary compound 49 (R 125 = octyl group, 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 group, j: 2.0, k: 2.0, Z: phosphate monoester (Z-2) / phosphate diester (Z-1)) was obtained.

[0239] [ka]

[0240] <Synthesis of Exemplary Compound 56> 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 at a pressure of 147 kPa and a temperature of 130°C, followed by the addition of 110 g (2.5 mol) of ethylene oxide.

[0241] Next, after confirming that no 2-ethylhexanol remains, the adduct is placed in a reactor, and the toluene solution is reacted with 47 g (0.33 mol) of phosphoric anhydride at 80° C. for 5 hours. After that, the adduct is washed with distilled water, and the solvent is distilled off under reduced pressure to obtain the following exemplary compound 56 (R 125 = 2-ethylhexyl group, 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 group, j: 2.5, k: 2.5, Z: phosphate monoester (Z-2) / phosphate diester (Z-1)).

[0242] [ka]

[0243] [Compound having a structure represented by general formula (D1)] 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.

[0244] [ka]

[0245] In general formula (D1), R 111 and R 113 R 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.

[0246] Generally, squarylium dyes have fluorescent properties, and light emission (radiation) during transition from the singlet excited state squarylium dye to the ground state can lead to deterioration of the dye due to photoexcitation of other surrounding squarylium dyes or cyanine dyes, or due to reactions of the squarylium dye itself in the singlet excited state with surrounding compounds such as oxygen or molecular cleavage reactions.

[0247] Therefore, there is room for improving lightfastness by quenching the emitted fluorescence. That is, it is believed that the inclusion of a copper compound having a structure represented by general formula (D1) can quench the fluorescence emitted by the squarylium dye through the heavy atom effect (the effect of the copper atom). That is, by promoting non-radiative deactivation from the excited squarylium dye to the ground state, deterioration of the squarylium dye itself and surrounding dyes due to photoexcitation can be prevented, thereby improving lightfastness.

[0248] Furthermore, since scattered light is generated during fluorescence emission, there is a possibility that the image quality of a camera equipped with a filter may be degraded. Therefore, since the squarylium dye used in the present invention also has fluorescence emission properties, the generation of scattered light can be suppressed by quenching the fluorescence, thereby improving the image quality of the camera.

[0249] In the present invention, the organic dye and the copper compound used are dissolved and mixed in a solution, whereby the organic dye interacts with copper ions, thereby quenching the fluorescence. The copper compound is preferably a compound having a structure represented by general formula (D1).

[0250] In general formula (D1), R 111 and R 112 represents an electron-withdrawing group having a Hammett's substituent constant (σp value) of 0.1 or more and 0.9 or less, and R 113 represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an amino group, which may have a substituent.

[0251] R 111 and R 112 Here, the following describes substituents having a σp value of 0.1 or more and 0.9 or less, as represented by the following formula: As the value of Hammett's substituent constant σp, it is preferable to use the values ​​described in the reports by Hansch, C. Leo et al. (for example, J. Med. Chem. 16, 1207 (1973); ibid. 20, 304 (1977)).

[0252] For example, examples of substituents or atoms with a σp value of 0.10 or more include a chlorine atom, a bromine atom, an iodine atom, a carboxy group, a cyano group, a nitro group, a halogen-substituted alkyl group (e.g., trichloromethyl, trifluoromethyl, chloromethyl, trifluoromethylthiomethyl, trifluoromethanesulfonylmethyl, perfluorobutyl), an aliphatic, aromatic, or heterocyclic acyl group (e.g., formyl, acetyl, benzoyl), an aliphatic, aromatic, or heterocyclic sulfonyl group (e.g., trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl), a carbamoyl group (e.g., carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chlorophenylcarbamoyl), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), a substituted aromatic group (e.g., pentachlorophenyl, pentafluorophenyl), phenyl, 2,4-dimethanesulfonylphenyl, 2-trifluoromethylphenyl), heterocyclic residues (e.g., 2-benzoxazolyl, 2-benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), azo groups (e.g., phenylazo), ditrifluoromethylamino groups, trifluoromethoxy groups, alkylsulfonyloxy groups (e.g., methanesulfonyloxy), acyloxy groups (e.g., acetyloxy, benzoyloxy), arylsulfonyloxy groups (e.g., benzenesulfonyloxy), phosphoryl groups (e.g., dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl groups (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), and the like.

[0253] In addition, examples of substituents with a σp value of 0.35 or more include a cyano group, a nitro group, a carboxy group, a fluorine-substituted alkyl group (e.g., trifluoromethyl, perfluorobutyl), an aliphatic, aromatic, or heterocyclic acyl group (e.g., acetyl, benzoyl, formyl), an aliphatic, aromatic, or heterocyclic sulfonyl group (e.g., trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl), a carbamoyl group (e.g., carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chlorophenylcarbamoyl), moyl), alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), fluorine- or sulfonyl-substituted aromatic groups (e.g., pentafluorophenyl, 2,4-dimethanesulfonylphenyl), heterocyclic residues (e.g., 1-tetrazolyl), azo groups (e.g., phenylazo), alkylsulfonyloxy groups (e.g., methanesulfonyloxy), phosphoryl groups (e.g., dimethoxyphosphoryl, diphenylphosphoryl), sulfamoyl groups, and the like.

[0254] 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 (for example, trifluoromethanesulfonyl, difluoromethanesulfonyl, methanesulfonyl, or benzenesulfonyl).

[0255] Preferably, R 111 and R 112 Examples of R include a halogenated alkyl group (particularly a fluorine-substituted alkyl group), a carbonyl group, a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, and an alkylsulfonyloxy group. 113 Preferred examples of the substituent include an alkyl group, an alkoxy group, and an amino group, and more preferred are an alkyl group or an alkoxy group.

[0256] Specific examples of general formula (D1) are shown below, but the invention is not limited to these.

[0257] [ka]

[0258] [ka]

[0259] [ka]

[0260] [ka]

[0261] [ka]

[0262] [ka]

[0263] [ka]

[0264] 〔solvent〕 The solvents applicable to the preparation of the near-infrared absorbing composition of the present invention will be described below.

