Resin composition, compound (Z), substrate (i), optical filter and use thereof

Abstract

To provide a resin composition that has an absorption maximum at around 700-750 nm in wavelength or around 720-900 nm in wavelength; has a high ratio of an absorbance in the infrared range to an absorbance in the visible light range; and has excellent light resistance (durability).SOLUTION: A resin composition has a resin, and a compound represented by formula (I). Cn+An-(I). [In the formula (I), Cn+ is a monovalent cation represented by formula (II), An- is a monovalent anion.] [A is a heterocyclic compound, B is a heterocyclic compound bound to the formula (II) by a double bond.]SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition, a compound (Z), a substrate (i), an optical filter, and a solid-state imaging device and an optical sensor device using the optical filter. [Background technology]

[0002] Solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions use CCD and CMOS image sensors, which are solid-state imaging elements for color images. These solid-state imaging elements use silicon photodiodes and the like that are sensitive to near-infrared light that cannot be sensed by the human eye in their light receiving sections. Silicon photodiodes and the like are also used in optical sensor devices. For example, solid-state imaging elements require visibility correction to make colors appear natural to the human eye, and optical filters (e.g., near-infrared cut filters) that selectively transmit or cut light in a specific wavelength range are often used.

[0003] As such near-infrared cut filters, those manufactured by various methods have been used in the past. For example, a near-infrared cut filter using a resin as a base material and containing a near-infrared absorbing dye in the resin is known (see, for example, Patent Document 1). However, the near-infrared cut filter described in Patent Document 1 may not necessarily have sufficient near-infrared absorbing properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2008-303130 A Summary of the Invention [Problem to be solved by the invention]

[0005] As the near infrared absorbing dye, polymethine-based, squarylium-based, porphyrin-based, dithiol metal complex-based, phthalocyanine-based, diimonium-based dyes have been conventionally used. Among them, polymethine-based and squarylium-based dyes are widely used because they have sufficient resistance to heat.

[0006] However, these dyes that have been used conventionally have the following characteristics: Since the absorption maximum wavelength is in the long wavelength region, compounds with an absorption maximum in the vicinity of 700 to 750 nm or 720 to 900 nm were required. The ratio of absorbance in the infrared range to absorbance in the visible range is small. The light resistance (durability) is insufficient, There was room for improvement in at least one of the above points.

[0007] Furthermore, conventional near-infrared cut filters may adversely affect images such as camera images due to the reflected light from the filter causing flare, ghosting, and the like. In particular, when the reflection band of the near-infrared cut filter overlaps with the wavelength band capable of photoelectric conversion by a sensor, the adverse effects may become more pronounced.

[0008] The present invention has been made in view of the above, and aims to provide a resin composition that has an absorption maximum in the wavelength range of about 700 to 750 nm or about 720 to 900 nm, has a large ratio of absorbance in the infrared range to absorbance in the visible light range, and is excellent in light resistance (durability). [Means for solving the problem]

[0009] As a result of intensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration examples, and have thus completed the present invention. In the present invention, the expression "A to B" or the like expressing a numerical range is synonymous with "A or more, B or less", and includes A and B in the numerical range. In addition, in the present invention, a wavelength of A to B nm represents characteristics at a wavelength resolution of 1 nm in a wavelength region of wavelengths of Am or more and wavelengths of B nm or less.

[0010] [1] A resin composition containing a resin and a compound (Z) represented by the following formula (I): Cn + An - (I) [In formula (I), Cn + is a monovalent cation represented by the following formula (II), and An - is a monovalent anion.

[0011] [ka] [In formula (II), The unit A is any one of the following formulae (AI) to (A-III): The unit B is any one of the following formulae (BI) to (B-III): Y A ~Y E each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, -NR g R h group, amide group, imide group, cyano group, silyl group, -Q 1 , -N=NQ 1 , -SQ 2 , -SSQ 2 , or -SO 2 Q 3 and Y A and Y C , Y B and Y D , Y C and Y Emay be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have =O, Y A and R in the following formula (A-III) 1 or R 5 , Y E and R in the following formula (B-III) 5 or R 1 may be bonded to each other to form a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, R g and R h are each independently a hydrogen atom, -C(O)R i Group or the following L a ~L h Q 1 are independent of each other, a ~L h Q 2 are independently a hydrogen atom or the following L a ~L h Q 3 is a hydroxyl group or the following L a ~L h Either i is the following L a ~L h ]

[0012] [ka] [In formulae (AI) to (A-III), -* represents Y in formula (II). A indicates that the carbon atom is bonded to a single bond, In the formulas (BI) to (B-III), =** represents Y in the formula (II). E indicates that the carbon atom is double bonded to the carbon atom to which it is bonded, In formulas (AI)~(B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR 8 - and R 1 ~R 6 each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -NR g R h Group, -SR i Group, -SO 2 R i Group, -OSO 2 R i group, -C(O)R i Group or the following L a ~L h Either Adjacent R 1 ~R 6 may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have =O, R 8 are independently a hydrogen atom, a halogen atom, or -C(O)R i Group, L below a ~L h Either R g and R h are each independently a hydrogen atom, -C(O)R i Group or the following L a ~L h Either R i are independent of each other, a ~L h Either (L a ): an aliphatic hydrocarbon group having 1 to 15 carbon atoms (L b): Halogen-substituted alkyl group having 1 to 15 carbon atoms (L c ): an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K (L d ): an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K (L e ): a heterocyclic group having 3 to 14 carbon atoms which may have a substituent K (L f ):-OR (R is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L). (L g ): an acyl group having 1 to 9 carbon atoms which may have a substituent L (L h ): an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L The substituent K is the L a ~L b and the substituent L is at least one selected from the group consisting of the L a ~L f At least one selected from the following.

[0013] [2] The resin composition according to [1], wherein the compound (Z) satisfies the following requirement (A): Requirement (A): In a transmission spectrum measured using a solution in which the compound (Z) is dissolved in dichloromethane (wherein the transmission spectrum is a spectrum in which the transmittance at the absorption maximum wavelength is 10%), the average transmittance at wavelengths of 430 to 580 nm is 93% or more.

[0014] [3] R 1 ~R 6 At least one of the L a , L c or L d The resin composition according to [1] or [2],

[0015] [4] The resin composition according to any one of [1] to [3], wherein the compound (Z) satisfies the following requirement (B-1): Requirement (B-1): In the absorption spectrum measured using a solution in which the compound (Z) is dissolved in dichloromethane, the maximum value is in the wavelength range of 720 to 900 nm.

[0016] [5] The resin composition according to any one of [1] to [3], wherein the compound (Z) satisfies the following requirement (B-2): Requirement (B-2): In the absorption spectrum measured using a solution in which the compound (Z) is dissolved in dichloromethane, the maximum value is in the wavelength range of 700 to 750 nm.

[0017] [6] The resin composition according to any one of [1] to [5], wherein the resin is at least one resin selected from the group consisting of cyclic (poly)olefin-based resins, aromatic polyether-based resins, polyimide-based resins, polyester-based resins, polycarbonate-based resins, polyamide-based resins, polyarylate-based resins, polysulfone-based resins, polyethersulfone-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate-based resins, fluorinated aromatic polymer-based resins, (modified) acrylic-based resins, epoxy-based resins, allyl ester-based curable resins, silsesquioxane-based ultraviolet-curable resins, acrylic-based ultraviolet-curable resins, and vinyl-based ultraviolet-curable resins.

[0018] [7] A substrate (i) containing a compound (Z) formed from the resin composition according to any one of [1] to [6].

[0019] [8] The substrate (i) a substrate comprising a resin layer containing the compound (Z); A substrate comprising two or more resin layers, at least one of which is a resin layer containing the compound (Z), or A substrate comprising a glass support and a resin layer containing the compound (Z), The substrate (i) according to [7].

[0020] [9] An optical filter comprising the substrate (i) according to [7] or [8] and a dielectric multilayer film.

[10] The optical filter according to [9], which is for use in a solid-state imaging device.

[11] The optical filter according to [9], which is for use in an optical sensor device.

[0021]

[12] A solid-state imaging device comprising the optical filter according to [9].

[13] An optical sensor device comprising the optical filter according to [9].

[0022]

[14] Compound (Z) represented by formula (III): Cn + An - (III) [In formula (III), Cn + is a monovalent cation represented by the following formula (IV), and An - is a monovalent anion.

[0023] [ka] [In formula (IV), The unit A is any one of the following formulae (AI) to (A-III): The unit B is any one of the following formulae (BI) to (B-III): Y A ~Y E each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, -NR g R h group, amide group, imide group, cyano group, silyl group, -Q 1 , -N=NQ 1 , -SQ 2 , -SSQ 2 , or -SO 2 Q 3 and Y A and Y C , Y B and Y D , Y C and Y Emay be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have =O, Y A and R in the following formula (A-III) 1 or R 5 , Y E and R in the following formula (B-III) 5 or R 1 may be bonded to each other to form a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, R g and R h are each independently a hydrogen atom, -C(O)R i Group or the following L a ~L h Q 1 are independent of each other, a ~L h Q 2 are independently a hydrogen atom or the following L a ~L h Q 3 is a hydroxyl group or the following L a ~L h Either i is the following L a ~L h ]

[0024] [ka] [In formulae (AI) to (A-III), -* represents Y in formula (II). A indicates that the carbon atom is bonded to a single bond, In the formulas (BI) to (B-III), =** represents Y in the formula (II). E indicates that the carbon atom is double bonded to the carbon atom to which it is bonded, In formulas (AI)~(B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR 8 - and R 1 ~R 6 each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -NR g R h Group, -SR i Group, -SO 2 R i Group, -OSO 2 R i group, -C(O)R i Group or the following L a ~L h Either Adjacent R 1 ~R 6 may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have =O, R 8 are independently a hydrogen atom, a halogen atom, or -C(O)R i Group, L below a ~L h Either R g and R h are each independently a hydrogen atom, -C(O)R i Group or the following L a ~L h Either R i are independent of each other, a ~L h Either (L a ): an aliphatic hydrocarbon group having 1 to 15 carbon atoms (L b): Halogen-substituted alkyl group having 1 to 15 carbon atoms (L c ): an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K (L d ): an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K (L e ): a heterocyclic group having 3 to 14 carbon atoms which may have a substituent K (L f ):-OR (R is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L). (L g ): an acyl group having 1 to 9 carbon atoms which may have a substituent L (L h ): an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L The substituent K is the L a ~L b and the substituent L is at least one selected from the group consisting of the L a ~L f At least one selected from the following. Effect of the Invention

[0025] According to the present invention, it is possible to provide a resin composition having an absorption maximum at a wavelength of about 700 to 750 nm or about 720 to 900 nm, a large ratio of absorbance in the infrared region to absorbance in the visible region, and sufficient resistance to heat and light. Furthermore, according to the present invention, it is possible to provide an optical filter having these characteristics, in particular, capable of transmitting a high proportion of light in the visible region while sufficiently blocking light in the infrared region. Therefore, according to the present invention, not only a near-infrared cut filter (NIR-CF), but also optical filters such as a visible-near-infrared selective transmission filter (DBPF) and a near-infrared transmission filter (IRPF) can be easily produced. In the present invention, having sufficient resistance to heat and light means that the optical properties do not change significantly before and after application of heat or irradiation with light.

[0026] As described above, according to the present invention, an optical filter having the above characteristics can be provided, and therefore, an optical filter capable of suppressing reflected light of wavelengths of about 700 to 750 nm or wavelengths of about 720 to 900 nm and providing a good image with less flare and ghost can be easily obtained. In addition, when the optical filter is a filter having a dielectric multilayer film, the incidence angle dependency due to the dielectric multilayer film can be suppressed. [Brief description of the drawings]

[0027] [Figure 1] 1 is a spectral transmittance spectrum of the substrate obtained in Example 20. [Diagram 2] 2 is a spectral transmittance spectrum of the substrate obtained in Example 28. [Diagram 3] 1 is a spectral transmittance spectrum of the optical filter obtained in Example 20. [Figure 4] 2 is a spectral transmittance spectrum of the optical filter obtained in Example 28. [Diagram 5] 1 is a spectral transmittance spectrum of the substrate obtained in Example 36. [Figure 6] 1 is a spectral transmittance spectrum of the optical filter obtained in Example 36. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] ≪Resin composition≫ The resin composition according to the present invention (hereinafter also referred to as "the composition") is not particularly limited as long as it contains a resin and the compound (Z). Examples of the form of such a resin composition include a resin film (resin layer, resin substrate) containing compound (Z); a resin film (resin layer) containing compound (Z) formed on a support (e.g., resin support, glass support); and a liquid composition containing a resin, compound (Z) and a solvent. The present composition may contain two or more types of resins, and may contain two or more types of compounds (Z).

[0029] <Compound (Z)> Compound (Z) is a compound represented by the following formula (I). The compound (Z) has high near-infrared cutting performance and high visible light transmitting performance at an absorption maximum in the wavelength range of about 700 to 750 nm or about 720 to 900 nm, and has excellent optical properties and sufficient resistance to heat and light. Cn + An - (I) [In formula (I), Cn + is a monovalent cation represented by the following formula (II), and An - is a monovalent anion.

[0030] [ka] [In formula (II), The unit A is any one of the following formulae (AI) to (A-III): The unit B is any one of the following formulae (BI) to (B-III): Y A ~Y E each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, -NR g R h group, amide group, imide group, cyano group, silyl group, -Q 1 , -N=NQ 1 , -SQ 2 , -SSQ 2 , or -SO 2 Q 3 and Y A and Y C , Y B and Y D , Y C and Y Emay be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have =O, Y A and R in the following formula (A-III) 1 or R 5 , Y E and R in the following formula (B-III) 5 or R 1 may be bonded to each other to form a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, R g and R h are each independently a hydrogen atom, -C(O)R i Group or the following L a ~L h Q 1 are independent of each other, a ~L h Q 2 are independently a hydrogen atom or the following L a ~L h Q 3 is a hydroxyl group or the following L a ~L h Either i is the following L a ~L h ]

[0031] [ka] [In formulae (AI) to (A-III), -* represents Y in formula (II). A indicates that the carbon atom is bonded to a single bond, In the formulas (BI) to (B-III), =** represents Y in the formula (II). E indicates that the carbon atom is double bonded to the carbon atom to which it is bonded, In formulas (AI)~(B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR 8 - and R 1 ~R 6 each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -NR g R h Group, -SR i Group, -SO 2 R i Group, -OSO 2 R i group, -C(O)R i Group or the following L a ~L h Either Adjacent R 1 ~R 6 may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have =O, R 8 are independently a hydrogen atom, a halogen atom, or -C(O)R i Group, L below a ~L h Either R g and R h are each independently a hydrogen atom, -C(O)R i Group or the following L a ~L h Either R i are independent of each other, a ~L h Either (L a ): an aliphatic hydrocarbon group having 1 to 15 carbon atoms (L b): Halogen-substituted alkyl group having 1 to 15 carbon atoms (L c ): an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K (L d ): an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K (L e ): a heterocyclic group having 3 to 14 carbon atoms which may have a substituent K (L f ):-OR (R is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L). (L g ): an acyl group having 1 to 9 carbon atoms which may have a substituent L (L h ): an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L The substituent K is the L a ~L b and the substituent L is at least one selected from the group consisting of the L a ~L f At least one selected from the following.

[0032] Moreover, the compound (Z) according to the present invention is a compound represented by the following formula (III). Cn + An - (III) [In formula (III), Cn + is a monovalent cation represented by the following formula (IV), and An - is a monovalent anion.

