Resin composition, compound, substrate, optical filter, solid-state imaging device and optical sensor device

Abstract

This invention provides a resin composition exhibiting extremely high absorption in the vicinity of 700 nm to 750 nm or 720 nm to 900 nm, with a large ratio of absorbance in the infrared region to absorbance in the visible region, and excellent lightfastness (durability). The resin composition comprises: a resin and a compound represented by formula (I). Cn+An- (I) [In formula (I), Cn+ is the monovalent cation represented by formula (II), and An- is the monovalent anion] [A is formula (AI) to (A-III), B is formula (BI) to (B-III), YA to YE are H, halogen atom, -OH, -COOH, -NO2, -NRgRh, amide group, amide group, -CN, silyl group, -Q1, -N=N-Q1, -S-Q2, -SSQ2, -SO2Q3, YA and YC, YB and YD, YC and YE, YA and R1 or R5 of (A-III), YE and R1 or R5 of (B-III) can bond to form a ring] [-* indicates a single bond with the carbon atom bonded to YA in formula (II), =** indicates a double bond with the carbon atom bonded to YE in formula (II), X is O, S, Se, Te or -NR8-, R1 to R6 are H, halogen atom, sulfonyl, -OH, -CN, -NO2, -COOH, phosphate group, -NRgRh group, -SRi group, -SO2Ri group, -OSO2Ri group, -C(O)Ri group or any of La to Lh, and adjacent R1 to R6 can bond to form a ring]

Description

Technical Field

[0001] The present invention relates to a resin composition, compound, substrate, optical filter, and solid-state imaging device and optical sensor device using said optical filter. Prior Technology

[0002] Solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions use charge-coupled devices (CCDs) or complementary metal-oxide-semiconductor (CMOS) image sensors as solid-state imaging elements for color images. These solid-state imaging elements utilize silicon photodiodes (SPADs) or similar devices in their light-receiving sections, which are sensitive to near-infrared light imperceptible to the human eye. Additionally, silicon photodiodes are also used in optical sensor devices. For example, in solid-state imaging elements, visual sensitivity correction is often required to reproduce colors naturally as perceived by the human eye, and optical filters (e.g., near-infrared cutoff filters) are used to selectively transmit or block light in specific wavelength ranges.

[0003] As such near-infrared cutoff filters, filters manufactured using various methods have been used since the past. For example, a near-infrared cutoff filter is known to use resin as a substrate and to contain near-infrared absorbing pigments in the resin (see, for example, Patent Document 1). However, the near-infrared cutoff filter described in Patent Document 1 sometimes does not have sufficient near-infrared absorption characteristics. [Existing technical documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2008-303130 Summary of the Invention

[0005] [The problem the invention aims to solve] Previously used near-infrared absorbing pigments included polymethyl, squaric acid-lactone, porphyrin, dithiol metal complex, phthalocyanine, and diimide pigments. Among these, polymethyl and squaric acid-lactone pigments were often used for their sufficient heat resistance.

[0006] However, these pigments that have been used previously have room for improvement in at least one of the following aspects: Since the absorption maximum wavelength is in the long wavelength region, there is a need for compounds with maximum absorption around 700 nm to 750 nm or around 720 nm to 900 nm. The aspect where the absorbance in the infrared region is smaller compared to the absorbance in the visible light region; The lightfastness (durability) is not adequate.

[0007] In addition, in previous near-infrared cutoff filters, reflected light from the filter sometimes caused adverse effects on images such as camera images as light spots or ghosting. In particular, when the reflection band of the near-infrared cutoff filter overlaps with the wavelength band that the sensor can photoelectrically convert, the adverse effects sometimes become more significant.

[0008] The present invention is made in view of the above circumstances, and aims to provide a resin composition that has extremely high absorption in the vicinity of 700 nm to 750 nm or in the vicinity of 720 nm to 900 nm, and has a large ratio of absorbance in the infrared region to absorbance in the visible light region, and excellent light resistance (durability). [Technical means to solve the problem]

[0009] The inventors conducted diligent research to solve the aforementioned problem, and as a result, discovered that the problem can be solved according to the following structural example, thus completing the present invention. The structural example of the present invention is shown below. Furthermore, in this invention, the designation "A~B" and the like, indicating a numerical range, have the same meaning as "A or more and B or less," and A and B are included within the stated numerical range. Additionally, in this invention, wavelength A nm to B nm refers to the wavelength resolution capability of 1 nm within the wavelength region where wavelength A nm or more and wavelength B nm or less.

[0010] [1] A resin composition comprising: 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 formula (II) below, and An- is a monovalent anion]

[0011] [Chemistry 1] In formula (II), Unit A is any one of the following equations (AI) to (A-III), Unit B is any one of the following formulas (BI) to (B-III), YA~YE are independently represented by hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, -NRgRh groups, amide groups, amide groups, cyano groups, silyl groups, -Q1, -N=N-Q1, -S-Q2, -SSQ2, or -SO2Q3, respectively. YA and YC, YB and YD, YC and YE can bond with each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms, a 4 to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom, or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom, or sulfur atom. These aromatic hydrocarbon groups, alicyclic groups, and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbon atoms, or halogen atoms. In addition, the alicyclic group may have =O. YA can bond with R1 or R5 in formula (A-III) below, and YE can bond with R5 or R1 in formula (B-III) below to form a 4- to 7-membered alicyclic group that may contain at least one nitrogen atom, oxygen atom, or sulfur atom. Rg and Rh are independently hydrogen atoms, -C(O)Ri groups, or any of the following La~Lh groups; Q1 is independently any of the following La~Lh groups; Q2 is independently hydrogen atoms or any of the following La~Lh groups; Q3 is a hydroxyl group or any of the following La~Lh groups; and Ri is any of the following La~Lh groups.

[0012] [Chemistry 2] In formulas (A1) to (A-III), -* indicates that the carbon atom bonded to YA in formula (II) forms a single bond. In equations (BI) to (B-III), the =** indicates a double bond with the carbon atom bonded to YE in equation (II). In equations (AI) to (B-III), X can be an oxygen atom, sulfur atom, selenium atom, tellurium atom, or -NR8-. R1 to R6 are each independently a hydrogen atom, a halogen atom, a sulfonyl group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, a -NRgRh group, a -SRi group, a -SO2Ri group, a -OSO2Ri group, a -C(O)Ri group, or any of the following La to Lh groups. Adjacent R1 to R6 groups can bond to each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms, a 4 to 7-membered alicyclic group containing at least one nitrogen, oxygen, or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen, oxygen, or sulfur atom. These aromatic hydrocarbon groups, alicyclic groups, and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbon atoms, or halogen atoms. In addition, the alicyclic group may have a =O symbol. R8 can be independently a hydrogen atom, a halogen atom, a -C(O)Ri group, or any of the following La~Lh groups. Rg and Rh are each independently a hydrogen atom, a -C(O)Ri group, or any of the following La~Lh groups. Ri is independently any of the following La~Lh, (La): an aliphatic hydrocarbon group with 1 to 15 carbon atoms. (Lb): Halogen-substituted alkyl groups having 1 to 15 carbon atoms. (Lc): an alicyclic hydrocarbon group with 3 to 14 carbon atoms that may have a substituent K. (Ld): An aromatic hydrocarbon group with 6 to 14 carbon atoms that may have a substituent K. (Le): A heterocyclic group with 3 to 14 carbon atoms that may have a substituent K. ‏(Lf):-OR (R is a hydrocarbon group with 1 to 12 carbon atoms that may have a substituent L) (Lg): A amide group with 1 to 9 carbon atoms that may have a substituent L. (Lh): An alkoxy carbonyl group having 1 to 9 carbon atoms and possibly having a substituent L. The substituent K is selected from at least one of La to Lb, and the substituent L is selected from at least one of La to Lf.

[0013] [2] According to the resin composition described in [1], wherein the compound (Z) satisfies the following necessary condition (A). Necessary condition (A): The average transmittance in the wavelength range of 430 nm to 580 nm is greater than 93% in the transmission spectrum (wherein the transmission spectrum is a spectrum with a transmittance of 10% at the wavelength of maximum absorption) measured using a solution of said compound (Z) dissolved in dichloromethane.