[0265] The solvent that can be used in the near-infrared absorbing composition of the present invention is not particularly limited, but examples thereof include hydrocarbon solvents, and more preferred examples thereof include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and halogenated solvents.

[0266] Examples of aliphatic hydrocarbon solvents include acyclic aliphatic hydrocarbon solvents such as hexane and heptane, cyclic aliphatic hydrocarbon solvents such as cyclohexane, alcohol solvents such as methanol, ethanol, n-propanol, and ethylene glycol, ketone solvents such as acetone and methyl ethyl ketone, and ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol monomethyl ether. Examples of aromatic hydrocarbon solvents include toluene, xylene, mesitylene, cyclohexylbenzene, and isopropyl biphenyl. Examples of halogen-based solvents include methylene chloride, 1,1,2-trichloroethane, and chloroform. Other examples include anisole, 2-ethylhexane, sec-butyl ether, 2-pentanol, 2-methyltetrahydrofuran, 2-propylene glycol monomethyl ether, 2,3-dimethyl-1,4-dioxane, sec-butylbenzene, and 2-methylcyclohexylbenzene. Among these, toluene and tetrahydrofuran are preferred in terms of boiling point and solubility.

[0267] [Solid content concentration] Furthermore, the ratio of the solid content to the near-infrared absorbing composition is preferably within a range of 5 to 30% by mass, since this provides an appropriate concentration of solids (e.g., copper complex fine particles), suppresses particle aggregation during storage, and provides better stability over time (dispersion stability and near-infrared absorbing properties of the copper complex fine particles). A range of 10 to 20% by mass is more preferable.

[0268] [Ultraviolet absorber] The near-infrared absorbing composition of the present invention preferably further contains an ultraviolet absorber from the viewpoints of spectral characteristics and light resistance.

[0269] The ultraviolet absorber is not particularly limited, but examples thereof include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylic acid ester-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers.

[0270] Examples of benzotriazole-based ultraviolet absorbers include 5-chloro-2-(3,5-di-sec-butyl-2-hydroxyphenyl)-2H-benzotriazole, (2-2H-benzotriazol-2-yl)-6-(linear and side chain dodecyl)-4-methylphenol, etc. Benzotriazole-based ultraviolet absorbers are also available as commercially available products, such as the TINUVIN (registered trademark) series, including TINUVIN 109, TINUVIN 171, TINUVIN 234, TINUVIN 326, TINUVIN 327, TINUVIN 328, and TINUVIN 928, all of which are commercially available products manufactured by BASF.

[0271] Examples of benzophenone-based ultraviolet absorbers 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).

[0272] Examples of salicylate-based ultraviolet absorbers include phenyl salicylate and p-tert-butyl salicylate.

[0273] Examples of cyanoacrylate ultraviolet absorbers include 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, and ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl)-acrylate.

[0274] Examples of triazine-based ultraviolet absorbers include 2-(2'-hydroxy-4'-hexyloxyphenyl)-4,6-diphenyltriazine, etc. Examples of commercially available triazine-based ultraviolet absorbers include TINUVIN (registered trademark) 477 (manufactured by BASF).

[0275] 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 content of the near-infrared absorber constituting the near-infrared absorbing composition. The term "near infrared absorbing agent" refers to a phosphonic acid and copper ions contained as components constituting the near infrared absorbing composition, or a phosphonic acid copper complex formed from phosphonic acid and copper ions.

[0276] When the amount of the ultraviolet absorber added is 0.1% by mass or more relative to 100% by mass of the near-infrared absorber content, the light resistance can be sufficiently increased, and when it is 5.0% by mass or less, the visible light transmittance of the obtained near-infrared absorbing composition is not impaired.

[0277] <<Method for producing near-infrared absorbing composition>> An example of a method for producing the near-infrared absorbing composition of the present invention will be described below, but the production method is not limited to the method exemplified here.

[0278] A copper salt such as copper acetate is added to a predetermined solvent such as tetrahydrofuran (THF) and dissolved by stirring or ultrasonic treatment, and a phosphate ester is then added to prepare Solution A. A phosphonic acid such as ethylphosphonic acid is added to a predetermined solvent such as THF and dissolved by stirring to prepare Solution B. A mixed solution of Solutions A and B is stirred at room temperature for over ten hours to prepare Solution C. A predetermined solvent such as toluene is then added to Solution C, and the solvent is volatilized by heat treatment at a predetermined temperature to prepare Solution D. An organic dye is added to a predetermined solvent such as diacetone alcohol and dissolved by stirring, and the resulting solution is added to Solution D to prepare Solution E. Solution E is then heated at a predetermined temperature to volatilize the solvent, thereby adjusting the solids concentration, and the near-infrared absorbing composition of the present invention can be obtained.

[0279] Near-infrared absorbing film One of the features of the present invention is that a near-infrared absorbing film is formed using the various organic dyes and metal compounds or the near-infrared absorbing composition of the present invention.

[0280] The near-infrared absorbing film of the present invention may have a single-layer structure containing an organic dye and a metal compound in the same layer, or a two-layer structure having an organic dye-containing layer 3 and a copper phosphonate-containing layer 2 as shown in FIG. 1 , and is not limited to the structures exemplified here.

[0281] Any of the various organic dyes and metal compounds, and the near-infrared absorbing composition of the present invention can be made into a liquid wet coating solution. Therefore, a near-infrared absorbing film can be easily produced by a simple process of forming a film by, for example, spin coating.

[0282] A method for forming the near-infrared absorbing film will be described below, but the method is not limited to the method exemplified here.

[0283] [Single layer configuration] The near-infrared absorbing film of the present invention can be formed in a single layer configuration containing an organic dye and a metal compound in the same layer.

[0284] The near-infrared absorbing film having a single layer configuration is formed by applying a coating liquid prepared by adding a matrix resin to the near-infrared absorbing composition according to the present invention onto a substrate by spin coating or a wet coating method using a dispenser, and then curing the coating film by subjecting the coating film to a predetermined heat treatment.

