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

Abstract

To provide a near-infrared ray absorbing composition having a low haze, excellent near-infrared ray absorbing ability, improved dispersion stability of a metal complex in the case of moisture incorporation, and improved thermal stability of a metal complex, and to provide a near-infrared ray absorbing film formed by using this composition and an image sensor for a solid-state imaging device including the near-infrared ray absorbing film.SOLUTION: There is provided, a near-infrared ray absorbing composition containing at least a near-infrared absorber, a metal compound, and a solvent, wherein the near-infrared absorber contains a metal ion, and the metal compound is a titanium octylene glycolate compound having a specific structure, or a compound having a structure represented by a General Formula (III): (OR3)n-mMn+(-OCOR4)m, where M represents at least one metal atom selected from titanium, zirconia, and aluminum, and R3 and 4 independently represent a C1-30 alkyl group.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a near-infrared absorbing composition, a near-infrared absorbing film using the same, and an image sensor for a solid-state imaging device, and more specifically to a near-infrared absorbing composition having excellent near-infrared absorbing ability and improved dispersion stability (moisture resistance) when moisture is mixed in, a near-infrared absorbing film using the same, and an image sensor for a solid-state imaging device comprising the near-infrared absorbing film. [Background technology]

[0002] In recent years, video cameras, digital still cameras, mobile phones with cameras, and other devices have come to use color solid-state imaging elements such as CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor) image sensors. These solid-state imaging elements use silicon photodiodes in their light receiving section that are sensitive to light in the near-infrared wavelength range, making it necessary to perform visibility correction, and for this reason, near-infrared cut filters are often used.

[0003] In recent years, a method has been disclosed in which a near-infrared absorbing composition using a copper phosphonate complex is used as a material for producing such a near-infrared cut filter (see, for example, Patent Documents 1 to 3).

[0004] In each of the above patent documents, in order to improve quality, the storage stability is improved by using a specific solvent as a dispersion medium, adding a solubilizer, or the like. However, all of these methods aim to solve the stability of the near-infrared absorbing composition after adding a resin component as a binder to a copper phosphonate. However, there is no mention of the stability of the near-infrared absorbing composition in a state in which no binder component is contained. As a result of investigations by the present inventors, it was found that the dispersion stability of the near-infrared absorbing composition at a stage before adding a binder resin has a significant effect on the final quality of the near-infrared cut filter.

[0005] In addition, the copper complex has a problem that, even in a dispersion liquid that does not contain a binder, aggregation occurs in a film containing a binder when moisture enters the copper complex. Furthermore, the aggregation is accelerated by applying heat. Patent Document 4 discloses an optical filter having a near-infrared light absorbing layer containing a copper complex obtained by reacting a phosphoric acid ester compound having an ethylene oxide structure or a phosphoric acid ester compound having a propylene oxide structure with a copper compound, but it was found that even when such a copper complex is used, the dispersibility of the copper complex and the dispersion stability (moisture resistance) when moisture is mixed in are insufficient. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 4684393 [Patent Document 2] Patent No. 4926699 [Patent Document 3] Patent No. 5890805 [Patent Document 4] Patent No. 4422866 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in consideration of the above problems and circumstances, and an object of the present invention is to provide a near-infrared absorbing composition which has low haze, excellent near-infrared light absorption ability, improved dispersion stability (moisture resistance) of a metal complex when mixed with moisture, and improved thermal stability of the metal complex, a near-infrared absorbing film formed using the composition, and an image sensor for solid-state imaging devices which includes the near-infrared absorbing film. [Means for solving the problem]

[0008] Means for Solving the Problem The present inventors have investigated the causes of the above problems in order to solve the above problems, and have found that, due to at least a physical or chemical interaction between a near-infrared absorbent containing a metal ion and a metal compound, a near-infrared absorbing composition can have low haze and excellent near-infrared light absorption ability, and the dispersion stability (moisture resistance) of the metal complex when moisture is mixed in can be improved, and the thermal stability of the metal complex can be improved, thereby completing the present invention.

[0009] That is, the above-mentioned problems of the present invention are solved by the following means.

[0010] 1. At least, near infrared absorbing agent titanium A near-infrared absorbing composition comprising a compound and a solvent, the near-infrared absorbing agent containing a metal ion, titanium The compound is a titanium octylene glycolate compound having a structure represented by the following formula II-10, formula II-11, or formula II-12: With things A near infrared absorbing composition comprising: [ka]

[0011] 2. The near infrared absorbing composition according to item 1, wherein the near infrared absorbing agent contains at least one of the following components (A) and (B): Component (A): A component consisting of a compound having a structure represented by the following general formula (IV) and a metal ion Component (B): A component consisting of a metal complex obtained by reacting a compound having a structure represented by the following general formula (IV) with a metal compound: General formula (IV) R0-OZ [In the above general formula (IV), R0 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R0 may further have an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a dialkylamino group, a trialkylsilyl group, a triarylsilyl group, a triheteroarylsilyl group, a benzyl group, an aryl group, or a heteroaryl group as a substituent. Z represents a structural unit selected from the following formulae (Z-1) to (Z-3). [ka] The * in the above formulae (Z-1) to (Z-3) represents a bonding site and bonds to O in the above general formula (IV).

[0012] 3. The compound having the structure represented by the general formula (IV) has a structure represented by the following general formula (V): Have 3. The near infrared absorbing composition according to item 2, characterized in that the near infrared absorbing composition is at least one compound selected from phosphoric acid ester compounds and sulfonic acid ester compounds. [ka] [In the above general formula (V), R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R may further have an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a dialkylamino group, a trialkylsilyl group, a triarylsilyl group, a triheteroarylsilyl group, a benzyl group, an aryl group, or a heteroaryl group as a substituent. Z represents a structural unit selected from the above formulae (Z-1) to (Z-3). R 21 ~R 24 each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, the compound having the structure represented by general formula (V) 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 21 ~R 24 are all hydrogen atoms. Condition (ii):R21 ~R 24 At least one of them is an alkyl group having 1 to 4 carbon atoms. In the general formula (V), l is R defined in the above proviso (i). 21 ~R 24 represents the number of partial structures in which all are hydrogen atoms, and m is R 21 ~R 24 At least one of the following represents the number of partial structures that are alkyl groups having 1 to 4 carbon atoms; l and m each represent A number in the range of 1 to 8. 〕 4. A near-infrared absorbing composition containing at least a near-infrared absorbent, a titanium compound, and a solvent, The near-infrared absorbent contains a metal ion and at least one of the following components (A) and (B): Component (A): A component comprising at least one compound selected from a phosphoric acid ester compound or a sulfonic acid ester compound having a structure represented by the following general formula (V) and a metal ion: Component (B): A component consisting of a metal complex obtained by reacting at least one compound selected from a phosphoric acid ester compound or a sulfonic acid ester compound having a structure represented by the following general formula (V) with a metal compound: [ka] [In the above general formula (V), R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R may further have an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a dialkylamino group, a trialkylsilyl group, a triarylsilyl group, a triheteroarylsilyl group, a benzyl group, an aryl group, or a heteroaryl group as a substituent. R 21 ~R 24 each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, the compound having the structure represented by general formula (V) 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 21 ~R 24 are all hydrogen atoms. Condition (ii):R 21 ~R 24 At least one of them is an alkyl group having 1 to 4 carbon atoms. In the general formula (V), l is R defined in the above proviso (i). 21 ~R 24 represents the number of partial structures in which all are hydrogen atoms, and m is R 21 ~R 24 At least one of the following represents the number of partial structures that are alkyl groups having 1 to 4 carbon atoms; and l and m are each numbers within the range of 1 to 8. Z represents a structural unit selected from the following formulae (Z-1) to (Z-3). [ka] The * in the above formulas (Z-1) to (Z-3) represents a bonding site and bonds to O in the above general formula (V). The titanium compound is a compound having a structure represented by the following general formula (III): General formula (III) (OR 3 ) n-m M n+ ( - O.C.O.R. 4 ) m [In the above general formula (III), M is titanium, n=4, and m=1, 2, 3, or 4. R 3 and R 4 each independently represents an alkyl group having 1 to 30 carbon atoms; R 3 and R 4 may further have an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a dialkylamino group, a trialkylsilyl group, a triarylsilyl group, a triheteroarylsilyl group, a benzyl group, an aryl group, or a heteroaryl group as a substituent. Characterized by Near infrared absorbing composition.

[0013] 5 .The above Titanium Compounds The composition according to any one of claims 1 to 3, characterized in that the composition contains the near infrared absorbing agent in an amount of 0.01 to 30% by mass. 4 The near infrared absorbing composition according to any one of claims 1 to 5.

[0016] 6 The metal ion or the metal constituting the metal complex contained in the near infrared absorber is , characterized in that it is copper Paragraph 2 or 4 The near infrared absorbing composition according to claim 1.

[0017] 7 . The composition according to any one of claims 1 to 5, characterized in that it contains a phosphonic acid compound. 6 The near infrared absorbing composition according to any one of claims 1 to 5.

[0018] 8 .Items 1 to 5 7 Item 1. A near-infrared absorbing film, comprising the near-infrared absorbing composition according to any one of items 1 to 5.

[0019] 9 .No. 8 2. An image sensor for a solid-state imaging device, comprising the near-infrared absorbing film according to claim 1. Effect of the Invention

[0020] By the above-mentioned means of the present invention, it is possible to provide a near-infrared absorbing composition having low haze, excellent near-infrared light absorption ability, improved dispersion stability (moisture resistance) of the metal complex when moisture is mixed in, and improved thermal stability of the metal complex, a near-infrared absorbing film formed using the same, and an image sensor for solid-state imaging elements comprising the near-infrared absorbing film.

[0021] Although the mechanism by which the effects of the present invention are expressed and the mechanism of action are not clear, they are speculated as follows.

[0022] The near-infrared absorbing composition of the present invention contains at least one metal compound selected from metal alkoxides, metal chelates and metal acylates, which acts on the near-infrared absorbing agent to improve the dispersion stability in the near-infrared absorbing composition, suppress the aggregation of the near-infrared absorbing agent, reduce the haze of the thin film formed from the near-infrared absorbing composition, and improve the visible light transmittance.Furthermore, it is considered that the formation of a metal oxide film by the crosslinking reaction of the metal compound can suppress the intrusion of water from the film surface, thereby improving the moisture resistance, and the physical adsorption or crosslinking between the metal compound and the near-infrared absorbing agent suppresses the thermal vibration of the near-infrared absorbing agent, thereby improving the heat resistance. [Brief description of the drawings]

[0023] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a camera module including a solid-state imaging device having the near-infrared absorbing film of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition containing at least a near-infrared absorbent, a metal compound, and a solvent, characterized in that the near-infrared absorbent contains a metal ion, and the metal compound is a compound having a structure represented by the general formula (I), general formula (II), or general formula (III). This feature is a technical feature common to the inventions according to the following embodiments.