[0033] [ka] [In formula (IV), The unit A is any one of the following formulae (AI) to (A-III): The unit B is any one of the following formulae (BI) to (B-III): Y A ~Y E each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, -NR g R hgroup, amide group, imide group, cyano group, silyl group, -Q 1 , -N=NQ 1 , -SQ 2 , -SSQ 2 , or -SO 2 Q 3 and Y A and Y C , Y B and Y D , Y C and Y E may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have =O, Y A and R in the following formula (A-III) 1 or R 5 , Y E and R in the following formula (B-III) 5 or R 1 may be bonded to each other to form a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, R g and R h are each independently a hydrogen atom, -C(O)R i Group or the following L a ~L h Q 1 are independent of each other, a ~L h Q 2 are independently a hydrogen atom or the following L a ~L h Q 3 is a hydroxyl group or the following L a ~L h Either i is the following L a ~L h ]

[0034] [ka] [In formulae (AI) to (A-III), -* represents Y in formula (II). A indicates that the carbon atom is bonded to a single bond, In the formulas (BI) to (B-III), =** represents Y in the formula (II). E indicates that the carbon atom is double bonded to the carbon atom to which it is bonded, In formulas (AI)~(B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR 8 - and R 1 ~R 6 each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -NR g R h Group, -SR i Group, -SO 2 R i Group, -OSO 2 R i group, -C(O)R i Group or the following L a ~L h Either Adjacent R 1 ~R 6 may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have =O, R 8 are independently a hydrogen atom, a halogen atom, or -C(O)R i Group, L below a ~L h Either R g and R hare each independently a hydrogen atom, -C(O)R i Group or the following L a ~L h Either R i are independent of each other, a ~L h Either (L a ): an aliphatic hydrocarbon group having 1 to 15 carbon atoms (L b ): Halogen-substituted alkyl group having 1 to 15 carbon atoms (L c ): an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K (L d ): an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K (L e ): a heterocyclic group having 3 to 14 carbon atoms which may have a substituent K (L f ):-OR (R is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L). (L g ): an acyl group having 1 to 9 carbon atoms which may have a substituent L (L h ): an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L The substituent K is the L a ~L b and the substituent L is at least one selected from the group consisting of the L a ~L f At least one selected from the following.

[0035] In addition, the above-mentioned -NR 8 - is a group represented by the following formula (a), and the -NR g R h The -SR group is a group represented by the following formula (b): i The -SO group is a group represented by the following formula (c): 2 R i The -OSO group is a group represented by the following formula (d): 2 R i The -C(O)R group is a group represented by the following formula (e): iThe group is a group represented by the following formula (f): In addition, the -SSQ 2 Ha-SSQ 2 The -SO 2 Q 3 In the group represented by the following formula (d), R i Q 3 This is a group replaced by

[0036] [ka]

[0037] In addition, when the unit A is the formula (AI) and the unit B is the formula (BI), Cn + is represented by the following formula (II-1). That is, the single bond (-) of "*-" in the formulas (AI) to (A-III) is the same as Y A The double bond (=) of "**=" in the formulas (BI) to (B-III) corresponds to the single bond between the carbon atom to which Y is bonded and the unit A. E corresponds to the double bond between the carbon atom to which it is attached and unit B.

[0038] [ka]

[0039] The above Y B and Y D are each independently preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, B and Y D a 4- to 6-membered alicyclic hydrocarbon group formed by bonding together (the alicyclic hydrocarbon group is a substituent R selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a hydroxyl group, a halogen atom, and =O); 9 )

[0040] In addition, Y B and Y Dare bonded to each other to form a 4- to 6-membered alicyclic hydrocarbon group, formula (II) or (IV) can preferably be represented by the following formulas (CI) to (C-III), respectively.

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] Substituent R 9 is preferably a hydrogen atom, a hydroxyl group, =O, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, or a cyclohexyl group, and more preferably a hydrogen atom, a hydroxyl group, =O, a methyl group, an ethyl group, or a tert-butyl group.

[0045] The above Y A , Y C and Y E are each independently more preferably a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a hydroxyl group, a phenylamino group (NHPh), a diphenylamino group, a methylphenylamino group, a dimethylamino group, a methyl group, a methoxy group, a phenyl group, a phenoxy group, a 4-methylphenoxy group, a methylthio group, a phenylthio group, or an -S-(4-tolyl) group.

[0046] Said L ais preferably a methyl group (Me), an ethyl group (Et), an n-propyl group, an isopropyl group (i-Pr), an n-butyl group, a sec-butyl group, a tert-butyl group (tert-Bu), a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, or a dodecyl group, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.

[0047] Said L a may be an alkenyl group such as a vinyl group, a 1-propenyl group, a 2-propenyl group, a butenyl group, a 1,3-butadienyl group, a 2-methyl-1-propenyl group, a 2-pentenyl group, or a hexenyl group; or an alkynyl group such as an ethynyl group, a propynyl group, a butynyl group, a 2-methyl-1-propynyl group, or a hexynyl group.

[0048] Said L b Examples of the halogen-substituted alkyl group having 1 to 15 carbon atoms in the formula (I) include groups in which at least one hydrogen atom of an alkyl group having 1 to 15 carbon atoms is substituted with a halogen atom, and preferred examples include a trichloromethyl group, a trifluoromethyl group, a 1,1-dichloroethyl group, a pentachloroethyl group, a pentafluoroethyl group, a heptachloropropyl group, and a heptafluoropropyl group.

[0049] Said L c Preferable examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K include cycloalkyl groups such as a cyclopropyl group, a cyclopropylmethyl group, a methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic groups such as a norbornane group and an adamantyl group.

[0050] Said L dThe aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K in the above formula is preferably a phenyl group, a tolyl group, a xylyl group, a mesityl group (trimethylphenyl group), a cumenyl group, a bis(trifluoromethyl)phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a phenanthryl group, a benzyl group (CH 2 Ph).

[0051] Said L e In the above formula, the heterocyclic group having 3 to 14 carbon atoms which may have a substituent K is preferably furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, morpholine, or pyridine.

[0052] Said L f -OR in the above formula is preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a methoxymethyl group, a methoxyethyl group, a pentyloxy group, a hexyloxy group, an octyloxy group, a phenoxy group (OPh), a 4-methylphenoxy group, or a cyclohexyloxy group.

[0053] Said L g The acyl group having 1 to 9 carbon atoms which may have a substituent L in the above formula is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group, or a trifluoromethylcarbonyl group.

[0054] Said L h The alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L in the above formula is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group.

[0055] The X is preferably an oxygen atom, a sulfur atom, or -NR 8 -, and particularly preferably an oxygen atom.

[0056] In formula (II) or (IV), the left and right units A and B may be the same or different, but it is preferred that they are the same for ease of synthesis. Here, the combinations in which the units A and B are the same are those of formula (AI) and formula (BI), formula (A-II) and formula (B-II), and formula (A-III) and formula (B-III).

[0057] R 1 ~R 6 are each independently preferably a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a 1,1-dimethylbutyl group, a cyclopropyl group, a cyclopropylmethyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,4,6-trimethylphenyl group, a 3,5-bis(trifluoromethyl)phenyl group, a hydroxyl group, an amino group, a dimethylamino group (NMe 2 ), diethylamino group (NEt 2 ), dibutylamino group (N(n-Bu) 2 ), cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, tert-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, benzyl group, diphenylmethyl group, trifluoromethyl group, difluoromethyl group, and methoxy group, and more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, a methyl group, an ethyl group, n-propyl group, an isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, phenyl group, amino group, benzyl group, diphenylmethyl group, trifluoromethyl group, difluoromethyl group, and methoxy group.

[0058] R 1 ~R 6At least one of the above L has high near-infrared cut performance and high visible light transmittance at an absorption maximum in the vicinity of a wavelength of 700 to 750 nm or a wavelength of 720 to 900 nm, and is excellent in optical properties, and a compound having sufficient resistance to heat and light can be easily obtained. a , L c or L d In addition, when the unit A is the formula (A-III) and the unit B is the formula (B-III), "R 1 ~R 6 At least one of the following is L a , L c or L d "is" means "R 1 , R 2 , R 4 , R 5 At least one of the following is L a , L c or L d It means "is."

[0059] R 8 is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a benzyl group, an n-pentyl group, an n-hexyl group, or a tert-butyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a benzyl group.

[0060] The above-mentioned An - There is no particular limitation on the monovalent anion, but it is preferably a chloride ion, a bromide ion, an iodide ion, or a PF 4 -, perchlorate anion, tristrifluoromethanesulfonylmethide anion, tetrafluoroborate anion, hexafluorophosphate anion, bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonate anion, tetrakis(pentafluorophenyl)borate anion, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion, and the like. More preferred are bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonate anion, tristrifluoromethanesulfonylmethide anion, tetrakis(pentafluorophenyl)borate anion, and the like. Among these, the tetrakis(pentafluorophenyl)borate anion and the tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion are more preferable, and from the viewpoint of being able to easily obtain a compound (Z) having superior heat resistance, the bis(trifluoromethanesulfonyl)imide anion, the tristrifluoromethanesulfonylmethide anion, the tetrakis(pentafluorophenyl)borate anion and the tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion are more preferable, and the tetrakis(pentafluorophenyl)borate anion is particularly preferable.

[0061] Specific examples of the compounds represented by formula (I) or (III) include compounds (z-1) to (z-173) shown in Tables 1 to 4 below. Specifically, these compounds (Z) can be synthesized, for example, by the methods described in the following examples.

[0062] [Table 1]

[0063] [Table 2]

[0064] [Table 3]

[0065] [Table 4]

[0066] In addition, R in Table 4 3 and R 4 In the column, "C-1, C-2" refer to R in the formula (AI) and the formula (BI). 3 and R 4 and C-1 are bonded to each other to form an aromatic hydrocarbon group having 6 carbon atoms. Specifically, it means that the portions corresponding to units A and B have structures represented by the following formulae C-1 and C-2. Also, Y in Table 4 A ,Y E , R 1 and R 5 "D-1" in the column is Y A and R in formula (A-III) 1 , Y E and R in the formula (B-III) 5 are bonded to each other to form a 6-membered alicyclic group, specifically, it means that the cation of compound (z-163) is represented by the following formula D-1.

[0067] [ka]

[0068] [ka]

[0069] Compound (Z) is preferably a compound soluble in an organic solvent, and particularly preferably a compound soluble in dichloromethane. Here, "soluble in an organic solvent" refers to the case where 0.1 g or more of compound (Z) dissolves in 100 g of an organic solvent at 25°C.

[0070] The compound (Z) is preferably a compound that satisfies the following requirement (A). Requirement (A): In a transmission spectrum (wherein the transmission spectrum is a spectrum in which the transmittance at the absorption maximum wavelength is 10%. Hereinafter, this transmission spectrum is also referred to as "the transmission spectrum of compound (Z)") measured using a solution in which compound (Z) is dissolved in dichloromethane, the average value of the transmittance at wavelengths of 430 to 580 nm is preferably 93% or more, more preferably 95% or more. Since a higher average value of the transmittance is preferable, the upper limit is not particularly limited and may be 100%. When the compound (Z) satisfies the requirement (A), it is possible to sufficiently block light having a wavelength in the near infrared region that is desired to be blocked, while further suppressing a decrease in the visible light transmittance.

[0071] In the present invention, the average transmittance for wavelengths A to B nm is a value calculated by measuring the transmittance at each wavelength from Anm to B nm in 1 nm increments and dividing the sum of the transmittances by the number of measured transmittances (wavelength range, B-A+1).

[0072] The compound (Z) is preferably a compound that satisfies the following requirement (B-1) or (B-2). Requirement (B-1): In an absorption spectrum measured using a solution obtained by dissolving compound (Z) in dichloromethane, the maximum value is preferably in the wavelength range of 720 to 900 nm, more preferably in the wavelength range of 740 to 880 nm, and particularly preferably in the wavelength range of 740 to 860 nm. When the absorption maximum wavelength of the compound (Z) is within the above range, it is possible to easily obtain an optical filter that can suppress reflected light having a wavelength of about 720 to 900 nm and can provide a good image with little flare or ghost. Suitable examples of the compound (Z) satisfying the requirement (B-1) include compounds in which the unit A is any one of the formulae (AI) to (A-II) and the unit B is any one of the formulae (BI) to (B-II).

[0073] Requirement (B-2): In an absorption spectrum measured using a solution obtained by dissolving compound (Z) in dichloromethane, the maximum value is preferably in the wavelength range of 700 to 750 nm, more preferably in the wavelength range of 705 to 748 nm, and particularly preferably in the wavelength range of 710 to 745 nm. When the absorption maximum wavelength of the compound (Z) is within the above range, it is possible to easily obtain an optical filter that can suppress reflected light having a wavelength of about 700 to 750 nm and can provide a good image with little flare or ghosting. Suitable examples of the compound (Z) satisfying the requirement (B-2) include compounds in which the unit A is represented by the formula (A-III) and the unit B is represented by the formula (B-III).

[0074] The compound (Z) is preferably a compound that satisfies the following requirement (C). Requirement (C): The retention rate D (=Af×100 / Ai) of absorbance Af at the maximum absorption wavelength λa in the wavelength range of 700 to 1000 nm of a resin plate made of a resin and a compound (Z) after the resin plate is irradiated with a fluorescent lamp for 30 days relative to absorbance Ai at the maximum absorption wavelength λa is preferably 95% or more, more preferably 97% or more. Since the retention rate D is preferably high, its upper limit is not particularly limited and may be 100%. The thickness of the resin plate is within a range of 90 to 110 μm, the content of compound (Z) relative to the resin is an amount such that the absorbance Ai at the maximum absorption wavelength λa of the resin plate is within a range of 0.5 to 1.5, and the resin used is Arton manufactured by JSR Corporation, and 0.3 parts by mass of Irganox 1010 (manufactured by BASF Japan Ltd.) is contained relative to 100 parts by mass of the resin in the resin plate.

[0075] The compound (Z) having a retention rate D within the above range can be said to have excellent light resistance (durability), and by using such a compound (Z), an optical filter exhibiting desired optical properties over a long period of time can be easily obtained. Specifically, the retention rate D can be measured by the method described in the following examples.

[0076] It is more preferable that the compound (Z) satisfies the following requirement (D). Requirement (D): In a spectroscopic absorption spectrum measured using a solution obtained by dissolving compound (Z) in dichloromethane, when the absorbance at the longest wavelength among the maximum absorption wavelengths is εa and the maximum absorbance at wavelengths of 430 to 580 nm is εbmax, εa / εbmax is preferably 20 or more, more preferably 25 or more, and further preferably 27 or more. Since a larger εa / εbmax is preferable, the upper limit is not particularly limited, but is, for example, 10,000 or less. When compound (Z) satisfies requirement (D), it can be said that the ratio of absorbance in the infrared region to the absorbance in the visible region is large, and the optical properties are excellent. In an optical filter having a dielectric multilayer film, the incidence angle dependency due to the multilayer film can be suppressed.

[0077] The content of compound (Z) in the present composition is preferably 0.02 to 2.0 parts by mass, more preferably 0.02 to 1.5 parts by mass, and particularly preferably 0.03 to 1.5 parts by mass, relative to 100 parts by mass of the resin. When the content of compound (Z) is within the above range, near-infrared rays having a wavelength of about 700 to 750 nm or about 720 to 900 nm can be efficiently cut, and a composition having excellent visible light transmittance can be easily obtained.

[0078] <Resin> The resin used in the present composition is not particularly limited, and any conventionally known resin can be used. The resin used in the present composition may be one type alone or two or more types.