[0285] The matrix resin used to form the near-infrared absorbing film is a resin that is transparent to visible light and near-infrared light and capable of dispersing fine particles of a metal complex or a copper phosphonate complex. Metal complexes and copper phosphonate complexes are substances with relatively low polarity and disperse well in hydrophobic materials. Therefore, a resin having an acrylic group, an epoxy group, or a phenyl group can be used as the matrix resin for forming the near-infrared absorbing film.

[0286] Among these, it is particularly preferable to use a resin having a phenyl group as the matrix resin of the near-infrared absorbing film. In this case, the matrix resin of the near-infrared absorbing film has high heat resistance. Furthermore, polysiloxane silicone resins are resistant to thermal decomposition, have high transparency to visible light and near-infrared light, and have high heat resistance, making them advantageous materials for image sensors for solid-state imaging devices. For this reason, it is also preferable to use polysiloxane as the matrix resin of the near-infrared absorbing film.

[0287] Polysiloxanes that can be used as the matrix resin of 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.

[0288] (Other additives) Other additives may be applied to the near-infrared absorbing film of the present invention within a range that does not impair the intended effects of the present invention. Examples of such additives include sensitizers, crosslinking agents, curing accelerators, fillers, thermal curing accelerators, thermal polymerization inhibitors, and plasticizers. Furthermore, an adhesion accelerator for the substrate surface and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension adjusters, and chain transfer agents) may also be used in combination.

[0289] By appropriately incorporating these components, it is possible to adjust the stability, film properties, and other properties of the near-infrared absorbing film to the desired level.

[0290] For these components, reference can be made to the contents described in, for example, paragraphs 0183 to 0260 of JP 2012-003225 A, paragraphs 0101 to 0102 of JP 2008-250074 A, paragraphs 0103 to 0104 of JP 2008-250074 A, paragraphs 0107 to 0109 of JP 2008-250074 A, etc.

[0291] [Two-layer configuration] The near-infrared absorbing film 1 of the present invention can also be formed in a two-layer structure including an organic dye-containing layer 3 and a copper phosphonate-containing layer 2, as shown in Fig. 1. The copper phosphonate-containing layer is, more specifically, a layer containing phosphonic acid and copper ions, or a copper phosphonate complex formed from phosphonic acid and copper ions.

[0292] For example, impurities contained in copper phosphonate fine particles may adversely affect the storage stability, such as light resistance and heat resistance, of organic dyes, but by using a two-layer structure or by providing an intermediate layer, the diffusion of these impurities can be suppressed, thereby preventing a decrease in storage stability.Furthermore, by using a two-layer structure, moisture permeability can be reduced, and heat and humidity resistance can be improved.

[0293] The mass of the organic dye contained in the organic dye-containing layer is, for example, 0.3 to 8% of the mass of the total final solid content of the organic dye-containing layer. The matrix resin used to form the organic dye-containing layer is a resin that is transparent to visible light and near-infrared light and capable of dispersing the organic dye. For example, resins such as polyester, polyacrylic, polyolefin, polycarbonate, polycycloolefin, and polyvinyl butyral can be used.

[0294] 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.

[0295] The matrix resin used to form the copper phosphonate-containing layer is a resin that is transparent to visible light and near-infrared light and capable of dispersing copper phosphonate microparticles. Copper phosphonate is a substance with relatively low polarity and disperses well in hydrophobic materials. For example, a resin having an acrylic group, an epoxy group, or a phenyl group can be used, and from the viewpoint of heat resistance, it is preferable to use a resin having a phenyl group. Furthermore, from the viewpoints of transparency to visible light and near-infrared light and heat resistance, it is preferable to use a polysiloxane (silicone resin). The mass of the copper phosphonate microparticles contained in the copper phosphonate-containing layer is, for example, 15 to 45% by mass of the total mass of the final solid content of the copper phosphonate-containing layer.

[0296] The average particle size of the copper phosphonate microparticles is, for example, 5 to 200 nm, preferably 5 to 100 nm. When the average particle size of the copper phosphonate microparticles is 5 nm or more, no special process for miniaturizing the copper phosphonate microparticles is required, and destruction of the copper phosphonate structure can be prevented. Furthermore, when the average particle size of the copper phosphonate microparticles is 200 nm or less, the copper phosphonate microparticles are hardly affected by light scattering such as Mie scattering, and a decrease in light transmittance can be prevented, thereby preventing a decrease in performance such as the contrast and haze of images formed by an imaging device. Furthermore, when the average particle size of the copper phosphonate microparticles is 100 nm or less, the influence of Rayleigh scattering is reduced, thereby increasing the transparency of the copper phosphonate-containing layer in the visible light region.

[0297] The thickness of the copper phosphonate-containing layer is, for example, 30 to 200 μm, preferably 30 to 120 μm, which can reduce the average light transmittance of the near-infrared absorbing film in the wavelength range of 800 to 1100 nm to 5% or less, and can maintain the average light transmittance of the near-infrared absorbing film in the wavelength range of 450 to 600 nm high (for example, 70% or more).

[0298] The organic dye-containing layer 3 of the two-layer near-infrared absorbing film can be formed, for example, as follows. A coating solution for the organic dye-containing layer, prepared by adding the organic dye and matrix resin used in the present invention to a solvent, is applied to a substrate by spin coating or a wet coating method using a dispenser, and the coating is then cured by subjecting the coating to a predetermined heat treatment. Spin coating is preferably used as the coating method, because the thickness of the organic dye-containing layer can be precisely adjusted by adjusting the rotation speed of the spin coater.

[0299] The copper phosphonate-containing layer 2 can be formed, for example, as follows: A copper salt such as copper acetate is added to a predetermined solvent such as tetrahydrofuran (THF) and dissolved by ultrasonic treatment or the like, and a phosphate ester is then added to prepare Solution A. A phosphonic acid such as ethylphosphonic acid is added to a predetermined solvent such as THF and stirred to prepare Solution B. A solution obtained by mixing Solutions A and B is stirred at room temperature for over 10 hours to prepare Solution C. A predetermined solvent such as toluene is added to Solution C, and the solvent is volatilized by heating at a predetermined temperature to prepare Solution D.