[0025] In the near-infrared absorbing composition of the present invention, from the viewpoint of further exhibiting the intended effects of the present invention, it is preferable that the near-infrared absorbent contains at least one of the components (A) and (B), in that better near-infrared light absorbing ability, dispersibility of the metal complex, and dispersion stability when moisture is mixed in (moisture resistance) can be obtained.

[0026] In addition, it is preferable that the near infrared absorber contains a metal compound having a structure represented by the general formula (I), general formula (II), or general formula (III) in an amount within a range of 0.01 to 30 mass % in order to obtain better heat and humidity resistance.

[0027] Moreover, it is preferable that the metal element M constituting the metal compound is titanium, since better haze performance and heat and humidity resistance can be obtained.

[0028] In addition, it is preferable that the metal compound is a compound having a structure represented by the general formula (II) above, since it is possible to obtain lower haze and more excellent transmission performance in the visible light region.

[0029] In addition, it is preferable that the metal constituting the metal ion or metal complex contained in the near infrared absorbing agent is copper, since this allows for obtaining superior transmittance in the near infrared region.

[0030] Furthermore, it is preferable that the composition contains a phosphonic acid compound, since this makes it possible to obtain better dispersion stability (heat and humidity resistance), visible light transmittance, and near-infrared light absorption ability.

[0031] 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" indicating a range of values ​​is used to mean that the values ​​before and after the symbol are included as the lower and upper limits.

[0032] <<Constitution of near infrared absorbing composition>> The near infrared absorbing composition of the present invention is characterized by containing at least a near infrared absorbing agent containing a metal ion and a metal compound having a structure represented by general formula (I), general formula (II), or general formula (III).

[0033] Hereinafter, the constituent materials of the near infrared absorbing composition of the present invention will be described in detail.

[0034] [Metal compound] The metal compounds having a metal alkoxide structure represented by the following general formula (I), a metal chelate structure represented by the following general formula (II), and a metal acylate structure represented by the following general formula (III), which are applicable to the near infrared absorbing composition of the present invention, will be described below.

[0035] General formula (I) M(OR1) n General formula (II) M n+ (O=R2-O - ) n General formula (III) (OR3) n-m M n+ ( - OCOR4) m In the above general formulas (I), (II) and (III), M is at least one metal atom selected from titanium, zirconia and aluminum, and when M is titanium or zirconia, n is 4 and m is 1, 2, 3 or 4. When M is aluminum, n is 3 and m is 1, 2 or 3.

[0036] R1 to R4 each independently represent an alkyl group having 1 to 30 carbon atoms, and R1 to R4 may further have a substituent.

[0037] The alkyl group having 1 to 30 carbon atoms represented by R1 to R4 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 groups. Each alkyl group may further have a substituent. The alkyl group has preferably 6 to 20 carbon atoms.

[0038] Examples of the substituent that each of R1 to R4 may have include an alkyl group (e.g., a methyl group, an ethyl group, a trifluoromethyl group, an isopropyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, etc.), a halogen atom (e.g., a fluorine atom, etc.), a cyano group, a nitro group, a dialkylamino group (e.g., a dimethylamino group, etc.), a trialkylsilyl group (e.g., a trimethylsilyl group, etc.), a triarylsilyl group (e.g., a triphenylsilyl group, etc.), a triheteroarylsilyl group (e.g., a tripyridylsilyl group, etc.), a benzyl group, an aryl group (e.g., a phenyl group, etc.), and a heteroaryl group (e.g., a pyridyl group, a carbazolyl group, etc.). Examples of the condensed ring include, but are not limited to, 9,9′-dimethylfluorene, carbazole, and dibenzofuran.

[0039] (Metal Compound Represented by General Formula (I)) Examples of compounds having a metal alkoxide structure represented by general formula (I) include titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium-t-butoxide, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium n-tetrabutoxide, zirconium tetra-t-butoxide, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-s-butoxide, and aluminum tri-t-butoxide.

[0040] Further examples include compounds I-1 to I-15 having the structures shown below. [ka]

[0041] In addition, metal alkoxides having a structure represented by the general formula (I) can also be obtained as commercially available products, for example, "Orgatix TA-8", "Orgatix TA-21", "Orgatix TA-23", "Orgatix TA-30", "Orgatix TA-12", "Orgatix TA-80", "Orgatix TA-90", "Orgatix ZA-45", "Orgatix ZA-65", "Orgatix AL-3001" (manufactured by Matsumoto Fine Chemical Co., Ltd.), "A-1", "B-1", "TOT", "TOG" (manufactured by Nippon Soda Co., Ltd.), "Plenact 46B", "Plenact 55", "Plenact 41B", "Plenact 38S", "Plenact 138S", "Plenact 238S", "Plenact 338X", "Plenact 44", "Plenact 9SA" (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and the like.

[0042] (Metal Compound Represented by General Formula (II)) Examples of compounds having a metal chelate structure represented by the general formula (II) include zirconium chelate compounds such as tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis(ethylacetoacetate) zirconium, n-butoxytris(ethylacetoacetate) zirconium, tetrakis(n-propylacetoacetate) zirconium, tetrakis(acetylacetoacetate) zirconium, and tetrakis(ethylacetoacetate) zirconium; titanium acetylacetonate; titanium tetraacetate; Titanium chelate compounds such as titanium ethyl acetoacetate, titanium octylene glycolate, titanium ethyl acetoacetate, diisopropoxy bis(ethyl acetoacetate) titanium, diisopropoxy bis(acetylacetate) titanium, diisopropoxy bis(acetylacetone) titanium, etc., diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis(ethyl acetoacetate) aluminum, isopropoxy Citrate bis(acetylacetonate), aluminium tris(ethylacetoacetate), aluminium tris(acetylacetonate), aluminium monoacetylacetonate bis(ethylacetoacetate), diisopropoxyaluminium monooleylacetoacetate, monoisopropoxyaluminium bisoleylacetoacetate, monoisopropoxyaluminium monooleate monoethylacetoacetate, diisopropoxyaluminium monolaurylacetoacetate, diisopropoxyaluminium monostearylacetoacetate, diisopropoxyaluminium monoisostearylacetoacetate, monoisopropoxyaluminium mono-N-lauroyl-β-alanate monolaurylacetoacetate, aluminium trisacetylacetonate, aluminium monoacetylacetonate bis(isobutylacetoacetate) chelate, aluminium monoacetylacetonate bis(2-ethylhexylacetoacetate) chelate, aluminium monoacetylacetonate bis(dodecylacetoacetate) chelate,Examples of the aluminum chelate compounds include monoacetylacetonate aluminum bis(oleylacetoacetate) chelate.

[0043] Further examples include compounds II-1 to II-14 having the structures shown below. [ka] [ka]

[0044] Such metal chelates are also available as commercially available products, for example, "Orgatics TC-100", "Orgatics TC-401", "Orgatics TC-710", "Orgatics TC-810", "Orgatics TC-1040", "Orgatics TC-201", "Orgatics TC-750", "Orgatics TC-120", "Orgatics TC-230", "Orgatics TC245", and "Orgatics ZC-150". ", "Orgatix ZC-162", "Orgatix ZC-540", "Orgatix ZC-700", "Orgatix ZC-580", "Orgatix AL-3100", "Orgatix AL-3200", "Orgatix AL-3215" (all manufactured by Matsumoto Fine Chemical Co., Ltd.), "T-50", "T-60" (all manufactured by Nippon Soda Co., Ltd.), and "Plenact AL-M" (manufactured by Ajinomoto Fine-Techno Co., Ltd.) are examples of such compounds.

[0045] (Metal Compound Represented by General Formula (III)) Examples of compounds having a metal acylate structure represented by general formula (III) include titanium isostearate, zirconium octylate compounds, zirconium stearate, polyhydroxytitanium stearate, and zirconium tributoxymonostearate.

[0046] Further examples include compounds III-1 to III-2 having the structures shown below. [ka] Such metal acylates are also available as commercially available products, such as "Orgatix TC-800", "Orgatix ZC-200", and "Orgatix ZC-320" (all manufactured by Matsumoto Fine Chemical Co., Ltd.), "TBSTA", "DPSTA-25", "S-151", "S-152", "S-181", and "TBP" (all manufactured by Nippon Soda Co., Ltd.), and "Plenact TTS" (manufactured by Ajinomoto Fine-Techno Co., Ltd.).

[0047] The metal compounds having the structures represented by the above general formulas (I), (II), and (III) can be obtained, for example, by referring to the synthesis methods described in JP-A-2011-219704.

[0048] [Near infrared absorbing agent] The near-infrared absorbing agent constituting the near-infrared absorbing composition of the present invention is characterized by containing a metal ion, and more preferably contains at least one component selected from the following component (A) and component (B):

[0049] Component (A): a component comprising a compound having a structure represented by the following general formula (IV) and a metal ion; Component (B): A component consisting of a metal complex obtained by reacting a compound having a structure represented by the following general formula (IV) with a metal compound.

[0050] General formula (IV) R0-OZ In the above general formula (IV), R0 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R0 may further have a substituent. Z represents a structural unit selected from the following formulae (Z-1) to (Z-3). [ka] The symbol * in the above formulae (Z-1) to (Z-3) represents a bonding site, and bonds to O in the above general formula (IV).

[0051] The compound represented by the general formula (IV), which is a typical component of the near infrared absorbing agent applied to the near infrared absorbing composition of the present invention, will be described below. However, the present invention is not limited to only the compounds having the constitution exemplified here.

[0052] (Compound having a structure represented by general formula (IV)) First, the compound according to the present invention having a structure represented by the following general formula (IV) will be described.

[0053] General formula (IV) R0-OZ In the above general formula (IV), R0 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R0 may further have a substituent. Z represents a structural unit selected from the above formulae (Z-1) to (Z-3).

[0054] Of the structural units selected from the above formulae (Z-1), (Z-2) and (Z-3), from the viewpoint of dispersibility of the metal complex, the structural unit represented by formula (Z-1) or (Z-2) is preferred.