[0079] The resin is not particularly limited as long as it does not impair the effects of the present invention, but examples thereof include resins having a glass transition temperature (Tg) of preferably 110 to 380° C., more preferably 110 to 370° C., and particularly preferably 120 to 360° C., from the viewpoints of being excellent in thermal stability and moldability into a film (plate) shape, and being able to easily obtain a film capable of forming a dielectric multilayer film by high-temperature deposition at a deposition temperature of about 100° C. or higher. Furthermore, resins having a Tg of 140° C. or higher are particularly preferred, since a film capable of forming a dielectric multilayer film by deposition at a higher temperature can be obtained.

[0080] The resin that can be used is one that provides a total light transmittance (JIS K 7375:2008) of a 0.1 mm-thick resin plate made of the resin of interest of preferably 75 to 95%, more preferably 78 to 95%, and particularly preferably 80 to 95%. By using a resin having a total light transmittance within the above range, a resin composition or optical filter having excellent transparency can be easily obtained.

[0081] The resin has a polystyrene-equivalent weight average molecular weight (Mw) of usually 15,000 to 350,000, preferably 30,000 to 250,000, and a number average molecular weight (Mn) of usually 10,000 to 150,000, preferably 20,000 to 100,000, as measured by gel permeation chromatography (GPC).

[0082] Examples of the resin include cyclic (poly)olefin resins, aromatic polyether resins, polyimide resins, polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curable resins, silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins, and vinyl ultraviolet curable resins. Specific examples of these resins include the resins described in WO 2019 / 168090.

[0083] <Other ingredients> The present composition may further contain other components such as a compound (X) other than the compound (Z) [an absorber other than an ultraviolet absorber], an antioxidant, an ultraviolet absorber, a fluorescence quencher, and a metal complex compound, within the scope of not impairing the effects of the present invention. Each of these other components may be used alone or in combination of two or more.

[0084] These other components may be mixed with the resin when preparing the composition, or may be added when synthesizing the resin. The amount of the other components added may be appropriately selected depending on the desired properties, etc., but is usually 0.01 to 5.0 parts by mass, and preferably 0.05 to 2.0 parts by mass, relative to 100 parts by mass of the resin.

[0085] [Compound (X)] The present composition may contain one or more compounds (X) [absorbing agents other than ultraviolet absorbers] other than the compound (Z). Examples of the compound (X) include squarylium-based compounds, phthalocyanine-based compounds, polymethine-based compounds, naphthalocyanine-based compounds, croconium-based compounds, octaphylline-based compounds, diimonium-based compounds, perylene-based compounds, and metal dithiolate-based compounds.

[0086] The compound (X) preferably includes a squarylium-based compound, and more preferably includes one or more squarylium-based compounds and one or more other compounds (X'). The other compounds (X') are particularly preferably phthalocyanine-based compounds and polymethine-based compounds.

[0087] The squarylium compound has a sharp absorption peak, excellent visible light transmittance, and a high molar extinction coefficient, but may generate fluorescence that causes scattered light when absorbing light. In this case, the squarylium compound can be used in combination with the compound (X') to suppress scattered light. When scattered light is suppressed in this way, the obtained camera image quality is improved when an optical filter obtained from the composition is used in an imaging device or the like.

[0088] The absorption maximum wavelength of the compound (X) is preferably 650 to 1100 nm, more preferably 650 to 950 nm, further preferably 680 to 850 nm, and particularly preferably 690 to 740 nm. By using the compound (X) having a maximum absorption wavelength within the above range, an optical filter having excellent luminous efficiency correction can be easily obtained.

[0089] [Ultraviolet absorber] Examples of the ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, anthracene compounds, and compounds described in JP-A-2019-014707.

[0090] In particular, azomethine compounds, indole compounds, benzotriazole compounds, and cyanoacrylate compounds are preferred. By containing these compounds, an optical filter having little incidence angle dependency even in the near-ultraviolet wavelength region can be easily obtained, and when the optical filter is used in an imaging device or the like, the obtained camera image quality is better.

[0091] [Antioxidants] Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5'-dimethyldiphenylmethane, and tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane.

[0092] <Additives> The present composition may further contain additives such as an organic solvent, a release agent, a surfactant, an antistatic agent, an adhesion aid, and a light diffusing material, provided the effects of the present invention are not impaired. Each of these additives may be used alone or in combination of two or more.

[0093] In particular, when the present composition is made into a liquid composition, it is preferable to use an organic solvent. Examples of the organic solvent are preferably solvents capable of dissolving resins, and specific examples thereof include esters, ketones, aromatic hydrocarbons, and halogen-containing compounds. Furthermore, when the resin layer is produced by cast molding, which will be described later, the production of the resin layer can be facilitated by using a leveling agent or an antifoaming agent.

[0094] ≪Base material (i)≫ The substrate (i) according to the present invention is a substrate containing the compound (Z) formed from the present composition. The substrate (i) may be a single layer or a multilayer, and may have a resin layer (hereinafter also referred to as the present resin layer) containing the compound (Z) formed from the present composition. The substrate (i) may have two or more present resin layers, and in this case, the two or more present resin layers may be the same or different.

[0095] When the substrate (i) is a single layer, the substrate (i) is composed of the present resin layer, that is, the present resin layer (resin substrate) is the substrate (i). When the substrate (i) is a multilayer substrate, examples of the substrate (i) include a substrate comprising two or more resin layers, at least one of which is the present resin layer, and a substrate comprising the present resin layer and a glass support. Suitable examples include a substrate (A) comprising a laminate in which the present resin layer is laminated on a support such as a glass support or a base resin support, and a substrate (B) comprising a laminate in which a resin layer, such as an overcoat layer made of a curable resin or the like, is laminated on the present resin layer. In terms of production costs, ease of adjusting optical properties, ability to achieve the scratch-removing effect of the resin layer, and improvement in scratch resistance of the substrate (i), the substrate (B) is particularly preferred as the substrate (i).

[0096] In addition, the resin layer such as the overcoat layer in the resin support or the substrate (B) refers to a resin layer that does not contain the compound (Z). The resin layer that does not contain the compound (Z) is not particularly limited as long as it contains a resin, and examples of the resin include the same resins as those described in the section on the present composition. In addition, the resin layer that does not contain the compound (Z) may be the following other functional film.

[0097] The glass support is preferably a transparent glass support or an absorbing glass support, and among these, an absorbing glass support is preferred because it can sufficiently block light with wavelengths in the near infrared region.

[0098] The thickness of the substrate (i) can be appropriately selected depending on the desired application and is not particularly limited, but is preferably 10 to 250 μm, more preferably 15 to 230 μm, and particularly preferably 20 to 150 μm. When the thickness of the substrate (i) is within the above range, the optical filter using the substrate (i) can be made thin and lightweight, and can be suitably used for various applications such as solid-state imaging devices, etc. In particular, when the single-layer substrate (i) is used in a lens unit of a camera module or the like, it is preferable because the lens unit can be made low-profile and lightweight.

[0099] [Method for producing substrate (i)] The resin layer, the resin support, and the resin layer such as the overcoat layer can be formed, for example, by melt molding or cast molding, and further, if necessary, after molding, a coating agent such as an antireflection agent, a hard coat agent, and / or an antistatic agent may be coated.

[0100] When the substrate (i) is a substrate (A), for example, the present composition is melt-molded or cast-molded onto the support, preferably by a method such as spin coating, slit coating, or inkjet, and then the solvent is dried and removed, and if necessary, light irradiation or heating is further performed, thereby producing a substrate having the present resin layer formed on the support.

[0101] Melt molding Specific examples of the melt molding include a method of melt-kneading the present composition to obtain pellets and melt-molding the pellets, a method of melt-molding the present composition, a method of removing the solvent from the present composition in a liquid state containing the solvent and melt-molding the pellets, etc. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding, etc.

[0102] Cast molding Examples of the cast molding include a method in which a liquid present composition containing a solvent is cast onto a suitable support and the solvent is removed; and a method in which a curable present composition containing a photocurable resin and / or a thermosetting resin as the resin is cast onto a suitable support and the solvent is removed, followed by curing by a suitable method such as ultraviolet irradiation or heating. When the substrate (i) is the single-layer substrate (i), the substrate (i) can be obtained by peeling off the coating film from the support after cast molding, and when the substrate (i) is the substrate (A), the substrate (i) can be obtained by not peeling off the coating film after cast molding.

[0103] Examples of the suitable support include a glass plate, a steel belt, a steel drum, and a support made of a resin (for example, a polyester film, a cyclic olefin resin film).

[0104] Furthermore, the resin layer can be formed on an optical component such as a glass plate, quartz, or plastic by coating the liquid composition and drying the solvent, or by coating the curable composition and curing and drying it.

[0105] When the resin support and the resin layer such as the overcoat layer are formed by melt molding or cast molding, a desired composition containing a resin (but not containing compound (Z)) may be used in place of the present composition in the melt molding or cast molding section.

[0106] The amount of residual solvent in the resin layer, the resin support, the overcoat layer, and other resin layers is preferably as small as possible. Specifically, the amount of residual solvent is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on the weight of the resin layer. When the amount of the residual solvent is within the above range, a resin layer that is resistant to deformation and changes in properties and can easily exhibit the desired functions can be obtained. When the substrate (i) is used in an optical filter, it is preferable to suppress the solvent content in the resin layers, such as the present resin layer, the resin support and the overcoat layer, to 100 ppm by mass or less.

[0107] <Optical Filter> The optical filter according to the present invention (hereinafter also referred to as "the present filter") comprises the above-mentioned substrate (i) and a dielectric multilayer film. From the viewpoint of more effectively exerting the effects of the present invention, specific examples of such a filter include a near-infrared cut filter (NIR-CF), a visible light-near-infrared selective transmission filter (DBPF), and a near-infrared transmission filter (IRPF). The filter can also be used as a filter for alternative light sources (ALS: Alternative Light Sources) used in scientific investigations and the like. These filters may have a conventionally known configuration except that they have the base material (i).

[0108] When the filter is an NIR-CF or DBPF, it is preferable that the filter satisfies the following characteristic (a). Property (a): In the wavelength region of 430 to 580 nm, the average transmittance measured from the vertical direction of the optical filter is preferably 75% or more, more preferably 80% or more. Since a higher average transmittance is preferable, the upper limit is not particularly limited and may be 100%. If the present filter satisfies the characteristic (a), it can adequately cut light of the desired wavelength in the near-infrared region while better suppressing the decrease in visible light transmittance, making it more suitable for use as an NIR-CF or DBPF.

[0109] When the base material (i) contains a compound satisfying the requirement (B-1) and the filter is an NIR-CF or DBPF, the filter preferably satisfies the following characteristic (b-1). Property (b-1): In the wavelength region of 700 to 800 nm, the average reflectance of non-polarized light incident at an angle of 5° from the perpendicular direction to at least one surface of the optical filter is preferably 25% or less, more preferably 15% or less. Since a lower average reflectance is preferable, the lower limit is not particularly limited and may be 0%. By using the present filter that satisfies the characteristic (b-1), it is possible to reduce the intensity of reflected light in the wavelength range of 700 to 800 nm, thereby eliminating image defects caused by the reflected light.

[0110] When the base material (i) contains a compound satisfying the requirement (B-2) and the filter is an NIR-CF or DBPF, the filter preferably satisfies the following characteristic (b-2). Characteristic (b-2): In the wavelength region of 650 to 800 nm, the average reflectance of non-polarized light incident at an angle of 5° from the perpendicular direction to at least one surface of the optical filter is preferably 25% or less, more preferably 15% or less. Since a lower average reflectance is preferable, the lower limit is not particularly limited and may be 0%. By using the present filter that satisfies the characteristic (b-2), it is possible to reduce the intensity of reflected light in the wavelength range of 650 to 800 nm, thereby eliminating image defects caused by the reflected light.

[0111] In the present invention, the average reflectance for wavelengths A to B nm is a value calculated by measuring the reflectance at each wavelength in 1 nm increments from A nm to B nm, and dividing the sum of the reflectances by the number of measured reflectances (wavelength range, B-A+1). Since it is extremely difficult to measure the reflectance of unpolarized light incident from the perpendicular direction, in the present invention, the reflection characteristics of unpolarized light incident at an angle of 5° from the perpendicular direction were measured.

[0112] "Non-polarized light" refers to light that has no bias in the polarization direction, and is a collection of waves in which the electric field is distributed more or less uniformly in all directions. The "average transmittance of non-polarized light" may be the average value of the "average transmittance of S-polarized light" and the "average transmittance of P-polarized light." The "average reflectance of non-polarized light" may be the average value of the "average reflectance of S-polarized light" and the "average reflectance of P-polarized light."

[0113] When the present filter satisfies the above-mentioned characteristics (a) and (b-1) or (b-2), it is possible to reduce the reflected light intensity of near-infrared light, particularly in the wavelength region of 650 to 800 nm, while maintaining good visible light transmittance. Therefore, in imaging devices such as digital still cameras, which have seen an increase in performance in recent years, it is possible to minimize the decrease in sensitivity in the visible light region and eliminate image defects caused by the reflected light.

[0114] The thickness of the present filter may be appropriately selected depending on the desired application, but in accordance with the recent trend toward thinner, lighter solid-state imaging devices, it is preferable that the thickness of the present filter is also thin. The present filter can be made thin because it contains the base material (i).

[0115] The thickness of the present filter is preferably 300 μm or less, more preferably 250 μm or less, further preferably 200 μm or less, particularly preferably 150 μm or less, and although there is no particular lower limit, it is desirable that the thickness is, for example, 20 μm.

[0116] <nir-cf> The NIR-CF is preferably an optical filter that has excellent cutting performance in the wavelength region of 850 to 1200 nm and excellent transmittance in the visible wavelength region. The dielectric multilayer film used in this NIR-CF is preferably a near-infrared reflective film.

[0117] When NIR-CF is used in a solid-state imaging device, it is preferable that the transmittance in the near-infrared wavelength region is low. In particular, it is known that the light receiving sensitivity of solid-state imaging devices is relatively high in the wavelength region of 800 to 1200 nm, and by reducing the transmittance in this wavelength region, it is possible to effectively perform visibility correction between the camera image and the human eye, and to achieve excellent color reproducibility. Furthermore, by reducing the transmittance in the wavelength region of 850 to 1200 nm, it is possible to effectively prevent near-infrared light used for security authentication function from reaching an image sensor, etc.

[0118] The average transmittance of the NIR-CF, measured in the vertical direction of the filter in the wavelength region of 850 to 1200 nm, is preferably 5% or less, more preferably 4% or less, even more preferably 3% or less, and particularly preferably 2% or less. When the average transmittance for wavelengths of 850 to 1200 nm is in this range, near infrared rays can be sufficiently blocked and excellent color reproducibility can be achieved, which is preferable.

[0119] When the NIR-CF is used in a solid-state imaging device, etc., it is preferable that the visible light transmittance is high. Specifically, in the wavelength region of 430 to 580 nm, the average transmittance measured from the vertical direction of the filter is preferably 75% or more, more preferably 80% or more, even more preferably 83% or more, and particularly preferably 85% or more. When the average transmittance at wavelengths of 430 to 580 nm is within this range, excellent imaging sensitivity can be achieved.

[0120] <dbpf> The DBPF is not particularly limited as long as it is an optical filter that transmits visible light and near-infrared light of a wavelength that is desired to be transmitted and cuts near-infrared light of a wavelength that is desired to be cut. The dielectric multilayer film used in this DBPF is preferably a film that transmits visible light and near-infrared light of wavelengths that are desired to be transmitted, and blocks near-infrared light of wavelengths that are desired to be blocked.