[0300] Next, a matrix resin such as silicone resin is added to Liquid D (a dispersion of copper phosphonate particles) and stirred to prepare a coating solution for the copper phosphonate-containing layer. The prepared coating solution is applied to a substrate by spin coating or wet coating using a dispenser, and then the coating is cured by subjecting the coating to a predetermined heat treatment. The same matrix resin and additives as those used in the single-layer structure can be used to form a near-infrared absorbing film with a two-layer structure.

[0301] Near-infrared absorbing filter The near-infrared absorbing filter of the present invention is characterized in that it is formed using the near-infrared absorbing film of the present invention, and can be easily produced by, for example, a coating method.

[0302] The near-infrared absorbing film used in the near-infrared absorbing filter of the present invention may have a single layer structure, but preferably has a two-layer structure. The layer arrangement of the near-infrared absorbing filter having a two-layer structure can be determined by reference to, for example, the contents described in Japanese Patent No. 6619828.

[0303] 2 shows an example of a near-infrared absorbing filter made of a near-infrared absorbing film having a two-layer structure. The near-infrared absorbing filter of the present invention is not limited to the structure exemplified here.

[0304] If an organic dye-containing layer is formed on the surface of the copper phosphonate-containing layer after the copper phosphonate-containing layer is formed, the properties of the copper phosphonate-containing layer may not be fully exhibited. Therefore, it is preferable to form the copper phosphonate-containing layer on the surface of the organic dye-containing layer after the organic dye-containing layer is formed. It is also preferable to place a transparent substrate or an intermediate protective layer between the organic dye-containing layer and the copper phosphonate-containing layer in order to fully exhibit the properties.

[0305] Furthermore, the near-infrared absorbing filter of the present invention may have an antireflection layer on the filter surface, which improves the light transmittance in the visible light region and enables the production of high-brightness images when the near-infrared absorbing filter is used in an imaging device such as a digital camera.

[0306] The near-infrared absorbing filter of the present invention preferably has a film thickness within the range of 30 to 120 μm, from the viewpoint of improving light transmittance in the visible light region.

[0307] In addition, the near-infrared absorbing film of the present invention is suitable as a component for, for example, visibility correction members for CCDs, CMOSs ​​or other light-receiving elements, photometric members, heat ray absorbing members, composite optical filters, lens members (eyeglasses, sunglasses, goggles, optical systems, optical waveguide systems), fiber members (optical fibers), noise cutting members, display covers or display filters such as plasma display front panels, projector front panels, light source heat ray cutting members, color tone correction members, illumination brightness adjusting members, optical elements (light amplification elements, wavelength conversion elements, etc.), Faraday elements, optical communication function devices such as isolators, elements for optical discs, etc.

[0308] <Image sensor for solid-state imaging element> The image sensor for a solid-state imaging device of the present invention is characterized in that it is formed using the near-infrared absorbing filter of the present invention. Specifically, the image sensor is characterized in that it is applied to the image sensor for a solid-state imaging device as a near-infrared absorbing filter on the light-receiving side of the solid-state imaging device substrate (for example, as a near-infrared absorbing filter for a wafer-level lens) or as a near-infrared absorbing filter on the back side (opposite to the light-receiving side) of the solid-state imaging device substrate.

[0309] By applying the near-infrared absorbing filter of the present invention to an image sensor for a solid-state imaging device, it is possible to improve the transmittance, heat resistance, and light resistance in the visible light region.

[0310] FIG. 3 is a schematic cross-sectional view showing the configuration of a camera module equipped with a solid-state imaging device equipped with the near-infrared absorbing filter of the present invention.

[0311] The camera module 101 shown in FIG. 3 is connected to a circuit board 112, which is a mounting board, via solder balls 111, which are connecting members.

[0312] In detail, the camera module 101 is configured to include a solid-state imaging element substrate 110 having an imaging element section 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 absorbing filter 109 provided on the planarization layer 108, a glass substrate 103 (light-transmitting substrate) arranged above the near-infrared absorbing filter 109, a lens holder 105 arranged above the glass substrate 103 and having an imaging lens 104 in its internal space, and a light-shielding and electromagnetic shield 106 arranged to surround the periphery of the solid-state imaging element substrate 110 and the glass substrate 103. The respective members are bonded with adhesives 102 and 107.

[0313] In a method for producing a camera module having a solid-state imaging element substrate and an infrared absorbing filter disposed on the light-receiving side of the solid-state imaging element substrate, a near-infrared absorbing film can be formed on the light-receiving side of the solid-state imaging element substrate by spin-coating the infrared absorbing composition of the present invention. The near-infrared absorbing film may have a single layer structure or a two-layer structure.

[0314] Therefore, in the camera module 101, for example, the various organic dyes and metal compounds, or the near-infrared absorbing composition of the present invention is spin-coated on the planarization layer 108 to form a near-infrared absorbing film, thereby forming the infrared absorbing filter 109.

[0315] In the camera module 101, incident light L from the outside passes through the imaging lens 104, the glass substrate 103, the infrared absorption filter 109, and the planarization layer 108 in that order, before reaching the imaging element section of the solid-state imaging element substrate 110.

[0316] Furthermore, the camera module 101 is connected to a circuit board 112 on the second main surface side of the solid-state imaging element substrate 110 via solder balls 111 (connecting material). [Example]

[0317] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these. In the examples, the terms "parts" and "%" are used, but unless otherwise specified, they represent "parts by mass" or "% by mass."

[0318] Example 1 [Preparation of near-infrared absorbing composition] <Synthesis of dyes> Dyes 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 with reference to the synthesis examples described above and known methods.

[0319] <Synthesis of exemplary compounds having a structure represented by general formula (I)> Exemplary compounds 7, 13, 19, 42, 54, 65, 72 and 77 of compounds having a structure represented by general formula (I) were synthesized with reference to the known methods described above.

[0320] <Synthesis of Compound Having a Structure Represented by General Formula (D1)> Compounds D-3, 19 and 43 having a structure represented by general formula (D1) were synthesized with reference to the known methods described in JP-A Nos. 2007-31425 and 2007-34264.

[0321] (Preparation of near-infrared absorbing composition 1) Near infrared absorbing composition 1 was prepared according to the following method.