[0014] [3] According to the resin composition described in [1] or [2], wherein at least one of R1 to R6 is La, Lc or Ld.

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

[0016] [5] The resin composition according to any one of [1] to [3], wherein the compound (Z) satisfies the following necessary condition (B-2). Necessary condition (B-2): The absorption spectrum measured using a solution of the compound (Z) dissolved in dichloromethane has a maximum value in the wavelength range of 700 nm 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 resins, aromatic polyether resins, polyimide resins, polyester resins, polycarbonate resins, polyamide resins, polyaryl ester resins, polyurethane resins, polyether ether resins, poly(terephthalamide) resins, polyamide-imide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curing resins, silsesquioxane UV curing resins, acrylic UV curing resins, and vinyl UV curing resins.

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

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

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

[10] The optical filter according to [9] is used in a solid-state photography device.

[11] The optical filter according to [9] is used in an optical sensor device.

[0021]

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

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

[0022]

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

[0023] [Chemistry 3] In formula (IV), Unit A is any one of the following equations (AI) to (A-III), Unit B is any one of the following formulas (BI) to (B-III), YA~YE are independently represented by hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, -NRgRh groups, amide groups, amide groups, cyano groups, silyl groups, -Q1, -N=N-Q1, -S-Q2, -SSQ2, or -SO2Q3, respectively. YA and YC, YB and YD, YC and YE can bond with each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms, a 4 to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom, or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom, or sulfur atom. These aromatic hydrocarbon groups, alicyclic groups, and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbon atoms, or halogen atoms. In addition, the alicyclic group may have =O. YA can bond with R1 or R5 in formula (A-III) below, and YE can bond with R5 or R1 in formula (B-III) below to form a 4- to 7-membered alicyclic group that may contain at least one nitrogen atom, oxygen atom, or sulfur atom. Rg and Rh are independently hydrogen atoms, -C(O)Ri groups, or any of the following La~Lh groups; Q1 is independently any of the following La~Lh groups; Q2 is independently hydrogen atoms or any of the following La~Lh groups; Q3 is a hydroxyl group or any of the following La~Lh groups; and Ri is any of the following La~Lh groups.

[0024] [Chemistry 4] In formulas (A1) to (A-III), -* indicates that the carbon atom bonded to YA in formula (II) forms a single bond. In equations (BI) to (B-III), the =** indicates a double bond with the carbon atom bonded to YE in equation (II). In equations (AI) to (B-III), X can be an oxygen atom, sulfur atom, selenium atom, tellurium atom, or -NR8-. R1 to R6 are each independently a hydrogen atom, a halogen atom, a sulfonyl group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, a -NRgRh group, a -SRi group, a -SO2Ri group, a -OSO2Ri group, a -C(O)Ri group, or any of the following La to Lh groups. Adjacent R1 to R6 groups can bond to each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms, a 4 to 7-membered alicyclic group containing at least one nitrogen, oxygen, or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen, oxygen, or sulfur atom. These aromatic hydrocarbon groups, alicyclic groups, and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbon atoms, or halogen atoms. In addition, the alicyclic group may have a =O symbol. R8 can be independently a hydrogen atom, a halogen atom, a -C(O)Ri group, or any of the following La~Lh groups. Rg and Rh are each independently a hydrogen atom, a -C(O)Ri group, or any of the following La~Lh groups. Ri is independently any of the following La~Lh, (La): an aliphatic hydrocarbon group with 1 to 15 carbon atoms. (Lb): Halogen-substituted alkyl groups having 1 to 15 carbon atoms. (Lc): an alicyclic hydrocarbon group with 3 to 14 carbon atoms that may have a substituent K. (Ld): An aromatic hydrocarbon group with 6 to 14 carbon atoms that may have a substituent K. (Le): A heterocyclic group with 3 to 14 carbon atoms that may have a substituent K. ‏(Lf):-OR (R is a hydrocarbon group with 1 to 12 carbon atoms that may have a substituent L) (Lg): A amide group with 1 to 9 carbon atoms that may have a substituent L. (Lh): An alkoxy carbonyl group having 1 to 9 carbon atoms and possibly having a substituent L. The substituent K is selected from at least one of La to Lb, and the substituent L is selected from at least one of La to Lf. [The effects of the invention]

[0025] According to the present invention, a resin composition exhibiting maximum absorption in the vicinity of 700 nm to 750 nm or 720 nm to 900 nm, a high ratio of absorbance in the infrared region to absorbance in the visible region, and sufficient resistance to heat or light can be provided. Furthermore, according to the present invention, an optical filter possessing these characteristics, particularly sufficient shielding of infrared light and the ability to transmit a high proportion of visible light, can be provided. Therefore, according to the present invention, not only can near-infrared ray cut-off filters (NIR-CF) be easily manufactured, but also visible-near-infrared selective transmission filters (dual bandpass filters (DBPF)) or near-infrared pass filters (IRPF) can be easily manufactured. Furthermore, in this invention, sufficient resistance to heat or light means that the optical properties do not change significantly before or after the application of heat or irradiation.

[0026] As described above, according to the present invention, an optical filter having the aforementioned characteristics can be provided, thus easily obtaining an optical filter that can suppress reflected light in the vicinity of wavelengths around 700 nm to 750 nm or wavelengths around 720 nm to 900 nm, and provide a good image with few light spots or ghosting. Furthermore, when the optical filter is a filter with a dielectric multilayer film, the incident angle dependence caused by the dielectric multilayer film can be suppressed. Simple Explanation of the Diagram

[0027] Figure 1 shows the spectral transmittance spectrum of the substrate obtained in Example 20. Figure 2 shows the spectral transmittance spectrum of the substrate obtained in Example 28. Figure 3 shows the spectral transmittance spectrum of the optical filter obtained in Example 20. Figure 4 shows the spectral transmittance spectrum of the optical filter obtained in Example 28. Figure 5 shows the spectral transmittance spectrum of the substrate obtained in Example 36. Figure 6 shows the spectral transmittance spectrum of the optical filter obtained in Example 36. Implementation

[0028] Resin Composition There are no particular limitations on the resin composition of the present invention (hereinafter also referred to as "this composition") if it contains a resin and the compound (Z). Examples of such resin compositions include: resin films (resin layers, resin substrates) containing compound (Z); resin films (resin layers) containing compound (Z) formed on a support (e.g., resin support, glass support); and liquid compositions containing resin, compound (Z) and solvent. This composition may contain two or more resins, or two or more compounds (Z).

[0029] <Compound(Z)> Compound (Z) is the compound represented by the following formula (I). The compound (Z) exhibits high near-infrared cutoff performance and high visible light transmittance at wavelengths of 700 nm to 750 nm or 720 nm to 900 nm, and also possesses excellent optical properties and sufficient resistance to heat or light. Cn+An- (I) [In formula (I), Cn+ is a monovalent cation represented by formula (II) below, and An- is a monovalent anion]

[0030] [Chemistry 5] In formula (II), Unit A is any one of the following equations (AI) to (A-III), Unit B is any one of the following formulas (BI) to (B-III), YA~YE are independently represented by hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, -NRgRh groups, amide groups, amide groups, cyano groups, silyl groups, -Q1, -N=N-Q1, -S-Q2, -SSQ2, or -SO2Q3, respectively. YA and YC, YB and YD, YC and YE can bond with each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms, a 4 to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom, or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom, or sulfur atom. These aromatic hydrocarbon groups, alicyclic groups, and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbon atoms, or halogen atoms. In addition, the alicyclic group may have =O. YA can bond with R1 or R5 in formula (A-III) below, and YE can bond with R5 or R1 in formula (B-III) below to form a 4- to 7-membered alicyclic group that may contain at least one nitrogen atom, oxygen atom, or sulfur atom. Rg and Rh are independently hydrogen atoms, -C(O)Ri groups, or any of the following La~Lh groups; Q1 is independently any of the following La~Lh groups; Q2 is independently hydrogen atoms or any of the following La~Lh groups; Q3 is a hydroxyl group or any of the following La~Lh groups; and Ri is any of the following La~Lh groups.

