Near-infrared absorbing composition, near-infrared absorbing cured film, and optical component

Abstract

To provide a near-infrared absorbing composition which offers superior dispersion stability and resin compatibility and reduces the environmental load, and to provide a near-infrared absorbing cured film and an optical member.SOLUTION: A near-infrared absorbing composition containing a near-infrared absorbing agent and a dispersion medium is provided, the dispersion medium containing a solvent having a value for the polar term δP of the Hansen solubility parameter in a range of 3 to 6 and a value for the hydrogen bond term δH in a range of 3 to 6.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a near-infrared absorbing composition, a near-infrared absorbing cured film, and an optical component. More specifically, it relates to a near-infrared absorbing composition, a near-infrared absorbing cured film, and an optical component that are excellent in dispersion stability and resin compatibility, and can reduce environmental impact. [Background technology]

[0002] In recent years, video cameras, digital still cameras, and mobile phones with camera functions have used CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor) image sensors, which are solid-state image sensors for color images. However, these solid-state image sensors use silicon photodiodes that are sensitive to light in the near-infrared wavelength range in their light-receiving section, so it is necessary to correct the visual sensitivity, and a near-infrared cut filter is often used as an optical filter.

[0003] These near-infrared cut filters can be broadly divided into absorption and reflection types. Conventionally, the reflection type has been used, utilizing light reflection by a dielectric multilayer film to block infrared or ultraviolet rays. However, because the reflective layer used in reflective filters is highly dependent on the angle of incidence, total absorption filters are currently the main focus of research, and optical filters using films containing light-absorbing agents have recently attracted attention. As described above, optical filters using films containing light-absorbing agents are advantageous in terms of miniaturizing and thinning imaging devices. Furthermore, because the transmittance characteristics of the optical filter are less affected by the angle of incidence when light is incident, good images with minimal color changes can be obtained during shooting, even when light is incident at an oblique angle.

[0004] For example, Patent Document 1 discloses a method for producing a near-infrared absorbing agent dispersion containing a phosphonic acid compound and copper ions, and a near-infrared absorbing agent dispersion. However, the only organic solvent used in the preparation of the dispersion described above is the reaction solvent for the near-infrared absorber, and toluene is used as this reaction solvent. However, volatile aromatic hydrocarbons such as benzene, toluene, and xylene are subject to the PRTR system, which poses a problem because they have an environmental impact.

[0005] Patent Document 2 discloses an optical filter comprising a transparent dielectric substrate and a light-absorbing layer containing a light-absorbing agent formed by a phosphonic acid having a phenyl group or a halogenated phenyl group and copper ions, as well as a light-absorbing composition for forming the light-absorbing layer. Here, the above-mentioned light absorber may aggregate or precipitate in relatively polar organic solvents such as alcohol. Therefore, the polarity of the light absorber is considered to be low enough to show affinity for low-polarity organic solvents such as toluene. In order to disperse this light absorber well, it is considered that such a low-polarity organic solvent is necessary. However, using toluene and the like presents the same environmental burden problem as described above. Furthermore, some resins have poor compatibility with dispersions containing toluene, which limits the range of resins that can be included in the light-absorbing composition. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2016-94512 [Patent Document 2] Patent No. 6339755 [Overview of the project] [Problems that the invention aims to solve]

[0007] This invention has been made in view of the above-mentioned problems and circumstances, and its objective is to provide a near-infrared absorbing composition, a near-infrared absorbing cured film, and an optical component that are excellent in dispersion stability and resin compatibility, and that can reduce environmental impact. [Means for solving the problem]

[0008] In order to solve the above problem, the inventors investigated the cause of the above problem and found that the dispersion medium contained in the near-infrared absorbing composition has a polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 6, and the hydrogen bond term δ H We discovered that the above problems can be solved by including a solvent in which the value of is within the range of 3 to 6, and thus arrived at the present invention. In other words, the above-mentioned problems according to the present invention are solved by the following means.

[0009] 1. A near-infrared absorbing composition containing a near-infrared absorbing agent and a dispersion medium, The near-infrared absorber contains at least the following component (A) or component (B): The dispersion medium is the polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 6, and the hydrogen bond term δ H The solvent contains a value within the range of 3 to 6. The solvent is an ether having a cyclopentyl group, a cyclohexyl group, or a tetrahydropyranyl group. A near-infrared absorbing composition characterized by the following:

[0011] Ingredients: (A) Components: Components consisting of a compound having the structure represented by the following general formula (I), a compound having the structure represented by the following general formula (II), and copper ions. (B) Component: A component consisting of a copper complex coordinated with a compound having the structure represented by the following general formula (I) and a copper complex coordinated with a compound having the structure represented by the following general formula (II).

[0012] [ka]

[0013] [In the above general formula (I), R 1 This represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have substituents.

[0014] [ka]

[0015] 〔In the above general formula (II), R 2 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have a substituent. R 21 to R 24 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m represents the average number of added units of the partial structural unit in which all of R 21 to R 24 are hydrogen atoms, and is in the range of 0 to 19. n represents the average number of added units of the partial structural unit in which at least one of R 21 to R 24 is an alkyl group having 1 to 4 carbon atoms, and is in the range of 0 to 19. m + n is the total number of m and n, and is in the range of 1 to 20. Z represents a structural unit selected from the following general formulas (Z-1) to (Z-3).〕

[0016]

Chemical formula

[0017] 2 . The dispersion medium contains at least one solvent in which the value of the dispersion term δ D of the Hansen solubility parameter is in the range of 16 to 22, and is characterized in that it is the near-infrared absorbing composition according to the first In the section description.

[0018] 3 . The dispersion medium contains at least one solvent in which the value of the polar term δ P of the Hansen solubility parameter is in the range of 3 to 5, and the value of the hydrogen bonding term δ H is in the range of 3 to 5, and is characterized in that it is the near-infrared absorbing composition according to item 1 or The In item 2 description.

[0019] 4 . The dispersion medium contains a solvent having a boiling point in the range of 80 to 150 °C, and is characterized in that it is from item 1 to the 3A near-infrared absorbing composition as described in any one of the items up to item [number].

[0023] 5 The dispersion medium is characterized in that it contains at least cyclopentyl methyl ether or 4-methyltetrahydropyran. 4 A near-infrared absorbing composition as described in any one of the items up to item [number].

[0024] 6 The dispersion medium is the polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 6, and the hydrogen bond term δ H The first to third paragraphs are characterized by containing a solvent in which the value is in the range of 3 to 6 in an amount of 20 to 95% by mass relative to the total amount of the near-infrared absorbing composition. 5 A near-infrared absorbing composition as described in any one of the items up to item [number].

[0025] 7 The first to the second terms of the general formula (II) are characterized in that m is in the range of 1 to 19 and n is in the range of 1 to 19. 6 A near-infrared absorbing composition as described in any one of the items up to item [number].

[0026] 8 The molar content of the compound having the structure represented by the general formula (I) is C A The molar content of the compound having the structure represented by the general formula (II) is set to C E The molar ratio C in this case A / C E The value is within the range of 3.8 to 10, and the molar content of copper ions is C C The molar content of reactive hydroxyl groups in the compound having the structure represented by the general formula (I) and the compound having the structure represented by the general formula (II) is set to C H The molar ratio C in this case H / C C The first to third paragraphs are characterized in that the value of is within the range of 1.5 to 2.5. 7 A near-infrared absorbing composition as described in any one of the items up to item [number].

[0027] 9 Articles 1 through 1 8 A near-infrared absorbing cured film characterized by containing a cured product of a near-infrared absorbing composition described in any one of the items up to item [number].

[0028] 10 Articles 1 through 1 8 An optical component characterized by containing a cured product of a near-infrared absorbing composition described in any one of the items up to item [number]. [Effects of the Invention]

[0029] The present invention provides a near-infrared absorbing composition, a near-infrared absorbing cured film, and an optical component that exhibit excellent dispersion stability and resin compatibility, and reduce environmental impact. Although the mechanism by which the effects of this invention manifest or the mechanism of action are not yet clear, we speculate as follows.

[0030] The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition comprising a near-infrared absorbing agent and a dispersion medium, wherein the dispersion medium is the polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 6, and the hydrogen bond term δ H It is characterized by containing a solvent in which the value is within the range of 3 to 6.

[0031] As mentioned above, the light absorbers contained in the films used in conventional optical filters have low polarity, and aggregation or sedimentation of these light absorbers was prevented by using them together with organic solvents such as toluene, which also have low polarity. However, since toluene and similar substances are subject to the PRTR system, there was a problem in terms of the environmental burden they placed on the environment. In this invention, it is possible to prevent aggregation or sedimentation of the light-absorbing material by controlling the value of the Hansen solubility parameter within a certain range, without using low-polarity organic solvents such as toluene. This is presumed to improve dispersion stability and resin compatibility, and reduce environmental impact. [Brief explanation of the drawing]

[0032] [Figure 1] A schematic cross-sectional diagram showing an example of the configuration of a near-infrared cut filter. [Figure 2] A schematic cross-sectional view showing an example of the configuration of an image sensor for a solid-state image sensor. [Figure 3] A schematic cross-sectional view showing an example of the camera module configuration. [Modes for carrying out the invention]

[0033] The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition comprising a near-infrared absorbing agent and a dispersion medium, wherein the dispersion medium is the polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 6, and the hydrogen bond term δ H It is characterized by containing a solvent in which the value is within the range of 3 to 6. This feature is a technical feature common to or corresponding to each of the embodiments (appearances) described below.