[0322] A copper acetate solution was prepared by mixing 2.0 g of copper (II) acetate monohydrate (Kanto Chemical Co., Inc.; hereinafter, simply referred to as "copper acetate") and 82 g of tetrahydrofuran (THF) as a solvent, stirring for 3 hours, and filtering to remove undissolved copper acetate.

[0323] 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 to this copper acetate solution with stirring over 30 minutes to prepare Solution A.

[0324] 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 solution B.

[0325] While stirring, Solution B was added to Solution A, and the mixture was stirred at room temperature for 16 hours to prepare Solution C. Next, 30 g of toluene was added to Solution C in a flask, and while heating at 50 to 100°C in an oil bath (Tokyo Rikakikai Co., Ltd., model: OSB-2100), the mixture was subjected to a solvent removal and acetic acid removal treatment for 30 minutes using a rotary evaporator (Tokyo Rikakikai Co., Ltd., model: N-1000) to prepare Solution D.

[0326] 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. Dye A1-1 2.00mg Dye C1-1 2.20mg

[0327] Solution E was placed in a flask and heated at 55 to 90°C in an oil bath (Tokyo Rikakikai Co., Ltd., model: OSB-2100) while undergoing a solvent and acetic acid removal treatment for 3 hours using a rotary evaporator (Tokyo Rikakikai Co., Ltd., model: N-1000).

[0328] Thereafter, the amount of solvent was adjusted so that the solid content concentration of the solution E in the flask would be 10 mass %. This was used as near-infrared absorbing composition 1.

[0329] (Preparation of near-infrared absorbing composition 2) Near infrared absorbing composition 2 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the organic dye shown in Table V was changed and S1 was used instead of the compound having a structure represented by general formula (I). The structural formula and synthetic method of S1 are shown below.

[0330] [ka]

[0331] 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 at a pressure of 147 kPa and a temperature of 130° C., followed by the addition of 88 g (2.0 mol) of ethylene oxide. Next, after confirming that no n-octanol remained, the adduct was placed in a reactor, and 117 g (1.0 mol) of chlorosulfonic acid was added dropwise to the toluene solution over about 1 hour to react. After the mixture was washed with distilled water, the solvent was removed by distillation under reduced pressure to obtain S1.

[0332] (Preparation of near-infrared absorbing compositions 3 to 13) Near infrared absorbing compositions 3 to 13 were prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the organic dyes and compounds having a structure represented by general formula (I) shown in Table V were used.

[0333] (Preparation of near-infrared absorbing compositions 14, 16 to 21) Near infrared absorbing compositions 14 and 16 to 21 were prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the organic dye and the compound having a structure represented by general formula (I) shown in Table VI were used and octylphosphonic acid was used instead of propylphosphonic acid.

[0334] (Preparation of near-infrared absorbing composition 15) A near infrared absorbing composition 15 was prepared in the same manner as in the preparation of the 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 VI were used, octylphosphonic acid was used instead of propylphosphonic acid, and the amount added was reduced to 80%.

[0335] (Preparation of near-infrared absorbing compositions 22 and 23) Near infrared absorbing compositions 22 and 23 were prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the organic dye and the compound having a structure represented by general formula (I) shown in Table VI were changed, octylphosphonic acid was used in place of propylphosphonic acid, and a compound having a structure represented by general formula (D1) shown in Table VI was added.

[0336] The procedure for adding the compound having the structure represented by general formula (D1) is shown below. D-3 or D-19, which is a compound having a structure represented by general formula (D1), was added together with the organic dye in an amount of 50 mass % of the organic dye used to Solution D to prepare Solution E. The subsequent treatment was carried out in the same manner as in the near-infrared absorbing composition 1.

[0337] (Preparation of near-infrared absorbing compositions 24 to 35) Near infrared absorbing compositions 24 to 35 were prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the organic dye and the compound having a structure represented by general formula (I) shown in Tables VI and VII were changed and a compound having a structure represented by general formula (D1) shown in Tables VI and VII was added. The procedure for adding the compound having a structure represented by general formula (D1) was the same as the above procedure.

[0338] (Preparation of near-infrared absorbing composition 36) A near infrared absorbing composition 36 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that phenylphosphonic acid was used in place of propylphosphonic acid.

[0339] (Preparation of Near-Infrared Absorbing Composition 37: Comparative Example) Near infrared absorbing composition 37 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the organic dye (diimmonium dye: KAYASORB IRG-022) and the compound having a structure represented by general formula (I) shown in Table VII were used.

[0340] (Preparation of Near-Infrared Absorbing Composition 38: Comparative Example) Near infrared absorbing composition 38 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the organic dye (diimmonium dye: KAYASORB IRG-022) and the compound having a structure represented by general formula (I) shown in Table VII were changed, and a compound having a structure represented by general formula (D1) shown in Table VII was added.

[0341] (Preparation of Near-Infrared Absorbing Composition 39: Comparative Example) Near infrared absorbing composition 39 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that propylphosphonic acid and the compound having a structure represented by general formula (I) were not added.

[0342] (Preparation of near-infrared absorbing composition 40: Comparative Example) A near infrared absorbing composition 40 was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the organic dyes ((a-18) and (c-1) described in Japanese Patent No. 6,331,392) and the compound having a structure represented by general formula (I) shown in Table VII were used.

[0343] The organic dye, phosphonic acid, compound having a structure represented by general formula (I), and compound having a structure represented by general formula (D1) used in preparing the near-infrared absorbing composition are shown below. In this example, the amounts of phosphonic acid and compound having a structure represented by general formula (I) added were 0.76 mol and 0.28 mol, respectively, per mol of copper acetate.

[0344] For octylphosphonic acid in Table VI, the amount of octylphosphonic acid added was reduced to 80%.

[0345] [Table 1]

[0346] [Table 6]

[0347] [Table 2]

[0348] 〔evaluation〕 The near-infrared absorbing compositions prepared as above were subjected to the following measurements and evaluations.

[0349] Each of the near infrared absorbing compositions 1 to 40 prepared above was diluted with toluene so that the particle concentration (solid content concentration) of the metal complex particles was 1.0 mass % to prepare an evaluation sample.