[0031] [Chemistry 6] In formulas (A1) to (A-III), -* indicates that the carbon atom bonded to YA in formula (II) forms a single bond. In equations (BI) to (B-III), the =** indicates a double bond with the carbon atom bonded to YE in equation (II). In equations (AI) to (B-III), X can be an oxygen atom, sulfur atom, selenium atom, tellurium atom, or -NR8-. R1 to R6 are each independently a hydrogen atom, a halogen atom, a sulfonyl group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, a -NRgRh group, a -SRi group, a -SO2Ri group, a -OSO2Ri group, a -C(O)Ri group, or any of the following La to Lh groups. Adjacent R1 to R6 groups can bond to each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms, a 4 to 7-membered alicyclic group containing at least one nitrogen, oxygen, or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen, oxygen, or sulfur atom. These aromatic hydrocarbon groups, alicyclic groups, and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbon atoms, or halogen atoms. In addition, the alicyclic group may have a =O symbol. R8 can be independently a hydrogen atom, a halogen atom, a -C(O)Ri group, or any of the following La~Lh groups. Rg and Rh are each independently a hydrogen atom, a -C(O)Ri group, or any of the following La~Lh groups. Ri is independently any of the following La~Lh, (La): an aliphatic hydrocarbon group with 1 to 15 carbon atoms. (Lb): Halogen-substituted alkyl groups having 1 to 15 carbon atoms. (Lc): an alicyclic hydrocarbon group with 3 to 14 carbon atoms that may have a substituent K. (Ld): An aromatic hydrocarbon group with 6 to 14 carbon atoms that may have a substituent K. (Le): A heterocyclic group with 3 to 14 carbon atoms that may have a substituent K. ‏(Lf):-OR (R is a hydrocarbon group with 1 to 12 carbon atoms that may have a substituent L) (Lg): A amide group with 1 to 9 carbon atoms that may have a substituent L. (Lh): An alkoxy carbonyl group having 1 to 9 carbon atoms and possibly having a substituent L. The substituent K is at least one selected from La to Lb, and the substituent L is at least one selected from La to Lf.

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

[0033] [Chemistry 7] In formula (IV), Unit A is any one of the following equations (AI) to (A-III), Unit B is any one of the following formulas (BI) to (B-III), YA~YE are independently represented by hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, -NRgRh groups, amide groups, amide groups, cyano groups, silyl groups, -Q1, -N=N-Q1, -S-Q2, -SSQ2, or -SO2Q3, respectively. YA and YC, YB and YD, YC and YE can bond with each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms, a 4 to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom, or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom, or sulfur atom. These aromatic hydrocarbon groups, alicyclic groups, and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbon atoms, or halogen atoms. In addition, the alicyclic group may have =O. YA can bond with R1 or R5 in formula (A-III) below, and YE can bond with R5 or R1 in formula (B-III) below to form a 4- to 7-membered alicyclic group that may contain at least one nitrogen atom, oxygen atom, or sulfur atom. Rg and Rh are independently hydrogen atoms, -C(O)Ri groups, or any of the following La~Lh groups; Q1 is independently any of the following La~Lh groups; Q2 is independently hydrogen atoms or any of the following La~Lh groups; Q3 is a hydroxyl group or any of the following La~Lh groups; and Ri is any of the following La~Lh groups.

[0034] [Chemistry 8] In formulas (A1) to (A-III), -* indicates that the carbon atom bonded to YA in formula (II) forms a single bond. In equations (BI) to (B-III), the =** indicates a double bond with the carbon atom bonded to YE in equation (II). In equations (AI) to (B-III), X can be an oxygen atom, sulfur atom, selenium atom, tellurium atom, or -NR8-. R1 to R6 are each independently a hydrogen atom, a halogen atom, a sulfonyl group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, a -NRgRh group, a -SRi group, a -SO2Ri group, a -OSO2Ri group, a -C(O)Ri group, or any of the following La to Lh groups. Adjacent R1 to R6 groups can bond to each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms, a 4 to 7-membered alicyclic group containing at least one nitrogen, oxygen, or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen, oxygen, or sulfur atom. These aromatic hydrocarbon groups, alicyclic groups, and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbon atoms, or halogen atoms. In addition, the alicyclic group may have a =O symbol. R8 can be independently a hydrogen atom, a halogen atom, a -C(O)Ri group, or any of the following La~Lh groups. Rg and Rh are each independently a hydrogen atom, a -C(O)Ri group, or any of the following La~Lh groups. Ri is independently any of the following La~Lh, (La): an aliphatic hydrocarbon group with 1 to 15 carbon atoms. (Lb): Halogen-substituted alkyl groups having 1 to 15 carbon atoms. (Lc): an alicyclic hydrocarbon group with 3 to 14 carbon atoms that may have a substituent K. (Ld): An aromatic hydrocarbon group with 6 to 14 carbon atoms that may have a substituent K. (Le): A heterocyclic group with 3 to 14 carbon atoms that may have a substituent K. ‏(Lf):-OR (R is a hydrocarbon group with 1 to 12 carbon atoms that may have a substituent L) (Lg): A amide group with 1 to 9 carbon atoms that may have a substituent L. (Lh): An alkoxy carbonyl group having 1 to 9 carbon atoms and possibly having a substituent L. The substituent K is at least one selected from La to Lb, and the substituent L is at least one selected from La to Lf.

[0035] Furthermore, -NR8- is the basis represented by equation (a) below, -NRgRh is the basis represented by equation (b) below, -SRi is the basis represented by equation (c) below, -SO2Ri is the basis represented by equation (d) below, -OSO2Ri is the basis represented by equation (e) below, and -C(O)Ri is the basis represented by equation (f) below. In addition, -SSQ2 is a basis represented by -SS-Q2, and -SO2Q3 is a basis formed by replacing Ri with Q3 in the basis represented by the following formula (d).

[0036] [Chemistry 9]

[0037] Furthermore, when unit A is the formula (AI) and unit B is the formula (BI), Cn+ is represented by the following formula (II-1). That is, the single bond (-) of “*-” in formulas (AI) to (A-III) is equivalent to the single bond between the carbon atom bonded by YA in formula (II) or (IV) and unit A, and the double bond (=) of “**=" in formulas (BI) to (B-III) is equivalent to the double bond between the carbon atom bonded by YE in formula (II) or (IV) and unit B.

[0038] [Chemistry 10]

[0039] The YB and YD are more preferably, independently, a 4-6 member alicyclic hydrocarbon group formed by the bonding of hydrogen atoms, chlorine atoms, fluorine atoms, methyl, ethyl, YB and YD with each other (the alicyclic hydrocarbon group may have a substituent R9 selected from hydrogen atoms, aliphatic hydrocarbon groups with 1 to 9 carbon atoms, hydroxyl groups, halogen atoms, and =O).

[0040] Furthermore, in the case of a 4-6 member alicyclic hydrocarbon group formed by the mutual bonding of YB and YD, formula (II) or formula (IV) can preferably be represented by the following formulas (CI) to (C-III).

[0041] [Chemistry 11]

[0042] [Chemistry 12]

[0043] [Chemistry 13]

[0044] As a substituent R9, it is preferably a hydrogen atom, hydroxyl group, =O, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, or cyclohexyl, and more preferably a hydrogen atom, hydroxyl group, =O, methyl, ethyl, or tert-butyl.

[0045] The YA, YC, and YE are more preferably hydrogen atoms, chlorine atoms, bromine atoms, fluorine atoms, hydroxyl groups, phenylamino groups (NHPh), diphenylamino groups, methylphenylamino groups, dimethylamino groups, methyl groups, methoxy groups, phenyl groups, phenoxy groups, 4-methylphenoxy groups, methylthio groups, phenylthio groups, and -S-(4-tolyl) groups (-S-(4-tolyl) groups).

[0046] The La is preferably methyl (Me), ethyl (Et), n-propyl, isopropyl (i-Pr), n-butyl, sec-butyl, tert-butyl (tert-Bu), pentyl, hexyl, octyl, nonyl, decyl, or dodecyl, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl.