[0034] In embodiments of the present invention, it is preferable that the near-infrared absorber contains at least component (A) or component (B) from the viewpoint of dispersion stability and resin compatibility.

[0035] The dispersion medium is the dispersion term δ of the Hansen solubility parameter. D From the viewpoint of dispersion stability, it is preferable to include at least one solvent in which the value of is in the range of 16 to 22.

[0036] The dispersion medium is the polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 5, and the hydrogen bond term δ H From the viewpoint of dispersion stability, it is preferable to include at least one solvent whose value is in the range of 3 to 5.

[0037] From the viewpoint of preventing cracking during film formation, it is preferable that the dispersion medium contains a solvent with a boiling point in the range of 80 to 150°C.

[0038] From the viewpoint of dispersibility, it is preferable that the dispersion medium contains at least a cycloalkyl group or an ether having a cycloether group.

[0039] From the viewpoint of dispersibility, it is more preferable that the cycloalkyl group is a cyclopentyl group or a cyclohexyl group.

[0040] From the viewpoint of dispersibility, it is more preferable that the cycloether group is a tetrahydrofuran group or a tetrapyran group.

[0041] It is even more preferable from the viewpoint of dispersibility that the dispersion medium contains at least cyclopentyl methyl ether or 4-methyltetrahydropyran.

[0042] The dispersion medium is the polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 6, and the hydrogen bond term δ H From the viewpoint of dispersion stability, it is more preferable to include a solvent with a value in the range of 3 to 6 in an amount of 20 to 95% by mass relative to the total amount of the near-infrared absorbing composition.

[0043] In the general formula (II) described above, it is preferable from the viewpoint of variability and dispersion stability that m is in the range of 1 to 19 and n is in the range of 1 to 19.

[0044] The molar content of the compound having the structure represented by the general formula (I) is C A The molar content of the compound having the structure represented by the general formula (II) is set to C E The molar ratio C in this case A / C E The value is within the range of 3.8 to 10, and the molar content of copper ions is C C The molar content of reactive hydroxyl groups in the compound having the structure represented by the general formula (I) and the compound having the structure represented by the general formula (II) is set to C H The molar ratio C in this case H / C CA value within the range of 1.5 to 2.5 is preferable from the viewpoint of improving near-infrared absorption, resistance to moist heat, and dispersibility of complex fine particles, and providing excellent visual sensitivity correction.

[0045] The near-infrared absorbing cured film of the present invention is characterized by containing a cured product of a near-infrared absorbing composition. This enables the effects of the present invention to be realized and solves the problem.

[0046] The optical component of the present invention is characterized by containing a cured product of a near-infrared absorbing composition. This enables the effects of the present invention to be realized and solves the problem.

[0047] The present invention, its components, and embodiments and models for carrying out the present invention will be described in detail below. In this application, "~" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0048] 1. Overview of Near-Infrared Absorbing Compositions The near-infrared absorbing composition of the present invention is a near-infrared absorbing composition comprising a near-infrared absorbing agent and a dispersion medium, wherein the dispersion medium is the polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 6, and the hydrogen bond term δ H It is characterized by containing a solvent in which the value is within the range of 3 to 6. Furthermore, the near-infrared absorbing composition of the present invention may contain other additives, and for example, the inclusion of an organic dye is preferable from the viewpoint of being able to adjust the absorption wavelength. Furthermore, the inclusion of an ultraviolet absorber is preferable from the viewpoint of spectral properties and light resistance.

[0049] (1.1) Dispersion medium The dispersion medium according to the present invention has a polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 6, and the hydrogen bond term δ H It contains a solvent whose value is within the range of 3 to 6.

[0050] (1.1.1) Hansen solubility parameters The Hansen solubility parameter (also known as the HSP value) is an index that represents the solubility of a substance, indicating how much of it dissolves in another substance. The solubility parameter, introduced by Hildebrand, has a dispersion term δ D , polarity term δ P , hydrogen bond term δ H This is a representation of the three components of the expression, expressed in three-dimensional space.

[0051] Dispersion term δ D This is the effect due to dispersion forces, polar term δ P This is the effect due to the dipole force, and the hydrogen bond term δ H This demonstrates the effect due to hydrogen bonding force. δ D Energy derived from intermolecular dispersion forces δ P Energy derived from intermolecular polar forces δ H : Energy derived from intermolecular hydrogen bonding forces This is how it is written (where each value δ D , δ P and δ H Each unit is MPa 1 / 2 (That is the case.)

[0052] The definition and calculation method of HSP values ​​are described in "Hansen Solubility Parameters: A Users Handbook" by Charles M. Hansen (CRC Press, 2007).

[0053] Dispersion term δ D δ is the van der Waals force, polar term δ P This is the dipole moment, hydrogen bond term δ H These reflect the effects of water, alcohol, etc., respectively. Furthermore, substances with similar vectors based on HSP values ​​can be judged to have high solubility, and the similarity of these vectors can be determined by the distance between Hansen solubility parameters (HSP distance). Furthermore, Hansen's solubility parameter can be used not only to judge solubility, but also as an indicator of how easily a substance can exist in another substance, that is, how well it disperses.

[0054] The HSP values ​​listed for the various solvents used in this invention were obtained using the commercially available computer software Hansen Solubility Parameters in Practice (HSPiP).

[0055] The dispersion medium according to the present invention has a dispersion term δ of the Hansen solubility parameter. D From the viewpoint of dispersion stability, it is preferable to include at least one solvent in which the value of is in the range of 16 to 22.

[0056] The dispersion medium according to the present invention is the polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 5, and the hydrogen bond term δ H From the viewpoint of dispersion stability, it is preferable to include at least one solvent whose value is in the range of 3 to 5.

[0057] The dispersion medium according to the present invention is the polar term δ of the Hansen solubility parameter. P The value is in the range of 3 to 6, and the hydrogen bond term δ H From the viewpoint of dispersion stability, it is more preferable to include a solvent with a value in the range of 3 to 6 in an amount of 20 to 95% by mass relative to the total amount of the near-infrared absorbing composition.

[0058] (1.1.2) solvent The dispersion medium according to the present invention has a polarity term δ of the Hansen solubility parameter. P The value is in the range of 3 to 6, and the hydrogen bond term δ H The solvent must contain a value within the range of 3 to 6. The solvents that can be used in the present invention are not particularly limited as long as they satisfy the requirements of the Hansen solubility parameter described above, but examples include hydrocarbon solvents, and among these hydrocarbon solvents, aliphatic hydrocarbon solvents, ether solvents, etc., are preferred. Furthermore, solvents having other chemical structures can be used as long as they do not hinder the effects of the present invention.

[0059] Examples of aliphatic hydrocarbon solvents include cyclic aliphatic hydrocarbon solvents such as cyclohexane, and ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol monomethyl ether. In particular, from the viewpoint of dispersibility, it is preferable that the dispersion medium contains, as a solvent, an ether having at least a cycloalkyl group or a cycloether group. Furthermore, from the viewpoint of dispersibility, it is more preferable that the cycloalkyl group is a cyclopentyl group or a cyclohexyl group, and that the cycloether group is a tetrahydrofuran group or a tetrapyran group.

[0060] In this invention, "dispersibility" refers to the performance or function of a dispersion medium that appropriately disperses copper ions, copper complexes, compounds having a structure represented by general formula (I) or (II), etc., which are included as components of the near-infrared absorbing composition, within the near-infrared absorbing composition. Furthermore, "dispersion stability" refers to the performance or function of maintaining an appropriate state in which the dispersion state of the various components constituting the near-infrared absorbing composition does not change or changes little over time due to changes in environmental conditions, etc.

[0061] For example, from the viewpoint of dispersibility, it is even more preferable that the dispersion medium contains at least cyclopentyl methyl ether or 4-methyltetrahydropyran and derivatives having a structure derived from these compounds or compounds having a similar structure. In particular, the dispersibility is further improved when the dispersion medium contains cyclopentyl methyl ether as a solvent.

[0062] Examples of compounds having structures derived from or similar to cyclopentyl methyl ether or 4-methyltetrahydropyran include the following compounds: [ka]

[0063] (boiling point) From the viewpoint of preventing cracking during film formation, it is preferable that the dispersion medium according to the present invention contains a solvent having a boiling point in the range of 80 to 150°C.

[0064] (Components other than the solvent) The ratio of solids (components other than the solvent) to the total amount of the near-infrared absorbing composition (dispersion) described later is preferably in the range of 5 to 30% by mass, as this ensures an appropriate concentration of solids (e.g., copper complex fine particles), suppresses particle aggregation during storage, and allows for better long-term stability (dispersion stability and near-infrared absorption of copper complex fine particles), and is more preferably in the range of 10 to 20% by mass.