[0350] <Light transmittance> The light transmittance of the prepared samples in the wavelength range of 450 to 1200 nm was measured using a JASCO V-780 spectrophotometer, and the average light transmittance in that range was calculated. The calculated average light transmittance in the wavelength range of 450 to 1200 nm was evaluated according to the following criteria. In addition, the wavelength at which the transmittance became 50% in the range of 600 to 700 nm for each waveform was measured and used as the cutoff wavelength.

[0351] Within the wavelength range of 450 nm or more and 600 nm or less ⊚: The average light transmittance in the range is 90% or more. ⊚: The average light transmittance in the range is 88% or more and less than 90%. ◯: The average light transmittance in the range is 85% or more and less than 88%. Δ: The average light transmittance in the range is 80% or more and less than 85%. ×: The average light transmittance in the range is less than 80%.

[0352] Within the wavelength range of 700 nm or more and less than 1000 nm ⊚: The average light transmittance in the range is less than 2%. ◯: The average light transmittance in the range is 2% or more and less than 5%. Δ: The average light transmittance in the range is 5% or more and less than 10%. ×: The average light transmittance in the range is 10% or more.

[0353] Within the wavelength range of 1000nm or more and 1200nm or less ⊚: The average light transmittance in the range is less than 2%. ◯: The average light transmittance in the range is 2% or more and less than 5%. Δ: The average light transmittance in the range is 5% or more and less than 10%. ×: The average light transmittance in the range is 10% or more.

[0354] The evaluation results of Example 1 are shown in Tables VIII to X below, together with the evaluation results of Example 2. The solvent was removed from each of the compositions, and the resulting single film was subjected to the same measurements as above, confirming that the same results as in the liquid state were obtained.

[0355] Example 2 [Single-layer filter] 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 mass %, to prepare each coating liquid for forming a near-infrared absorbing film.

[0356] Next, each near-infrared absorbing film-forming coating solution was applied to a glass substrate by spin coating (rotation speed: 300 rpm) to form a coating film. This coating film was pre-baked on a hot plate at 50°C for 60 minutes. Next, the coating film was cured by heat treatment on a hot plate at 150°C for 2 hours to prepare a single-layer near-infrared absorbing filter.

[0357] The near-infrared absorbing filter was subjected to the following measurements and evaluations.

[0358] 〔evaluation〕 <Light resistance> The prepared samples were exposed to light for 120 hours using a xenon fade meter, and the light resistance was calculated from the ratio of the reflection spectral density at the maximum absorption wavelength in the visible region before and after exposure, and evaluated based on the following criteria. Lightfastness (%) = (maximum absorption wavelength concentration of exposed sample / maximum absorption wavelength concentration of unexposed sample) x 100

[0359] ◎: Light resistance is 95% or more 〇: Light resistance is 90% or more but less than 95% △: Light resistance is 80% or more but less than 90% ×: Light resistance is less than 80% If it is above ○, there is no problem in practical use.

[0360] <Heat resistance> The prepared samples were stored for 7 days under conditions of 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. Heat resistance (%) = (concentration after storage / concentration before storage) x 100 ◎: Heat resistance is 95% or more 〇: Heat resistance is 80% or more but less than 95% △: Heat resistance is 60% or more but less than 80% ×: Heat resistance is less than 60% If it is above ○, there is no problem in practical use.

[0361] The evaluation results of Examples 1 and 2 are summarized in Tables VIII to X below. The measurement results of the average light transmittance and cutoff wavelength shown in each table were obtained by the method and conditions described in Example 1, and were converted into light transmittance corrected to a state where reflections due to glass interfaces, etc. were canceled, and then evaluated.

[0362] [Table 3]

[0363] [Table 9]

[0364] [Table 4]

[0365] Example 3 [Preparation and Evaluation of Two-Layer Filter] A coating solution for the organic dye-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. Next, 2 g of polyvinyl butyral resin (Sumitomo Chemical Co., Ltd., S-LEC KS-10) was added and stirred for 1 hour. After that, 1 g of 2,4-triylene diisocyanate was added and stirred to obtain a coating solution for the organic dye-containing layer.

[0366] The coating solution for the organic dye-containing layer was applied to a glass substrate by spin coating (rotation speed: 500 rpm) to form a coating film. The coating film was then heat-treated at 140°C for 60 minutes to harden the coating film, forming an organic dye-containing layer. The thickness of the organic dye-containing layer was approximately 2 μm.

[0367] A coating solution for an intermediate protective layer was prepared as follows: 2.83 g of glycidoxypropyltrimethoxysilane, 0.11 g of epoxy resin (SR-6GL, manufactured by Sakamoto Pharmaceutical Co., Ltd.), 5.68 g of tetraethoxysilane, 0.06 g of an ethanol-diluted solution of nitric acid (nitric acid concentration: 10 wt%), and 5.5 g of water were added to 11.5 g of ethanol, in that order, and stirred for about 1 hour to obtain a coating solution for an intermediate protective layer.

[0368] The intermediate protective layer coating solution was applied to the surface of the organic dye-containing layer by spin coating (rotation speed: 300 rpm) to form a coating film, which was then heat-treated at 150°C for 20 minutes to harden the coating film, forming an intermediate protective layer.

[0369] As the coating liquid for the copper phosphonate-containing layer, Solution D before the addition of the organic dye in the near-infrared absorbing composition 1 of Example 1 could be used, and was prepared in the same manner. Next, Solution D 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 mass %, to obtain a coating liquid for the copper phosphonate-containing layer.

[0370] The coating solution for the copper phosphonate-containing layer was applied to the surface of the intermediate protective layer by spin coating (rotation speed: 300 rpm) to form a coating film. This 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 prepare a near-infrared absorbing filter having a two-layer structure (excluding the intermediate layer).

[0371] The near-infrared absorbing filter was subjected to the same measurements and evaluations as in Examples 1 and 2, and the same results were confirmed.