[0121] Like NIR-CF, when DBPF is used in a solid-state imaging device or the like, it is preferable that the visible light transmittance is high, and for the same reasons as above, it is preferable that the average transmittance at wavelengths of 430 to 580 nm is in the same range as that of NIR-CF.

[0122] <irpf> The IRPF is not particularly limited as long as it is an optical filter that blocks visible light and transmits near-infrared light of a desired wavelength. The dielectric multilayer film used in this IRPF is preferably a film that cuts off light of a wavelength that is to be cut off (a part of visible light and / or near infrared light). The IRPF may also use a visible light absorber to block visible light.

[0123] IRPF can be suitably used in optical systems such as infrared surveillance cameras, vehicle-mounted infrared cameras, infrared communications, various sensing systems, infrared warning devices, and night vision devices. When used for these applications, it is preferable for the transmittance of light of wavelengths other than the near-infrared light that is to be transmitted to be low. In particular, in the wavelength region of 380 to 700 nm, the average transmittance measured in the perpendicular direction of the present filter is preferably 10% or less, and more preferably 5% or less.

[0124] In addition, it is preferable that the IRPF has a high transmittance of the near infrared ray to be transmitted. Specifically, the IRPF has a light transmission band Ya in a wavelength region of 750 nm or more, and has a maximum transmittance (T IR ) is preferably 45% or more, more preferably 50% or more.

[0125] <Dielectric multilayer film> The filter of the present invention comprises the substrate (i) and a dielectric multilayer film, such as a laminate in which layers of a material with a high refractive index and layers of a material with a low refractive index are alternately laminated. The dielectric multilayer film may be provided on one side or both sides of the substrate (i). When provided on one side, it is possible to obtain an optical filter that is excellent in manufacturing cost and ease of manufacturing, and when provided on both sides, it is possible to obtain an optical filter that has high strength and is less prone to warping or twisting. When the present filter is used in a solid-state imaging device or the like, it is preferable that the filter has less warping or twisting, so it is preferable to provide the dielectric multilayer film on both sides of the substrate (i).

[0126] The material constituting the high refractive index material layer includes a material having a refractive index of 1.7 or more, and a material having a refractive index of 1.7 to 2.5 is usually selected. Examples of such materials include those containing titania, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, or the like as a main component, and containing a small amount (for example, 0 to 10 mass % of the main component) of titania, tin oxide, and / or cerium oxide, or the like.

[0127] The low refractive index material layer may be made of a material having a refractive index of 1.6 or less, and a material having a refractive index of 1.2 to 1.6 is usually selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

[0128] The method for laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film is formed by laminating these material layers. For example, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated can be formed directly on the substrate (i) by a CVD method, a sputtering method, a vacuum deposition method, an ion-assisted deposition method, an ion plating method, or the like.

[0129] The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ to 0.5λ, where λ (nm) is the wavelength of the light to be blocked (e.g., near infrared rays). In the case of NIR-CF, the value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness of each of the high refractive index material layer and the low refractive index material layer is within this range, the optical film thickness, which is the product (n×d) of the refractive index (n) and the film thickness (d), is approximately the same value as λ / 4, and the blocking and transmission of a specific wavelength tends to be easily controlled based on the relationship between the optical properties of reflection and refraction.

[0130] For example, in the case of NIR-CF, the total number of layers of high refractive index material layers and low refractive index material layers in the dielectric multilayer film is preferably 16 to 70 layers in the entire optical filter, and more preferably 20 to 60. When the thickness of each layer, the thickness of the dielectric multilayer film as the entire optical filter, and the total number of layers are within the above ranges, sufficient manufacturing margins can be ensured, and warping of the optical filter and cracks in the dielectric multilayer film can be reduced.

[0131] In this filter, by appropriately selecting the material types constituting the high refractive index material layer and the low refractive index material layer, the thickness of each of the high refractive index material layers and the low refractive index material layers, the order of lamination, and the number of laminations in accordance with the absorption characteristics, etc. of compound (Z), it is possible to ensure sufficient transmittance in the wavelength range to be transmitted (e.g., visible range), while having sufficient light blocking characteristics in the wavelength range to be blocked (e.g., near-infrared range), and to reduce the reflectance when light (e.g., near-infrared) is incident from an oblique direction.

[0132] Here, in order to optimize the conditions of the dielectric multilayer film, for example, optical thin film design software (e.g., Essential Macleod, manufactured by Thin Film Center) may be used to set parameters so as to achieve both an anti-reflection effect in the wavelength range to be transmitted (e.g., visible range) and a light blocking effect in the wavelength range to be blocked (e.g., near-infrared range). In the case of the above software, for example, when forming a dielectric multilayer film of NIR-CF, a parameter setting method may be used in which the target transmittance for wavelengths of 400 to 700 nm is set to 100% and the Target Tolerance value is set to 1, and the target transmittance for wavelengths of 705 to 950 nm is set to 0% and the Target Tolerance value is set to 0.5. These parameters can also be used to change the Target Tolerance value by dividing the wavelength range into smaller sections in accordance with various characteristics of the base material (i).

[0133] <Other functional films> In the present filter, a functional film such as an anti-reflection film, a hard coat film or an anti-static film may be appropriately provided between the substrate (i) and the dielectric multilayer film, on the surface of the substrate (i) opposite to the surface on which the dielectric multilayer film is provided, or on the surface of the dielectric multilayer film opposite to the surface on which the substrate (i) is provided, for the purposes of improving the surface hardness of the substrate (i) or the dielectric multilayer film, improving the chemical resistance, preventing static electricity and removing scratches, etc., within a range that does not impair the effects of the present invention.

[0134] The present filter may include one layer of the functional membrane, or may include two or more layers. When the present filter includes two or more layers of the functional membrane, the functional membrane may include two or more layers of the same membrane, or two or more layers of different membranes.

[0135] The method for laminating the functional film is not particularly limited, but examples thereof include a method in which a coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent is melt-molded or cast-molded onto the substrate (i) or the dielectric multilayer film in the same manner as described above.

[0136] Alternatively, the film can be produced by applying a curable composition containing a coating agent or the like onto the substrate (i) or the dielectric multilayer film with a bar coater or the like, and then curing the composition by exposure to ultraviolet light or the like.

[0137] Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins, and more specifically, examples thereof include vinyl compounds, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based and epoxy acrylate-based resins. The coating agent may be used alone or in combination of two or more kinds. Examples of the curable compositions containing these coating agents include vinyl-based, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based and epoxy acrylate-based curable compositions.

[0138] The curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or a thermal polymerization initiator may be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. The polymerization initiator may be used alone or in combination of two or more kinds.

[0139] The blending ratio of the polymerization initiator in the curable composition is preferably 0.1 to 10 mass%, more preferably 0.5 to 10 mass%, and further preferably 1 to 5 mass%, when the total amount of the curable composition is taken as 100 mass%. When the blending ratio of the polymerization initiator is within the above range, a curable composition excellent in curing characteristics and handling properties can be easily obtained, and a functional film such as an antireflection film, a hard coat film, or an antistatic film having a desired hardness can be easily obtained.

[0140] Furthermore, the curable composition may contain an organic solvent as a solvent, and a known solvent may be used as the organic solvent.Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; and amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0141] The thickness of the functional film is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 0.7 to 5 μm.

[0142] In addition, for the purpose of increasing the adhesion between the substrate (i) and the functional film and / or the dielectric multilayer film, or between the functional film and the dielectric multilayer film, the surface of the substrate (i), the functional film or the dielectric multilayer film may be subjected to a surface treatment such as a corona treatment or a plasma treatment.

[0143] [Optical filter applications] This filter is excellent in, for example, the ability to cut off light of a wavelength in the region to be cut off and the ability to transmit light of a wavelength to be transmitted. Therefore, it is useful for correcting the visibility of solid-state imaging elements such as CCD and CMOS image sensors in camera modules. In particular, it is useful for digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, cameras for wearable devices, PC cameras, surveillance cameras, automobile cameras, infrared cameras, televisions, car navigation systems, personal digital assistants, video game consoles, portable game consoles, fingerprint authentication systems, digital music players, various sensing systems, infrared communications, etc. Furthermore, it is also useful as a heat-cutting filter to be attached to glass plates of automobiles, buildings, etc.

[0144] <Solid-state imaging device> The solid-state imaging device according to the present invention includes the filter. Here, the solid-state imaging device is a device equipped with a solid-state imaging element such as a CCD or CMOS image sensor, and specifically can be used for applications such as digital still cameras, cameras for smartphones, cameras for mobile phones, cameras for wearable devices, and digital video cameras.

[0145] <Optical sensor device> The optical sensor device according to the present invention is not particularly limited as long as it is equipped with the present filter, and may have a conventionally known configuration. For example, a device having a light receiving element and the present filter can be mentioned, and specifically, a device having a light receiving element (semiconductor substrate), a protective film, the present filter, another filter, etc. can be mentioned. EXAMPLES

[0146] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0147] [Synthesis example] The compounds (Z) and (X) used in the following examples were synthesized based on generally known synthesis methods. Compound (Z) can be synthesized with reference to the methods described in, for example, JP 2009-108267 A, JP 5-59291 A, JP 2014-95007 A, JP 2011-52218 A, WO 2007 / 114398 A, JP 2003-246940 A, Chemistry of Heterocyclic Compounds: The Cyanine Dyes and Related Compounds, Volume 18 (Wiley, 1964), and Near-Infrared Dyes for High Technology Applications (Springer, 1997). Compound (X) can be synthesized with reference to the methods described in, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, JP-A-60-228448, JP-A-1-146846, JP-A-1-228960, Japanese Patent No. 4081149, JP-A-63-124054, "Phthalocyanine -Chemistry and Function-" (IPC, 1997), JP-A-2007-169315, JP-A-2009-108267, JP-A-2010-241873, Japanese Patent No. 3699464, and Japanese Patent No. 4740631.

[0148] [Intermediate synthesis example 1] [ka]

[0149] In a 200mL eggplant-shaped flask containing a stirrer, 21.8g of ethyl pivalate was added to 8.33g of compound a-1 synthesized by the method described in Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 11, p. 2826-2831, and 5 minutes later, 4.0g of sodium hydride (60%, dispersion in paraffin liquid) was added and stirred at 80°C for 3 hours. After that, it was cooled to room temperature, neutralized by adding 100mL of 1N aqueous hydrochloric acid, transferred to a separatory funnel, and the organic phase was extracted with 150mL of ethyl acetate. Next, 15g of magnesium sulfate was added to the extracted organic phase and stirred for 15 minutes, after which magnesium sulfate was removed by filter filtration, the filtrate was placed in a 300mL eggplant-shaped flask, and the solvent was distilled off using an evaporator to obtain compound a-2.

[0150] A stirrer was placed in the eggplant-shaped flask containing compound a-2, 20 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40°C. After stirring for 1 hour, the reaction solution was cooled on ice and neutralized by adding 200 mL of 1N aqueous sodium hydroxide solution. The mixture was then transferred to a separatory funnel, and 150 mL of ethyl acetate was added to extract the organic phase, after which 15 g of magnesium sulfate was added and stirred for 15 minutes. The magnesium sulfate was then removed by filtration, and the filtrate was placed in a 300 mL eggplant-shaped flask, and the solvent was removed using an evaporator. The compound remaining in the flask was then isolated and purified by silica gel chromatography to obtain 5.0 g of the desired compound a-3. The compound was identified by LC-MS and 1 This was analyzed by H-NMR.

[0151] [Intermediate synthesis example 2] [ka]

[0152] In a 200 mL eggplant-shaped flask equipped with a stirrer, 3 g of compound a-3 and 30 mL of diethyl ether were placed and cooled on ice while stirring. After 5 minutes of cooling on ice, 13.5 mL of 1 mol / L methylmagnesium iodide diethyl ether solution was added over 10 minutes, and then the mixture was heated to 35°C and stirred for 2 hours. Next, the reaction solution was cooled on ice, 30 mL of 20% aqueous perchloric acid was added, and the precipitated solid was filtered, washed with 20 mL of water, and dried under reduced pressure at 50°C to obtain 2.5 g of compound a-4. The compound was identified as follows: 1 This was analyzed by H-NMR.

[0153] [Synthesis example of compound (z-1)] [ka]

[0154] In a 100mL eggplant flask containing a stirrer, 1.5g of compound a-4, 0.6g of N-[2-chloro-3-(phenylamino)-2-propenylidene]-benzenamine monohydrochloride, 25mL of acetonitrile, 7.5mL of acetic anhydride, and 0.6mL of pyridine were added and heated under reflux for 5 hours. The mixture was then cooled to room temperature, and the solvent was removed using an evaporator. Then, 5mL of acetic acid was added and the mixture was cooled and allowed to stand at 5°C for 2 days. The precipitated solid was then filtered under reduced pressure, and washed with 5mL of acetic acid and 10mL of hexane to obtain 0.17g of compound a-5.

[0155] In a 100 mL eggplant flask containing a stirrer, 0.1 g of compound a-5, 0.2 g of lithium tetrakispentafluorophenylborate, 20 mL of dichloromethane, and 10 mL of water were added and stirred at room temperature for 1 hour. The mixture was then transferred to a separatory funnel, the aqueous phase was removed, and the organic phase was washed twice with 20 mL of water, and 1 g of sodium sulfate was added and stirred for 15 minutes. Sodium sulfate was then removed by filtration, and the filtrate was placed in a 300 mL eggplant flask, the solvent was removed using an evaporator, and the mixture was dried under reduced pressure at 50°C to obtain 0.05 g of compound (z-1). The compound was identified by LC-MS and 1 This was analyzed by H-NMR.

[0156] [Intermediate synthesis example 3] [ka]

[0157] In a 300 mL eggplant-shaped flask containing a stirrer, 5 g of flavone (compound a-6) and 50 mL of THF were added and cooled on ice. After 5 minutes of cooling on ice, 24.7 mL of a 1 mol / L solution of methylmagnesium iodide in diethyl ether was added over 10 minutes, and the mixture was then heated to 35°C and stirred for 2 hours. The reaction solution was then cooled on ice, and 50 mL of a 20% aqueous solution of perchloric acid was added. The precipitated solid was filtered, washed with 50 mL of water, and dried under reduced pressure at 50°C to obtain 4.5 g of compound a-7. The compound was identified as follows: 1 This was analyzed by H-NMR.

[0158] [Synthesis example of compound (z-16)] [ka]

[0159] In a 100mL eggplant flask containing a stirrer, 0.7g of compound a-7, 0.26g of malonaldehyde dianilide hydrochloride, 10mL of acetonitrile, 5mL of acetic anhydride, and 0.2mL of pyridine were added and heated under reflux for 2 hours. After that, the mixture was cooled to room temperature, and the precipitated solid was collected by filtration under reduced pressure and washed with 10mL of diethyl ether to obtain 0.6g of compound a-8.

[0160] In a 100 mL eggplant flask containing a stirrer, 0.1 g of compound a-8, 0.2 g of lithium tetrakispentafluorophenylborate, 20 mL of dichloromethane, and 10 mL of water were added and stirred at room temperature for 3 hours. The mixture was then transferred to a separatory funnel, and the aqueous phase was removed. The organic phase was washed twice with 20 mL of water, and the solvent was removed from the organic phase using an evaporator. The residue was then dissolved in 0.5 mL of acetone, 10 mL of methanol was added, and the mixture was cooled on ice. The precipitated solid was collected by suction filtration and dried under reduced pressure at 50°C to obtain 0.07 g of compound (z-16). The compound was identified by LC-MS and 1 This was analyzed by H-NMR.