[0065] (1.2) Near-infrared absorbers From the viewpoint of dispersion stability and resin compatibility, it is preferable that the near-infrared absorber according to the present invention contains at least the following component (A) or component (B).

[0066] Ingredients: (A) Components: Components consisting of a compound having the structure represented by the following general formula (I), a compound having the structure represented by the following general formula (II), and copper ions. (B) Component: A component consisting of a copper complex coordinated with a compound having the structure represented by the following general formula (I) and a copper complex coordinated with a compound having the structure represented by the following general formula (II).

[0067] (1.2.1) Compounds having a structure represented by general formula (I) Compounds having the structure represented by the following general formula (I) are phosphonic acid compounds that can absorb near-infrared light by forming copper phosphonic acid complexes, as described later.

[0068] [ka]

[0069] [In the above general formula (I), R 1 This represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have substituents.

[0070] R 1 Examples of substituents that may be present include alkyl groups (e.g., methyl group, ethyl group, trifluoromethyl group, isopropyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), halogen atoms (e.g., fluorine atom, etc.), cyano groups, nitro groups, dialkylamino groups (e.g., dimethylamino group, etc.), trialkylsilyl groups (e.g., trimethylsilyl group, etc.), triarylsilyl groups (e.g., triphenylsilyl group, etc.), triheteroarylsilyl groups (e.g., tripyridylsilyl group, etc.), benzyl groups, and heteroaryl groups (e.g., pyridyl group, carbazolyl group, etc.). Examples of fused rings include 9,9′-dimethylfluorene, carbazole, and dibenzofuran.

[0071] In the structure represented by the above general formula (I), R 1 It is preferable that the alkyl group has 1 to 20 carbon atoms, as this provides good resistance to moist heat and near-infrared absorption. Also, R 1 However, alkyl groups with 1 to 4 carbon atoms are more preferable because they can achieve both near-infrared absorption and visible light transmission.

[0072] (Compound example) Among compounds having a structure represented by general formula (I) (phosphonic acid compounds), R 1Examples of alkyl groups having 1 to 20 carbon atoms include methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, and decylphosphonic acid. Also, R 1 Examples of compounds in which the group has 6 to 20 carbon atoms as an aryl group include phenylphosphonic acid, 4-methoxyphenylphosphonic acid, (4-aminophenyl)phosphonic acid, (4-bromophenyl)phosphonic acid, 3-phosphonobenzoic acid, 4-phosphonobenzoic acid, and (4-hydroxyphenyl)phosphonic acid.

[0073] The compound having the structure represented by general formula (I) (phosphonic acid compound) to be added can be a commercially available product. Examples of compounds (phosphonic acid compounds) having a structure represented by general formula (I) are shown below as compounds (H-1) to (H-8).

[0074] [ka]

[0075] In the present invention, the compound having the structure represented by general formula (I) (phosphonic acid compound) is preferably at least one alkylphosphonic acid selected from the following group of phosphonic acid compounds.

[0076] 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

[0077] (1.2.2) Compounds having a structure represented by general formula (II) Compounds having the structure represented by the following general formula (II) are phosphate ester compounds or sulfate ester compounds, and contribute to dispersing the copper phosphonate complex and suppressing the increase in particle size of the particles formed by the copper phosphonate complex.

[0078] [ka]

[0079] [In the above general formula (II), R 2 R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have substituents. 21 ~R 24 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m is R 21 ~R 24 n represents the average number of additions to substructure units that are all hydrogen atoms, and is in the range of 0 to 19. 21 ~R 24 At least one of the substructure units is an alkyl group with 1 to 4 carbon atoms, representing the average number of additions, and is within the range of 0 to 19. m+n is the total number of m and n, and is within the range of 1 to 20. Z represents a structural unit selected from the following general formulas (Z-1) to (Z-3).

[0080] [ka]

[0081] (Ethylene oxide structure and alkyl-substituted ethylene oxide structure) In this application, R in the structure represented by the following general formula (II) 21 ~R 24When all atoms are hydrogen atoms, the substructure within the parentheses in the formula is called an "ethylene oxide structure," and in the formula, m is the average number of ethylene oxide structure units added. Furthermore, R in the structure represented by the following general formula (II) 21 ~R 24 The substructure in parentheses in the formula, in which at least one of the elements is an alkyl group having 1 to 4 carbon atoms and the others are hydrogen atoms, is also called an "alkyl-substituted ethylene oxide structure," where n is the average number of added alkyl-substituted ethylene oxide structural units.

[0082] The compounds having the structure represented by general formula (II) according to the present invention are characterized in that the average number of additions m of the ethylene oxide structure and the average number of additions n of the alkyl-substituted ethylene oxide structure are either 1 or more. The phosphoric acid and sulfuric acid structures have high complex-forming ability with copper and contribute to enhancing their effect as dispersants.

[0083] In the general formula (II) described above, it is preferable from the viewpoint of variability and dispersion stability that m is in the range of 1 to 19 and n is in the range of 1 to 19.

[0084] In general formula (II), combining the ethylene oxide structure and the alkyl-substituted ethylene oxide structure increases the number of isomers, which increases entropy and contributes to enhancing the effect as a dispersant. Also, substituent (R 21 ~R 24 The steric hindrance of the copper complex is suppressed, allowing it to form a fine dispersion state. This enables a balanced expression of the effects of both the ethylene oxide structure and the alkyl-substituted ethylene oxide structure, ensuring dispersibility and dispersion stability.

[0085] In the structure represented by general formula (II), the alkyl group having 6 to 16 carbon atoms is preferable from the viewpoint of the dispersibility of the copper complex and its resistance to moist heat.

[0086] (Structural unit Z: General formula (Z-1)~(Z-3)) In general formula (II), Z represents a structural unit selected from the following general formulas (Z-1) to (Z-3).

[0087] The compound having the structure represented by general formula (II) becomes a diester when Z is (Z-1), and becomes a monoester when Z is (Z-2) or (Z-3).

[0088] The mixing ratio of the diester and the monoester is preferably such that the molar ratio of the monoester to the total amount of the diester and the monoester is within the range of 20 to 95%.

[0089] (Compound Example) Specific examples of the compound (phosphoric acid ester compound or sulfuric acid ester compound) having the structure represented by general formula (II) are shown in Tables I to V below, but the compound having the structure represented by general formula (II) according to the present invention is not limited to these compounds.

[0090] In Tables I to V, the "ethylene oxide structure" refers to the partial structure within the parentheses in the formula when all of R[[ID=ID=20]] 21 ~R 24 are all hydrogen atoms in the structure represented by the general formula (II) above, and m in the formula is the average addition number of the ethylene oxide structural units. Also, the "alkyl-substituted ethylene oxide structure" refers to the partial structure within the parentheses in the formula when at least one of R 21 ~R 24 is an alkyl group having 1 to 4 carbon atoms and the others are hydrogen atoms in the structure represented by the general formula (II) above, and n in the formula is the average addition number of the alkyl-substituted ethylene oxide structural units.

[0091] In Tables I to V, the column of "Z: Structure" indicates which of the general formulas (Z-1), (Z-2), and (Z-3) Z in the formula is, and the exemplified compounds described with both general formula (Z-1) and general formula (Z-2) are mixtures of the compound with Z being (Z-1) and the compound with Z being (Z--2). Furthermore, in Tables I to V, the column "Z: Molar ratio of monoester [%]" shows the molar ratio of monoester [%].

[0092] [Table 1]

[0093] [Table 2]

[0094] [Table 3]

[0095] [Table 4]

[0096] [Table 5]

[0097] Below, we will specifically describe some of the example compounds listed in Tables I to V.

[0098] [Example Compound 1] Example compound 1 is a mixture of a compound (diester) where Z is general formula (Z-1) and a compound (monoester) where Z is general formula (Z-2). A compound (monoester) where Z is general formula (Z-2) is represented by the structure of example compound 1-1 below, and a compound (diester) where Z is general formula (Z-1) is represented by the structure of example compound 1-2 below.

[0099] [ka]

[0100] In the case of example compound 1, the molar ratio of the compound (monoester) where Z is general formula (Z-2) is 50%, and example compound 1-1 and example compound 1-2 are included in the same molar amounts.

[0101] Since m and n are average addition numbers, even in example compound 1 where m is 5 and n is 5, it is not necessarily the case that there are 5 ethylene oxide structures and 5 alkyl-substituted ethylene oxide structures in a single molecule.

[0102] [Example Compound 6] Example compound 6 is a compound in which Z is general formula (Z-3), and is represented, for example, by example compound 6-1 below.

[0103] [ka]

[0104] Since m and n are the average addition numbers, even in example compound 6 where m is 10 and n is 5, it is not necessarily the case that there are 10 ethylene oxide structures and 5 alkyl-substituted ethylene oxide structures in a single molecule.

[0105] 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 each structure is arranged randomly are also included in the compounds defined in the present invention. The order of the ethylene oxide structure and the alkyl-substituted ethylene oxide structure can be arbitrarily changed depending on the synthesis method. For example, the following example compound 6-2 is also included in example compound 6.