[0372] From the results in Tables VIII to X above, it is clear that the near-infrared absorbing composition and near-infrared absorbing film of the present invention are excellent in both transmittance in the visible light region and absorbency in the near-infrared region, and in addition, the near-infrared absorbing filter produced from the near-infrared absorbing composition of the present invention is excellent in heat resistance over time and also in light resistance. [Industrial Applicability]

[0373] The near-infrared absorbing composition of the present invention has both transmittance in the visible light region and absorbance in the near-infrared region, and is excellent in heat resistance and light resistance over time. Furthermore, by using the infrared absorbing composition, it is possible to provide a near-infrared absorbing film, a near-infrared absorbing filter, and an image sensor for a solid-state imaging device, which have both transmittance in the visible light region and absorbance in the near-infrared region, and are excellent in heat resistance and light resistance over time. [Explanation of symbols]

[0374] 1. Near-infrared absorbing film 2. Copper phosphonate-containing layer 3 Organic dye-containing layer 11 Near-infrared absorbing filter 12 Anti-reflection coating 13 Copper phosphonate-containing layer 14 Intermediate protective layer 15 Organic dye-containing layer 16 boards 101 Camera Module 102 Adhesive 103 Glass substrate 104 Imaging Lens 105 Lens Holder 106 Light-shielding and electromagnetic shield 107 Adhesive 108 Planarization layer 109 Near-infrared absorbing film (near-infrared absorbing filter) 110 Solid-state imaging element board 111 Solder ball 112 Circuit Board 113 Image sensor section

Claims

1. A near-infrared absorbing composition containing an organic dye and a metal compound, 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, and Contains a cyanine dye (C) having an absorption maximum wavelength of 760 nm or more, The squarylium dye (A) is a compound having a structure represented by any one of the following general formulas (A1) to (A4) (hereinafter, simply referred to as "dye A1," "dye A2," "dye A3," and "dye A4"), The cyanine dye (B) is a compound having a structure represented by the following general formula (B1) (hereinafter simply referred to as "dye B1"), The cyanine dye (C) is a compound having a structure represented by either of the following general formulas (C1) and (C2) (hereinafter simply referred to as "dye C1" and "dye C2"), Further, the composition contains at least a phosphonic acid and a copper ion, or a phosphonic acid copper complex formed from a phosphonic acid and a copper ion, the phosphonic acid is an alkylphosphonic acid, Furthermore, the present invention contains a copper complex formed from a compound having a structure represented by the following general formula (I) and copper ions, or a compound having a structure represented by the following general formula (I) and copper ions. A near-infrared absorbing composition comprising: Squarylium dye (A) 【Chemical 1】 (In the formula, R 1 represents an alkyl group, an aryl group, or a heterocyclic group. 2 and R 3 are each R represents a hydrogen atom, a halogen atom or a substituent. 4 represents an alkyl group, alkoxy group, aryl group or heterocyclic group having 1 to 4 carbon atoms; Z1 represents an atomic group necessary to form a 5- or 6-membered ring. 【Chemistry 2】 (In the formula, R 11 and R 12 are each independently a hydrogen atom, a hydroxy group, or —NHCOR 16 or -NHSO 2 R 17 and cannot be a hydrogen atom at the same time. 13 and R 14 R each independently represents a hydrogen atom, a halogen atom or a substituent. 15 represents a substituent. 1 represents an integer of 0 to 5. 16 and R 17 each independently represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a heterocyclic group. 【Chemistry 3】 (In the formula, R 21 and R 22 R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. 23 each independently represents a hydroxy group, -NHCOR 26 or -NHSO 2 R 27 Represents R 24 R each independently represents a hydrogen atom or a substituent. 25 Each independently represents a substituent. 2 Each of R represents an integer of 0 to 4. 26 and R 27 each independently represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a heterocyclic group. 【Chemistry 4】 (In the formula, R 31 and R 32 R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. 33 is a hydroxy group, -NHCOR 38 or -NHSO 2 R 39 Represents R 34 and R 36 R each independently represents a halogen atom or a substituent. 35 represents an alkyl group, an aryl group, or a heterocyclic group. 3 represents an integer of 0 to 3. 3 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 having 1 to 4 carbon atoms, an aryl group, or a heterocyclic group. Cyanine dye (B) 【Chemistry 5】 (In the formula, R 41 R each independently represents an alkyl group, an aryl group, or a heterocyclic group. 42 R each independently represents a halogen atom or a substituent. 43 ~R 45 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. 4 Each independently represents an integer of 0 to 6. 41 represents a halogen ion or an anion atomic group. Cyanine dye (C) 【Chemistry 6】 (In the formula, R 51 and R 52 each independently represents a halogen atom or a substituent, and adjacent substituents may be joined together to form a 5- or 6-membered ring. 51 and n 52 R represents an integer of 0 to 4 and an integer of 0 to 5, respectively. 53 and R 54 R each independently represents an alkyl group, an aryl group, or a heterocyclic group. 55 ~R 59 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. 55 and R 57 , R 56 and R 58 or R 57 and R 59 and may be bonded to form a 5- or 6-membered ring. 51 is -S- or -CR 511 R 512 - represents Y 51 represents an anionic atom or an anionic atomic group. 511 and R 512 each independently represents a hydrogen atom, an alkyl group, or an aryl group. 【Chemistry 7】 (In the formula, R 61 and R 62 each independently represents a halogen atom or a substituent, and adjacent substituents may be joined together to form a 5- or 6-membered ring. 61 and n 62 R each independently represents an integer of 0 to 4. 63 and R 64 R each independently represents an alkyl group, an aryl group, or a heterocyclic group. 65 ~R 71 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. 65 and R 67 , R 66 and R 68 , R 67 and R 69 , R 68 and R 70 or R 69 and R 71 and may be bonded to form a 5- or 6-membered ring. 61 and X 62 are each independently —O—, —S—, or —CR 611 R 612 - represents Y 61 represents an anionic atom or an anionic atomic group. 611 and R 612 each independently represents a hydrogen atom or an alkyl group. 【Chemistry 8】 (In the above 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 may further have a substituent. Z represents a structural unit selected from the following formulae (Z-1) and (Z-2). 【Chemistry 9】 * in the above formulas (Z-1) and (Z-2) represents a bonding site, which bonds to O in the above general formula (I). R 121 to R 124 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, the compound having the structure represented by the general formula (I) above simultaneously has at least one partial structure that satisfies the following condition (i) and at least one partial structure that satisfies the following condition (ii): do. Condition (i): R 121 to R 124 are all hydrogen atoms. Condition (ii): At least one of R 121 to R 124 is an alkyl group having 1 to 4 carbon atoms. In the above general formula (I), j represents the number of partial structures that satisfy the above condition (i) and is a number from 1 to 10. k represents the number of partial structures that satisfy the above condition (ii) and is a number from 1 to 10.