[0161] [Intermediate synthesis example 4] [ka]

[0162] Compound a-9 4g and ethyl pivalate 21.8g were added to a 200mL eggplant flask containing a stirrer and stirred. After 5 minutes, sodium hydride (60%, dispersion in paraffin liquid) 3.2g was added, and the mixture was stirred at 80°C for 3 hours. The mixture was then cooled to room temperature, neutralized by adding 30mL of 1N aqueous hydrochloric acid, and the organic phase was extracted with 150mL of ethyl acetate. Next, magnesium sulfate 15g was added to the organic phase and stirred for 15 minutes, after which magnesium sulfate was removed by filter filtration, and the filtrate was placed in a 300mL eggplant flask and the solvent was removed using an evaporator to obtain compound a-10.

[0163] A stirrer was placed in the eggplant-shaped flask containing compound a-10, 20 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40°C. After stirring for 1 hour, the reaction solution was cooled on ice and neutralized by adding 240 mL of 1N aqueous sodium hydroxide solution. The mixture was then transferred to a separatory funnel, and 200 mL of ethyl acetate was added to extract the organic phase, after which 15 g of magnesium sulfate was added and stirred for 15 minutes. Magnesium sulfate was then removed by filtration, the filtrate was placed in a 300 mL eggplant-shaped flask, and the solvent was removed using an evaporator. The compound remaining in the flask was then isolated and purified by silica gel chromatography to obtain 2.0 g of the target compound a-11. The compound was identified by LC-MS and 1 This was analyzed by H-NMR.

[0164] [Intermediate synthesis example 5] [ka]

[0165] In a 200 mL eggplant-shaped flask containing a stirrer, 2.7 g of compound a-11 and 50 mL of diethyl ether were added and cooled on ice. After 5 minutes of cooling on ice, 24.7 mL of 1 mol / L methylmagnesium iodide diethyl ether solution was added over 10 minutes, and then the mixture was heated to 35°C and stirred for 2 hours. Next, the reaction solution was cooled on ice, 50 mL of 20% aqueous perchloric acid was added, and the precipitated solid was filtered, washed with 50 mL of water, and dried under reduced pressure at 50°C to obtain 0.7 g of compound a-12. The compound was identified as follows: 1 This was analyzed by H-NMR.

[0166] [Synthesis example of compound (z-59)] [ka]

[0167] In a 100mL eggplant flask containing a stirrer, 0.5g of compound a-12, 0.22g of malonaldehyde dianilide hydrochloride, 7.5mL of acetonitrile, 2.5mL of acetic anhydride, and 0.2mL of pyridine were added and heated under reflux for 2 hours. After that, the mixture was cooled to room temperature, and the precipitated solid was collected by vacuum filtration, washed with 10mL of acetic acid and 10mL of acetonitrile, and dried at 50°C under reduced pressure to obtain 0.35g of compound a-13.

[0168] In a 100 mL eggplant flask containing a stirrer, 0.3 g of compound a-13, 0.8 g of lithium tetrakispentafluorophenylborate, 50 mL of dichloromethane, and 20 mL of water were added and stirred at room temperature for 3 hours. The mixture was then transferred to a separatory funnel, and the aqueous phase was removed. The organic phase was washed twice with 20 mL of water, and the solvent was removed from the organic phase using an evaporator. The residue was then dissolved in 20 mL of acetone, 100 mL of water was added, and 13 g of the solvent was removed using an evaporator, followed by ice cooling. The precipitated solid was then collected by suction filtration, washed with 50 mL of methanol, and the solid was dried under reduced pressure at 50°C to obtain 0.5 g of compound (z-59). The compound was identified using LC-MS and 1 This was analyzed by H-NMR.

[0169] [Intermediate Synthesis Example 6] [ka]

[0170] Compound a-14 4.5g, isobutyric acid 21.8g were added to a 200mL eggplant flask with a stirrer, and stirred. After 5 minutes, sodium hydride (60%, dispersion in paraffin liquid) 3.2g was added, and the mixture was stirred at 80°C for 3 hours. After that, the mixture was cooled to room temperature, neutralized by adding 1N hydrochloric acid aqueous solution 30mL, and the organic phase was extracted with ethyl acetate 150mL. Next, magnesium sulfate 15g was added to the organic phase and stirred for 15 minutes, after which magnesium sulfate was removed by filter filtration, and the filtrate was placed in a 300mL eggplant flask, and the solvent was removed using an evaporator to obtain compound a-15.

[0171] A stirrer was placed in the eggplant-shaped flask containing compound a-15, 20 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40°C. After stirring for 1 hour, the reaction solution was cooled on ice and neutralized by adding 240 mL of 1N aqueous sodium hydroxide solution. The mixture was then transferred to a separatory funnel, and 200 mL of ethyl acetate was added to extract the organic phase, after which 15 g of magnesium sulfate was added and stirred for 15 minutes. Next, magnesium sulfate was removed by filtration, the filtrate was placed in a 300 mL eggplant-shaped flask, and the solvent was removed using an evaporator. The compound remaining in the flask was then isolated and purified by silica gel chromatography to obtain 0.4 g of the target compound a-16. The compound was identified by LC-MS and 1 This was analyzed by H-NMR.

[0172] [Intermediate Synthesis Example 7] [ka]

[0173] In a 100 mL eggplant-shaped flask containing a stirrer, 0.4 g of compound a-16 and 10 mL of diethyl ether were added and cooled on ice. After 5 minutes of cooling on ice, 5.0 mL of 1 mol / L methyl magnesium iodide diethyl ether solution was added over 10 minutes, and then the mixture was heated to 35°C and stirred for 2 hours. Next, the reaction solution was cooled on ice, 10 mL of 20% aqueous perchloric acid was added, followed by 20 mL of dichloromethane, which was then transferred to a separatory funnel to recover the organic phase. The solvent was removed from the organic phase using an evaporator, the solid residue was stirred, 20 mL of diethyl ether was added, and the mixture was stirred for 20 minutes. Next, the solid was filtered by suction filtration and dried under reduced pressure at 50°C to obtain 0.5 g of compound a-17. The compound was identified as follows: 1 This was analyzed by H-NMR.

[0174] [Synthesis example of compound (z-62)] [ka]

[0175] In a 100mL eggplant flask containing a stirrer, 0.4g of compound a-17, 0.16g of malonaldehyde dianilide hydrochloride, 7.5mL of acetonitrile, 2.5mL of acetic anhydride, and 0.2mL of pyridine were added and heated under reflux for 2 hours. After that, the mixture was cooled to room temperature, and the precipitated solid was collected by filtration under reduced pressure, washed with 10mL of diethyl ether, and dried under reduced pressure at 50°C to obtain 0.35g of compound a-18.

[0176] In a 100 mL eggplant flask containing a stirrer, 0.3 g of compound a-18, 0.8 g of lithium tetrakispentafluorophenylborate, 50 mL of dichloromethane, and 20 mL of water were added and stirred at room temperature for 3 hours. The mixture was then transferred to a separatory funnel, and the aqueous phase was removed. The organic phase was washed twice with 20 mL of water, and the solvent was removed from the organic phase using an evaporator. The solid was dried under reduced pressure at 50°C to obtain 0.4 g of compound (z-62). The compound was identified using LC-MS and 1 This was analyzed by H-NMR.

[0177] [Intermediate synthesis example 8] [ka]

[0178] In a 200 mL eggplant flask containing a stirrer, 15 g of compound a-19 and 28.7 g of methyl 4,4-dimethyl-3-oxovalerate were added and stirred at 180°C for 24 hours. After that, it was cooled to room temperature, and 250 mL of hexane and 200 mL of 1N aqueous hydrochloric acid were added, and the mixture was transferred to a separatory funnel to remove the aqueous phase. Next, the solvent was removed from the organic phase using an evaporator, and the compound remaining in the flask was isolated and purified by silica gel chromatography to obtain 7 g of the target compound a-20. The compound was identified using LC-MS and 1 This was analyzed by H-NMR.

[0179] [Intermediate Synthesis Example 9] [ka]

[0180] Compound a-20 3.5g and diethyl ether 20mL were added to a 100mL eggplant flask containing a stirrer, and the mixture was cooled on ice. After 5 minutes of cooling on ice, 14.0mL of 1mol / L methyl magnesium iodide diethyl ether solution was added over 10 minutes, and then the mixture was heated to 35°C and stirred for 2 hours. The temperature was then naturally lowered to room temperature, and the resulting reaction solution was added to a beaker containing 100mL of water and a stirrer over 5 minutes. Then, 20g of 40% aqueous fluoroboric acid solution was added over 10 minutes, and the mixture was stirred for 30 minutes, and then transferred to a separatory funnel. Next, 30mL of dichloromethane was added, and the aqueous phase was removed by separation, and the solvent was removed from the organic phase using an evaporator. The residue was then dissolved in 30 mL of dichloromethane, 50 mL of diisopropyl ether was added, 40 g of the solvent was removed using an evaporator, and the mixture was cooled on ice. The precipitated solid was collected by suction filtration and dried under reduced pressure at 50°C to obtain 2.3 g of compound a-21. The compound was identified as follows: 1 This was analyzed by H-NMR.

[0181] [Synthesis example of compound (z-151)] [ka]

[0182] In a 100 mL eggplant flask containing a stirrer, 0.5 g of compound a-21, 0.18 g of malonaldehyde dianilide hydrochloride, and 15 mL of pyridine were added and heated under reflux for 2 hours. After cooling to room temperature, the solvent was distilled off using an evaporator, and the mixture was separated by column chromatography to obtain 0.2 g of compound a-22.

[0183] In a 100 mL eggplant flask containing a stirrer, 0.2 g of compound a-22, 0.8 g of lithium tetrakispentafluorophenylborate, 50 mL of dichloromethane, and 20 mL of water were added and stirred at room temperature for 3 hours. The mixture was then transferred to a separatory funnel, and the aqueous phase was removed. The organic phase was washed twice with 20 mL of water, and the solvent was removed from the organic phase using an evaporator. The compound was separated by column chromatography to obtain 0.2 g of compound (z-151). The compound was identified using LC-MS and 1 This was analyzed by H-NMR.

[0184] [Intermediate Synthesis Example 10] [ka]

[0185] In a 200mL eggplant-shaped flask containing a stirrer, 1.9g of compound a-23 and 2.0g of ethyl pivalate were added and stirred. After 5 minutes, 0.3g of sodium hydride (60%, dispersion in paraffin liquid) was added, and the mixture was stirred at 80°C for 3 hours. After that, the mixture was cooled to room temperature, neutralized by adding 30mL of 1N aqueous hydrochloric acid, and the organic phase was extracted with 150mL of ethyl acetate. Next, 5g of magnesium sulfate was added to the organic phase and stirred for 15 minutes, after which the magnesium sulfate was removed by filter filtration, and the filtrate was placed in a 300mL eggplant-shaped flask, and the solvent was removed using an evaporator, to obtain 1.3g of compound a-24.

[0186] A stirrer was placed in an eggplant-shaped flask containing 1.3 g of compound a-24, 20 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40°C. After stirring for 1 hour, the reaction solution was cooled on ice and neutralized by adding 240 mL of 1N aqueous sodium hydroxide solution. The mixture was then transferred to a separatory funnel, and 200 mL of ethyl acetate was added to extract the organic phase, after which 5 g of magnesium sulfate was added and stirred for 15 minutes. The magnesium sulfate was then removed by filtration, the filtrate was placed in a 300 mL eggplant-shaped flask, and the solvent was removed using an evaporator. The compound remaining in the flask was then isolated and purified by silica gel chromatography to obtain 1.1 g of compound a-25. The compound was identified by LC-MS and 1 This was analyzed by H-NMR.

[0187] [Intermediate Synthesis Example 11] [ka]

[0188] In a 200 mL eggplant-shaped flask containing a stirrer, 1.5 g of compound a-25 and 50 mL of diethyl ether were added and cooled on ice. After 5 minutes of cooling on ice, 1.5 mL of 1 mol / L methylmagnesium iodide diethyl ether solution was added over 10 minutes, and then the mixture was heated to 35°C and stirred for 2 hours. Next, the reaction solution was cooled on ice, 50 mL of 20% aqueous perchloric acid was added, and the precipitated solid was filtered, washed with 50 mL of water, and dried under reduced pressure at 50°C to obtain 3.0 g of compound a-26. The compound was identified as follows: 1 This was analyzed by H-NMR.

[0189] [Synthesis example of compound (z-157)] [ka]

[0190] In a 100mL eggplant flask containing a stirrer, 7.0g of compound a-26, 2.5g of malonaldehyde dianilide hydrochloride, 50mL of acetonitrile, 10mL of acetic anhydride, and 10mL of pyridine were added and heated under reflux for 2 hours. After that, the mixture was cooled to room temperature, and the precipitated solid was collected by vacuum filtration, washed with 10mL of acetic acid and 10mL of acetonitrile, and dried at 50°C under reduced pressure to obtain 5.1g of compound a-27.

[0191] In a 100 mL eggplant flask containing a stirrer, 0.6 g of compound a-27, 1.2 g of lithium tetrakispentafluorophenylborate, 50 mL of dichloromethane, and 50 mL of water were added and stirred at room temperature for 3 hours. The mixture was then transferred to a separatory funnel, and the aqueous phase was removed. The organic phase was washed twice with 20 mL of water, and the solvent was removed from the organic phase using an evaporator. The residue was then dissolved in 20 mL of acetone, 100 mL of water was added, and 10 g of the solvent was removed using an evaporator, followed by ice cooling. The precipitated solid was then collected by suction filtration, washed with 50 mL of methanol, and the solid was dried under reduced pressure at 50°C to obtain 1.0 g of compound (z-157). The compound was identified using LC-MS and 1 This was analyzed by H-NMR.

[0192] [Intermediate Synthesis Example 12] [ka]

[0193] 22 g of 1-adamantanecarbonyl chloride (compound a-28) and 5.2 g of methylenecyclohexane were added to a 200 mL eggplant-shaped flask containing a stirrer, and the mixture was heated to 90°C, and then stirred for 10 minutes while adding 10 g of trifluoromethanesulfonic acid dropwise. The mixture was then cooled to 0°C, and 150 mL of hexane, 50 mL of diethyl ether, and 50 mL of water were added and stirred. The precipitated solid was filtered off and dried under reduced pressure at 50°C to obtain 4.2 g of compound a-35. The compound was identified as follows: 1 H-NMR analysis was performed.

[0194] [Synthesis example of compound (z-163)] [ka]

[0195] In a 100 mL eggplant flask containing a stirrer, 0.5 g of compound a-35, 0.1 g of malonaldehyde dianilide hydrochloride, 4 mL of acetonitrile, 1 mL of acetic anhydride, and 1 mL of pyridine were added and stirred at 90°C for 10 minutes. After cooling to 0°C, the precipitated solid was filtered off, washed with 2 mL of acetonitrile, and dried under reduced pressure at 50°C to obtain 0.3 g of compound a-36. The compound was identified as follows: 1 H-NMR analysis was performed.

[0196] In a 100 mL eggplant flask containing a stirrer, 0.3 g of compound a-36, 0.4 g of lithium tetrakispentafluorophenylborate, 20 mL of dichloromethane, and 20 mL of water were added and stirred at room temperature for 4 hours. The mixture was then transferred to a separatory funnel, and the aqueous phase was removed. The organic phase was washed twice with 20 mL of water, and the solvent was removed from the organic phase using an evaporator. The residue was then dissolved in dichloromethane, methanol was added, and the precipitated solid was collected by suction filtration and dried under reduced pressure at 50°C to obtain 0.4 g of compound (z-163). The compound was identified by LC-MS and 1 This was analyzed by H-NMR.