[0055] In the above general formula (IV), when Z is a structural unit represented by formula (Z-1), it becomes a diester, and when Z is a structural unit represented by formula (Z-2) or (Z-3), it becomes a monoester. From the viewpoint of dispersibility of the metal complex, it is preferable that the diester and the monoester are a mixture, and among the monoester and the diester, the molar ratio of the monoester is preferably within the range of 20 to 95%.

[0056] In the above general formula (IV), the alkyl group having 1 to 20 carbon atoms represented by R0 may be linear or branched, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, 2-butyloctyl group, 2-hexyloctyl group, n-decyl group, 2-hexyldecyl group, n-dodecyl group, and n-stearyl group. Each alkyl group may further have a substituent. From the viewpoint of dispersibility and moisture resistance of the metal complex, an alkyl group having 6 to 16 carbon atoms is preferable.

[0057] Examples of the aryl group having 6 to 20 carbon atoms represented by R0 include a phenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, 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 preferably a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a biphenylyl group, and a fluorenonyl group. Each of the aryl groups may further have a substituent.

[0058] Examples of the substituent that R0 may have include an alkyl group (e.g., a methyl group, an ethyl group, a trifluoromethyl group, an isopropyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, etc.), a halogen atom (e.g., a fluorine atom, etc.), a cyano group, a nitro group, a dialkylamino group (e.g., a dimethylamino group, etc.), a trialkylsilyl group (e.g., a trimethylsilyl group, etc.), a triarylsilyl group (e.g., a triphenylsilyl group, etc.), a triheteroarylsilyl group (e.g., a tripyridylsilyl group, etc.), a benzyl group, an aryl group (e.g., a phenyl group, etc.), and a heteroaryl group (e.g., a pyridyl group, a carbazolyl group, etc.). Examples of the condensed ring include, but are not limited to, 9,9′-dimethylfluorene, carbazole, and dibenzofuran.

[0059] Representative compounds represented by general formula (IV) are shown below. [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] (Compound having a structure represented by general formula (V)) In the present invention, the compound having the structure represented by the above-described general formula (IV) is more preferably a compound having a structure represented by the following general formula (V). [ka] In the above general formula (V), R has the same meaning as R0 in the above general formula (IV), and Z has the same meaning as the structural units represented by the formulae (Z-1), (Z-2), and (Z-3) in the above general formula (IV).

[0064] In the above general formula (V), l represents the number of partial structures satisfying the condition (i) described below, and m represents the number of partial structures satisfying the condition (ii) described below, where l and m are each a number of 0 or more, and the total number of l and m (l+m) is 1 or more. The compound having a structure represented by general formula (V) is at least one compound selected from phosphate ester compounds or sulfonate ester compounds. In the above general formula (V), the alkyl group having 1 to 20 carbon atoms represented by R may be linear or branched, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, 2-butyloctyl group, 2-hexyloctyl group, n-decyl group, 2-hexyldecyl group, n-dodecyl group, and n-stearyl group. Each alkyl group may further have a substituent. From the viewpoint of the absorption characteristics of the copper complex, the alkyl group having 1 to 10 carbon atoms is preferable. Examples of the aryl group having 6 to 20 carbon atoms represented by R include a phenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, 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 preferably a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a biphenylyl group, and a fluorenonyl group. Each of the aryl groups may further have a substituent. Examples of the substituent that R may have include an alkyl group (e.g., a methyl group, an ethyl group, a trifluoromethyl group, an isopropyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, etc.), a halogen atom (e.g., a fluorine atom, etc.), a cyano group, a nitro group, a dialkylamino group (e.g., a dimethylamino group, etc.), a trialkylsilyl group (e.g., a trimethylsilyl group, etc.), a triarylsilyl group (e.g., a triphenylsilyl group, etc.), a triheteroarylsilyl group (e.g., a tripyridylsilyl group, etc.), a benzyl group, an aryl group (e.g., a phenyl group, etc.), and a heteroaryl group (e.g., a pyridyl group, a carbazolyl group, etc.). Examples of the condensed ring include, but are not limited to, 9,9′-dimethylfluorene, carbazole, and dibenzofuran.

[0065] In the above general formula (V), R 21 ~R 24 each represents 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.

[0066] In the compound having a structure represented by general formula (V) according to the present invention, it is preferable that the compound has at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the following condition (ii) simultaneously within its molecular structure.

[0067] Condition (i): R 21 ~R 24 are all hydrogen atoms.

[0068] Condition (ii):R 21 ~R 24 At least one of them is an alkyl group having 1 to 4 carbon atoms.

[0069] The partial structure that satisfies condition (ii) is R 21 ~R 24 When at least one of them is an alkyl group having 1 to 4 carbon atoms, and two more are the same alkyl group, structures in which three are the same alkyl group and all four are the same alkyl group are included. From the viewpoint of dispersibility of the metal complex, it is preferable that only one of them is an alkyl group having 1 to 4 carbon atoms.

[0070] The substructure that satisfies condition (i) is R 21 ~R 24 is an ethylene oxide structure in which all 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 moisture is mixed in due to the entropy effect.

[0071] In the general formula (V), l is R defined in the above proviso (i). 21 ~R 24 represents the number of partial structures in which all are hydrogen atoms, and m is R 21 ~R 24 represents the number of partial structures that are alkyl groups having 1 to 4 carbon atoms, and as described above, l and m are each a number of 0 or more, and the total number of l and m (l+m) is 1 or more.

[0072] l and m respectively represent the average number of moles of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure added.

[0073] In addition, it is preferable that the compound having the structure represented by the above general formula (V) simultaneously has at least one partial structure satisfying the following condition (i) and at least one partial structure satisfying the following condition (iii).

[0074] Condition (i): R 21 ~R 24 are all hydrogen atoms.

[0075] Condition (iii):R 21 ~R 24 Any one of the above is an alkyl group having 1 to 4 carbon atoms, and the remaining three are a hydrogen atom.

[0076] For example, when the alkyl group represented by condition (iii) is a methyl group, the compound has an ethylene oxide structure and a propylene oxide structure in the same structure.

[0077] In the present 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, and 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.

[0078] In addition, in a more preferred embodiment, the compound having the structure represented by the above general formula (V) is a phosphate ester having the structure represented by the following general formula (VI). [ka] In the above general formula (VI), R, R 21 ~R 24, l and m have the same meanings as those in the above general formula (V). n is 1 or 2, and when n is 2, the structures in [ ] may be the same or different.

[0079] Next, specific examples of the compound having the structure represented by general formula (V) will be described.

[0080] First, an example of the structure of a representative example compound will be described.

[0081] Example Compound (V-1) Exemplary compound (V-1) is as shown in Table I below: R: methyl group, Condition (i): R 21 ~R 24 =H Condition (ii):R 21 =H, R 22 = methyl group, R 23 = methyl group, R 24 =H Z:Z-3 l:1.0 m:8.0 For example, it can be represented by the structure of the following exemplary compound (V-1-1). [ka] In the above exemplary compound (V-1-1), the order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure can be arbitrarily changed depending on the synthesis method applied, and the following exemplary compound (V-1-2) is also included in the exemplary compound (V-1). [ka] 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.

[0082] Example Compound (V-2) Exemplary compound (V-2) is as shown in Table I below: R: methyl group, Condition (i): R 21 ~R 24 =H Condition (ii):R 21 =H, R 22 =H, R 23 = methyl group, R 24 =H Z: Z-1, Z-2 l:2.0 m:3.0 The compound has the structure shown above, but is represented by the structure of Exemplary Compound (V-2-1) in which Z is Z-2, and the structure of Exemplary Compound (V-2-2) in which Z is Z-1. [ka] In the case of the exemplary compound (V-2), the monoester ratio is 50%, and the exemplary compounds (V-2-1) and (V-2-2) are contained in equal molar amounts.

[0083] As in the above-mentioned exemplary compound (V-1), in the exemplary compound (V-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 (V-2-3) and (V-2-4) are also included in the exemplary compound (V-2). [ka] 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.

[0084] Next, specific examples of compounds having a structure represented by general formula (V) are listed in the following Tables I to IV, but the present invention is not limited to these exemplary compounds. [Table 1]

[0085] [Table 2]

[0086] [Table 3]

[0087] [Table 4]

[0088] The compound having a structure represented by general formula (V) according to the present invention can be synthesized by referring to known methods described in, for example, JP-A-2005-255608, JP-A-2015-000396, JP-A-2015-000970, JP-A-2015-178072, JP-A-2015-178073, Japanese Patent No. 4422866, etc.

[0089] Synthesis of Example Compounds Next, representative examples of the synthesis of the compound having the structure represented by general formula (V) according to the present invention will be given, but the present invention is not limited to these synthesis methods.

[0090] Synthesis of exemplary compound (V-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 under conditions of a pressure of 147 kPa and a temperature of 130°C using potassium hydroxide as a catalyst, and then 88 g (2.0 mol) of ethylene oxide was added thereto.

[0091] Next, after confirming that no n-octanol remains, the adduct is placed in a reactor, and 47 g (0.33 mol) of phosphoric anhydride is reacted with the toluene solution at 80° C. for 5 hours. The adduct is then washed with distilled water, and the solvent is distilled off under reduced pressure to obtain Example Compound (V-49) (R=octyl group, Condition (i): R 21 =H, R 22 =H, R 23 =H, R 24 =H, condition (ii): R 21 =H, R 22=H, R 23 = methyl group, R 24 =H, l: 2.0, m: 2.0, Z: phosphate monoester (Z-2) / phosphate diester (Z-1)) was obtained. [ka]

[0092] Synthesis of exemplary compound (V-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 under conditions of a pressure of 147 kPa and a temperature of 130°C using potassium hydroxide as a catalyst, and then 110 g (2.5 mol) of ethylene oxide was added thereto.

[0093] Next, after confirming that no 2-ethylhexanol remains, the adduct is placed in a reactor, and reacted with 47 g (0.33 mol) of phosphoric anhydride in toluene at 80° C. for 5 hours. The adduct is then washed with distilled water, and the solvent is distilled off under reduced pressure to obtain the following exemplary compound (V-56) (R=2-ethylhexyl group, Condition (i): R 21 =H, R 22 =H, R 23 =H, R 24 =H, condition (ii): R 21 =H, R 22 =H, R 23 = methyl group, R 24 =H, l: 2.5, m: 2.5, Z: phosphate monoester (Z-2) / phosphate diester (Z-1)) was obtained. [ka]

[0094] Synthesis of exemplary compound (V-59) 130 g (1.0 mol) of 2-ethylhexanol was placed in an autoclave, and 58 g (1.0 mol) of propylene oxide was added thereto under conditions of a pressure of 147 kPa and a temperature of 130°C using potassium hydroxide as a catalyst, and then 132 g (3.0 mol) of ethylene oxide was added thereto.