2. The organic dyes are contained as a combination of at least the dye A1 and the dye C2, or a combination of the dye A4 and the dye C2. The near-infrared absorbing composition according to claim 1 .

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

4. Furthermore, the compound having a structure represented by the following general formula (D1) is contained. The near-infrared absorbing composition according to any one of claims 1 to 3. 【Chemistry 10】 (In the formula, R 111 and R 113 R 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.

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

6. an organic dye-containing layer containing an organic dye; a copper phosphonate-containing layer containing phosphonic acid and copper ions or a copper phosphonate complex formed from phosphonic acid and copper ions; The organic dye is 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, and Contains a cyanine dye (C) having an absorption maximum wavelength of 760 nm or more, The squarylium dye (A) is a compound having a structure represented by any one of the following general formulas (A1) to (A4) (hereinafter, simply referred to as "dye A1," "dye A2," "dye A3," and "dye A4"), The cyanine dye (B) is a compound having a structure represented by the following general formula (B1) (hereinafter simply referred to as "dye B1"), The cyanine dye (C) is a compound having a structure represented by either of the following general formulas (C1) and (C2) (hereinafter simply referred to as "dye C1" and "dye C2"), the phosphonic acid is an alkylphosphonic acid, The copper phosphonate-containing layer further contains a compound having a structure represented by the following general formula (I) and copper ions, or a copper complex formed from a compound having a structure represented by the following general formula (I) and copper ions: A near-infrared absorbing film characterized by: Squarylium dye (A) 【Chemistry 11】 (In the formula, R 1 represents an alkyl group, an aryl group, or a heterocyclic group. R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or a substituent. R 4 represents an alkyl group, alkoxy group, aryl group, or heterocyclic group having 1 to 4 carbon atoms. Z1 represents an atomic group necessary to form a 5- or 6-membered ring.) 【Chemistry 12】 (In the formula, R 11 and R 12 each independently represent a hydrogen atom, a hydroxy group, —NHCOR 16 or —NHSO 2 R 17 , and are not both hydrogen atoms. R 13 and R 14 each independently represent a hydrogen atom, a halogen atom or a substituent. R 15 represents a substituent. n 1 represents an integer of 0 to 5. R 16 and R 17 each independently represent an alkyl group, aryl group or heterocyclic group having 1 to 4 carbon atoms.) 【Chemistry 13】 (In the formula, R 21 and R 22 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R 23 each independently represent a hydroxy group, —NHCOR 26 , or —NHSO 2 R 27 . R 24 each independently represent a hydrogen atom or a substituent. R 25 each independently represent a substituent.) n2 represents an integer of 0 to 4. R26 and R27 each independently represent an alkyl group, an aryl group, or a heterocyclic group having 1 to 4 carbon atoms. 【Chemistry 14】 (In the formula, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R 33 represents a hydroxy group, —NHCOR 38 , or —NHSO 2 R 39 . R 34 and R 36 each independently represent a halogen atom or a substituent. R 35 represents an alkyl group, an aryl group, or a heterocyclic group. n 3 represents an integer of 0 to 3. m 3 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 represent an alkyl group, aryl group, or heterocyclic group having 1 to 4 carbon atoms.) Cyanine dye (B) 【Chemistry 15】 (In the formula, each R 41 independently represents an alkyl group, an aryl group, or a heterocyclic group. Each R 42 independently represents a halogen atom or a substituent. Each R 43 to R 45 independently represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Each n 4 independently represents an integer of 0 to 6. Each Y 41 independently represents a halogen ion or an anionic atomic group.) Cyanine dye (C) 【Chemistry 16】 (In the formula, R 51 and R 52 each independently represent a halogen atom or a substituent, and adjacent substituents may combine with each other to form a 5- or 6-membered ring. n 51 and n 52 represent integers of 0 to 4 and 0 to 5, respectively. R 53 and R 54 each independently represent an alkyl group, an aryl group, or a heterocyclic group. R 55 to R 59 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R 55 and R 57 , R 56 and R 58 , or R 57 and R 59 may be bonded together to form a 5- or 6-membered ring. X 51 represents -S- or -CR 511 R 512 -. Y 51 represents an anionic atom or an anionic atomic group. R 511 and R 512 each independently represents a hydrogen atom, an alkyl group, or an aryl group. 【Chemistry 17】 (In the formula, R 61 and R 62 each independently represent a halogen atom or a substituent, and adjacent substituents may combine with each other to form a 5- or 6-membered ring. n 61 and n 62 each independently represent an integer of 0 to 4. R 63 and R 64 each independently represent an alkyl group, an aryl group or a heterocyclic group. R 65 to R 71 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. R 65 and R 67 , R 66 and R 68 , R 67 and R 69 , R 68 and R 70 , or R 69 and R 71 may be bonded together to form a 5- or 6-membered ring. X 61 and X 62 each independently represent —O—, —S—, or —CR 611 R 612 —. Y R 611 represents an anionic atom or an anionic atomic group. R 611 and R 612 each independently represent a hydrogen atom or an alkyl group. 【Chemistry 18】 (In the above 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 may further have a substituent. Z represents a structural unit selected from the following formulae (Z-1) and (Z-2). 【Chemistry 19】 * in the above formulas (Z-1) and (Z-2) represents a bonding site, which bonds to O in the above general formula (I). R 121 to R 124 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, the compound having the structure represented by the general formula (I) above simultaneously 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 to R 124 are all hydrogen atoms. Condition (ii): At least one of R 121 to R 124 is an alkyl group having 1 to 4 carbon atoms. In the above general formula (I), j represents the number of partial structures that satisfy the above condition (i) and is a number from 1 to 10. k represents the number of partial structures that satisfy the above condition (ii) and is a number from 1 to 10.

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

8. The near-infrared absorbing filter according to claim 7 is provided.

1. An image sensor for a solid-state imaging device, comprising:

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