[0197] [Intermediate Synthesis Example 13] [ka]

[0198] Ethyl pivalate (50.0 g) was added to a solution of compound a-37 (20.0 g) in t-BuOH (150 mL), and then 5.5 g of sodium hydride (60%, dispersion in paraffin liquid) was added, followed by stirring at 80°C for 3 hours. The mixture was then cooled to room temperature, and 20 mL of concentrated hydrochloric acid was added. After separation and washing with ethyl acetate and water, sodium sulfate was added to dry the mixture, and the solvent was removed using an evaporator to obtain compound a-38.

[0199] Compound a-38 was not purified, and 60 mL of concentrated hydrochloric acid was added and stirred at 40°C. After 1 hour, the reaction solution was ice-cooled and neutralized by adding 1N aqueous sodium hydroxide solution. After separation and washing with ethyl acetate and water, sodium sulfate was added to dry, and the solvent was removed using an evaporator. The resulting mixture was purified by silica gel column chromatography to obtain compound a-39 (15.4 g). The compound was identified by LC-MS and 1 This was analyzed by H-NMR.

[0200] [Intermediate Synthesis Example 14] [ka]

[0201] Compound a-39 (15.4 g), phenylboronic acid (11.7 g), tetrakis(triphenylphosphine)palladium (1.0 g), and potassium carbonate (60.0 g) were dissolved in a mixed solution of 50 mL of toluene and 50 mL of water, and heated at 110°C for 12 hours with vigorous stirring. After cooling to room temperature, the mixture was separated and washed with toluene and water, sodium sulfate was added to the organic layer to dry it, and the solvent was removed using an evaporator. The resulting mixture was purified by silica gel column chromatography to obtain compound a-40 (12.4 g).

[0202] Compound a-40 (12.4 g) and 90 mL of tetrahydrofuran were ice-cooled while stirring. After 5 minutes of ice-cooling, a methylmagnesium iodide diethyl ether solution (1 mol / L, 50 mL) was added dropwise, and the mixture was heated to 35°C and stirred for 2 hours. The reaction solution was then ice-cooled, and 90 mL of a 20% aqueous perchloric acid solution was added. The precipitated solid was filtered, washed with 60 mL of water, and dried under reduced pressure at 50°C to obtain compound a-41 (10.4 g). The compound was identified as follows: 1 This was analyzed by H-NMR.

[0203] [Synthesis example of compound (z-156)] [ka]

[0204] In a 100mL eggplant flask containing a stirrer, 7.0g of compound a-41, 2.5g of malonaldehyde dianilide hydrochloride, 50mL of acetonitrile, 10mL of acetic anhydride, and 10mL of pyridine were added and heated under reflux for 2 hours. After that, the mixture was cooled to room temperature, and the precipitated solid was collected by vacuum filtration, washed with 10mL of acetic acid and 10mL of acetonitrile, and dried at 50°C under reduced pressure to obtain 5.0g of compound a-42.

[0205] In a 100 mL eggplant flask containing a stirrer, 0.6 g of compound a-42, 1.2 g of lithium tetrakispentafluorophenylborate, 50 mL of dichloromethane, and 50 mL of water were added and stirred at room temperature for 3 hours. The mixture was then transferred to a separatory funnel, and the aqueous phase was removed. The organic phase was washed twice with 20 mL of water, and the solvent was removed from the organic phase using an evaporator. The residue was then dissolved in 20 mL of acetone, 100 mL of water was added, and 10 g of the solvent was removed using an evaporator, followed by ice cooling. The precipitated solid was then collected by suction filtration, washed with 50 mL of methanol, and the solid was dried under reduced pressure at 50°C to obtain 1.0 g of compound (z-156). The compound was identified using LC-MS and 1 This was analyzed by H-NMR.

[0206] [Intermediate Synthesis Example 15] [ka]

[0207] In dichloromethane (100 mL), compound a-43 (20.0 g), oxalyl dichloride (21.4 g), pyridine (13.4 g) and DMF (1 mL) were stirred at room temperature for 1 hour. Dichloromethane was removed by an evaporator to obtain a mixture containing compound a-44.

[0208] [Synthesis example of compound (z-161)] [ka]

[0209] Compound a-45 was obtained in the same manner as in Intermediate Synthesis Example 10, except that ethyl pivalate was changed to compound a-44.

[0210] Compound (z-161) was obtained in the same manner as in Intermediate Synthesis Example 11 and Compound (z-157) Synthesis Example, except that compound a-23 was changed to compound a-45 and malonaldehyde dianilide hydrochloride was changed to N-[2-chloro-3-(phenylamino)-2-propenylidene]-benzenamine monohydrochloride. The compound was identified by LC-MS and 1 This was analyzed by H-NMR.

[0211] <Requirements (A)> The above requirement (A) was measured using a solution in which the compound (Z) or (X) used in the following test was dissolved in dichloromethane and the transmission spectrum (wherein the transmission spectrum is a spectrum in which the transmittance at the maximum absorption wavelength is 10%) measured using a spectrophotometer (V-7200) manufactured by JASCO Corporation. The results are shown in Table 5. Note that requirements A to D in Table 5 respectively refer to requirements (A), (B-1), (C) and (D) in the above column for <Compound (Z)>.

[0212] <Requirements (B)> The above requirement (B) was measured using a solution in which the compound (Z) or (X) used in the following test was dissolved in dichloromethane and the absorption spectrum was measured using a spectrophotometer (V-7200) manufactured by JASCO Corp. The results are shown in Table 5.

[0213] <Requirements (C)> A solution with a resin concentration of 20% by mass was prepared by adding 100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 0.3 parts by mass of Irganox 1010 (manufactured by BASF Japan Ltd.), compound (Z) or (X) used in the following test, and dichloromethane to a container. In addition, when the following compounds (z-1), (x-3), and (z-163) were used, the amount was 0.05 parts by mass, when the following compound (z-16) was used, the amount was 0.06 parts by mass, when the following compounds (z-59), (z-62), (z-156), (z-157), (z-158), (z-159), (z-160), (z-161), and (z-162) were used, the amount was 0.04 parts by mass, when the following compound (z-151) was used, the amount was 0.08 parts by mass, and when the following compound (x-4) was used, the amount was 0.03 parts by mass. The amount of each of these compounds used was adjusted according to the molar extinction coefficient of each compound so that the absorbance at the absorption maximum wavelength of the obtained solution was about 1.

[0214] The obtained solution was cast onto a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100° C. under reduced pressure for 8 hours to obtain a resin layer for light resistance evaluation having a thickness of 0.1 mm, length of 210 mm, and width of 210 mm. The absorbance of the resin layer for evaluating light resistance was measured using a spectrophotometer (V-7200) manufactured by JASCO Corporation, and the absorbance Ai at the maximum absorption wavelength λa in the wavelength range of 700 to 1000 nm was measured. Thereafter, a fluorescent lamp (TWINBIRD Corporation, arm-type touch inverter fluorescent lamp LK-H766B, total luminous flux: 1334 lm) was installed at a distance of 30 cm directly above the surface of the resin layer for evaluating light resistance in the vertical direction, and the fluorescent lamp was irradiated for 30 days. The absorbance Af of the resin layer for evaluating light resistance at the λa after 30 days of irradiation with the fluorescent lamp was measured, and the absorbance retention rate D (=Af×100 / Ai) was calculated. The results are shown in Table 5.

[0215] <Requirements (D)> The compound (Z) or (X) used in the following test was dissolved in dichloromethane, and the absorption spectrum was measured using a spectrophotometer (V-7200) manufactured by JASCO Corporation. The absorbance at the longest wavelength among the maximum absorption wavelengths was defined as εa, and the maximum absorbance at wavelengths of 430 to 580 nm was defined as εbmax. εa / εbmax was calculated. The results are shown in Table 5.

[0216] [Table 5]

[0217] <Molecular weight> The molecular weight of the resin was measured by the following method (a) or (b), taking into consideration the solubility of each resin in a solvent, etc. (a) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a gel permeation chromatography (GPC) apparatus manufactured by WATERS (150C type, column: Tosoh H-type column, developing solvent: o-dichlorobenzene). (b) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a Tosoh Corporation GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF).

[0218] For the resin synthesized in Resin Synthesis Example 3 described later, the inherent viscosity was measured by the following method (c) instead of the molecular weight measurement by the above method. (c) A portion of the polyimide solution was poured into anhydrous methanol to precipitate the polyimide, which was then separated from the unreacted monomer by filtration and vacuum dried for 12 hours at 80° C. 0.1 g of the resulting polyimide was dissolved in 20 mL of N-methyl-2-pyrrolidone (dilute polyimide solution), and the logarithmic viscosity (μ) at 30° C. was calculated using a Cannon-Fenske viscometer according to the following formula: μ={ln(ts / t0)} / C t0: Flow time of the solvent (N-methyl-2-pyrrolidone) ts: Flow time of dilute polyimide solution C: 0.5 g / dL

[0219] <Glass transition temperature (Tg)> The glass transition temperature of the resin was measured using a differential scanning calorimeter (DSC6200) manufactured by Hitachi High-Tech Science Corporation at a temperature rise rate of 20° C. per minute under a nitrogen gas flow.

[0220] [Resin synthesis example 1] 8-Methyl-8-methoxycarbonyltetracyclo[4.4.0.1] represented by the following formula (a) 2,5 .1 7,10 100 parts by mass of dodeca-3-ene (hereinafter also referred to as "DNM"), 18 parts by mass of 1-hexene (molecular weight regulator), and 300 parts by mass of toluene (solvent for ring-opening polymerization reaction) were charged into a nitrogen-substituted reaction vessel, and the solution was heated to 80°C. Next, 0.2 parts by mass of a toluene solution of triethylaluminum (0.6 mol / L) and 0.9 parts by mass of a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / L) were added as polymerization catalysts to the solution in the reaction vessel, and the solution was heated and stirred at 80°C for 3 hours to cause a ring-opening polymerization reaction, thereby obtaining a ring-opened polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

[0221] [ka]

[0222] 1,000 parts by mass of the ring-opened polymer solution obtained above was charged into an autoclave, and RuHCl(CO)[P(C 6 H 5 ) 3 ] 3 0.12 parts by mass was added, and hydrogen gas pressure was 100 kg / cm 2 The mixture was heated and stirred for 3 hours at a reaction temperature of 165°C to carry out a hydrogenation reaction. The resulting reaction solution (hydrogenated polymer solution) was cooled, and the hydrogen gas pressure was released. The resulting reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was then dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The resulting resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165°C.

[0223] [Resin synthesis example 2] In a 3L four-neck flask, 35.12g (0.253mol) of 2,6-difluorobenzonitrile, 87.60g (0.250mol) of 9,9-bis(4-hydroxyphenyl)fluorene, 41.46g (0.300mol) of potassium carbonate, 443g of N,N-dimethylacetamide, and 111g of toluene were added. Then, a thermometer, a stirrer, a three-way cock with a nitrogen inlet tube, a Dean-Stark tube, and a cooling tube were attached to the four-neck flask. Next, after replacing the inside of the flask with nitrogen, the obtained solution was reacted at 140°C for 3 hours, and the generated water was removed from the Dean-Stark tube as needed. When the generation of water was no longer observed, the temperature was gradually increased to 160°C, and the reaction was continued at that temperature for 6 hours. Then, it was cooled to room temperature (25°C), the generated salt was removed with filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The residue was vacuum dried overnight at 60°C to obtain a white powder (hereinafter also referred to as "Resin B") (yield 95%). The obtained Resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285°C.

[0224] [Resin synthesis example 3] In a 500 mL five-neck flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a dropping funnel with a side tube, a Dean-Stark tube, and a cooling tube, 27.66 g (0.08 mol) of 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene and 7.38 g (0.02 mol) of 4,4'-bis(4-aminophenoxy)biphenyl were placed under a nitrogen stream and dissolved in 68.65 g of γ-butyrolactone and 17.16 g of N,N-dimethylacetamide. The resulting solution was cooled to 5°C using an ice-water bath, and while maintaining the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 0.50 g (0.005 mol) of triethylamine, an imidization catalyst, were added all at once. After the addition was completed, the temperature was raised to 180°C, and the mixture was refluxed for 6 hours while distilling off the distillate as needed. After the reaction was completed, the mixture was air-cooled until the internal temperature reached 100°C, and then 143.6 g of N,N-dimethylacetamide was added to dilute the mixture, and the mixture was cooled with stirring to obtain 264.16 g of a polyimide solution with a solid content of 20 mass%. A part of this polyimide solution was poured into 1 L of methanol to precipitate the polyimide. The filtered polyimide was washed with methanol and then dried in a vacuum dryer at 100°C for 24 hours to obtain a white powder (hereinafter also referred to as "resin C"). The IR spectrum of the obtained resin C was measured, and it was found to have a peak at 1704 cm specific to the imide group. -1 , 1770cm -1 Resin C had a glass transition temperature (Tg) of 310° C., and its inherent viscosity was measured to be 0.87.

[0225] [Example 1] [Preparation of substrate] In a container, 100 parts by mass of resin A obtained in Resin Synthesis Example 1, 0.20 parts by mass of the following compound (z-1) (maximum absorption wavelength in dichloromethane: 787 nm) as compound (Z), 0.038 parts by mass of the following compound (x-1) (maximum absorption wavelength in dichloromethane: 711 nm) as compound (X), 0.075 parts by mass of the following compound (x-2) (maximum absorption wavelength in dichloromethane: 738 nm), and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a resin layer (1) having a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm.

[0226] ·Compound (z-1) [ka]

[0227] ·Compound (x-1) [ka]

[0228] ·Compound (x-2) [ka]

[0229] The following resin composition (1) was applied to one side of the obtained resin layer (1) using a bar coater so that the thickness of the obtained resin layer (2) was 3 μm, and the coating was heated in an oven at 70° C. for 2 minutes to volatilize and remove the solvent. Next, the coating was exposed (exposure dose 500 mJ / cm 2 ) using a UV conveyor-type exposure machine (manufactured by Eye Graphics Co., Ltd., Eye ultraviolet curing device, model US2-X0405, 60 Hz). 2 , Illuminance: 200mW / cm 2 ) was carried out to cure the resin composition (1) and form a resin layer (2) on the resin layer (1). In the same manner, a resin layer (2) made of the resin composition (1) was formed on the other surface of the resin layer (1). This resulted in a substrate having a resin layer (2) not containing the compound (Z) on both surfaces of the resin layer (1) containing the compound (Z).

[0230] Resin composition (1): A composition containing 60 parts by mass of tricyclodecane dimethanol acrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, and methyl ethyl ketone (solvent, used so that the solids concentration in the resulting composition is 30% by mass).

[0231] (Lightfastness) The obtained substrate was exposed to indoor fluorescent light for 500 hours, and the light resistance of the near-infrared absorbing dye contained in the resin was evaluated. The light resistance was evaluated by calculating the dye remaining rate (%) from the change in absorbance before and after exposure to the fluorescent light at the wavelength at which the substrate has the highest absorption intensity (hereinafter referred to as "λa". If the substrate has multiple absorption maxima, λa is the wavelength at which the absorption intensity is the highest among them). The pigment remaining rate after 500 hours of exposure to fluorescent light was marked as "○" when it was 95% or more, and marked as "×" when it was less than 95%. The results are shown in Table 8.

[0232] [Preparation of Optical Filter] A dielectric multilayer film (I) was formed on one surface of the substrate obtained by the above-mentioned substrate preparation, and a dielectric multilayer film (II) was further formed on the other surface of the substrate, to obtain an optical filter having a thickness of about 0.110 mm.