[0106] [ka]

[0107] (1.2.3) Method for synthesizing compounds having a structure represented by general formula (II) Compounds having the structure represented by general formula (II) according to the present invention can be synthesized by referring to known methods described in, for example, Japanese Patent Publication No. 2005-255608, Japanese Patent Publication No. 2015-000396, Japanese Patent Publication No. 2015-000970, Japanese Patent Publication No. 2015-178072, Japanese Patent Publication No. 2015-178073, Japanese Patent No. 4422866, etc.

[0108] Below, we will specifically describe some of the synthesis methods for the example compounds listed in Tables I to V. Furthermore, the synthesis method for compounds having the structure represented by general formula (II) according to the present invention is not limited to the synthesis method described below.

[0109] (Synthesis method for example compound 53) 130 g (1.0 mol) of n-octanol was placed in an autoclave, and using potassium hydroxide as a catalyst, 116 g (2.0 mol) of propylene oxide was added under conditions of 147 kPa pressure and 130°C, followed by the addition of 88 g (2.0 mol) of ethylene oxide.

[0110] Next, after confirming that no n-octanol remains, the adduct is placed in a reactor and reacted with 47 g (0.33 mol) of anhydrous phosphoric acid in toluene solution at 80°C for 5 hours. After washing with distilled water and removing the solvent under reduced pressure, the exemplary compound 53 shown below can be obtained.

[0111] [ka]

[0112] (Synthesis method for example compound 54) 130 g (1.0 mol) of n-octanol was placed in an autoclave, and using potassium hydroxide as a catalyst, 116 g (2.0 mol) of propylene oxide was added under conditions of 147 kPa pressure and 130°C, followed by the addition of 44 g (1.0 mol) of ethylene oxide.

[0113] Next, after confirming that no n-octanol remains, the adduct is placed in a reactor and reacted with 47 g (0.33 mol) of anhydrous phosphoric acid in toluene solution at 80°C for 5 hours. After washing with distilled water and removing the solvent under reduced pressure, the exemplary compound 54 shown below can be obtained.

[0114] [ka]

[0115] (Method of synthesis of example compound 60) 130 g (1.0 mol) of 2-ethylhexanol was placed in an autoclave, and using potassium hydroxide as a catalyst, 145 g (2.5 mol) of propylene oxide was added under conditions of 147 kPa pressure and 130°C, followed by the addition of 110 g (2.5 mol) of ethylene oxide.

[0116] Next, after confirming that no 2-ethylhexanol remains, the adduct is placed in a reactor and reacted with 47 g (0.33 mol) of anhydrous phosphoric acid in toluene solution at 80°C for 5 hours. After washing with distilled water and removing the solvent under reduced pressure, the exemplary compound 60 shown below can be obtained.

[0117] [ka]

[0118] (Synthesis method for example compound 61) 130 g (1.0 mol) of 2-ethylhexanol was placed in an autoclave, and using potassium hydroxide as a catalyst, 87 g (1.5 mol) of propylene oxide was added under conditions of 147 kPa pressure and 130°C, followed by the addition of 66 g (1.5 mol) of ethylene oxide.

[0119] Next, after confirming that no 2-ethylhexanol remains, the adduct is placed in a reactor and reacted with 47 g (0.33 mol) of anhydrous phosphoric acid in toluene solution at 80°C for 5 hours. After washing with distilled water and removing the solvent under reduced pressure, the exemplary compound 61 shown below can be obtained.

[0120] [ka]

[0121] (1.2.4) Copper component Component (A) according to the present invention is a component comprising a compound having the structure represented by the general formula (I), a compound having the structure represented by the general formula (II), and copper ions, and therefore contains copper ions. On the other hand, component (B) according to the present invention is a component consisting of a copper complex coordinated with a compound having the structure represented by the general formula (I) and a copper complex coordinated with a compound having the structure represented by the general formula (II), and therefore contains a copper complex. The following sections will explain copper ions and copper complexes.

[0122] (Copper ions and compounds that serve as sources of copper ions) The copper ions contained in the near-infrared absorber according to the present invention are divalent copper ions and may be solvated. As the compound that serves as the copper ion source, a copper salt capable of supplying divalent copper ions can be used, for example, a copper salt of an organic acid or a copper salt of an inorganic acid. Specifically, examples include copper salts of organic acids such as 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, and copper citrate anhydrous, as well as hydrates or hydrates of these copper salts of organic acids; copper salts of inorganic acids such as copper oxide, copper chloride, copper sulfate, copper nitrate, copper phosphate, basic copper sulfate, and basic copper carbonate, as well as hydrates or hydrates of these copper salts of inorganic acids; and copper hydroxide.

[0123] (copper complex) The aforementioned component (B) is a copper complex coordinated with a compound having a structure represented by general formula (I) and a copper complex coordinated with a compound having a structure represented by general formula (II). Furthermore, the near-infrared absorber according to the present invention may have a copper complex (for example, copper acetate) to which other compounds are coordinated.

[0124] The copper phosphate ester complex or copper sulfate ester complex according to the present invention is preferable because, by using a phosphonic acid compound in combination, a near-infrared absorbing composition with even better temporal stability (dispersion stability of copper complex particles and near-infrared cut stability) can be obtained.

[0125] Furthermore, between copper phosphate ester complexes and copper sulfate ester complexes, copper phosphate ester complexes are preferred because they possess superior dispersibility and near-infrared cut stability.

[0126] <Copper complexes coordinated with compounds having a structure represented by general formula (I)> A copper complex (copper phosphonate complex) coordinated to a compound having the structure represented by the following general formula (I) is defined as one compound having the structure represented by the following general formula (I) that is coordinated, and also includes those in which other compounds are coordinated together.

[0127] [ka]

[0128] [In the above general formula (I), R 1 This represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have substituents.

[0129] The structure of a copper complex (copper phosphonate complex) to which a compound having the structure represented by the above general formula (I) is coordinated can be represented, for example, by the following general formula (IC).

[0130] [ka]

[0131] 〔In the above general formula (IC), R 1 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have a substituent.〕

[0132] In the near-infrared absorbing composition of the present invention, the copper complex (copper phosphonate complex) coordinated with the compound having the structure represented by the general formula (I) is mainly in the form of fine particles.

[0133] In the present application, among the hydroxy groups of the compound having the structure represented by the general formula (I), the hydroxy group directly bonded to the phosphorus atom is also referred to as the "reactive hydroxy group".

[0134] The copper complex having the structure represented by the general formula (IC) is formed by the reaction of two reactive hydroxy groups of the compound having the structure represented by the general formula (I) with the same two copper ions. However, the form of the copper complex coordinated with the compound having the structure represented by the general formula (I) according to the present invention is not limited to this form.

[0135] <Copper complex coordinated with a compound having the structure represented by the general formula (II)> The copper complex (copper phosphate ester complex or copper sulfate ester complex) coordinated with the compound having the structure represented by the following general formula (II) means that at least one compound having the structure represented by the following general formula (II) is coordinated, and those in which other compounds are coordinated together are also included.

Chemical formula

[0136] 〔In the above general formula (II), R 2 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have a substituent. R 21 ~R 24 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m is R 21~R 24 n represents the average number of additions to substructure units that are all hydrogen atoms, and is in the range of 0 to 19. 21 ~R 24 At least one of the substructure units is an alkyl group with 1 to 4 carbon atoms, representing the average number of additions, and is within the range of 0 to 19. m+n is the total number of m and n, and is within the range of 1 to 20. Z represents a structural unit selected from the following general formulas (Z-1) to (Z-3).

[0137] [ka]

[0138] In the near-infrared absorbing composition of the present invention, the copper complex (phosphate ester copper complex or sulfate ester copper complex) to which a compound having the structure represented by general formula (II) is coordinated is mainly in the form of fine particles or dissolved state.

[0139] In this application, among the hydroxyl groups in a compound having the structure represented by general formula (II), a hydroxyl group that is directly bonded to a phosphorus atom or a sulfur atom is also called a "reactive hydroxyl group."

[0140] Furthermore, the form of the copper complex to which the compound having the structure represented by general formula (II) according to the present invention is coordinated is not limited to a form in which both reactive hydroxyl groups of the compound having the structure represented by general formula (II) react with the same copper ion.

[0141] (Average particle size of copper complex nanoparticles) In the near-infrared absorbing composition of the present invention, it is preferable that the copper complex fine particles are uniformly dispersed when a near-infrared absorbing cured film, as described later, is formed, from the viewpoint of spectral properties. For this reason, it is preferable that the particle size of the copper complex fine particles in the near-infrared absorbing dispersion is small.

[0142] The average particle size of copper complex fine particles in a near-infrared absorbing dispersion is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 80 nm or less.

[0143] The average particle size of copper complex nanoparticles in a near-infrared absorbing dispersion can be measured by dynamic light scattering using the ELSZ-1000ZS zeta potential / particle size measurement system manufactured by Otsuka Electronics Co., Ltd.