[0095] Next, after confirming that no 2-ethylhexanol remains, the adduct is placed in a reactor, and 117 g (1.0 mol) of chlorosulfonic acid in a toluene solution is dropped into the reactor over about 1 hour to react with the adduct. The adduct is then washed with distilled water, and the solvent is distilled off under reduced pressure to obtain Example Compound (V-59) (R = 2-ethylhexyl group, Condition (i): R 21 =H, R 22 =H, R 23 =H, R 24 =H, condition (ii): R 21 =H, R 22 =H, R 23 = methyl group, R 24 = H, l: 3.0, m: 1.0, Z: sulfonic acid (Z-3)) was obtained. [ka]

[0096] Synthesis of Example Compound (V-94) 270g (1.0 mol) of stearyl alcohol was placed in an autoclave, and 174g (2.5 mol) of propylene oxide was added thereto under conditions of a pressure of 147 kPa and a temperature of 130°C using potassium hydroxide as a catalyst, and then 130g (3.0 mol) of ethylene oxide was added thereto.

[0097] Next, after confirming that no stearyl alcohol remains, the adduct is placed in a reactor, and reacted with 47 g (0.33 mol) of phosphoric anhydride in toluene at 80° C. for 5 hours. The adduct is then washed with distilled water, and the solvent is distilled off under reduced pressure to obtain the following exemplary compound (V-94) (R=stearyl group, Condition (i): R 21 =H, R 22 =H, R 23 =H, R 24 =H, condition (ii): R 21 =H, R 22 =H, R 23 = methyl group, R 24 =H, l: 3.0, m: 3.0, Z: phosphate monoester (Z-2) / phosphate diester (Z-1)) was obtained. [ka]

[0098] (Metal Components) The near-infrared absorbent according to the present invention preferably contains at least one of component (A) consisting of a compound having a structure represented by general formula (V) and a metal ion, and component (B) consisting of a metal complex obtained by a reaction between a compound having a structure represented by general formula (V) and a metal compound.

[0099] Metal species applicable to the metal ions in the above component (A) or the metal complexes in the component (B) include metal species belonging to Groups I to VIII of the periodic table, and are monovalent and polyvalent metals. Specific examples include aluminum, cobalt, chromium, copper, iron, magnesium, manganese, nickel, tin, titanium, zinc, etc., among which nickel, copper, chromium, cobalt, and zinc are preferred, and copper is most preferred.

[0100] In addition, in the near infrared absorbing agent according to the present invention, it is preferable that the metal species is applied as a complex, and in the case of copper, which is a representative example, the copper salt used is a copper salt capable of supplying divalent copper ions.For example, copper salts of organic acids such as anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous copper acetoacetate, anhydrous copper ethylacetoacetate, anhydrous copper methacrylate, anhydrous copper pyrophosphate, anhydrous copper naphthenate, anhydrous copper citrate, etc., hydrates or hydrates of the copper salts of the organic acids; copper oxide, copper chloride, copper sulfate, copper nitrate, copper phosphate, basic copper sulfate, basic copper carbonate, etc., copper salts of inorganic acids, hydrates or hydrates of the copper salts of the inorganic acids; copper hydroxide.

[0101] (Metal Complexes) As a method for synthesizing a metal complex obtained by reacting a compound having a structure represented by the above general formula (V) according to the present invention with a metal compound, for example, the methods described in Japanese Patent No. 4422866 and Japanese Patent No. 5953322 can be applied.

[0102] The general formula (V) according to the present invention is bound to a metal ion by a coordinate bond and / or an ionic bond via a phosphoric acid group or a sulfonic acid group represented by Z, and the metal ion is dissolved or dispersed in the near-infrared light absorbing film while being surrounded by the general formula (V). In the case of a copper ion, which is a representative example of a metal species, near-infrared light is selectively absorbed by electronic transition between d orbitals of the copper ion. In addition, in the case of a phosphoric acid group, which is a representative example of Z, it has been confirmed that the content of phosphorus atoms in the near-infrared light absorbing film is preferably 1.5 or less per mole of copper ion, and further, that is, the content ratio of phosphorus atoms to copper ions (hereinafter referred to as "P / Cu") is 0.3 to 1.3 in molar ratio, which is very suitable from the viewpoints of moisture resistance of the near-infrared light absorbing film, moisture resistance of the near-infrared light absorbing film, and dispersibility of copper ions in the near-infrared light absorbing layer.

[0103] If the molar ratio of P / Cu is less than 0.3, the copper ions coordinated to the compound represented by the general formula (V) become excessive, and the copper ions tend to be difficult to disperse uniformly in the near-infrared light absorbing film. On the other hand, if the molar ratio of P / Cu is more than 1.3, when the thickness of the near-infrared light absorbing film is thinned to increase the content of copper ions, devitrification tends to occur easily, and this tendency is particularly noticeable in a high-temperature and high-humidity environment. Furthermore, it is more preferable that the molar ratio of P / Cu is 0.8 to 1.3 mol. If this molar ratio is 0.8 or more, the dispersibility of copper ions in the resin can be reliably and sufficiently increased.

[0104] In addition, if the content of copper ions in the near-infrared absorbing film is less than the above lower limit, it tends to be difficult to obtain sufficient near-infrared light absorption when the thickness of the near-infrared absorbing film is made thinner than about 1 mm. On the other hand, if the content of copper ions exceeds the above upper limit, it tends to be difficult to disperse the copper ions in the near-infrared absorbing film.

[0105] (Average particle size of metal complex) The average particle size of the metal complex according to the present invention is preferably within a range of 1 to 200 nm, more preferably within a range of 1 to 100 nm, and particularly preferably within a range of 1 to 50 nm.

[0106] The average particle size of the metal complex in the present invention can be determined by dynamic light scattering using, for example, a Zeta potential / particle size measuring system ELSZ-1000ZS manufactured by Otsuka Electronics Co., Ltd. as a measuring device.

[0107] As another method, an electron micrograph of the metal complex particles is taken with a transmission electron microscope (magnification 500,000 to 2,000,000 times), the projected area of ​​the particle is measured, and the diameter when the measured value is taken as the area of ​​a circle corresponding to the projected area is measured as the particle size. The arithmetic average value of the measurements for 100 particles can be calculated as the average particle size.

[0108] [Phosphonic acid compounds, phosphoric acid compounds, sulfonic acid compounds and their metal complex compounds] The near infrared absorbing composition of the present invention preferably contains a phosphonic acid compound, a phosphoric acid compound, a sulfonic acid compound, or a metal complex compound thereof. It is further preferable to contain the phosphonic acid described below.

[0109] (Phosphate Compounds) Examples of the phosphoric acid compound include 1) Phosphate methyl ester 2) Phosphate Ethyl Ester 3) n-Propyl phosphate 4) i-Propyl phosphate 5) n-Butyl phosphate 6) t-Butyl Phosphate 7) n-Pentyl Phosphate 8) n-Hexyl Phosphate 9) 2-Ethylhexyl Phosphate 10) n-Heptyl Phosphate 11) Phosphate n-Octyl Ester 12) Cyclohexyl Phosphate etc. can be mentioned.

[0110] (Sulfonic acid compounds) Examples of the sulfonic acid compound include compounds described in JP-A-2015-430638.

[0111] (Phosphonic acid compounds) The near infrared absorbing composition of the present invention preferably contains a phosphonic acid compound having a structure represented by the following general formula (1). [ka] In the above general formula (1), R 1 represents a branched, linear or cyclic alkyl group, alkenyl group, alkynyl group, aryl group or allyl group having 1 to 30 carbon atoms, in which 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 carboxyl group, a hydroxyl group, or a group having an aromatic ring.

[0112] Examples of the phosphonic acid compound having the structure represented by general formula (1) 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, 4-methoxyphenylphosphonic acid, and the like, examples of which are illustrated as the following compounds (H-1) to (H-8).

[0113] [ka]

[0114] In the present invention, the phosphonic acid constituting the phosphonate copper complex is preferably at least one alkylphosphonic acid selected from the following phosphonic acid group:

[0115] 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 <Phosphonic acid metal complex> Next, the phosphonic acid metal complex suitable for the present invention will be described.

[0116] In the present invention, the metal constituting the phosphonic acid metal complex includes those which form complexes of metals belonging to Groups I to XIV of the periodic table, and are monovalent and polyvalent metals.Specific examples include aluminum, cobalt, chromium, copper, iron, magnesium, manganese, nickel, tin, titanium, zinc, etc., among which nickel, copper, chromium, cobalt, and zinc are preferred, and copper is most preferred.

[0117] Hereinafter, a phosphonic acid copper complex applicable to the present invention will be described as a representative example. The phosphonic acid copper complex has a structure represented by the following general formula (2). [ka] In general formula (2), R is an alkyl group, a phenyl group, or a benzyl group.

[0118] The copper salt used to form the phosphonic acid copper complex having the structure represented by the general formula (2) 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, and hydrates or hydrates of the copper salts of the organic acids; copper salts of inorganic acids such as copper oxide, copper chloride, copper sulfate, copper nitrate, copper phosphate, basic copper sulfate, and basic copper carbonate, and hydrates or hydrates of the copper salts of the inorganic acids; and copper hydroxide.

[0119] In the present invention, the phosphonic acid constituting the phosphonic acid copper complex is preferably an alkylphosphonic acid, and examples thereof include ethylphosphonic acid copper complex, propylphosphonic acid copper complex, butylphosphonic acid copper complex, pentylphosphonic acid copper complex, hexylphosphonic acid copper complex, octylphosphonic acid copper complex, 2-ethylhexylphosphonic acid copper complex, 2-chloroethylphosphonic acid copper complex, 3-bromopropylphosphonic acid copper complex, 3-methoxybutylphosphonic acid copper complex, 1,1-dimethylpropylphosphonic acid copper complex, 1,1-dimethylethylphosphonic acid copper complex, and 1-methylpropylphosphonic acid copper complex.

[0120] 〔solvent〕 Next, a solvent applicable to the preparation of the near-infrared absorbing composition of the present invention will be described.

[0121] 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-based solvents, and more preferably, aliphatic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, and halogenated solvents.