[0233] The dielectric multilayer film (I) was deposited at a deposition temperature of 100°C using silica (SiO 2 ) layer and titania (TiO 2 The dielectric multilayer film (II) is a laminate of alternating layers of silica (SiO 2 ) layer and titania (TiO 2 ) layers are alternately laminated (a total of 22 layers). In both dielectric multilayer films (I) and (II), silica layers and titania layers were alternately laminated in the following order from the substrate side: titania layer, silica layer, titania layer, ...silica layer, titania layer, silica layer, with the silica layer being the outermost layer of the optical filter.

[0234] The thickness and number of each layer were optimized using optical thin film design software (Essential Macleod, Thin Film Center) in accordance with the wavelength-dependent characteristics of the refractive index of the substrate and the absorption characteristics of the compounds (Z) and (X) used, so as to achieve good transmittance in the visible range and reflectance performance in the near-infrared range. When performing optimization, the input parameters (target values) to the software in this embodiment were as shown in Table 6 below.

[0235] [Table 6]

[0236] As a result of optimizing the film configuration, the dielectric multilayer film (I) was a multilayer deposition film with 26 layers, in which a silica layer with a physical thickness of about 37 to 168 nm and a titania layer with a physical thickness of about 11 to 104 nm were alternately laminated, and the dielectric multilayer film (II) was a multilayer deposition film with 22 layers, in which a silica layer with a physical thickness of about 40 to 191 nm and a titania layer with a physical thickness of about 10 to 110 nm were alternately laminated. An example of the optimized film configuration is shown in Table 7 below.

[0237] [Table 7]

[0238] For the obtained optical filter, the average value T of the spectral transmittance measured from the vertical direction of the optical filter at wavelengths of 430 to 580 nm and the average value R of the spectral reflectance of non-polarized light incident at an angle of 5° from the vertical direction on the dielectric multilayer film (II) side at wavelengths of 700 to 800 nm were obtained. The spectral transmittance and spectral reflectance were measured using a spectrophotometer (V-7200) manufactured by JASCO Corporation. The results are shown in Table 8.

[0239] [Example 2] A substrate was obtained in the same manner as in Example 1, except that 0.08 parts by mass of the following compound (z-16) (maximum absorption wavelength in dichloromethane: 825 nm) was used instead of 0.2 parts by mass of compound (z-1) in Example 1, and resin B was used instead of resin A. The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0240] ·Compound (z-16) [ka]

[0241] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0242] [Example 3] A substrate was obtained in the same manner as in Example 1, except that 0.14 parts by mass of the following compound (z-59) (maximum absorption wavelength in dichloromethane: 770 nm) was used instead of 0.2 parts by mass of compound (z-1) in Example 1, and resin C was used instead of resin A. The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0243] ·Compound (z-59) [ka]

[0244] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0245] [Example 4] A substrate was obtained in the same manner as in Example 1, except that 0.2 parts by mass of the following compound (z-62) (maximum absorption wavelength in dichloromethane: 757 nm) was used instead of 0.2 parts by mass of the compound (z-1) in Example 1, and Acriview manufactured by Nippon Shokubai Co., Ltd. was used instead of Resin A. The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0246] ·Compound (z-62) [ka]

[0247] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0248] [Example 5] A substrate was obtained in the same manner as in Example 1, except that 0.08 parts by mass of compound (z-151) (maximum absorption wavelength in dichloromethane: 824 nm) was used instead of 0.2 parts by mass of compound (z-1). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0249] ·Compound (z-151) [ka]

[0250] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0251] [Example 6] A container was charged with 100 parts by mass of resin A obtained in Resin Synthesis Example 1, 0.38 parts by mass of compound (x-1) as compound (X), 0.75 parts by mass of compound (x-2), and dichloromethane to prepare a solution with a resin concentration of 20% by mass. The solution was then filtered through a Millipore filter having a pore size of 5 μm to obtain a resin solution (E6-1). Similarly, 100 parts by mass of resin A, 2 parts by mass of compound (z-1) as compound (Z), and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass, and the solution was filtered through a Millipore filter having a pore size of 5 μm to obtain resin solution (E6-2).

[0252] The following resin composition (2) was applied by spin coating to both sides of a transparent glass support "OA-10G" (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd., cut to a size of 200 mm x 200 mm, so that the film thickness after drying would be approximately 1 μm, and then heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent, thereby forming an adhesive layer that functions as an adhesive layer between the glass support and the coating resin layer (1) and coating resin layer (2) described below.

[0253] Next, a resin solution (E6-1) was applied to one side of the glass support on which the adhesive layer was formed using a spin coater so that the film thickness after drying would be 10 μm, and the solution was heated on a hot plate at 80° C. for 5 minutes to volatilize and remove the solvent, thereby forming a coating resin layer (2). Furthermore, a resin solution (E6-2) was applied to the other surface of the glass support on which the adhesive layer was formed using a spin coater so that the film thickness after drying would be 10 μm, and the solution was heated on a hot plate at 80° C. for 5 minutes to volatilize and remove the solvent, thereby forming a coating resin layer (1). This resulted in a substrate having a thickness of 222 μm, in which a resin layer containing compound (Z) was laminated on one surface of the glass support and a resin layer not containing compound (Z) was laminated on the other surface. The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 9.

[0254] Resin composition (2): 30 parts by mass of isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toa Gosei Co., Ltd.), 20 parts by mass of 1,9-nonanediol diacrylate, 20 parts by mass of methacrylic acid, 30 parts by mass of glycidyl methacrylate, 5 parts by mass of 3-glycidoxypropyltrimethoxysilane, 5 parts by mass of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by BASF Japan Ltd.), and 1 part by mass of San-Aid SI-110 base agent (manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed and dissolved in propylene glycol monomethyl ether acetate to a solid content concentration of 50% by mass, and then filtered through a Millipore filter having a pore size of 0.2 μm.

[0255] Next, with reference to Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers are alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.226 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 9.

[0256] [Example 7] A substrate was obtained in the same manner as in Example 1, except that 0.01 part by mass of the following compound (x-3) (maximum absorption wavelength in dichloromethane: 931 nm) was additionally used. The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0257] ·Compound (x-3) [ka]

[0258] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0259] [Example 8] A substrate was obtained in the same manner as in Example 1, except that 0.03 parts by mass of the following compound (x-5) (maximum absorption wavelength in dichloromethane: 1095 nm) was additionally used. The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0260] ·Compound (x-5) [ka]

[0261] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0262] [Example 9] A substrate was obtained in the same manner as in Example 1, except that 0.16 parts by mass of compound (z-16) (maximum absorption wavelength in dichloromethane: 825 nm) and 0.12 parts by mass of compound (z-59) (maximum absorption wavelength in dichloromethane: 770 nm) were used instead of 0.2 parts by mass of compound (z-1). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0263] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0264] [Example 10] A substrate was obtained in the same manner as in Example 1, except that 0.17 parts by mass of the following compound (y-1) (maximum absorption wavelength in dichloromethane: 394 nm) was additionally used. The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0265] ·Compound (y-1) [ka]

[0266] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0267] [Example 11] In Example 6, a substrate was obtained in the same manner as in Example 6, except that a near-infrared absorbing glass substrate "BS-11" (thickness 0.2 mm) manufactured by Matsunami Glass Industry Co., Ltd. was used instead of a transparent glass support "OA-10G" (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd. The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 9.

[0268] Next, in the same manner as in Example 6, silica (SiO 2 ) layer and titania (TiO 2 ) layers are alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.226 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 9.

[0269] [Example 12] A substrate was obtained in the same manner as in Example 1, except that 0.1 parts by mass of the following compound (z-156) (maximum absorption wavelength in dichloromethane: 785 nm) was used instead of 0.2 parts by mass of compound (z-1). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0270] ·Compound (z-156) [ka]

[0271] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0272] [Example 13] A substrate was obtained in the same manner as in Example 12, except that 0.1 parts by mass of the following compound (z-157) (maximum absorption wavelength in dichloromethane: 788 nm) was used instead of 0.1 parts by mass of the compound (z-156). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0273] ·Compound (z-157) [ka]

[0274] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0275] [Example 14] A substrate was obtained in the same manner as in Example 12, except that 0.1 parts by mass of the following compound (z-158) (maximum absorption wavelength in dichloromethane: 790 nm) was used instead of 0.1 parts by mass of the compound (z-156). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0276] ·Compound (z-158) [ka]

[0277] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0278] [Example 15] A substrate was obtained in the same manner as in Example 12, except that 0.1 parts by mass of the following compound (z-159) (maximum absorption wavelength in dichloromethane: 800 nm) was used instead of 0.1 parts by mass of the compound (z-156). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0279] ·Compound (z-159) [ka]

[0280] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0281] [Example 16] A substrate was obtained in the same manner as in Example 12, except that 0.1 parts by mass of the following compound (z-160) (maximum absorption wavelength in dichloromethane: 791 nm) was used instead of 0.1 parts by mass of the compound (z-156). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0282] ·Compound (z-160) [ka]

[0283] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0284] [Example 17] A substrate was obtained in the same manner as in Example 12, except that 0.1 parts by mass of the following compound (z-161) (maximum absorption wavelength in dichloromethane: 800 nm) was used instead of 0.1 parts by mass of the compound (z-156). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0285] ·Compound (z-161) [ka]

[0286] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0287] [Example 18] A substrate was obtained in the same manner as in Example 12, except that 0.1 parts by mass of the following compound (z-162) (maximum absorption wavelength in dichloromethane: 810 nm) was used instead of 0.1 parts by mass of the compound (z-156). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0288] ·Compound (z-162) [ka]

[0289] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0290] [Example 19] A substrate was obtained in the same manner as in Example 12, except that 0.1 parts by mass of the following compound (z-163) (maximum absorption wavelength in dichloromethane: 760 nm) was used instead of 0.1 parts by mass of the compound (z-156). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0291] ·Compound (z-163) [ka]

[0292] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0293] [Comparative Example 1] A substrate was obtained in the same manner as in Example 1, except that the compound (Z) was not used. The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0294] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0295] [Comparative Example 2] A substrate was obtained in the same manner as in Example 1, except that compound (Z) was not used and 0.038 parts by mass of compound (x-1), 0.075 parts by mass of compound (x-2), and 0.2 parts by mass of compound (x-3) (maximum absorption wavelength in dichloromethane: 931 nm) were used as compound (X). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0296] ·Compound (x-3) [ka]

[0297] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0298] [Comparative Example 3] A substrate was obtained in the same manner as in Example 1, except that no compound (Z) was used, and 0.038 parts by mass of compound (x-1), 0.075 parts by mass of compound (x-2), and 0.08 parts by mass of compound (x-4) (maximum absorption wavelength in dichloromethane: 760 nm) were used as compound (X). The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0299] ·Compound (x-4) [ka]

[0300] Next, in the same manner as in Example 1, silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (I) of 26 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (II) having a total of 22 layers, thereby obtaining an optical filter having a thickness of about 0.110 mm. The dielectric multilayer film was designed using the same design parameters as in Example 1, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 1. For the obtained optical filter, the average values ​​T and R were determined in the same manner as in Example 1. The results are shown in Table 8.

[0301] [Table 8]

[0302] [Table 9]

[0303] The optical filters obtained in Examples 1 to 19 are capable of reducing the reflected light intensity of near-infrared light, particularly in the wavelength region of 700 to 800 nm, while maintaining good visible light transmittance. Therefore, they are useful in imaging devices such as digital still cameras, which have become increasingly high-performance in recent years, because they can minimize the decrease in sensitivity in the visible light region and eliminate image defects caused by the reflected light.

[0304] [Synthesis example of compound (z-164)] Acetyl chloride (2 equivalents) and tert-butyl alcohol (1 equivalent) were charged into a recovery flask and stirred while heating in an oil bath adjusted to 85°C. Trifluoromethanesulfonic acid (1 equivalent) was added dropwise over 5 minutes, and after the dropwise addition was completed, the temperature of the oil bath was set to 100°C and stirred for 30 minutes. After cooling to room temperature, diethyl ether and water were added, and the precipitated solid was filtered to obtain the following compound (m-1).

[0305] ·Compound (m-1) [ka]

[0306] The compound (m-1) (1 equivalent) obtained above and malonaldehyde dianilide hydrochloride (0.5 equivalent) were charged into a recovery flask, and acetonitrile and acetic anhydride were added thereto and stirred. Next, pyridine (1 equivalent) was dropped and stirred at room temperature for 2 hours. Then, acetonitrile, acetic anhydride, and pyridine were removed with an evaporator, and a liquid separation operation was performed with methylene chloride / water. The organic phase was collected, and 1.5 equivalents of LiFABA (lithium tetrakis(pentafluorophenyl)borane) and water were added thereto and vigorously stirred for 3 hours. Then, the organic phase was collected, and methylene chloride was removed with an evaporator to obtain compound (z-164).

[0307] Compound (z-164): Maximum absorption wavelength in dichloromethane: 715 nm [ka]

[0308] [Synthesis example of compound (z-165)] Compound (z-165) was obtained in the same manner as in Synthesis Example of Compound (z-164), except that acetyl chloride was changed to 1-methylcyclopropanecarboxylic acid chloride.

[0309] Compound (z-165): Maximum absorption wavelength in dichloromethane: 727 nm [ka]

[0310] [Synthesis example of compound (z-166)] Compound (z-166) was obtained in the same manner as in Synthesis Example of Compound (z-164), except that acetyl chloride was changed to 1-methylcyclohexanecarboxylic acid chloride.

[0311] Compound (z-166): Maximum absorption wavelength in dichloromethane: 719 nm [ka]

[0312] [Synthesis example of compound (z-167)] Compound (z-167) was obtained in the same manner as in Synthesis Example of Compound (z-164), except that acetyl chloride was changed to 1-adamantanecarboxylic acid chloride.

[0313] Compound (z-167): Maximum absorption wavelength in dichloromethane: 721 nm [ka]

[0314] [Synthesis example of compound (z-168)] Compound (z-168) was obtained in the same manner as in the synthesis example of compound (z-164), except that malonaldehyde dianilide hydrochloride was changed to the following compound (m-2).

[0315] ·Compound (m-2) [ka]

[0316] Compound (z-168): Maximum absorption wavelength in dichloromethane: 720 nm [ka]

[0317] [Synthesis example of compound (z-169)] Compound (z-169) was obtained in the same manner as in the synthesis example of compound (z-167), except that malonaldehyde dianilide hydrochloride was changed to compound (m-2).

[0318] Compound (z-169): Maximum absorption wavelength in dichloromethane: 726 nm [ka]

[0319] [Synthesis example of compound (z-170)] Compound (z-170) was obtained in the same manner as in the synthesis example of compound (z-169), except that compound (m-2) in the synthesis example was changed to the following compound (m-3).

[0320] ·Compound (m-3) [ka]

[0321] Compound (z-170): Maximum absorption wavelength in dichloromethane: 739 nm [ka]

[0322] [Synthesis example of compound (z-171)] Compound (z-171) was obtained in the same manner as in the synthesis example of compound (z-167), except that compound (m-1) was changed to the following compound (m-4).

[0323] ·Compound (m-4) [ka]

[0324] Compound (z-171): Maximum absorption wavelength in dichloromethane: 734 nm [ka]

[0325] [Synthesis example of compound (z-172)] Compound (z-172) was obtained in the same manner as in the synthesis example of compound (z-167), except that compound (m-1) was changed to the following compound (m-5).

[0326] ·Compound (m-5) [ka]

[0327] Compound (z-172): Maximum absorption wavelength in dichloromethane: 738 nm [ka]

[0328] [Synthesis example of compound (z-173)] Compound (z-173) was obtained in the same manner as in the synthesis example of compound (z-169), except that compound (m-2) in the synthesis example was changed to the following compound (m-6).