[0144] (1.2.5) Molar ratio C A / C E and molar ratio C H / C C value The molar content of the compound having the structure represented by the general formula (I) is C A The molar content of the compound having the structure represented by the general formula (II) is set to C E The molar ratio C in this case A / C E The value is within the range of 3.8 to 10, and the molar content of copper ions is C C The molar content of reactive hydroxyl groups in the compound having the structure represented by the general formula (I) and the compound having the structure represented by the general formula (II) is set to C H The molar ratio C in this case H / C C A value within the range of 1.5 to 2.5 is preferable from the viewpoint of improving near-infrared absorption, resistance to moist heat, and dispersibility of complex fine particles, and providing excellent visual sensitivity correction.

[0145] The compound having the structure represented by the general formula (I) is a phosphonic acid compound, and the compound having the structure represented by the general formula (II) is a phosphate ester or sulfate ester compound.

[0146] The ratio of the molar content of a compound having the structure represented by the general formula (I) to the molar content of a compound having the structure represented by the general formula (II), i.e., the molar ratio C A / C EWhen the value is 3.8 or higher, the proportion of copper phosphonate complex, which is effective in absorbing near-infrared rays, is large, resulting in good near-infrared absorption. Furthermore, the low proportion of ester compounds, which cause turbidity in high-temperature and high-humidity environments, results in good resistance to moist heat.

[0147] A certain amount of phosphate ester compound or sulfate ester compound is necessary to maintain the dispersibility of copper complex fine particles. Therefore, molar ratio C A / C E However, it is preferable that it be 10 or less.

[0148] The above molar ratio C H / C C When within this range, the transmittance of light in the visible light wavelength range of 400-700 nm is increased, and there is no leakage of transmitted light near 1100 nm in the near-infrared region, allowing for efficient maintenance of absorption performance. Furthermore, it is possible to achieve spectral transmission characteristics that also exhibit some absorption properties at 700 nm, which is the long wavelength end of visible light, making it suitable for luminous sensitivity correction.

[0149] The term "compound having the structure represented by general formula (I)" includes not only the compound having the structure represented by general formula (I) used as a starting material, but also compounds that have reacted with other components. For example, when a compound having a structure represented by general formula (I) reacts with copper ions to form a copper complex, the "part of the copper complex that had the structure represented by general formula (I)" is also C A It shall be considered a "compound having a structure represented by general formula (I)" in the provisions of [the relevant law]. In other words, in the case of a copper complex having multiple "parts that were represented by general formula (I)", C A In the provisions of this law, "compounds having a structure represented by general formula (I)" are counted not as compound units, but as "parts of the copper complex that had the structure represented by general formula (I)". For example, in the case of a copper complex having two "parts that were represented by general formula (I)", C AIn the provisions of this law, "compounds having a structure represented by general formula (I)" are counted as two.

[0150] C E In the provisions, "compound having a structure represented by general formula (II)" is not limited to the compound having a structure represented by general formula (II) used as a raw material, but also includes compounds that have reacted with other components. For example, when a compound having a structure represented by general formula (II) reacts with copper ions to form a copper complex, the "part of the copper complex that had the structure represented by general formula (II)" is also C E It shall be considered a "compound having a structure represented by general formula (II)" in the provisions of [the relevant law]. In other words, in the case of a copper complex having multiple "parts that were represented by general formula (II)", C E In the provisions of this law, "compounds having a structure represented by general formula (II)" are counted not as compound units, but as "parts of the copper complex that had the structure represented by general formula (II)". For example, in the case of a copper complex having two "parts that were represented by general formula (II)", C E In the provisions of this law, "compounds having a structure represented by general formula (II)" are counted as two.

[0151] The molar content of copper ions C C In the provisions of this law, "copper constituting a copper ion or copper compound" means copper at the atomic level that constitutes a copper ion or copper compound.

[0152] The molar content C of reactive hydroxyl groups in the compound having the structure represented by the general formula (I) and the compound having the structure represented by the general formula (II) HIn the provisions of this Act, "reactive hydroxyl groups possessed by compounds having a structure represented by general formula (I) and compounds having a structure represented by general formula (II)" means hydroxyl groups that are directly bonded to a phosphorus atom or a sulfur atom among the hydroxyl groups possessed by compounds having a structure represented by general formula (I) and compounds having a structure represented by general formula (II), and further includes cases in which such hydroxyl groups have reacted with other components, for example, in which hydrogen is liberated and oxygen is coordinated to a copper ion. Furthermore, other additives can be applied as long as they do not impair the intended effects of the present invention.

[0153] 2. Near-infrared absorbing cured film The near-infrared absorbing cured film of the present invention is characterized by containing a cured product of a near-infrared absorbing composition.

[0154] The near-infrared absorbing cured film of the present invention (a near-infrared absorbing composition in the state of a film cured together with a curable resin) is suitable for use as a visual sensitivity correction member for CCDs, CMOS sensors, or other photodetectors, a photometric member, a heat absorbing member, a composite optical filter, a lens member (glasses, sunglasses, goggles, optical systems, optical waveguides), a fiber member (optical fiber), a noise-cutting member, a display cover or display filter such as a plasma display front panel, a projector front panel, a light source heat ray cutting member, a color correction member, an illumination brightness adjustment member, an optical element (optical amplification element, wavelength conversion element, etc.), a Faraday element, an optical communication functional device such as an isolator, an optical disc element, and so on.

[0155] The near-infrared absorbing cured film can be manufactured by preparing a coating solution for forming a near-infrared absorbing cured film by dissolving a curable resin in the near-infrared absorbing composition (dispersion) of the present invention, which contains the aforementioned near-infrared absorbing composition and a dispersion medium; applying the coating solution onto a substrate by a spin coating or wet coating method using a dispenser; and curing the coating film by performing a predetermined heat treatment.

[0156] The thickness of the near-infrared absorbing cured film of the present invention is preferably in the range of 10 to 500 μm, and more preferably in the range of 10 to 300 μm.

[0157] The film thickness of the near-infrared absorbing cured film of the present invention can be measured using, for example, a film thickness meter with the following combination. Terminal: DIGIMICRO MH-15M (manufactured by Nikon) Stand: DIGIMICRO STAND MS-5C (made by Nikon) Reader: DIGITAL READ OUT TC-101A (manufactured by Nikon)

[0158] (2.1) Curing resin The matrix resin (also called binder resin) used in forming a near-infrared absorbing cured film is preferably a curable resin that is light-transmitting to visible light and near-infrared light, and capable of dispersing fine particles of the near-infrared absorbing composition. A copper complex (copper phosphonate complex) to which a compound having the structure represented by general formula (I) according to the present invention is coordinated is a relatively low-polarity substance and disperses well in hydrophobic materials. Therefore, it is preferable to use a resin having a polysiloxane structure (silicone), or a resin having acrylic groups, epoxy groups, or phenyl groups, as the matrix resin for forming near-infrared absorbing films.

[0159] Among these, resins having a polysiloxane structure are particularly preferred because they are resistant to thermal decomposition, have high light transmittance to visible light and near-infrared rays, and also have high heat resistance.

[0160] Specific examples of resins having a polysiloxane structure include, for example, 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., and SS-6203, SS-6309, VS-9301, and VS-9506 manufactured by Sanyurec Co., Ltd.

[0161] From the viewpoint of low gas permeability and moisture resistance, it is also preferable to use a matrix resin having epoxy groups.

[0162] Specific examples of epoxy resins include KJC-X5 (manufactured by Shin-Etsu Chemical Co., Ltd.), NLD-L-672 (manufactured by Sanyurec Co., Ltd.), LE-1421 (manufactured by Sanyurec Co., Ltd.), and the EpiFine series (manufactured by KISCO Corporation).

[0163] Furthermore, it is also preferable to use a resin having both the polysiloxane structure and epoxy groups mentioned above as the matrix resin. This resin exhibits high heat resistance and moisture resistance, making it suitable as a material for image sensors for solid-state image sensors.

[0164] Specific examples of resins having both a polysiloxane structure and epoxy groups include, for example, the EpiFine series (manufactured by KISCO) and the ILLUMIKA series (manufactured by Kaneka Corporation).

[0165] (Components other than the solvent) Furthermore, the ratio of solid content (components other than the solvent) to the total near-infrared absorbing composition (dispersion) is preferably in the range of 5 to 30% by mass, as this ensures an appropriate concentration of solids (e.g., copper complex fine particles), suppresses particle aggregation during storage, and allows for better long-term stability (dispersion stability and near-infrared absorption of copper complex fine particles). It is more preferably in the range of 10 to 20% by mass.

[0166] (2.2) Other additives Other additives can be applied to the coating liquid for forming near-infrared absorbing curing films, to the extent that they do not impair the intended effects of the present invention. Examples include sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, thermal polymerization inhibitors, and plasticizers. Furthermore, components such as adhesion promoters to the substrate surface and other auxiliary agents (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, surface treatment agents, etc.) may also be used in combination. By appropriately incorporating these components, the stability and physical properties of the desired near-infrared absorbing curing film can be adjusted.