[0122] Examples of the aliphatic hydrocarbon solvent include non-cyclic aliphatic hydrocarbon solvents such as hexane and heptane, cyclic aliphatic hydrocarbon solvents such as cyclohexane, alcohol solvents such as methanol, ethanol, n-propanol, 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 the aromatic hydrocarbon solvent include toluene, xylene, mesitylene, cyclohexylbenzene, and isopropyl biphenyl. Examples of the halogen-based solvent include methylene chloride, 1,1,2-trichloroethane, and chloroform. In addition, examples of the halogen-based solvent 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.

[0123] In the near infrared absorbing composition of the present invention, at least one of the solvents preferably has a structure represented by the following general formula (3) and has a molecular weight of 190 or less. [ka] In the above general formula (3), R1 represents a hydrogen atom or a monovalent to tetravalent organic group, R2 represents an alkylene group having 2 to 4 carbon atoms, R3 represents a hydrogen atom, an alkyl group or an acyl group, a represents an integer of 0 to 10, and b represents an integer of 1 to 4. a is preferably an integer of 1 to 10. When b is 2 or more, the structures represented in parentheses may be the same or different.

[0124] Among the compounds represented by the above general formula (3), compounds in which b is 1 are preferred.

[0125] Furthermore, in the general formula (3), R1 represents a hydrogen atom, an acyl group having 2 to 10 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group having 6 to 10 carbon atoms, and at least one hydrogen atom bonded to a carbon atom constituting the alkyl group may be substituted with a halogen atom, a heteroatom or an aromatic ring, so long as the molecular weight is 190 or less. R2 represents an alkylene group having 2 to 4 carbon atoms, and n represents 1 to 10. The number of carbon atoms in the acyl group is preferably 2 to 10. The number of carbon atoms in the alkyl group is preferably 1 to 15. The number of carbon atoms in the aryl group or the aralkyl group is preferably 6 to 20. The number of carbon atoms in the alkylene group represented by R2 is preferably 2 to 3, more preferably 2.

[0126] In the above general formula (3), the acyl group represented by R1 includes a divalent acid group derived from a dicarboxylic acid, and examples thereof include a 2-ethylbutanoyl group, a (meth)acryloyl group, a propionyl group, a butyryl group, a valeryl group, an isovaleryl group, a hexanoyl group, and a heptane dioyl group. Among these, a (meth)acryloyl group and a 2-ethylhexanoyl group are preferred. Furthermore, examples of the alkyl group represented by R1 include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, and a nonyl group. Among these, a methyl group and a lauryl group are preferred. Furthermore, examples of the aryl group or aralkyl group represented by R1 include a phenyl group and a 4-nonylphenyl group. Furthermore, examples of the alkylene group represented by R2 include an ethylene group, a propylene group, a butylene group, and a tetramethylene group. By adopting such a group, the solubility and dispersibility of the copper-containing phosphate in the resin can be significantly improved.

[0127] An example of the solvent compound applicable to the present invention is shown below.

[0128] 1) PGMEA: Propylene glycol monomethyl ether acetate (molecular weight: 132) 2) PGEEA: Propylene glycol monoethyl ether acetate (molecular weight: 146) 3) PGBEA: Propylene glycol monobutyl ether acetate (molecular weight: 174) 4) Ethylene glycol diacetate (molecular weight: 146) 5) Ethylene glycol diglycidyl ether (molecular weight: 174) 6) Ethylene glycol monomethyl ether acetate (molecular weight: 118) 7) Ethylene glycol monoethyl ether acetate (molecular weight: 132) 8) Ethylene glycol monobutyl ether acetate (molecular weight: 160) 9) Ethylene glycol dibutyl ether (molecular weight: 174) 10) Ethylene glycol monoacetate (molecular weight: 104) 11) Ethylene glycol monoisopropyl ether (molecular weight: 104) 12) Ethylene glycol monoethyl ether (molecular weight: 90) 13) Ethylene glycol monomethoxymethyl ether (molecular weight: 106) 14) Glycerol 1,3-diacetate (molecular weight: 176) 15) Glycerol 1,2-dimethyl ether (molecular weight: 120) 16) Glycerol 1,3-dimethyl ether (molecular weight: 120) 17) Glycerol 1,3-diethyl ether (molecular weight: 148) 18) 2-chloro-1,3-propanediol (molecular weight 110) 19) 3-chloro-1,2-propanediol (molecular weight 110) 20) Diethylene glycol ethyl methyl ether (molecular weight: 148) 21) Diethylene glycol dimethyl ether (molecular weight: 134) 22) Diethylene glycol monoethyl ether acetate (molecular weight: 176) 23) Diethylene glycol monobutyl ether (molecular weight: 162) 24) Diethylene glycol monomethyl ether (molecular weight: 120) 25) Dipropylene glycol (molecular weight: 134) 26) Dipropylene glycol monopropyl ether (molecular weight: 176) 27) Triethylene glycol (molecular weight: 150) 28) Triethylene glycol dimethyl ether (molecular weight: 178) 29) Triethylene glycol monoethyl ether (molecular weight: 178) 30) Triethylene glycol monomethyl ether (molecular weight: 164) 31) Propylene glycol (molecular weight: 76) 32) Propylene glycol monoethyl ether (molecular weight: 104) Among the above solvents, the solvents shown in 1) to 17), 20) to 24), 26), 28) to 30), and 32) are particularly preferable.

[0129] (Other Solvents) Examples of other solvents that can be used in combination with the solvent having the structure represented by the above general formula (3) include dioxyethylene lauryl ether, trioxyethylene lauryl ether, tetraoxyethylene lauryl ether, pentaoxyethylene lauryl ether, hexaoxyethylene lauryl ether, heptaoxyethylene lauryl ether, octaoxyethylene lauryl ether, nonaoxyethylene lauryl ether, decaoxyethylene lauryl ether, undecaoxyethylene lauryl ether, dodecaoxyethylene lauryl ether, tridecaoxyethylene lauryl ether, and tetraoxyethylene lauryl ether. Examples of suitable ether compounds include ether compounds such as oxyethylene lauryl ether and tetradecaoxyethylene lauryl ether, diethylene glycol dimethacrylate (NK Ester 2G, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 242), triethylene glycol dimethacrylate (molecular weight: 286), polyethylene glycol #200 dimethacrylate (NK Ester 4G, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 330), tripropylene glycol propyl ether, triethylene glycol bis(2-ethylhexanate) (manufactured by Acros Co., Ltd.), and 1,3-butylene glycol dimethacrylate.

[0130] In addition, 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 particles), suppresses particle aggregation during storage, and provides better stability over time (dispersion stability and near-infrared absorbing ability of copper complex particles).The ratio is more preferably within a range of 10 to 20% by mass.

[0131] [Near infrared absorption regulator] In the near infrared absorbing composition of the present invention, it is preferable to add at least one near infrared absorption regulator having an absorption maximum wavelength in the wavelength range of 650 to 800 nm as an additive for adjusting the absorption waveform from the viewpoint of spectral characteristics. As the near infrared absorption regulator applied to the present invention, it is preferable to apply a near infrared absorbing dye having an absorption maximum wavelength in the wavelength range of 650 to 800 nm.

[0132] Examples of near-infrared absorbing dyes suitable for the present invention include cyanine dyes, squarylium dyes, croconium dyes, azo dyes, anthraquinone dyes, naphthoquinone dyes, phthalocyanine dyes, naphthalocyanine dyes, quaterrylene dyes, dithiol metal complex dyes, etc. Among these, phthalocyanine dyes, naphthalocyanine dyes, and quaterrylene dyes are particularly preferred in that they sufficiently absorb near-infrared rays, have high visible light transmittance, and are highly heat resistant.

[0133] Specific examples of the phthalocyanine compound include compounds described in, for example, JP-A-2000-26748, JP-A-2000-63691, JP-A-2001-106689, JP-A-2004-149752, JP-A-2004-18561, JP-A-2005-220060, JP-A-2007-169343, JP-A-2016-204536, JP-A-2016-218167, and the like, and can be synthesized according to the methods described in these publications.

[0134] Specific examples of the quaterrylene dye include the compounds described in JP-A-2008-009206 and JP-A-2011-225608, and the compounds can be synthesized according to the methods described in these publications.

[0135] The near-infrared absorbing dyes are also commercially available, for example, FDR002, FDR003, FDR004, FDR005, FDN001 (all manufactured by Yamada Chemical Industry Co., Ltd.), Excolor TX-EX720, Excolor TX-EX708K (all manufactured by Nippon Shokubai Co., Ltd.), Lumogen IR765, Lumogen IR788 (all manufactured by BASF), ABS694, IRA735, IRA742, IRA751, IRA764, IRA788, IRA800 (all manufactured by Exciton), epolight5548, epolight5768 (all manufactured by aako), VIS680E, VIS695A, NIR700B, NIR735B, NIR757A, NIR762A, NIR775B, NIR778A, NIR783C, NIR783I, NIR790B, NIR795A (all manufactured by QCR Examples of such products include trade names such as DLS740A, DLS740B, DLS740C, DLS744A, DLS745B, DLS771A, DLS774A, DLS774B, DLS775A, DLS775B, DLS780A, DLS780C, DLS782F (all manufactured by Crystalin), B4360, B4361, D4773, and D5013 (all manufactured by Tokyo Chemical Industry Co., Ltd.).

[0136] The near infrared absorbing dye is preferably added in an amount within a range of 0.01 to 0.1% by mass relative to 100% by mass of the near infrared absorbing agent constituting the near infrared absorbing composition.

[0137] When the amount of the near-infrared absorbing dye added is 0.01% by mass or more relative to 100% by mass of the near-infrared absorbent, the near-infrared absorption can be sufficiently increased, and when the amount is 0.1% by mass or less, the visible light transmittance of the obtained near-infrared absorbing composition is not impaired.

[0138] [Ultraviolet absorber] In the near infrared absorbing composition of the present invention, it is preferable from the viewpoints of spectral characteristics and light resistance that it further contains an ultraviolet absorbing agent in addition to the near infrared absorbing agent and the solvent.

[0139] The ultraviolet absorbing agent is not particularly limited, but examples thereof include benzotriazole-based ultraviolet absorbing agents, benzophenone-based ultraviolet absorbing agents, salicylic acid ester-based ultraviolet absorbing agents, cyanoacrylate-based ultraviolet absorbing agents, and triazine-based ultraviolet absorbing agents.