[0047] The La may also be: vinyl, 1-propenyl, 2-propenyl, butenyl, 1,3-butadienyl, 2-methyl-1-propenyl, 2-pentenyl, hexenyl and other alkenyl groups; ethynyl, propynyl, butynyl, 2-methyl-1-propynyl, hexynyl and other alkynyl groups.

[0048] As the halogen-substituted alkyl group having 1 to 15 carbon atoms in the Lb, for example, a group formed by substituting at least one hydrogen atom of an alkyl group having 1 to 15 carbon atoms with a halogen atom can be listed, preferably trichloromethyl, trifluoromethyl, 1,1-dichloroethyl, pentachloroethyl, pentafluoroethyl, heptachloropropyl, heptafluoropropyl.

[0049] The alicyclic hydrocarbon group with 3 to 14 carbon atoms that may have a substituent K in the Lc is preferably cyclopropyl, cyclopropylmethyl, methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl and cyclooctyl, etc.; and polycyclic alicyclic groups such as norbornel and adamantyl.

[0050] The aromatic hydrocarbon group with 6 to 14 carbon atoms that may have a substituent K in the Ld is preferably phenyl, tolyl, xylyl, mesitylelel (trimethylphenyl), cumenel, bis(trifluoromethyl)phenyl, 1-naphthyl, 2-naphthyl, anthracenel, phenanthrene, or benzyl (CH2Ph).

[0051] The heterocyclic group having a substituent K and having 3 to 14 carbon atoms in the Le is preferably furan, thiophene, pyrrole, indole, dihydroindole, pseudoindole, benzofuran, benzothiophene, morpholine, or pyridine.

[0052] The -OR in the Lf is preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, methoxymethyl, methoxyethyl, pentoxy, hexoxy, octoxy, phenoxy (OPh), 4-methylphenoxy, or cyclohexoxy.

[0053] The acetylated group in the Lg that may have a substituent L and has 1 to 9 carbon atoms is preferably acetylated, propionic, butyl, isobutyl, benzoyl, 4-propylbenzoyl, or trifluoromethylcarbonyl.

[0054] The alkoxycarbonyl group having 1 to 9 carbon atoms and substituent L in the Lh is preferably methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, 2-trifluoromethylethoxycarbonyl, or 2-phenylethoxycarbonyl.

[0055] X is preferably an oxygen atom, a sulfur atom, or -NR8-, and is particularly preferably an oxygen atom.

[0056] In formula (II) or formula (IV), the left and right units A and B can be the same or different. If they are the same, it is easier to synthesize them, so it is preferred. Furthermore, here, the same combinations of units A and B are equation (AI) and equation (BI), equation (A-II) and equation (B-II), and equation (A-III) and equation (B-III).

[0057] R1 to R6 are each independently preferably composed of hydrogen atom, chlorine atom, fluorine atom, bromine atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, cyclopropyl, cyclopropylmethyl, cyclohexyl, adamantyl, phenyl, 2,4,6-trimethylphenyl, 3,5-bis(trifluoromethyl)phenyl, hydroxyl, amino, dimethylamino (NMe2), diethylamino (NEt2), dibutylamino (N(n-Bu)2), cyano, Nitro, acetylamino, propioniclamino, N-methylacetylamino, trifluoromethoxylamino, pentafluoroacetylamino, tert-butyllamino, cyclohexyllamino, n-butylsulfonyl, benzyl, diphenylmethyl, trifluoromethyl, difluoromethyl, methoxy, more preferably hydrogen atom, chlorine atom, fluorine atom, bromine atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclohexyl, phenyl, amino, benzyl, diphenylmethyl, trifluoromethyl, difluoromethyl, methoxy.

[0058] In terms of readily obtainable compounds exhibiting high near-infrared cutoff performance and high visible light transmittance at absorption maxima near wavelengths of 700 nm to 750 nm or 720 nm to 900 nm, as well as excellent optical properties and sufficient resistance to heat or light, it is preferable that at least one of R1 to R6 is La, Lc, or Ld. Furthermore, when unit A is of formula (A-III) and unit B is of formula (B-III), "at least one of R1 to R6 is La, Lc, or Ld" means "at least one of R1, R2, R4, and R5 is La, Lc, or Ld."

[0059] The preferred form of R8 is hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, benzyl, n-pentyl, n-hexyl, or tert-butyl, and more preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, or benzyl.

[0060] As for the An-, if it is a monovalent anion, there are no particular limitations, and preferably include: chloride ion, bromide ion, iodide ion, PF4-, perchlorate anion, tri-trifluoromethanesulfonylmethyl compound anion, tetrafluoroborate anion, hexafluorophosphate anion, bis(trifluoromethanesulfonyl)imidion, trifluoromethanesulfonate anion, tetra(pentafluorophenyl)borate anion, tetra(3,5-bis(trifluoromethyl)phenyl)borate anion, etc., more preferably bis(trifluoromethanesulfonyl)imidion, trifluoromethanesulfonate anion, tri-trifluoromethanesulfonylmethyl compound anion, tetra(pentafluorophenyl)borate anion, tetra(3,5-bis(trifluoromethyl)phenyl)borate anion, etc. In terms of the readily available superior heat resistance of compounds (Z), bis(trifluorophenyl)borate anion, tri-trifluoromethyl methylate anion, tetra(pentafluorophenyl)borate anion, and tetra(3,5-bis(trifluoromethyl)phenyl)borate anion are preferred, especially tetra(pentafluorophenyl)borate anion.