[0329] ·Compound (m-6) [ka]

[0330] Compound (z-173): Maximum absorption wavelength in dichloromethane: 724 nm [ka]

[0331] [Examples 20 to 32 and Comparative Examples 4 to 7] [Preparation of substrate] A substrate was prepared in the same manner as in Example 1, specifically as follows. A solution with a resin concentration of 20% by mass was prepared by adding resin, compound (Z), compound (X), compound (Y) and dichloromethane in the proportions shown in Table 12. The obtained solution was cast on a smooth glass plate, dried at 20°C for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100°C for 8 hours to obtain a resin layer (1) with a thickness of 0.1 mm, length of 210 mm and width of 210 mm. The numerical values ​​shown in the columns for compound (Z), compound (X), and compound (Y) in Table 12 indicate the content (parts by mass) of each compound relative to 100 parts by mass of the resin.

[0332] In addition, compound (x-6) in Table 12 is a compound represented by the following formula (maximum absorption wavelength in dichloromethane: 717 nm). [ka]

[0333] The following resin composition (1) was applied to one side of the obtained resin layer (1) using a bar coater so that the thickness of the obtained resin layer (2) was 3 μm, and the coating was heated in an oven at 70° C. for 2 minutes to volatilize and remove the solvent. Next, the coating was exposed (exposure dose 500 mJ / cm 2 ) using a UV conveyor-type exposure machine (manufactured by Eye Graphics Co., Ltd., Eye ultraviolet curing device, model US2-X0405, 60 Hz). 2 , Illuminance: 200mW / cm 2 ) was carried out to cure the resin composition (1) and form a resin layer (2) on the resin layer (1). In the same manner, a resin layer (2) made of the resin composition (1) was formed on the other surface of the resin layer (1).

[0334] Resin composition (1): A composition containing 60 parts by mass of tricyclodecane dimethanol acrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, and methyl ethyl ketone (solvent, used so that the solids concentration in the resulting composition is 30% by mass).

[0335] <Spectral transmittance> The transmittance of the obtained substrate in the near infrared region with a wavelength of 650 to 800 nm and the visible light transmittance with a wavelength of 430 to 580 nm were measured using a spectrophotometer (V-7200) manufactured by JASCO Corporation. This transmittance was measured using the spectrophotometer under the condition that light was incident perpendicularly to the surface of the substrate. The parameters measured using this device are as follows. The results are shown in Table 12. The spectral transmittance spectra of the substrates obtained in Example 20 and Example 28 are shown in FIGS. 1 and 2, respectively. In addition, the following Tc and Td were measured by heating the obtained substrate for 7 hours in an oven preheated to 155° C., and measuring the transmittance of the substrate after this heating test (heat resistance evaluation). Te and Tf were also prepared by applying a UV exposure device (Iwasaki Electric Co., Ltd., Eye UV curing device US2-KO4501, illuminance: 180 mW / cm 2 , Irradiation amount: 560mJ / cm 2 ) was used to irradiate the substrate with UV light, and the transmittance of the substrate after this UV irradiation was measured (UV resistance evaluation).

[0336] Xa: The wavelength of light at which the transmittance measured from the perpendicular direction of the substrate is the lowest in the wavelength range of 650 to 800 nm Ta: The minimum transmittance measured perpendicular to the substrate at a wavelength of 650 to 800 nm Tb: Average transmittance of light with wavelengths of 430 to 580 nm measured from the perpendicular direction of the substrate Tc: The minimum transmittance of light with a wavelength of 650 to 800 nm after a heating test, measured from the perpendicular direction of the substrate Td: Average transmittance of light with wavelengths of 430 to 580 nm measured from the vertical direction of the substrate after the heating test Te: The minimum transmittance of light with a wavelength of 650 to 800 nm after UV irradiation, measured from the perpendicular direction of the substrate. Tf: Average transmittance of light with wavelengths of 430 to 580 nm after UV irradiation, measured from the vertical direction of the substrate

[0337] [Preparation of Optical Filter] A dielectric multilayer film (III) was formed on one surface of the substrate obtained by the above-mentioned substrate preparation, and a dielectric multilayer film (IV) was further formed on the other surface of the substrate, to obtain an optical filter having a thickness of about 0.110 mm.

[0338] The dielectric multilayer film (III) was deposited at a deposition temperature of 100°C using silica (SiO 2 ) layer and titania (TiO 2 The dielectric multilayer film (IV) is a laminate of alternating layers of silica (SiO 2 ) layer and titania (TiO 2 ) layers are alternately laminated (total of 24 layers). In both of the dielectric multilayer films (III) and (IV), the silica layer and the titania layer were alternately laminated in the following order from the substrate side: titania layer, silica layer, titania layer, ...silica layer, titania layer, silica layer, and the outermost layer of the optical filter was the silica layer.

[0339] The thickness and number of each layer were optimized using optical thin film design software (Essential Macleod, Thin Film Center) in accordance with the wavelength-dependent characteristics of the refractive index of the substrate and the absorption characteristics of the compounds (Z) and (X) used, so as to achieve good transmittance in the visible range and reflectance performance in the near-infrared range. When performing optimization, the input parameters (target values) to the software in this embodiment were as shown in Table 10 below.

[0340] [Table 10]

[0341] As a result of optimizing the film configuration, the dielectric multilayer film (III) is a multilayer deposition film with 28 layers, in which a silica layer with a physical thickness of about 32 to 159 nm and a titania layer with a physical thickness of about 9 to 94 nm are alternately laminated, and the dielectric multilayer film (IV) is a multilayer deposition film with 24 layers, in which a silica layer with a physical thickness of about 39 to 193 nm and a titania layer with a physical thickness of about 12 to 117 nm are alternately laminated. An example of the optimized film configuration is shown in Table 11 below.

[0342] [Table 11]

[0343] <Spectral transmittance> The transmittance of the obtained optical filter in the near infrared region with a wavelength of 650 to 800 nm and the visible light transmittance with a wavelength of 430 to 580 nm were measured using a spectrophotometer (V-7200) manufactured by JASCO Corporation. This transmittance was measured using the spectrophotometer under the condition that light was incident perpendicularly to the optical filter. The parameters measured using this device are as follows. The results are shown in Table 12. The spectral transmittance spectra of the optical filters obtained in Example 20 and Example 28 are shown in FIGS. 3 and 4, respectively.

[0344] Tg: Average transmittance of light with wavelengths of 650 to 800 nm measured from the vertical direction of the optical filter Th: Average transmittance of light with wavelengths of 430 to 580 nm measured from the vertical direction of the optical filter

[0345] [Examples 33 to 43 and Comparative Example 8] A substrate was prepared in the same manner as in Example 6, specifically as follows. Resin A, compound (X), compound (Y) and dichloromethane were added in the proportions shown in Table 13 to prepare a solution with a resin concentration of 20% by mass, and the solution was filtered through a Millipore filter having a pore size of 5 μm to obtain resin solution (E-1). Resin A, compound (Z), and dichloromethane were added in the proportions shown in Table 13 to prepare a solution with a resin concentration of 20% by mass, and the solution was filtered through a Millipore filter having a pore size of 5 μm to obtain resin solution (E-2).

[0346] The following resin composition (2) was applied by spin coating to both sides of a transparent glass support "OA-10G" (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd., cut to a size of 200 mm x 200 mm, so that the film thickness after drying would be approximately 1 μm, and then heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent, thereby forming an adhesive layer that functions as an adhesive layer between the glass support and the coating resin layer (1) and coating resin layer (2) described below. In Example 39 only, a near-infrared absorbing glass substrate "BS-11" (thickness 200 μm) manufactured by Matsunami Glass Industry Co., Ltd., cut to a size of 200 mm×200 mm, was used instead of "OA-10G".

[0347] Next, using a spin coater, resin solution (E-1) was applied to one side of the glass support on which the adhesive layer was formed so that the film thickness after drying would be 10 μm, and the solution was heated on a hot plate at 80° C. for 5 minutes to volatilize and remove the solvent, thereby forming a coating resin layer (2). Furthermore, the resin solution (E-2) was applied to the other surface of the glass support on which the adhesive layer was formed using a spin coater so that the film thickness after drying would be 10 μm, and the solution was heated on a hot plate at 80° C. for 5 minutes to volatilize and remove the solvent, thereby forming a coating resin layer (1). This resulted in a substrate having a thickness of 222 μm, in which a resin layer containing compound (Z) was laminated on one surface of the glass support and a resin layer not containing compound (Z) was laminated on the other surface. In addition, the numerical values ​​shown for compounds z-164 to z-173 in Table 13 indicate the content (parts by mass) of each compound relative to 100 parts by mass of the resin in the resin layer (1), and the numerical values ​​shown for compounds x-1, x-2 and y-1 in Table 13 indicate the content (parts by mass) of each compound relative to 100 parts by mass of the resin in the resin layer (2). The Xa and Ta to Tf of the substrate were measured in the same manner as in Example 20. The results are shown in Table 13. The spectral transmittance spectrum of the substrate obtained in Example 36 is shown in FIG.

[0348] Resin composition (2): 30 parts by mass of isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toa Gosei Co., Ltd.), 20 parts by mass of 1,9-nonanediol diacrylate, 20 parts by mass of methacrylic acid, 30 parts by mass of glycidyl methacrylate, 5 parts by mass of 3-glycidoxypropyltrimethoxysilane, 5 parts by mass of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by BASF Japan Ltd.), and 1 part by mass of San-Aid SI-110 base agent (manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed and dissolved in propylene glycol monomethyl ether acetate to a solid content concentration of 50% by mass, and then filtered through a Millipore filter having a pore size of 0.2 μm.

[0349] Next, in the same manner as in Example 20, silica (SiO 2 ) layer and titania (TiO 2 ) layers are alternately laminated to form a dielectric multilayer film (III) of 28 layers in total, and a silica (SiO 2 ) layer and titania (TiO 2 ) layers were alternately laminated to form a dielectric multilayer film (IV) having a total of 24 layers, thereby obtaining an optical filter having a thickness of about 0.226 mm. The dielectric multilayer film was designed using the same design parameters as in Example 20, taking into consideration the wavelength dependency of the refractive index of the substrate, as in Example 20. The Tg and Th of the optical filter were measured in the same manner as in Example 20. The results are shown in Table 13. The spectral transmittance spectrum of the optical filter obtained in Example 36 is shown in FIG.

[0350] [Table 12]

[0351] [Table 13]

[0352] The optical filters obtained in Examples 20 to 43 are capable of reducing the reflected light intensity of near-infrared light, particularly in the wavelength region of 700 to 750 nm, while maintaining good visible light transmittance. Therefore, they are useful in imaging devices such as digital still cameras, which have become increasingly high-performance in recent years, because they can minimize the decrease in sensitivity in the visible light region and eliminate image defects caused by the reflected light.< / irpf> < / dbpf>

Claims

1. An optical filter comprising: a substrate (i) containing a compound (Z) formed from a resin composition containing a resin and a compound (Z) represented by the following formula (I); and a dielectric multilayer film. Cn + An - (I) [In formula (I), Cn + is a monovalent cation represented by the following formula (II), An - is a monovalent anion. 【Chemistry 1】 [In formula (II), Unit A is represented by the following formula (A-III): The unit B is represented by the following formula (B-III): Y A ~Y E each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, or -NR g R h group, amide group, imide group, cyano group, silyl group, -Q 1 , -N=N-Q 1 , -S-Q 2 , -SSQ 2 , or -SO 2 Q 3 and Y A and Y C , Y B and Y D , Y C and Y E may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have =O, Y A and R in the following formula (A-III): 1 Or R 5 , Y E and R in the following formula (B-III): 5 Or R 1 may be bonded to each other to form a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, R g and R h each independently represents a hydrogen atom, -C(O)R i Group or the following L a ~L h Q 1 are independently a ~L h Q 2 are independently a hydrogen atom or the following L a ~L h Q 3 is a hydroxyl group or the following L a ~L h R i is the following L a ~L h Either 【Chemistry 2】 [In formula (A-III), -* represents Y in formula (II). A indicates that the carbon atom is bonded to a single bond, In formula (B-III), =** represents Y in formula (II). E indicates that the carbon atom is double bonded to the carbon atom to which it is bonded, In formulas (A-III) and (B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR 8 - and R 1 , R 2 , R 4 and R 5 each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -NR g R h Group, -SR i Group, -SO 2 R i Group, -OSO 2 R i group, -C(O)R i Group or the following L a ~L h Either R 8 are independently a hydrogen atom, a halogen atom, or -C(O)R i Group L below a ~L h Either R g and R h each independently represents a hydrogen atom, -C(O)R i Group or the following L a ~L h Either R i are independently a ~L h Either (L a ): an aliphatic hydrocarbon group having 1 to 15 carbon atoms (L b ): a halogen-substituted alkyl group having 1 to 15 carbon atoms (L c ): an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K (L d ): an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K (L e ) a heterocyclic group having 3 to 14 carbon atoms which may have a substituent K (L f ):-OR (R is a hydrocarbon group having 1 to 12 carbon atoms) (L g ): an acyl group having 1 to 9 carbon atoms which may have a substituent L (L h ): an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L The substituent K is the L a ~L b The substituent L is at least one selected from the group consisting of a ~L f At least one selected from the following.

2. The optical filter according to claim 1 , wherein the compound (Z) satisfies the following requirement (A): Requirement (A): In a transmission spectrum measured using a solution in which the compound (Z) is dissolved in dichloromethane (wherein the transmission spectrum is a spectrum in which the transmittance at the absorption maximum wavelength is 10%), the average transmittance at wavelengths of 430 to 580 nm is 93% or more.

3. The R 1 , R 2 , R 4 and R 5 At least one of the L a , L c Or L d 3. The optical filter according to claim 1, wherein

4. The optical filter according to any one of claims 1 to 3, wherein the compound (Z) satisfies the following requirement (B-1): Requirement (B-1): The compound (Z) has a maximum value in the wavelength range of 720 to 900 nm in an absorption spectrum measured using a solution obtained by dissolving the compound (Z) in dichloromethane.

5. The optical filter according to any one of claims 1 to 3, wherein the compound (Z) satisfies the following requirement (B-2): Requirement (B-2): In the absorption spectrum measured using a solution in which the compound (Z) is dissolved in dichloromethane, the maximum value is in the wavelength range of 700 to 750 nm.

6. The optical filter according to any one of claims 1 to 5, wherein the resin is at least one resin selected from the group consisting of cyclic (poly)olefin-based resins, aromatic polyether-based resins, polyimide-based resins, polyester-based resins, polycarbonate-based resins, polyamide-based resins, polyarylate-based resins, polysulfone-based resins, polyethersulfone-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate-based resins, fluorinated aromatic polymer-based resins, (modified) acrylic-based resins, epoxy-based resins, allyl ester-based curable resins, silsesquioxane-based ultraviolet-curable resins, acrylic-based ultraviolet-curable resins, and vinyl-based ultraviolet-curable resins.

7. The substrate (i) is A substrate comprising a resin layer containing the compound (Z); A substrate comprising two or more resin layers, at least one of which is a resin layer containing the compound (Z), or A substrate comprising a glass support and a resin layer containing the compound (Z), The optical filter according to any one of claims 1 to 6.

8. The optical filter according to any one of claims 1 to 7, which is for use in a solid-state imaging device.

9. The optical filter according to any one of claims 1 to 7, which is for use in an optical sensor device.

10. A solid-state imaging device comprising the optical filter according to any one of claims 1 to 7.

11. An optical sensor device comprising the optical filter according to any one of claims 1 to 7.

Images