[0167] The above components can be referenced, for example, from paragraphs 0183 to 0260 of Japanese Patent Publication No. 2012-003225, paragraphs 0101 to 0102 of Japanese Patent Publication No. 2008-250074, paragraphs 0103 to 0104 of Japanese Patent Publication No. 2008-250074, paragraphs 0107 to 0109 of Japanese Patent Publication No. 2008-250074, etc.

[0168] 3. Spectral properties of near-infrared absorbing compositions and near-infrared absorbing cured films (3.1) Spectral properties of near-infrared absorbing composition (dispersion) (spectral transmittance) In the near-infrared absorbing composition of the present invention, when diluted with a solvent in the state of a near-infrared absorbing dispersion, to the point of visible light transmittance, it is preferable that the average spectral transmittance in the wavelength region of 450 to 600 nm is 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0169] For measuring spectral transmittance, for example, a spectrophotometer V-570 manufactured by JASCO Corporation can be used.

[0170] (3.2) Spectral characteristics of near-infrared absorbing cured films (Average spectral transmittance) In the case of the near-infrared absorbing cured film of the near-infrared absorbing composition of the present invention, it is preferable in terms of visible light transmittance that the average spectral transmittance is 80% or more within the wavelength range of 450 to 600 nm.

[0171] Also, it is preferable in terms of near-infrared absorption that it is 10% or less within the wavelength range of 850 to 1000 nm.

[0172] Also, it is more preferable in terms of near-infrared absorption that it is 1% or less within the wavelength range of 850 to 1080 nm.

[0173] (Cutoff wavelength) In the case of the near-infrared absorbing cured film of the near-infrared absorbing composition of the present invention, the spectral transmittance decreases with an increase in wavelength within the wavelength range of 600 to 700 nm, and when the wavelength at which the spectral transmittance becomes 50% within the wavelength range of 600 to 800 nm is defined as the cutoff wavelength, it is preferable in terms of near-infrared absorption that the cutoff wavelength for light incident at an incident angle of 0° with respect to the surface is within the range of 600 to 750 nm.

[0174] The spectral transmittance in the state of the near-infrared absorbing film can also be measured using a spectrophotometer V-570 manufactured by JASCO Corporation. It can be measured using this.

[0175] 4. Optical member The optical member of the present invention is characterized by containing a cured product of a near-infrared absorbing composition. The near-infrared absorbing cured film of the present invention can be used as various optical members or parts. For example, it is suitable for use as a visual sensitivity correction member for CCDs, CMOS or other photodetectors, a photometering member, a heat-absorbing member, an optical filter, a fiber member (optical fiber), a noise-canceling member, a display cover or display filter such as a plasma display front panel, a projector front panel, a light source heat-cutting member, a color correction member, an illumination brightness adjustment member, an optical element (optical amplification element, wavelength conversion element, etc.), a Faraday element, an optical communication functional device such as an isolator, or an optical disc element. The following describes examples of applications of near-infrared absorbing compositions or near-infrared absorbing cured films as optical components or parts.

[0176] (4.1) Near-infrared cut filter The near-infrared cut filter according to the present invention is a near-infrared cut filter comprising a near-infrared absorbing layer on at least one surface of a transparent dielectric substrate, characterized in that the near-infrared absorbing layer contains the near-infrared absorbing composition or near-infrared absorbing cured film of the present invention.

[0177] Furthermore, it is preferable to further include a dielectric multilayer film on at least one surface of the transparent dielectric substrate, as this allows for more flexible adjustment of the spectral characteristics of the near-infrared cut filter.

[0178] The near-infrared absorbing layer and the dielectric multilayer film may be in contact with the transparent dielectric substrate, or they may be provided via other intermediate layers.

[0179] Figure 1 is a schematic cross-sectional view showing an example of the configuration of the near-infrared cut filter of the present invention.

[0180] The near-infrared cut filter 9 shown in Figure 1 comprises a near-infrared absorbing layer 22 on one surface of a transparent dielectric substrate 21, and a dielectric multilayer film 23 on the other surface.

[0181] The transparent dielectric substrate is not particularly limited in material, as long as the objective of the present invention is achieved. For example, it may be made of glass, or it may be made of optical resins such as polycarbonate (PC), polymethyl methacrylate (PMMA), cycloolefin polymer (COP), or silicone.

[0182] The thickness of the transparent dielectric substrate is preferably 0.01 to 1 mm.

[0183] Since the transparent dielectric substrate needs to transmit visible light, it is preferable that its average spectral transmittance in the wavelength range of 450 to 600 nm be 80% or higher.

[0184] The near-infrared absorbing film of the present invention can be applied to the near-infrared absorbing layer. As mentioned above, a near-infrared cut filter can be manufactured by directly forming a near-infrared absorbing film as a near-infrared absorbing layer on a transparent dielectric substrate.

[0185] Dielectric multilayer films are films formed by stacking multiple layers made of materials with different refractive indices, and are used to control the transmittance of light at various wavelengths. By incorporating a near-infrared absorption layer, the spectral characteristics of the near-infrared cut filter can be adjusted more freely.

[0186] The spectral characteristics of dielectric multilayer films can be adjusted by controlling the thickness and material type of each layer. For each layer, dielectric materials such as titanium oxide, silicon oxide, aluminum oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride can be used.

[0187] A near-infrared cut filter including a dielectric multilayer film can be manufactured by laminating each dielectric layer on a transparent dielectric substrate by a method such as a vacuum evaporation method, a chemical vapor deposition (CVD) method, or a sputtering method. Alternatively, it can also be manufactured by bonding a separately prepared dielectric multilayer film to a transparent dielectric substrate with an adhesive.

[0188] (4.2) Image sensor for solid-state imaging device The image sensor for a solid-state imaging device according to the present invention is characterized by including the near-infrared cut filter of the present invention.

[0189] An image sensor for a solid-state imaging device refers to a member mainly composed of a solid-state imaging device substrate provided with light-receiving elements.

[0190] The image sensor for a solid-state imaging device according to the present invention is not particularly limited in other members etc. as long as it includes the near-infrared cut filter of the present invention. For example, it may include a planarization layer, a glass substrate, etc.

[0191] FIG. 2 is a schematic cross-sectional view showing a configuration example of the image sensor for a solid-state imaging device of the present invention.

[0192] The image sensor 14 for a solid-state imaging device shown in FIG. 2 includes a solid-state imaging device substrate 10 provided with light-receiving elements on the light-receiving side surface of a silicon substrate, a planarization layer 8 provided on the solid-state imaging device substrate 10, a near-infrared cut filter 9 provided on the planarization layer 8, and a glass substrate (light-transmissive substrate) 3 disposed above the near-infrared cut filter 9. Each member is adhered by an adhesive 2.

[0193] (4.3) Camera module The camera module according to the present invention is characterized by including the image sensor for a solid-state imaging device of the present invention.

[0194] The camera module of the present invention is not particularly limited in terms of other components, as long as it is equipped with the image sensor for solid-state image sensors of the present invention. For example, it may consist of an imaging lens, a lens holder, a light shield and electromagnetic shield, etc.

[0195] Figure 3 is a schematic cross-sectional view showing an example configuration of the camera module of the present invention.

[0196] The camera module 1 shown in Figure 3 comprises a solid-state image sensor (solid-state image sensor substrate 10, planarization layer 8, near-infrared cut filter 9, glass substrate 3), a lens holder 5 positioned above the solid-state image sensor and having an imaging lens 4 in its internal space, and a light-shielding and electromagnetic shield 6 positioned to surround the solid-state image sensor. Each component is bonded together with adhesive 7.

[0197] Furthermore, the camera module 1 is connected to the circuit board 12, which is the mounting board, via solder balls 11 (connecting material), which are connecting members.

[0198] In camera module 1, incident light L from the outside passes sequentially through the imaging lens 4, glass substrate 3, infrared cut filter 9, and planarization layer 8 before reaching the light-receiving element of the solid-state image sensor substrate 10. [Examples]

[0199] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, the units "parts" or "%" are used, and unless otherwise specified, they represent "parts by mass" or "mass%".

[0200] A. Near-infrared absorber The following near-infrared absorbing materials, consisting of phosphonic acid compounds and phosphate or sulfate ester combinations, were used in the examples or comparative examples.

[0201] (Compounds having a structure represented by general formula (I): Phosphonic acid compounds) • Phenylphosphonic Acid (manufactured by Tokyo Chemical Industry Co., Ltd.) • Ethylphosphonic Acid (manufactured by Tokyo Chemical Industry Co., Ltd.) • Propylphosphonic Acid (manufactured by Tokyo Chemical Industry Co., Ltd.) • Butylphosphonic Acid (manufactured by Tokyo Chemical Industry Co., Ltd.) • 4-Bromophenylphosphonic Acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0202] (Compounds having a structure represented by general formula (II): phosphate esters or sulfate esters) • Exemplary compound 68 • Exemplary compound 70 • 76 example compounds • Exemplary compound 92 • Example compound 99 Server Exemplary Compound 100

[0203] The example compounds 68, 70, 76, 92, and 100 above were synthesized using the following methods.