[0140] Benzotriazole-based ultraviolet absorbents include, for example, 5-chloro-2-(3,5-di-sec-butyl-2-hydroxylphenyl)-2H-benzotriazole, (2-2H-benzotriazol-2-yl)-6-(straight-chain and side-chain dodecyl)-4-methylphenol, etc. Benzotriazole-based ultraviolet absorbents are also available as commercial products, such as the TINUVIN series, including TINUVIN109, TINUVIN171, TINUVIN234, TINUVIN326, TINUVIN327, TINUVIN328, and TINUVIN928, all of which are commercial products manufactured by BASF.

[0141] 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).

[0142] Examples of the salicylic acid ester-based ultraviolet absorbers include phenyl salicylate and p-tert-butyl salicylate.

[0143] Examples of cyanoacrylate ultraviolet absorbers include 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, and ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl)-acrylate.

[0144] Examples of triazine-based ultraviolet absorbents include 2-(2'-hydroxy-4'-hexyloxyphenyl)-4,6-diphenyltriazine, etc. Examples of commercially available triazine-based ultraviolet absorbents include TINUVIN477 (manufactured by BASF).

[0145] The amount of the ultraviolet absorbing agent added is preferably within a range of 0.1 to 5.0% by mass relative to 100% by mass of the near infrared absorbing agent constituting the near infrared absorbing composition.

[0146] 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, 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.

[0147] Near-infrared absorbing film and its application fields One of the features of the present invention is that a near-infrared absorbing film is formed using the near-infrared absorbing composition of the present invention.

[0148] The near infrared absorbing film of the present invention is formed by adding a matrix resin to the near infrared absorbing composition of the present invention, and dispersing, for example, fine particles of a metal complex, and further, if necessary, a phosphonic acid metal complex, for example, a phosphonic acid copper complex, in the matrix resin. In addition, at least one of the near infrared dyes having an absorption maximum wavelength in the wavelength range of 650 to 800 nm can be added as an additive for adjusting the absorption waveform.

[0149] The near-infrared absorbing film-forming coating solution having the above-mentioned composition is applied onto a substrate by spin coating or a wet coating method using a dispenser to form a near-infrared absorbing film. Then, the coating film is cured by subjecting the coating film to a predetermined heat treatment to form a near-infrared absorbing film.

[0150] 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 can disperse fine particles of metal complexes and copper phosphonate complexes. Metal complexes and copper phosphonate complexes are relatively low polarity substances and disperse well in hydrophobic materials. For this reason, resins 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. Among them, 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. In addition, polysiloxane silicone resins are difficult to thermally decompose, have high transparency to visible light and near-infrared light, and have high heat resistance, so they have advantageous properties as 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. Polysiloxanes that can be used as the matrix resin of the near-infrared absorbing film are available as commercially available products, 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.

[0151] (Other additives) Other additives can be applied to the near-infrared absorbing film of the present invention within a range that does not impair the intended effect of the present invention. Examples of such additives include sensitizers, crosslinking agents, curing accelerators, fillers, heat curing accelerators, thermal polymerization inhibitors, plasticizers, etc., and further, adhesion accelerators to the substrate surface and other auxiliary agents (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension adjusters, chain transfer agents, etc.) may be used in combination.

[0152] By appropriately incorporating these components, it is possible to adjust the properties such as the stability and film properties of the near infrared absorbing film as desired.

[0153] For information on these components, reference can be made to the contents described in, for example, paragraphs 0183 to 0185 of JP 2012-003225 A, paragraphs 0101 to 0102 of JP 2008-250074 A, paragraphs 0103 to 0104 of JP 2008-250074 A, and paragraphs 0107 to 0109 of JP 2008-250074 A.

[0154] The near infrared absorbing composition of the present invention can be made into a liquid wet coating liquid, and therefore, for example, a near infrared absorbing film, for example, a near infrared cut filter, can be easily produced by a process having a simple coating device in which a film is formed by spin coating.

[0155] <Application to solid-state image sensors> The near-infrared absorbing film of the present invention is suitable for constituting, 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 adjustment members, optical elements (light amplification elements, wavelength conversion elements, etc.), Faraday elements, optical communication function devices such as isolators, elements for optical disks, etc.

[0156] The use of the near-infrared absorbing film having the near-infrared absorbing composition of the present invention is characterized in that it is applied to image sensors for solid-state imaging elements, particularly as a near-infrared cut filter on the light-receiving side of a solid-state imaging element substrate (for example, as a near-infrared cut filter for a wafer-level lens) or as a near-infrared cut filter on the back side (opposite to the light-receiving side) of a solid-state imaging element substrate.

[0157] By applying the near-infrared absorbing film of the present invention to an image sensor for a solid-state imaging device, it is possible to improve the visible transmittance, near-infrared absorption efficiency, heat and humidity resistance, and the like.

[0158] Specifically, the near-infrared absorbing film (near-infrared cut filter) of the present invention is provided on an image sensor for a solid-state imaging device.

[0159] FIG. 1 is a schematic cross-sectional view showing the configuration of a camera module equipped with a solid-state imaging device having an infrared cut filter that is the near-infrared absorbing film of the present invention.

[0160] A camera module 1 shown in FIG. 1 is connected to a circuit board 12, which is a mounting board, via solder balls 11, which are connecting members.

[0161] In detail, the camera module 1 is configured to include a solid-state imaging element substrate 10 having an imaging element section 13 on a first main surface of a silicon substrate, a planarization layer 8 provided on the first main surface side (light receiving side) of the solid-state imaging element substrate 10, a near-infrared cut filter (near-infrared absorbing film) 9 provided on the planarization layer 8, a glass substrate 3 (light-transmitting substrate) arranged above the near-infrared cut filter 9, a lens holder 5 arranged above the glass substrate 3 and having an imaging lens 4 in its internal space, and a light-shielding and electromagnetic shield 6 arranged to surround the periphery of the solid-state imaging element substrate 10 and the glass substrate 3. The respective members are bonded with adhesives 2 and 7.

[0162] The present invention relates to a method for manufacturing a camera module having a solid-state imaging element substrate and an infrared cut filter arranged on the light-receiving side of the solid-state imaging element substrate, and 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 liquid composition of the present invention.

[0163] Therefore, in the camera module 1, for example, the near-infrared absorbing composition of the present invention is spin-coated on the planarizing layer 8 to form a near-infrared absorbing film, thereby forming the infrared cut filter 9.

[0164] In the camera module 1, incident light L from the outside passes through the imaging lens 4, the glass substrate 3, the infrared cut filter 9, and the planarization layer 8 in this order, before reaching the imaging element portion of the solid-state imaging element substrate .

[0165] Moreover, the camera module 1 is connected to a circuit board 12 on the second main surface side of the solid-state imaging element substrate 10 via solder balls 11 (connecting material). EXAMPLES

[0166] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the examples, the terms "parts" and "%" are used, and unless otherwise specified, they represent "parts by mass" or "% by mass". Furthermore, unless otherwise specified, each operation was carried out at room temperature (25°C).

[0167] Example 1 Preparation of near-infrared absorbent (Preparation of near infrared absorber 1) Near infrared absorbent 1 was prepared according to the following method.

[0168] 16.54 g of copper acetate and 661.46 g of tetrahydrofuran (abbreviation: THF) as a solvent were mixed, and the copper acetate was dissolved using an ultrasonic irradiation machine. Undissolved copper acetate was removed by filtration, and 678 g of a copper acetate solution was obtained.

[0169] Next, a solution prepared by dissolving 43.86 g of exemplary compound (V-1), which is a compound represented by general formula (V), in 80.0 g of THF was added to 678 g of this copper acetate solution while stirring over a period of 30 minutes. Then, after stirring at room temperature for 16 hours, 238.97 g of toluene was added, and the solvent THF was evaporated over a period of 3 hours in an environment of 55 to 90°C to prepare 251.0 g of near-infrared absorbent 1 so that the solid content became 10 mass%.

[0170] (Preparation of near infrared absorber 2) Near infrared absorbent 2 was prepared in the same manner as in the preparation of near infrared absorbent 1, except that the same mole of nickel acetate was used instead of copper acetate.

[0171] (Preparation of near infrared absorber 3) Near infrared absorbent 3 was prepared in the same manner as in the preparation of near infrared absorbent 1, except that the same mole of cobalt acetate was used instead of copper acetate.

[0172] (Preparation of near infrared absorbers 4 to 9) Near infrared absorbents 4 to 9 were prepared in the same manner as in the preparation of the near infrared absorbent 1, except that the same moles of each of the exemplary compounds shown in Table V were used instead of the exemplary compound (V-1), which is a compound represented by general formula (V).

[0173] (Preparation of near infrared absorbers 10 to 19) In the preparation of the near infrared absorbent 1, 27% by mass of the exemplary compound (V-1) was changed to each of the exemplary compounds (same moles) shown in Tables V and VI. A solution in which each of the exemplary compounds was dissolved in 35 mL of THF was dropped into the copper acetate solution while stirring for 15 minutes. After stirring for 30 minutes, 45 mL of a THF solution in which the remaining 73% by mass was changed to each of the ligand compounds (same moles) shown in Table V was dropped into the solution over 15 minutes. The solution was stirred at room temperature for 16 hours, and then 238.97 g of anisole was added. The solvent THF was evaporated in an environment of 55 to 90° C. for 3 hours so that the solid content became 10% by mass, thereby preparing near infrared absorbents 10 to 19.

[0174] The ligand compound (indicated by *1 in the table) used in the preparation of near-infrared absorbent 19 described in Table VI is A-26 described in Table 1 in paragraph (0021) of JP2015-43063A.

[0175] (Preparation of near infrared absorber 20) In the preparation of the near-infrared absorbent 4, the exemplary compound (V-56) was dropped into a copper acetate solution and stirred at room temperature for 16 hours. Then, as shown in Table VI, 9.04 mg of a near-infrared absorbing dye FDR004 (maximum absorption wavelength: 716 nm, manufactured by Yamada Chemical Co., Ltd.) was added as a near-infrared absorption regulator, and 238.97 g of anisole was further added. The solvent THF was volatilized in an environment of 55 to 90° C. over 3 hours to adjust the solid content to 10 mass %, thereby preparing a near-infrared absorbent 20.