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

[0062] [Table 1] compound A,B X YA, YE YB,YD YC R1 R2 R3 R4 R5 R6 An (z-1) (AI), (BI) O H H Cl H tert-Bu H H i-Pr H B(C6F5)4 (z-2) (A-I),(B-I) N H H H H tert-Bu H H H H B(C6F5)4 (z-3) (A-I),(B-I) S H H H H tert-Bu H H H H B(C6F5)4 (z-4) (A-I),(B-I) O CH3 H H H tert-Bu H H H H B(C6F5)4 (z-5) (A-I),(B-I) O H H F H tert-Bu H H H H B(C6F5)4 (z-6) (A-I),(B-I) O H H Cl H tert-Bu H H H H B(C6F5)4 (z-7) (A-I),(B-I) O H H Br H tert-Bu H H H H B(C6F5)4 (z-8) (A-I),(B-I) O H H CH3 H tert-Bu H H H H B(C6F5)4 (z-9) (A-I),(B-I) O H H OCH3 H tert-Bu H H H H B(C6F5)4 (z-10) (A-I),(B-I) O H H OPh H tert-Bu H H H H B(C6F5)4 (z-11) (AI), (BI) O H H N(CH3)2 H tert-Bu H H H H B(C6F5)4 (z-12) (AI), (BI) O H H NHPh H tert-Bu H H H H B(C6F5)4 (z-13) (AI), (BI) O H H NPh2 H tert-Bu H H H H B(C6F5)4 (z-14) (AI), (BI) O H H SCH3 H tert-Bu H H H H 0 B(C6F5)4 1 2 (z-15)3 4 (A-I),(B-I)5 6 O7 8 H9 0 H1 2 SPh3 4 H5 6 tert-Bu7<00,00590>8 H9 0 H1 2 H3 4 H5 6 B(C6F5)4 7 8 (z-16)9 0 (A-I),(B-I)1 2 O3 4 H5 6 H7 8 H9 0 HI 2 Ph3 4 H5 6 H7 8 H9 0 H1 2 B(C6F5)4 3 4 (z-17)5 6 (A-I),(B-I)7 8 O9 0 H1 F H3 [[ID=V]]4 H5 6 H7 8 i-Pr9 0 H1 2 H3 4 H5 6 H7 8 B(C6F5)4 9 0 (z-18)1 2 (A-I),(B-I)3 4 O5 6 H​​​​​​​​​​​​​​​​​​​​ (AI), (BI) O H H H H Cyclopropylmethyl H H H H B(C6F5)4 (z-20) (AI), (BI) O H H H H Cyclohexyl H H H H B(C6F5)4 (z-21) (AI), (BI) O H H H H adamantyl H H H H B(C6F5)4 (z-22) (AI), (BI) O H H H H 2,4,6-Trimethylphenyl H H H H B(C6F5)4 (z-23) (AI), (BI) O H H H H 3,5-Bis(trifluoromethyl)phenyl H H H H B(C6F5)4 (z-24) (A-I),(B-I) O H H H H tert-Bu Cl H H H B(C6F5)4 (z-25) (A-I),(B-I) O H H H H tert-Bu Br H H H B(C6F5)4 (z-26) (A-I),(B-I) O H H H H tert-Bu Ph H H<(END) H B(C6F5)4 (z-27) (A-I),(B-I) O H H H H tert-Bu Me H H H B(C6F5)4 (z-28) (A-I),(B-I) O H H H H tert-Bu i-Pr H H H B(C6F5)4 (z-29) (A-I),(B-I) O H H H H tert-Bu NHCOCF3 H H H B(C6F5)4 (z-30) (A-I),(B-I) O H H H H tert-Bu H F H H B(C6F5)4 (z-31) (A-I),(B-I) O H H H H tert-Bu H Cl H H B(C6F5)4 (z-32) (A-I),(B-I) O H H H H tert-Bu H Br H H B(C6F5)4 (z-33) (A-I),(B-I) O H H H H tert-Bu H Me H H B(C6F5)4 (z-34) (A-I),(B-I) O H H H H tert-Bu H i-Pr H H B(C6F5)4 (z-35) (A-I),(B-I) O H H H H tert-Bu H OCH3 H H B(C6F5)4 (z-36) (A-I),(B-I) O H H H H tert-Bu H CF3 H H B(C6F5)4 (z-37) (A-I),(B-I) O H H H H tert-Bu H H F H B(C6F5)4 (z-38) (A-I),(B-I) O H H H H tert-Bu H H Cl H B(C6F5)4 (z-39) (A-I),(B-I) O H H H H tert-Bu H H Br H B(C6F5)4 (z-40) (A-I),(B-I) O H H H H tert-Bu H H Me H B(C6F5)4 (z-41) (A-I),(B-I) O H H H H tert-Bu H H i-Pr H B(C6F5)4 (z-42) (A-I),(B-I) O H H H H tert-Bu H H OCH3 H B(C6F5)4 (z-43) (A-I),(B-I) O H H H H tert-Bu H H NHCOCF3 H B(C6F5)4 (z-44) (A-I),(B-I) O H H H H tert-Bu H H H F B(C6F5)4 (z-45) (A-I),(B-I) O H H H H tert-Bu H H H Cl B(C6F5)4 (z-46) (A-I),(B-I) O H H H H tert-Bu H H H Br B(C6F5)4 (z-47) (A-I),(B-I) O H H H H tert-Bu H H H H N(SO2CF3)2 (z-48) (A-I),(B-I) O H H H H tert-Bu H H H H C(SO2CF3)3 (z-49) (A-I),(B-I) O H H H H tert-Bu H H H H BF4 (z-50) (A-I),(B-I) O H H H H tert-Bu H H H H ClO4

[0063] [Table 2] Compound A,B X YA,YE YB,YD YC R1 R2 R3 R4 R5 [[ID=5​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ H H H tert-Bu H H H H Br (z-54) (A-I),(B-I) O H H H H tert-Bu H H H H I (z-55) (A-I),(B-I) O H H Cl H tert-Bu H H F H B(C6F5)4 (z-56) (A-I),(B-I) O H H Cl H tert-Bu H H Cl H B(C6F5)4 (z-57) (A-I),(B-I) O H H Cl H tert-Bu H H Br H B(C6F5)4 (z-58) (A-I),(B-I) O H H Cl H tert-Bu H H Me H B(C6F5)4 (z-59) (A-I),(B-I) O H H H H tert-Bu H H H H B(C6F5)4 (z-60) (A-I),(B-I) O H H Cl H tert-Bu H H OCH3 H B(C6F5)4 (z-61) (A-I),(B-I) O H H Cl H tert-Bu H H NHCOCF3 H B(C6F5)4 (z-62) (A-I),(B-I) O H H H H i-Pr H F H H B(C6F5)4 (z-63) (A-I),(B-I) O H H H H i-Pr H Cl H H B(C6F5)4 (z-64) (A-I),(B-I) O H H H H i-Pr H Br H H B(C6F5)4 (z-65) (A-I),(B-I) O H H H H i-Pr H Me H H B(C6F5)4 (z-66) (A-I),(B-I) O H H H H i-Pr H i-Pr H H B(C6F5)4 (z-67) (A-I),(B-I) O H H H H i-Pr H OCH3 H H B(C6F5)4 (z-68) (A-I),(B-I) O H H H H i-Pr H CF3 H H B(C6F5)4 (z-69) (A-I),(B-I) O H H H H Ph H H F H B(C6F5)4 (z-70) (A-I),(B-I) O H H H H Ph H H Cl H B(C6F5)4 (z-71) (A-I),(B-I) O H H H H Ph H H Br H B(C6F5)4 (z-72) (A-I),(B-I) O H H H H Ph H H Me H B(C6F5)4 (z-73) (A-I),(B-I) O H H H H Ph H H i-Pr H B(C6F5)4 (z-74) (A-I),(B-I) O H H H H Ph H H OCH3 H B(C6F5)4 (z-75) (A-I),(B-I) O H H H H Ph H H NHCOCF3 H B(C6F5)4 (z-76) (A-II),(B-II) N H H H H tert-Bu H H H H B(C6F5)4 (z-77) (A-II),(B-II) S H H H H tert-Bu H H H H B(C6F5)4 (z-78) (A-II),(B-II) Oh CH3 H H H tert-Bu H H H H B(C6F5)4 (z-79) (A-II),(B-II) Oh H H F H tert-Bu H H H H B(C6F5)4 (z-80) (A-II),(B-II) Oh H H Cl H tert-Bu H H H H B(C6F5)4 (z-81) (A-II),(B-II) Oh H H Br H tert-Bu H H H H B(C6F5)4 (z-82) (A-II),(B-II) Oh H H CH3 H tert-Bu H H H H B(C6F5)4 (z-83) (A-II),(B-II) Oh H H OCH3 H tert-Bu H H H H B(C6F5)4 (z-84) (A-II),(B-II) Oh H H OPh H tert-Bu H H H H B(C6F5)4 (z-85) (A-II),(B-II) O H H N(CH3)2 H tert-Bu H H H H B(C6F5)4 (z-86) (A-II),(B-II) O H H NHPh H tert-Bu H H H H B(C6F5)4 (z-87) (A-II),(B-II) O H H NPh2 H tert-Bu H H H H B(C6F5)4 (z-88) (A-II),(B-II) O H H SCH3 H tert-Bu H H H H B(C6F5)4 (z-89) (A-II),(B-II) O H H SPh H tert-Bu H H H H B(C6F5)4 (z-90) (A-II),(B-II) O H H H H Ph H H H H B(C6F5)4 (z-91) (A-II),(B-II) O H H H H i-Pr H H H H B(C6F5)4 (z-92) (A-II),(B-II) O H H H H Cyclopropyl H H H H B(C6F5)4 (z-93) (A-II),(B-II) O H H H H Cyclopropylmethyl H H H H B(C6F5)4 (z-94) (A-II), (B-II) O H H H H Cyclohexyl H H H H B(C6F5)4 (z-95) (A-II), (B-II) O H H H H adamantyl H H H H B(C6F5)4 (z-96) (A-II), (B-II) O H H H H 2,4,6-Trimethylphenyl H H H H B(C6F5)4 (z-97) (A-II), (B-II) O H H H H 3,5-Bis(trifluoromethyl)phenyl H H H H B(C6F5)4 (z-98) (A-II),(B-II) O H H H H tert-Bu Cl H H H B(C6F5)4 (z-99) (A-II),(B-II) O H H H H tert-Bu Br H H H B(C6F5)4 (z-100) (A-II),(B-II) O H H H H tert-Bu Ph H H H B(C6F5)4