[0204] (Synthesis method for example compound 68) 158 g (1.0 mol) of n-decanol was placed in an autoclave, and using potassium hydroxide as a catalyst, 108 g (1.5 mol) of butylene oxide was added under conditions of 147 kPa pressure and 130°C, followed by the addition of 66 g (1.5 mol) of ethylene oxide.

[0205] Next, after confirming that no n-decanol remains, the adduct is placed in a reactor and reacted with 47 g (0.33 mol) of anhydrous phosphoric acid in toluene solution at 80°C for 5 hours. After washing with distilled water and removing the solvent under reduced pressure, exemplary compound 68 shown in Table IV above can be obtained.

[0206] (Synthesis method for example compound 70) 158 g (1.0 mol) of n-decanol was placed in an autoclave, and using potassium hydroxide as a catalyst, 87 g (1.5 mol) of propylene oxide was added under conditions of 147 kPa pressure and 130°C, followed by the addition of 66 g (1.5 mol) of ethylene oxide.

[0207] Next, after confirming that no n-decanol remains, the adduct is placed in a reactor and reacted with 47 g (0.33 mol) of anhydrous phosphoric acid in toluene solution at 80°C for 5 hours. After washing with distilled water and removing the solvent under reduced pressure, exemplary compound 70 shown in Table IV above can be obtained.

[0208] (Synthesis method for example compound 76) 186 g (1.0 mol) of n-dodecanol was placed in an autoclave, and using potassium hydroxide as a catalyst, 116 g (2.0 mol) of propylene oxide was added under conditions of 147 kPa pressure and 130°C, followed by the addition of 88 g (2.0 mol) of ethylene oxide.

[0209] Next, after confirming that no n-dodecanol remains, the adduct is placed in a reactor and reacted with 47 g (0.33 mol) of anhydrous phosphoric acid in toluene solution at 80°C for 5 hours. After washing with distilled water and removing the solvent under reduced pressure, exemplary compound 76 shown in Table IV above can be obtained.

[0210] (Synthesis method for example compound 92) 270 g (1.0 mol) of n-stearyl alcohol was placed in an autoclave, and using potassium hydroxide as a catalyst, 174 g (3.0 mol) of propylene oxide was added under conditions of 147 kPa pressure and 130°C, followed by the addition of 132 g (3.0 mol) of ethylene oxide.

[0211] Next, after confirming that no n-stearyl alcohol remains, the adduct is placed in a reactor and reacted with 47 g (0.33 mol) of anhydrous phosphoric acid in toluene solution at 80°C for 5 hours. After washing with distilled water and removing the solvent under reduced pressure, exemplary compound 70 shown in Table IV above can be obtained.

[0212] (Example compound 99) Example compound 99 was not synthesized, but rather a commercially available product, Prisurf A208F (phosphate ester type anionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used (see Table V above for details). Example compound 99 has R in general formula (II). 2 This is a phosphate ester compound in which C8 is an alkyl group, the average number of additions n in the ethylene oxide structure is 3, and the average number of additions m in the alkyl-substituted ethylene oxide structure is 0.

[0213] (Synthesis method for example compound 100) 186 g (1.0 mol) of n-dodecanol was placed in an autoclave, and 174 g (3.0 mol) of propylene oxide was added using potassium hydroxide as a catalyst under conditions of 147 kPa pressure and 130°C.

[0214] Next, after confirming that no n-dodecanol remains, the adduct is placed in a reactor and reacted with 47 g (0.33 mol) of anhydrous phosphoric acid in toluene solution at 80°C for 5 hours. After washing with distilled water and removing the solvent under reduced pressure, exemplary compound 100 shown in Table V above can be obtained.

[0215] B. Solvent contained in the dispersion medium The solvent to be included in the dispersion medium was selected from Table VI below. Table VI also includes reference candidates that, although not used in the examples and comparative examples, could be used as examples and comparative examples of the present invention. The names, structural formulas, HSP values, and boiling points of the solvents to be contained in the dispersion medium are shown in Table VI. Furthermore, the specific structures of each structural formula No. (1) to (20) in Table VI are shown below.

[0216] The definition and calculation method of HSP values ​​are described in "Hansen Solubility Parameters: A Users Handbook" by Charles M. Hansen (CRC Press, 2007), as mentioned above. However, for the values ​​listed in Table VI, we used values ​​calculated using HSPiP for each solvent.

[0217] [Table 6]

[0218] [ka]

[0219] C. Preparation of near-infrared absorbing composition (dispersion) (C.1) Preparation of near-infrared absorbing composition (dispersion) No. 1 (C.1.1) Preparation of copper acetate solution The following copper ion source compounds and solvents were mixed in the following quantities, stirred for 3 hours, and filtered to remove insoluble matter to prepare copper acetate solution [1].

[0220] (Compounds and solvents that serve as copper ion sources) Copper(II) acetate monohydrate (manufactured by Kanto Chemical Co., Ltd.) 1.82g (molar content C) C (=10 mmol) THF (Tetrahydrofuran) 82g The copper(II) acetate monohydrate mentioned above will also be simply referred to as "copper acetate" below.

[0221] (C.1.2) Preparation of Solution [1] A compound (phosphate ester) having the structure represented by the following general formula (II) was dissolved in the following solvent in the following quantities to prepare a solution. Copper acetate solution [1] was added to this solution, and the mixture was stirred at room temperature for 30 minutes to prepare solution [1]. The compounds having the structure represented by the general formula (II) below were synthesized using the method described above.

[0222] (Compounds (phosphate esters) and solvents having a structure represented by general formula (II)) Example compound 76 (phosphate ester) 0.99g (molar content C) E (=1.6 mmol) THF 7g

[0223] (C.1.3) Preparation of Solution [2] A compound (phosphonic acid) having the structure represented by the following general formula (I) was dissolved in the following solvent in the following quantities to prepare solution [2].

[0224] (Compounds (phosphonic acid) and solvents having a structure represented by general formula (I)) Propylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.09g (molar content C) A (=8.8 mmol) THF 7g

[0225] (C.1.4) Final preparation of near-infrared absorbing composition (dispersion) After adding solution [2] to solution [1] while stirring, stir at room temperature for 16 hours to obtain a mixture of solution [1] and solution [2] (molar content C H A solution (20.2 mmol) was prepared, and this mixture and 30 g of THF were placed in a flask. Desolvent and acetic acid removal treatment was performed for 30 minutes using a rotary evaporator (Tokyo Rikakikai Co., Ltd., model: N-1000) while heating at 50-100°C in an oil bath (Tokyo Rikakikai Co., Ltd., model: OSB-2100).

[0226] Subsequently, the amount of solvent was adjusted so that the solid content concentration (components other than the solvent) in the flask was 10% by mass, and this was designated as near-infrared absorbing composition (dispersion) No. 1. In this context, "solid content concentration (components other than solvent)" refers to copper acetate used in the preparation of copper acetate solution, the compound having the structure represented by general formula (II) (phosphate ester) used in the preparation of solution [1], and the compound having the structure represented by general formula (I) (phosphonic acid) used in the preparation of solution [2]. "Components other than solvent" in Tables VII and VIII refers to these components.

[0227] (molar content C) H (Calculation method) Furthermore, the molar content C of the reactive hydroxyl groups in compounds having the structure represented by general formula (I) and compounds having the structure represented by general formula (II) H The answer was calculated as follows:

[0228] The molar content of reactive hydroxyl groups in a compound having the structure represented by general formula (I) is (a) 8.8 mmol × 2 = 17.6 mmol. The molar content of reactive hydroxyl groups in a compound having the structure represented by general formula (II) is (b) (1.6 mmol × 60% × 2) + (1.6 mmol × 40% × 1) = 2.56 mmol. Therefore, the total molar content of reactive hydroxyl groups in compounds having the structure represented by general formula (I) and compounds having the structure represented by general formula (II) is C H (a) mmol + (b) mmol equals 21.16 mmol ≈ 20.2 mmol.

[0229] (C.2) Preparation of near-infrared absorbing compositions (dispersions) No. 2-6 and 11-35 Near-infrared absorbing compositions (dispersions) Nos. 2-6 and 11-35 were prepared in the same manner as the preparation of near-infrared absorbing composition (dispersion) No. 1, except that the compound (phosphate ester) and solvent having the structure represented by general formula (II) in the preparation of solution [1] and the compound (phosphonic acid) and solvent having the structure represented by general formula (I) in the preparation of solution [2] were changed as shown in Tables VII and VIII.

[0230] For example, in the preparation of near-infrared absorbing composition (dispersion) No. 1, the solvent used in solution [1] and solution [2] is THF. Although solution [1] and solution [2] are prepared with the same type of solvent, the solvent content in Tables VII and VIII represents the total amount of solvent contained in the dispersion after desolvent and deacetic acid treatment.

[0231] Furthermore, the non-solvent components in Tables VII and VIII refer to the solid content (non-solvent components) relative to the entire near-infrared absorbing composition (dispersion).

[0232] (C.3) Preparation of near-infrared absorbing composition (dispersion) No. 7 Except for the final preparation of the near-infrared absorbing composition (dispersion), the composition was prepared in the same manner as near-infrared absorbing composition (dispersion) No. 1. The final preparation method described above is shown below.