[0176] (Preparation of near infrared absorber 21) In the preparation of the near-infrared absorbent 13, the exemplary compound (V-56) was dropped into a copper acetate solution, and the solution was stirred at room temperature for 16 hours. Thereafter, 9.04 mg of a near-infrared absorbing dye FDR004 (maximum absorption wavelength: 716 nm, manufactured by Yamada Chemical Co., Ltd.) was added as a near-infrared absorption regulator shown in Table V, and 238.97 g of anisole was further added. The solvent THF was evaporated in an environment of 55 to 90° C. for 3 hours to adjust the solid content to 10 mass %, so as to prepare a near-infrared absorbent 21 in the same manner.

[0177] (Preparation of near infrared absorber 22) In the preparation of the near-infrared absorbent 13, the exemplary compound (V-56) was dropped into a copper acetate solution and stirred at room temperature for 16 hours, and then a near-infrared absorbent 22 was prepared in the same manner as above, except that 9.04 mg of FDR004, which is a near-infrared absorbing dye, and 21.59 mg of LumogenIR765 (manufactured by BASF) were used as the near-infrared absorption regulator shown in Table VI.

[0178] Preparation of near-infrared absorbing composition (Preparation of near infrared absorbing composition 1) To 100 g of near-infrared absorbent 1 having a solid content of 10 mass%, 5 g of a metal compound solution in which an exemplary compound (II-10, trade name: Orgatix TC-201, metal type: Ti, manufactured by Matsumoto Fine Chemical Co., Ltd.) which is a metal compound represented by general formula (II) was dissolved in THF at a concentration of 10 mass%, was added, and the mixture was stirred at room temperature for 10 minutes to prepare near-infrared absorbing composition 1. In near-infrared absorbing composition 1, the content of exemplary compound (II-10) which is a metal compound relative to near-infrared absorbent 1 is 5.0 mass%.

[0179] (Preparation of Near Infrared Absorbing Compositions 2 to 4) Near infrared absorbing compositions 2 to 4 were prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the near infrared absorbing agent 1 was changed to near infrared absorbing agents 2 to 4, respectively.

[0180] (Preparation of near infrared absorbing composition 5) Near infrared absorbing composition 5 was prepared in the same manner as in the preparation of the near infrared absorbing composition 4, except that, as the metal compound, exemplary compound (II-10) was changed to exemplary compound I-2 (trade name: Orgatix TA-21, metal type: Ti, manufactured by Matsumoto Fine Chemical Co., Ltd.), which is a compound represented by general formula (I).

[0181] (Preparation of near infrared absorbing composition 6) Near infrared absorbing composition 6 was prepared in the same manner as in the preparation of near infrared absorbing composition 4, except that, as the metal compound, exemplary compound (II-10) was changed to exemplary compound (III-1, Orgatix TC-800, metal type: Ti, manufactured by Matsumoto Fine Chemical Co., Ltd.), which is a compound represented by general formula (III).

[0182] (Preparation of near infrared absorbing composition 7) Near infrared absorbing composition 7 was prepared in the same manner as in the preparation of the near infrared absorbing composition 4, except that, as the metal compound, exemplary compound (II-10) was changed to exemplary compound (II-6, product name: Orgatix AL-3100, metal type: Al, manufactured by Matsumoto Fine Chemical Co., Ltd.), which is a compound represented by general formula (II).

[0183] (Preparation of near infrared absorbing composition 8) Near infrared absorbing composition 8 was prepared in the same manner as in the preparation of near infrared absorbing composition 4, except that, as the metal compound, exemplary compound (II-10) was changed to exemplary compound (II-5, product name: Orgatix ZC-700, metal type: Zr, manufactured by Matsumoto Fine Chemical Co., Ltd.), which is a compound represented by general formula (II).

[0184] (Preparation of near infrared absorbing composition 9) Near infrared absorbing composition 9 was prepared in the same manner as in the preparation of the near infrared absorbing composition 4, except that, as the metal compound, exemplary compound (II-10) was changed to exemplary compound (II-1, product name: Orgatix TC-100, metal type: Ti, manufactured by Matsumoto Fine Chemical Co., Ltd.), which is a compound represented by general formula (II).

[0185] (Preparation of near infrared absorbing composition 10) In the preparation of the near-infrared absorbing composition 4, the exemplary compound (II-10) was changed to an exemplary compound (II-3, product name: Orgatix TC-750, metal type: Ti, manufactured by Matsumoto Fine Chemical Co., Ltd.) which is a compound represented by general formula (II) as the metal compound, in the same manner as above, to prepare the near-infrared absorbing composition 10.

[0186] (Preparation of near infrared absorbing compositions 11 to 15) Near infrared absorbing compositions 11 to 15 were prepared in the same manner as in the preparation of the near infrared absorbing composition 4, except that the near infrared absorbing agent 1 was changed to near infrared absorbing agents 5 to 9, respectively.

[0187] (Preparation of near infrared absorbing composition 16) A near infrared absorbing composition 16 was prepared in the same manner as in the preparation of the near infrared absorbing composition 4, except that the amount of the exemplary compound (II-10) added to the near infrared absorbent 4 was changed to 0.01 mass %.

[0188] (Preparation of near infrared absorbing composition 17) Near infrared absorbing composition 17 was prepared in the same manner as in the preparation of the near infrared absorbing composition 4, except that the amount of the exemplary compound (II-10) added to the near infrared absorbent 4 was changed to 15.0 mass %.

[0189] (Preparation of near infrared absorbing composition 18) Near infrared absorbing composition 18 was prepared in the same manner as in the preparation of the near infrared absorbing composition 4, except that the amount of the exemplary compound (II-10) added to the near infrared absorbent 4 was changed to 30.0%.

[0190] (Preparation of near infrared absorbing compositions 19 to 22) Near infrared absorbing compositions 19 to 22 were prepared in the same manner as in the preparation of the near infrared absorbing composition 17, except that the near infrared absorbing agent 1 was changed to the near infrared absorbing agents 10 to 13. (Preparation of near infrared absorbing compositions 23 to 25) Near infrared absorbing compositions 23 to 25 were prepared in the same manner as in the preparation of the near infrared absorbing composition 22, except that the exemplary compound (II-10) was changed to exemplary compounds II-12 to II-14, which are compounds represented by general formula (II), as the metal compound.

[0191] (Preparation of near infrared absorbing composition 26) Near infrared absorbing composition 26 was prepared in the same manner as in preparation of near infrared absorbing composition 22, except that, as the metal compound, exemplary compound (II-10) was changed to exemplary compound (I-2, described above), which is a compound represented by general formula (I).

[0192] (Preparation of near infrared absorbing composition 27) A near infrared absorbing composition 27 was prepared in the same manner as in the preparation of the near infrared absorbing composition 22, except that, as the metal compound, the exemplary compound (II-10) was changed to the exemplary compound (III-1, described above), which is a compound represented by general formula (III).

[0193] (Preparation of near infrared absorbing composition 28) Near infrared absorbing composition 28 was prepared in the same manner as in the preparation of the near infrared absorbing composition 22, except that, as the metal compound, exemplary compound (II-10) was changed to exemplary compound (II-6, described above), which is a compound represented by general formula (II).

[0194] (Preparation of near infrared absorbing composition 29) A near infrared absorbing composition 29 was prepared in the same manner as in the preparation of the near infrared absorbing composition 22, except that, as the metal compound, the exemplary compound (II-10) was changed to the exemplary compound (II-5, described above), which is a compound represented by general formula (II).

[0195] (Preparation of near infrared absorbing compositions 30 to 38) Near infrared absorbing compositions 30 to 38 were prepared in the same manner as in the preparation of the near infrared absorbing composition 22, except that the near infrared absorbing agent 13 was changed to near infrared absorbing agents 14 to 22, respectively.

[0196] (Preparation of near infrared absorbing composition 39) A near infrared absorbing composition 39 was prepared in the same manner as in the preparation of the near infrared absorbing composition 17, except that the amount of the exemplary compound (II-10) added to the near infrared absorbent 4 was changed to 0.005 mass %.

[0197] (Preparation of near infrared absorbing composition 40) A near infrared absorbing composition 40 was prepared in the same manner as in the preparation of the near infrared absorbing composition 17, except that the amount of the exemplary compound (II-10) added to the near infrared absorbent 4 was changed to 35.0 mass %.

[0198] (Preparation of near infrared absorbing composition 41) Near infrared absorbing composition 41, which is a comparative example, was prepared in the same manner as in the preparation of the near infrared absorbing composition 1, except that the exemplary compound (II-10), which is a metal oxide, was not added.

[0199] (Preparation of near infrared absorbing composition 42) A near infrared absorbing composition 42, which is a comparative example, was prepared in the same manner as in the preparation of the near infrared absorbing composition 22, except that the exemplary compound (II-10) which is a metal oxide was not added.

[0200] The constitution of the near infrared absorbing composition prepared as above is shown in Tables V and VI. [Table 5]

[0201] [Table 6]

[0202] Evaluation of near-infrared absorbing composition For each of the near-infrared absorbing compositions prepared as above, the haze, transmittance of visible light and near-infrared light, and heat and humidity resistance were evaluated according to the following methods.

[0203] [Haze Measurement] Each near infrared absorbing composition was applied onto a glass substrate by spin coating, and heat-treated in an environment of 100° C. for 10 minutes to prepare an evaluation sample A for each composition.

[0204] Using NDH7000 (manufactured by Nippon Denshoku Industries Co., Ltd.), light was irradiated from the surface of each evaluation sample A on which the near infrared absorbing composition was applied, and the haze value of the light at that time (the ratio of diffuse transmittance to total light transmittance) was measured. The haze of the evaluation sample A measured by the above method was ranked according to the following criteria, and the haze was evaluated.

[0205] ◎: Haze is less than 1.0% ○: Haze is 1.0% or more and less than 5.0% △: Haze is 5.0% or more and less than 10.0% ×: Haze is 10.0% or more

[0206] [Evaluation of Spectral Transmittance] (Preparation of Evaluation Sample A) The spectral transmittance of the prepared evaluation sample A in the wavelength range of 300 to 1200 nm was measured using a spectrophotometer V-570 manufactured by JASCO Corporation as a measuring device. Next, the spectral transmittance was evaluated at 500 nm as the visible region and at 700 nm and 800 nm as the near-infrared region.

[0207] (Evaluation of transmittance 1 in the visible light region) The transmittance of each evaluation sample A measured by the above method at a wavelength of 500 nm was ranked according to the following criteria, and evaluation was performed with a transmittance of 1 in the visible region. ◎: Transmittance 1 at a wavelength of 500 nm is 95% or more ○: Transmittance 1 at a wavelength of 500 nm is 90% or more and less than 95% △: Transmittance 1 at a wavelength of 500 nm is 80% or more and less than 90% ×: The transmittance 1 at a wavelength of 500 nm is less than 80%.