[0064] [Table 3] Compound A,B X YA,YE YB,YD YC R1 R2 R3 R4 R5 R6 I (z-101) (A-II),(B-II) O H H H H third-Bu Me H H H B(C6F5)4 (z-102) (A-II),(B-II) O H H H H third-Bu i-Pr H H H B(C6F5)4 (z-103) (A-II),(B-II) O H H H H third-Bu NHCOCF3 H H H B(C6F5)4 (z-104) (A-II),(B-II) O H H H H third-Bu H F H H B(C6F5)4 (z-105) (A-II),(B-II) Oh H H H H tert-Bu H Cl H H B(C6F5)4 (z-106) (A-II),(B-II) Oh H H H H tert-Bu H Br H H B(C6F5)4 (z-107) (A-II),(B-II) Oh H H H H tert-Bu H Me H H B(C6F5)4 (z-108) (A-II),(B-II) Oh H H H H tert-Bu H i-Pr H H B(C6F5)4 (z-109) (A-II),(B-II) Oh H H H H tert-Bu H OCH3 H H B(C6F5)4 (z-110) (A-II),(B-II) Oh H H H H tert-Bu H CF3 H H B(C6F5)4 (z-111) (A-II),(B-II) Oh H H H H tert-Bu H H F H B(C6F5)4 (z-112) (A-II),(B-II) Oh H H H H tert-Bu H H Cl H B(C6F5)4 (z-113) (A-II),(B-II) Oh H H H H tert-Bu H H Br H B(C6F5)4 (z-114) (A-II),(B-II) Oh H H H H tert-Bu H H Me H B(C6F5)4 (z-115) (A-II),(B-II) Oh H H H H tert-Bu H H i-Pr H B(C6F5)4 (z-116) (A-II),(B-II) Oh H H H H tert-Bu H H OCH3 H B(C6F5)4 (z-117) (A-II),(B-II) Oh H H H H tert-Bu H H NHCOCF3 H B(C6F5)4 (z-118) (A-II),(B-II) Oh H H H H tert-Bu H H H F B(C6F5)4 (z-119) (A-II),(B-II) Oh H H H H tert-Bu H H H Cl B(C6F5)4 (z-120) (A-II),(B-II) Oh H H H H tert-Bu H H H Br B(C6F5)4 (z-121) (A-II),(B-II) Oh H H H H tert-Bu H H H H N(SO2CF3)2 (z-122) (A-II),(B-II) Oh H H H H tert-Bu H H H H C(SO2CF3)3 (z-123) (A-II),(B-II) O H H H H tert-Bu H H H H BF4 (z-124) (A-II),(B-II) O H H H H tert-Bu H H H H ClO4 (z-125) (A-II),(B-II) O H H H H tert-Bu H H H H PF4 (z-126) (A-II),(B-II) O H H H H tert-Bu H H H H Cl (z-127) (A-II),(B-II) Oh H H H H tert-Bu H H H H Br (z-128) (A-II),(B-II) Oh H H H H tert-Bu H H H H I (z-129) (A-II),(B-II) Oh H H Cl H tert-Bu H H F H B(C6F5)4 (z-130) (A-II),(B-II) Oh H H Cl H tert-Bu H H Cl H B(C6F5)4 (z-131) (A-II),(B-II) Oh H H Cl H tert-Bu H H Br H B(C6F5)4 (z-132) (A-II),(B-II) Oh H H Cl H tert-Bu H H Me H B(C6F5)4 (z-133) (A-II),(B-II) Oh H H Cl H tert-Bu H H i-Pr H B(C6F5)4 (z-134) (A-II),(B-II) Oh H H Cl H tert-Bu H H OCH3 H B(C6F5)4 (z-135) (A-II),(B-II) Oh H H Cl H tert-Bu H H NHCOCF3 H B(C6F5)4 (z-136) (A-II),(B-II) O H H H H i-Pr H F H H B(C6F5)4 (z-137) (A-II),(B-II) O H H H H i-Pr H Cl H H B(C6F5)4 (z-138) (A-II),(B-II) O H H H H i-Pr H Br H H B(C6F5)4 (z-139) (A-II),(B-II) O H H H H i-Pr H Me H H B(C6F5)4 (z-140) (A-II),(B-II) Oh H H H H i-Pr H i-Pr H H B(C6F5)4 (z-141) (A-II),(B-II) Oh H H H H i-Pr H OCH3 H H B(C6F5)4 (z-142) (A-II),(B-II) Oh H H H H i-Pr H CF3 H H B(C6F5)4 (z-143) (A-II),(B-II) Oh H H H H Ph H H F H B(C6F5)4 (z-144) (A-II),(B-II) Oh H H H H Ph H H Cl H B(C6F5)4 (z-145) (A-II),(B-II) Oh H H H H Ph H H Br H B(C6F5)4 (z-146) (A-II),(B-II) Oh H H H H Ph H H Me H B(C6F5)4 (z-147) (A-II),(B-II) Oh H H H H Ph H H i-Pr H B(C6F5)4 (z-148) (A-II),(B-II) Oh H H H H Ph H H OCH3 H B(C6F5)4 (z - 149) (A-II),(B-II) O H H H H Ph H H NHCOCF3 H B(C6F5)4 (z - 150) (A-I),(B-I) O H H H H tert-Bu H NMe2 H H B(C6F5)4

[0065] [Table 4] Compound A,B X YA,YE YB,YD YC R1 R2 R3 R4 R5 R6 An (z - 151) (A-I),(B-I) O H H H H tert-Bu H NEt2 H H B(C6F5)4 (z-152) (A-I),(B-I) O H H H H tert-Bu H N(n-Bu)2 H H B(C6F5)4 (z-153) (A-I),(B-I) O H H Cl H tert-Bu H NEt2 H H B(C6F5)4 (z-154) (A-I),(B-I) O H H H H tert-Bu H NEt2 H H N(SO2CF3)2 (z-155) (A-I),(B-I) O H H Me H tert-Bu H NEt2 H H B(C6F5)4 (z-156) (A-I),(B-I) O H H H H tert-Bu Ph H Me H B(C6F5)4 (z-157) (AI), (BI) O H H H H tert-Bu C-1, C-2 H H B(C6F5)4 (z-158) (AI), (BI) O H H H H 1,1-Dimethylbutyl C-1, C-2 H H B(C6F5)4 (z-159) (AI), (BI) O H H H H Cyclopropylmethyl C-1, C-2 H H B(C6F5)4 (z-160) (AI), (BI) O H H Br H tert-Bu Ph H Me H B(C6F5)4 (z-161) (AI), (BI) O H H Cl H 1,1-Dimethylbutyl C-1, C-2 H H B(C6F5)4 (z-162) (AI), (BI) O H H Cl H Cyclopropylmethyl C-1, C-2 H H B(C6F5)4 (z-163) (A-III), (B-III) O D-1 H H D-1 adamantyl - adamantyl D-1 - B(C6F5)4 (z-164) (A-III), (B-III) O H H H H tert-Bu - tert-Bu H - B(C6F5)4 (z-165) (A-III), (B-III) O H H H H methylcyclopropyl - methylcyclopropyl H - B(C6F5)4 (z-166) (A-III), (B-III) O H H H H methylcyclohexyl - methylcyclohexyl H - B(C6F5)4 (z-167) (A-III), (B-III) O H H H H adamantyl - adamantyl H - B(C6F5)4 (z-168) (A-III), (B-III) O H H Cl H tert-Bu - tert-Bu H - B(C6F5)4 (z-169) (A-III), (B-III) O H H Cl H adamantyl - adamantyl H - B(C6F5)4 (z-170) (A-III), (B-III) O H H OCH3 H adamantyl - adamantyl H - B(C6F5)4 (z-171) (A-III), (B-III) O H H H H adamantyl - adamantyl CH3 - B(C6F5)4 (z-172) (A-III), (B-III) O CH3 H H H adamantyl - adamantyl H - B(C6F5)4 (z-173) (A-III), (B-III) O H H CH3 H adamantyl - adamantyl H - B(C6F5)4

[0066] Furthermore, "C-1, C-2" in the R3 and R4 columns of Table 4 refers to the fact that R3 and R4 in the above formula (AI) and formula (BI) are bonded to each other to form an aromatic hydrocarbon group with 6 carbons. Specifically, it refers to the part corresponding to unit A and unit B having the structure represented by the following formulas C-1 and C-2. In addition, “D-1” in the YA, YE, R1 and R5 column of Table 4 refers to YA being bonded to R1 in formula (A-III) and YE being bonded to R5 in formula (B-III) 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] [Chemistry 14]

[0068] [Chemistry 15]

[0069] Compound (Z) is preferably a compound soluble in organic solvents, and particularly preferably a compound soluble in dichloromethane. Here, "soluble in organic solvents" means that more than 0.1 g of compound (Z) dissolves relative to 100 g of organic solvent at 25°C.