[0233] After adding solution [2] to solution [1] while stirring, stir at room temperature for 16 hours to obtain a mixture of solution [1] and solution [2] (molar content C H A mixture (20.2 mmol) was prepared, and this mixture and 30 g of methylcyclohexane (solvent 1) were placed in a flask. The mixture was heated at 50-100°C in an oil bath (Tokyo Rikakikai Co., Ltd., model: OSB-2100) and subjected to desolvation and deacetic acid removal treatment for 40 minutes using a rotary evaporator (Tokyo Rikakikai Co., Ltd., model: N-1000) until the solid content concentration (components other than solvent) was 20% by mass. Subsequently, cyclopentyl methyl ether (solvent 2) was added to prepare the flask so that the solid content concentration (components other than the solvent) was 10% by mass.

[0234] (C.4) Preparation of near-infrared absorbing compositions (dispersions) No. 8-10 The near-infrared absorbing composition (dispersion) was prepared in the same manner as near-infrared absorbing composition (dispersion) No. 7, except that solvents 1 and 2 were changed as shown in Table VII during the final preparation.

[0235] [Table 7]

[0236] [Table 8]

[0237] D. Rating (D.1) Dispersibility: Average particle size of fine particles in the dispersion. (Evaluation method) Near-infrared absorbing compositions (dispersions) No. 1 to 35 were each diluted with toluene to a solid content concentration of 0.5% by mass. The average particle size of the fine particles in the diluted dispersion was measured by dynamic light scattering using the ELSZ-1000ZS zeta potential / particle size measurement system manufactured by Otsuka Electronics Co., Ltd., and evaluated according to the evaluation criteria below. The evaluation results are shown in Tables IX and X.

[0238] (Evaluation Criteria) ◎: The average particle size is 100 nm or less. ○: The average particle size is greater than 100 nm and less than or equal to 150 nm. △: The average particle size is greater than 150 nm and less than or equal to 200 nm. ×: The average particle size is greater than 200 nm.

[0239] (D.2) Dispersion (storage) stability (Evaluation method) Near-infrared absorbing compositions (dispersions) No. 1 to 35 were left at room temperature for one week, and then each was diluted with toluene to a solid content concentration of 0.5% by mass. The average particle size of the fine particles in each diluted dispersion was measured by dynamic light scattering using the ELSZ-1000ZS zeta potential / particle size measurement system manufactured by Otsuka Electronics Co., Ltd., and evaluated according to the following criteria. The evaluation results are shown in Tables X and XI.

[0240] (Evaluation Criteria) ◎: The average particle size is 100 nm or less. ○: The average particle size is greater than 100 nm and less than or equal to 150 nm. △: The average particle size is greater than 150 nm and less than or equal to 200 nm. ×: The average particle size is greater than 200 nm.

[0241] (D.3) Resin compatibility (Evaluation method) Each of the near-infrared absorbing compositions (dispersions) No. 1 to 35 prepared above was mixed with resins (1) to (4) so ​​that the solid content ratio of the resin was 70% by mass, and each coating solution for forming a near-infrared absorbing cured film was prepared. The details of the resins listed in Tables X and XI are as follows:

[0242] • Resin 1: Urethane acrylate "CN975N" (manufactured by Satomer) • Resin 2: Urethane acrylate "R1403M" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) • Resin 3: Hyperbranch polyester "CN2304" (manufactured by Satomer) • Resin 4: Silicone resin "KR311" (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0243] Next, each near-infrared absorbing curing film forming coating solution was cast onto a glass substrate to a thickness that would result in a maximum spectral transmittance of 10% in the wavelength range of 850-1000 nm after curing, and then pre-baked on a hot plate at 50°C for 60 minutes. Next, the near-infrared absorbing cured films were formed by curing them on a hot plate at 150°C for 2 hours using resins (1) to (4) with each of the near-infrared absorbing compositions No. 1 to 35. The spectral transmittance of the near-infrared absorbing cured films No. 1 to 35 in the wavelength range of 450 to 600 nm was measured using a spectrophotometer V-570 manufactured by JASCO Corporation, and the average spectral transmittance in that range was calculated. In this case, the influence of reflection at the interface was eliminated by using the glass substrate as a base. The average spectral transmittance within the calculated wavelength range of 450-600 nm was evaluated according to the following criteria. The evaluation results are shown in Tables IX and X.

[0244] (Evaluation Criteria) ◎: The average spectral transmittance in the range is 90% or higher. ○: The average spectral transmittance in the range is 80% or more and less than 90%. △: The average spectral transmittance in the range is 70% or more and less than 80%. ×: The average spectral transmittance in that range is less than 70%.

[0245] [Table 1]

[0246] [Table 10]

[0247] E. Summary From Tables IX and X, it can be seen that the examples have no "×" ratings for any of the evaluation items, while the comparative examples have at least one "×" rating. Therefore, the examples are practically usable and overall superior. Furthermore, since the examples do not use substances subject to the PRTR system, such as toluene, it can be seen that the environmental impact can be reduced. [Explanation of symbols]

[0248] 1 Camera Module 2.7 Adhesive 3. Glass substrate 4 imaging lenses 5 Lens holder 6. Light-blocking and electromagnetic shielding 8 Planarization layer 9. Near-infrared cut filter 10 Solid-state image sensor substrate 11 Solder ball 12 Circuit boards 14 Image sensors for solid-state image sensors 21 Transparent dielectric substrate 22 Near-infrared absorption layer 23 Dielectric Multilayer Film

Claims

1. A near-infrared absorbing composition containing a near-infrared absorbing agent and a dispersion medium, The near-infrared absorber contains at least the following component (A) or component (B): The dispersion medium is the polarity term δ of the Hansen solubility parameter. Ｐ The value is in the range of 3 to 6, and the hydrogen bond term δ Ｈ It contains a solvent in which the value is in the range of 3 to 6. The solvent is an ether having a cyclopentyl group, a cyclohexyl group, or a tetrahydropyranyl group. A near-infrared absorbing composition characterized by the following: <Ingredients>: (A) Components: Components consisting of a compound having the structure represented by the following general formula (I), a compound having the structure represented by the following general formula (II), and copper ions. (B) Component: A component consisting of a copper complex coordinated with a compound having the structure represented by the following general formula (I) and a copper complex coordinated with a compound having the structure represented by the following general formula (II). 【Chemistry 1】 [In the above general formula (I), R1 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have substituents.] 【Chemistry 2】 [In the above general formula (II), R2 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may further have substituents. R21 to R24 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m represents the average number of additions to a substructure unit in which all R21 to R24 are hydrogen atoms, and is in the range of 0 to 19. n represents the average number of additions to a substructure unit in which at least one of R21 to R24 is an alkyl group having 1 to 4 carbon atoms, and is in the range of 0 to 19. m+n is the total number of m and n, and is in the range of 1 to 20. Z represents a structural unit selected from the following general formulas (Z-1) to (Z-3).] 【Transformation 3】

2. The dispersion medium is the dispersion term δ of the Hansen solubility parameter. Ｄ It contains at least one solvent whose value is in the range of 16 to 22. The near-infrared absorbing composition according to feature 1.

3. The dispersion medium is the polarity term δ of the Hansen solubility parameter. Ｐ The value is within the range of 3 to 5, and the hydrogen bonding term δ Ｈ It contains at least one solvent whose value is in the range of 3 to 5. The near-infrared absorbing composition according to claim 1 or 2.

4. The dispersion medium contains a solvent whose boiling point is in the range of 80 to 150°C. The near-infrared absorbing composition according to any one of claims 1 to 3.

5. The dispersion medium contains at least cyclopentyl methyl ether or 4-methyltetrahydropyran. The near-infrared absorbing composition according to any one of claims 1 to 4.

6. The dispersion medium is the polarity term δ of the Hansen solubility parameter. Ｐ The value is in the range of 3 to 6, and the hydrogen bond term δ Ｈ The near-infrared absorbing composition contains a solvent with a value in the range of 3 to 6 in an amount of 20 to 95% by mass relative to the total amount of the composition. The near-infrared absorbing composition according to any one of claims 1 to 5.

7. In the above general formula (II), m is in the range of 1 to 19, and n is in the range of 1 to 19. The near-infrared absorbing composition according to any one of claims 1 to 6.

8. Let the molar content of the compound having the structure represented by the general formula (I) be C Ａ and the molar content of the compound having the structure represented by the general formula (II) be C Ｅ When the molar ratio C Ａ / C Ｅ is within the range of 3.8 to 10, and The molar content of copper ions is C Ｃ The molar content of reactive hydroxyl groups in the compound having the structure represented by the general formula (I) and the compound having the structure represented by the general formula (II) is set to C Ｈ The molar ratio C in this case Ｈ / C Ｃ The value is within the range of 1.5 to 2.

5. The near-infrared absorbing composition according to any one of claims 1 to 7.

9. Contains a cured product of the near-infrared absorbing composition described in any one of claims 1 to 8. A near-infrared absorbing cured film characterized by the following features.

10. Contains a cured product of the near-infrared absorbing composition described in any one of claims 1 to 8. An optical component characterized by the following features.

Images