[0208] (Transmittance evaluation in the near infrared region) The transmittance 2 at 700 nm and the transmittance 3 at 800 nm of each evaluation sample A measured by the above method were ranked according to the following criteria to evaluate the transmittance in the near infrared region. <Transmittance 2> ◎: Transmittance 2 at a wavelength of 700 nm is less than 5.0% ○: Transmittance 2 at a wavelength of 700 nm is 5.0% or more and less than 10.0% △: The transmittance 2 at a wavelength of 700 nm is 10.0% or more and less than 20.0%. ×: The transmittance 2 at a wavelength of 700 nm is 20.0% or more. <Transmittance 3> ◎: The transmittance 3 at a wavelength of 800 nm is less than 5.0% ○: The transmittance 3 at a wavelength of 800 nm is 5.0% or more and less than 10.0%. △: The transmittance 3 at a wavelength of 800 nm is 10.0% or more and less than 20.0%. ×: The transmittance 3 at a wavelength of 800 nm is 20.0% or more.

[0209] [Evaluation of heat and humidity resistance] Each of the evaluation samples A prepared above was left to stand for 10 days in an environment of 80° C. and 80% RH to obtain each of the evaluation samples B.

[0210] Next, for each sample B, the spectral transmittance in the wavelength range of 300 to 1200 nm was measured using a spectrophotometer V-570 manufactured by JASCO Corporation in the same manner as above.

[0211] Next, the average transmittance Tave1 in the wavelength range of 700 to 1200 nm of Sample A immediately after preparation and the average transmittance Tave2 in the wavelength range of 700 to 1200 nm of Sample B were calculated, and the decrease in visible light transmittance of Sample B's average transmittance Tave2 relative to the average transmittance Tave1 of Sample A (Tave1-Tave2) was determined. The visible light transmittance after storage was ranked according to the following criteria, and this was used as a measure of heat and humidity resistance.

[0212] ◎: The decrease in average transmittance is less than 1.0% ○: The decrease in average transmittance is 1.0% or more and less than 3.0%. △: The decrease in average transmittance is 3.0% or more and less than 5.0%. ×: The decrease in average transmittance is 5.0% or more. The results obtained are shown in Table VII. [Table 7]

[0213] As is clear from the results shown in Table VII, the near-infrared absorbing composition of the present invention has a lower haze, excellent spectral characteristics, a higher transmittance in the visible region (500 nm), and a lower transmittance in the near-infrared region (700 nm, 800 nm) than the comparative examples, and has an excellent near-infrared light blocking ability. In addition, the near-infrared absorbing composition of the present invention has a superior average transmittance stability to the comparative examples even when stored for a long period of time in a high-temperature environment in the presence of moisture.

[0214] In addition, as demonstrated in the near infrared absorbing compositions 19 to 31, it is found that the above-mentioned overall properties are further improved by adding a specific phosphonic acid compound, and further, as demonstrated in the near infrared absorbing compositions 33 to 35, it is found that the above-mentioned overall properties are further improved by adding a specific near infrared absorbing dye.

[0215] Furthermore, the near infrared absorbing composition of the present invention is inhibited from decreasing in average visible transmittance when stored in a high-temperature environment. This means that deterioration in transmittance caused by aggregation of metal complex particles due to the effects of heat and humidity is inhibited, and it is found that the near infrared absorbing composition of the present invention is particularly excellent in stability under heat and humidity storage.

[0216] Example 2 <<Preparation of near-infrared absorbing film>> A coating liquid for forming a near-infrared absorbing film was prepared by adding a polysiloxane silicone resin (KR-255, manufactured by Shin-Etsu Chemical Co., Ltd.) to each near-infrared absorbing composition prepared in Example 1 and stirring the mixture. The prepared coating liquid was applied onto a substrate by spin coating to produce near-infrared absorbing films 1 to 39.

[0217] Next, the near-infrared absorbing film was subjected to a predetermined heat treatment to harden the coating film, thereby producing near-infrared cut filters 1 to 39 applicable to image sensors for solid-state imaging devices.

[0218] For each of the near-infrared cut filters prepared above, the visible light transmittance and near-infrared transmittance in the film state were evaluated in the same manner as in Example 1. As a result, it was confirmed that the same effects could be obtained in the near-infrared cut filter system.

[0219] In addition, the near-infrared cut filters prepared were stored for 10 days in an environment of 80°C and 80% RH, and then similar measurements were carried out. As a result, it was confirmed that the near-infrared cut filters using the near-infrared absorbing film of the present invention did not generate haze and showed good spectral characteristics similar to those before storage. [Industrial Applicability]

[0220] The near-infrared absorbing composition of the present invention has low haze and excellent near-infrared light absorption ability, improves the dispersion stability (moisture resistance) of the metal complex when moisture is mixed in, and has excellent thermal stability of the metal complex. A near-infrared absorbing film prepared from the near-infrared absorbing composition can be suitably used for image sensors for solid-state imaging devices applied to video cameras, digital still cameras, mobile phones with camera functions, etc. [Explanation of symbols]

[0221] 1 Camera module 2, 7 Adhesive 3. Glass substrate 4 Imaging lens 5 Lens holder 6 Light shielding and electromagnetic shielding 8 Planarization layer 9. Near-infrared absorbing film (near-infrared cut filter) 10 Solid-state image sensor board 11 Solder ball 12 Circuit Board 13. Image sensor section

Claims

1. A near-infrared absorbing composition containing at least a near-infrared absorbent, a titanium compound, and a solvent, wherein the near-infrared absorbent contains a metal ion, and the titanium compound is a titanium octylene glycolate compound having a structure represented by the following formula II-10, formula II-11, or formula II-12. 【Chemistry 1】

2. 2. The near-infrared absorbing composition according to claim 1, wherein the near-infrared absorbing agent contains at least one of the following components (A) and (B): Component (A): A component consisting of a compound having a structure represented by the following general formula (IV) and a metal ion Component (B): A component consisting of a metal complex obtained by reacting a compound having a structure represented by the following general formula (IV) with a metal compound. General formula (IV) R ０ -O-Z [In the above general formula (IV), R ０ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R ０ The substituents may further include alkyl groups, alkoxy groups, halogen Z may have a structural unit selected from the following formulae (Z-1) to (Z-3): 【Chemistry 2】 The symbol * in the above formulas (Z-1) to (Z-3) represents a bonding site, and bonds to O in the above general formula (IV).

3. 3. The near infrared absorbing composition according to claim 2, wherein the compound having a structure represented by the general formula (IV) is at least one compound selected from a phosphoric acid ester compound or a sulfonic acid ester compound having a structure represented by the following general formula (V): 【Chemistry 3】 [In the above general formula (V), R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R may further have an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a dialkylamino group, a trialkylsilyl group, a triarylsilyl group, a triheteroarylsilyl group, a benzyl group, an aryl group, or a heteroaryl group as a substituent. Z represents a structural unit selected from the above formulae (Z-1) to (Z-3). R ２１ ~R ２４ each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, the compound having the structure represented by formula (V) 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 ２１ ~R ２４ are all hydrogen atoms. Condition (ii): R ２１ ~R ２４ At least one of the groups is an alkyl group having 1 to 4 carbon atoms. In the general formula (V), l is R defined in the above condition (i). ２１ ~R ２４ represents the number of partial structures in which all are hydrogen atoms, and m is R ２１ ~R ２４ At least one of the above represents the number of partial structures that are alkyl groups having 1 to 4 carbon atoms, and l and m are each numbers within the range of 1 to 8.

4. A near-infrared absorbing composition containing at least a near-infrared absorbent, a titanium compound, and a solvent, The near-infrared absorbent contains a metal ion and at least one of the following components (A) and (B): Component (A): a component comprising at least one compound selected from a phosphoric acid ester compound or a sulfonic acid ester compound having a structure represented by the following general formula (V) and a metal ion. Component (B): a compound obtained by reacting at least one compound selected from a phosphoric acid ester compound or a sulfonic acid ester compound having a structure represented by the following general formula (V) with a metal compound. A component consisting of a metal complex obtained by 【Chemistry 4】 [In the above general formula (V), R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R may further have an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a dialkylamino group, a trialkylsilyl group, a triarylsilyl group, a triheteroarylsilyl group, a benzyl group, an aryl group, or a heteroaryl group as a substituent. R 21 to R 24 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, the compound having the structure represented by formula (V) 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 21 to R 24 are all hydrogen atoms. Condition (ii): At least one of R 21 to R 24 is an alkyl group having 1 to 4 carbon atoms. In general formula (V), l represents the number of partial structures in which R 21 to R 24 as specified in the above condition (i) are all hydrogen atoms, m represents the number of partial structures in which at least one of R 21 to R 24 as specified in the above condition (ii) is an alkyl group having 1 to 4 carbon atoms, and l and m are each numbers within the range of 1 to 8. Z represents a structural unit selected from the following formulas (Z-1) to (Z-3). 【Chemistry 5】 The symbol * in the above formulas (Z-1) to (Z-3) represents a bonding site, and bonds to O in the above general formula (V). The titanium compound is a compound having a structure represented by the following general formula (III): General formula (III) (OR 3) nm M n+ (-OCOR 4) m [In the above general formula (III), M is titanium, n=4, and m=1, 2, 3, or 4. R 3 and R 4 each independently represent an alkyl group having 1 to 30 carbon atoms, and R 3 and R 4 may further have, as a substituent, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a dialkylamino group, a trialkylsilyl group, a triarylsilyl group, a triheteroarylsilyl group, a benzyl group, an aryl group, or a heteroaryl group.] A near infrared absorbing composition comprising:

5. The near infrared absorbing composition according to any one of claims 1 to 4, characterized in that the titanium compound is contained in an amount within a range of 0.01 to 30 mass % relative to the near infrared absorbing agent.

6. The metal ion or the metal complex contained in the near infrared absorbent is copper.

5. The near infrared absorbing composition according to claim 2, wherein

7. The near infrared absorbing composition according to any one of claims 1 to 6, characterized in that it contains a phosphonic acid compound.

8. A near-infrared absorbing film, comprising the near-infrared absorbing composition according to any one of claims 1 to 7.

9. An image sensor for a solid-state imaging device, comprising the near-infrared absorbing film according to claim 8.

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