[0070] Compound (Z) is preferably a compound that satisfies the following necessary condition (A). Necessary condition (A): In the transmission spectrum (wherein the transmission spectrum is a spectrum with a transmittance of 10% at the wavelength of maximum absorption, also referred to below as the "transmission spectrum of compound (Z)") measured using a solution of compound (Z) dissolved in dichloromethane, the average transmittance in the wavelength range of 430 nm to 580 nm is preferably 93% or more, more preferably 95% or more. The average transmittance is preferably high, therefore there is no particular upper limit, and it can be 100%. If compound (Z) satisfies the necessary condition (A), it can not only fully block light of the wavelength in the near-infrared region to be blocked, but also further suppress the decrease in visible light transmittance.

[0071] Furthermore, in this invention, the average transmittance at wavelengths A nm to B nm is calculated by measuring the transmittance at each wavelength above A nm and below B nm in units of 1 nm and dividing the total transmittance by the number of measured transmittances (wavelength range, B-A+1).

[0072] Compound (Z) is preferably a compound that satisfies either the necessary condition (B-1) or the necessary condition (B-2) below. Necessary condition (B-1): The absorption spectrum measured using a solution of compound (Z) dissolved in dichloromethane has a maximum value in the preferred wavelength range of 720 nm to 900 nm, more preferably in the wavelength range of 740 nm to 880 nm, and particularly preferably in the wavelength range of 740 nm to 860 nm. If the absorption maximum wavelength of compound (Z) is within the range described above, an optical filter that can suppress reflected light near wavelengths of 720 nm to 900 nm and provide a good image with few light spots or ghosting can be easily obtained. Suitable examples of compounds (Z) that satisfy the necessary condition (B-1) include compounds in which unit A is any one of formulas (AI) to (A-II) and unit B is any one of formulas (BI) to (B-II).

[0073] Necessary condition (B-2): The absorption spectrum measured using a solution of compound (Z) dissolved in dichloromethane has a maximum value in the preferred wavelength range of 700 nm to 750 nm, more preferably in the wavelength range of 705 nm to 748 nm, and particularly preferably in the wavelength range of 710 nm to 745 nm. If the absorption maximum wavelength of compound (Z) is within the aforementioned range, an optical filter that can suppress reflected light near wavelengths of 700 nm to 750 nm and provide a good image with few light spots or ghosting can be easily obtained. Suitable examples of compounds (Z) that satisfy the necessary condition (B-2) include compounds in which unit A is of formula (A-III) and unit B is of formula (B-III).

[0074] Compound (Z) is preferably a compound that satisfies the following necessary condition (C). Necessary condition (C): The retention rate D (=Af×100 / Ai) of the absorbance Ai at the maximum absorption wavelength λa in the wavelength range of 700 nm to 1000 nm relative to the resin plate containing the resin and compound (Z), after irradiating the resin plate with a fluorescent lamp for 30 days, is preferably 95% or more, more preferably 97% or more. The retention rate D is preferably high, so there is no particular upper limit to it, and it can be 100%. Furthermore, the thickness of the resin plate is in the range of 90 μm to 110 μm, and the content of compound (Z) relative to the resin is such that the absorbance Ai at the maximum absorption wavelength λa of the resin plate is in the range of 0.5 to 1.5. The resin is ARTON manufactured by JSR Corporation, and 0.3 parts by mass of Irganox 1010 (manufactured by BASF Japan Corporation) are included relative to 100 parts by mass of the resin in the resin plate.

[0075] Compound (Z) with a retention rate D in the aforementioned range can be said to have excellent lightfastness (durability). By using such compound (Z), optical filters that exhibit the desired optical properties over a long period of time can be easily obtained. Specifically, the retention rate D can be determined using the methods described in the following embodiments.

[0076] Compound (Z) is more preferably satisfied with the following necessary condition (D). Necessary condition (D): In the spectroscopic absorption spectrum measured using a solution of compound (Z) dissolved in dichloromethane, when the absorbance at the longest wavelength of the maximum absorption wavelength is defined as εa and the maximum absorbance at wavelengths from 430 nm to 580 nm is defined as εbmax, εa / εbmax is preferably 20 or more, more preferably 25 or more, and even more preferably 27 or more. εa / εbmax is preferably large, therefore its upper limit is not particularly limited, for example, it is 10000 or less. If compound (Z) satisfies the necessary condition (D), it can be said that the ratio of absorbance in the infrared region to absorbance in the visible region is large, indicating excellent optical properties. In optical filters with dielectric multilayer films, the incident angle dependence caused by the multilayer films can be suppressed.

[0077] The content of compound (Z) in this composition is preferably 0.02 to 2.0 parts by mass relative to 100 parts by mass of resin, more preferably 0.02 to 1.5 parts by mass, and particularly preferably 0.03 to 1.5 parts by mass. If the content of compound (Z) is within the range described above, it is easy to obtain a composition that can efficiently cut off near-infrared light in the wavelength range of 700 nm to 750 nm or 720 nm to 900 nm, and has even better visible light transmittance.

[0078] <Resin> There are no particular restrictions on the resins used in this composition; any existing and known resins may be used. The resin used in this composition may be a single type or two or more types.

[0079] As for the resin, there are no particular limitations as long as the effects of the present invention are not impaired. For example, in terms of excellent thermal stability and formability to the shape of the film (plate), and the ease with which a dielectric multilayer film can be formed by high-temperature vapor deposition at a deposition temperature of 100°C or higher, resins with a glass transition temperature (Tg) preferably of 110°C to 380°C, more preferably of 110°C to 370°C, and particularly preferably of 120°C to 360°C can be obtained. In addition, if the Tg of the resin is 140°C or higher, a film that can be vapor deposited at a higher temperature to form a dielectric multilayer film can be obtained, and therefore it is particularly preferred.

[0080] As the resin, a resin with a total light transmittance (Japanese Industrial Standards (JIS) K 7375:2008) of 75% to 95%, more preferably 78% to 95%, and particularly preferably 80% to 95% can be used for a resin plate with a thickness of 0.1 mm containing the resin. If a resin with a total light transmittance within the aforementioned range is used, resin compositions or optical filters with excellent transparency can be easily obtained.

[0081] The weight-average molecular weight (Mw) of the resin, determined by gel permeation chromatography (GPC) and converted from polystyrene, is typically 15,000 to 350,000, preferably 30,000 to 250,000, and the number-average molecular weight (Mn) is typically 10,000 to 150,000, preferably 20,000 to 100,000.

[0082] Examples of resins include: cyclic (poly)olefin resins, aromatic polyether resins, polyimide resins, polyester resins, polycarbonate resins, polyamide (aromatic polyamide) resins, polyarylate resins, polyurethane resins, polyether ether resins, poly(terephthalamide) resins, polyamide-imide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curing resins, silsesquioxane UV-curing resins, acrylic UV-curing resins, and vinyl UV-curing resins. Specific examples of these resins include the resin described in International Publication No. 2019 / 168090.

[0083] <Other Ingredients> Without impairing the effects of the present invention, the composition may further contain other components such as compound (X) other than compound (Z) [absorbent other than ultraviolet absorber], antioxidant, ultraviolet absorber, fluorescent matting agent and metal complex compound.

[0084] These other ingredients can be used individually or in combination with two or more. These other components can be mixed with the resin during the preparation of this composition, or added during the synthesis of the resin. Furthermore, the amount added can be appropriately selected based on the desired properties, and is typically 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, relative to 100 parts by weight of the resin.

[0085] [Compound(X)] This composition may also contain one or more compounds (X) other than compound (Z) [absorbers other than ultraviolet absorbers]. Examples of compounds (X) include: squaric acid endomonium compounds, phthalocyanine compounds, polymethyl compounds, naphthalene phthalocyanine compounds, ketone endomonium compounds, octaphyrin compounds, diammonium compounds, perylene compounds, and metal dithiolate compounds.

[0086] The compound (X) is preferably a squaric acid-lactonium compound, and more preferably a compound that comprises one or more squaric acid-lactonium compounds and other compounds (X'). The other compounds (X') are particularly preferably phthalocyanine compounds and polymethyl compounds.

[0087] The squaric acid-internium compounds have sharp absorption peaks and excellent visible light transmittance and high molar absorptivity, but sometimes they produce fluorescence upon light absorption, which is a cause of scattered light. In this case, by combining the squaric acid-internium compounds with the compound (X'), scattered light can be suppressed. Thus, if scattered light is suppressed, the resulting camera image quality is improved when the optical filter obtained from this composition is used in photographic devices, etc.

[0088] The maximum absorption wavelength of the compound (X) is preferably 650 nm to 1100 nm, more preferably 650 nm to 950 nm, even more preferably 680 nm to 850 nm, and particularly preferably 690 nm to 740 nm. By using a compound (X) that has a maximum absorption wavelength in the range, an optical filter with superior visual sensitivity correction can be easily obtained.

[0089] [UV absorber] Examples of ultraviolet absorbers include, for example, compounds described in azobenzene compounds, indole compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, anthracene compounds, and compounds disclosed in Japanese Patent Application Publication No. 2019-014707.

[0090] Especially preferred are azobenzene compounds, indole compounds, benzotriazole compounds, and cyanoacrylate compounds. By containing these compounds, optical filters with low incident angle dependence in the near-ultraviolet wavelength region can be easily obtained, and when these optical filters are used in photographic devices, the resulting camera image quality is improved.

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

[0092] <Additives> Without impairing the effects of the present invention, the composition may further contain additives such as organic solvents, release agents, surfactants, antistatic agents, bonding aids, and light-diffusing materials. These additives can be used individually or in combination.

[0093] In particular, when the composition is prepared as a liquid composition, an organic solvent is preferred. Examples of such organic solvents are preferably solvents that can dissolve resins, specifically including esters, ketones, aromatic hydrocarbons, and halogen-containing compounds. In addition, when the resin layer is manufactured by casting as described later, the resin layer can be easily manufactured by using a leveling agent or a defoamer.

[0094] Substrate (i) The substrate (i) of the present invention is a substrate formed from the composition and containing the compound (Z). The substrate (i) may be a single layer or multiple layers, as long as it has a resin layer (hereinafter also referred to as "the resin layer") formed by the composition and containing the compound (Z). The substrate (i) may have two or more resin layers, in which case the two or more resin layers may be the same or different.

[0095] When the substrate (i) is a single layer, the substrate (i) is composed of this resin layer, that is, this resin layer (resin substrate) is the substrate (i). When the substrate (i) is multilayered, examples of the substrate (i) include: a substrate comprising two or more resin layers, wherein at least one of the two or more resin layers is the resin layer; or a substrate comprising the resin layer and a glass support. Examples of suitable substrates include: substrate (A), comprising a laminate formed by depositing the resin layer on a support such as a glass support or a resin support as a substrate; substrate (B), comprising a laminate formed by depositing an outer coating or resin layer comprising a curable resin on the resin layer. In terms of ease of manufacturing cost or optical property adjustment, thereby achieving the effect of eliminating damage to the cost resin layer, or improving the damage resistance of the substrate (i), the substrate (i) is particularly preferred to be substrate (B).

[0096] Furthermore, the resin layer, such as the outer coating, in the resin support or substrate (B) refers to a resin layer that does not contain compound (Z). There are no particular limitations on whether the resin layer does not contain compound (Z) or resin; examples of such resins include those listed in the "Composition" section. Alternatively, the resin layer that does not contain compound (Z) may also be other functional films as described below.

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

[0098] The thickness of the substrate (i) can be appropriately selected according to the desired application and is not particularly limited. It is preferably 10 μm to 250 μm, more preferably 15 μm to 230 μm, and particularly preferably 20 μm to 150 μm. If the thickness of the substrate (i) is within the aforementioned range, the optical filter using the substrate (i) can be made thinner and lighter, making it suitable for various applications such as solid-state imaging devices. In particular, when the single-layer substrate (i) is used in the lens unit of a camera module or the like, the lens unit can be made thinner and lighter, which is therefore preferred.

[0099] [Method for manufacturing substrate (i)] The resin layer, the resin support, and the outer coating are formed, for example, by melt molding or casting. Furthermore, if necessary, antireflective agents, hardening agents, and / or antistatic agents can be applied after molding.

[0100] When the substrate (i) is substrate (A), for example, the composition is melt-formed or cast-formed on the support, and preferably coated by spin coating, slot coating, inkjet or other methods, and the solvent is dried and removed, and then light irradiation or heating is performed as needed, thereby manufacturing a substrate on which the resin layer is formed on the support.

[0101] Melt molding Specifically, examples of melt forming include: a method for melt forming particles obtained by melt mixing the composition; a method for melt forming the composition; and a method for melt forming particles obtained by removing the solvent from a liquid composition containing a solvent. Examples of melt forming methods include: injection molding, melt extrusion molding, and blow molding.

[0102] ·Tape casting Examples of casting molding include: a method of casting a liquid composition containing a solvent onto a suitable support to remove the solvent; and a method of casting a curable composition containing a photocurable resin and / or a thermocurable resin onto a suitable support to remove the solvent, followed by curing using appropriate methods 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 from the support after casting. Alternatively, when the substrate (i) is the substrate (A), the substrate (i) can be obtained without peeling off the coating after casting.

[0103] Suitable supports include, for example, glass plates, steel strips, steel cylinders, and resin supports (e.g., polyester films, cyclic olefin resin films).

[0104] Furthermore, the resin layer can also be formed on optical components using methods such as: applying the liquid composition to an optical component made of glass, quartz, or plastic and drying the solvent; or applying the curable composition and then curing and drying it.

[0105] When the resin support and outer coating are formed by melt forming or casting, the desired composition containing the resin (wherein, compound (Z) is not present) can be used instead of the composition in the melt forming or casting section.

[0106] The residual solvent content in the resin layer, the resin support, and the outer coating should be as low as possible. Specifically, relative to the weight of the resin layer, the residual solvent content is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. If the amount of residual solvent is within the range, a resin layer that is difficult to deform or whose properties are difficult to change can be obtained and can easily perform the desired function. When the substrate (i) is used in an optical filter, it is preferable to suppress the solvent content in the resin layer, the resin support and the outer coating to 100 ppm by mass or less.

[0107] Optical Filters The optical filter of the present invention (hereinafter also referred to as "the filter") has the substrate (i) and a dielectric multilayer film. In order to further enhance the effects of this invention, specific examples of such filters include: near-infrared cutoff filters (NIR-CF), visible-near-infrared selective transmission filters (DBPF), and near-infrared transmission filters (IRPF). Furthermore, this filter can also be used as a filter for alternative light sources (ALS) used in scientific investigations, etc. These filters, apart from having the aforementioned substrate (i), can be constructed using previously known structures.

[0108] In the case of this filter being an NIR-CF or DBPF, a filter that satisfies the following characteristic (a) is preferred. Characteristic (a): In the wavelength region of 430 nm to 580 nm, the average transmittance measured in the direction perpendicular to the optical filter is preferably 75% or more, more preferably 80% or more. The average transmittance is preferably high, so there is no particular upper limit, and it can be 100%. If this filter satisfies the aforementioned characteristic (a), it can not only fully block light of the wavelength in the near-infrared region to be blocked, but also further suppress the reduction of visible light transmittance, thus making it more suitable for use as an NIR-CF or DBPF.

[0109] When the substrate (i) contains a compound that satisfies the necessary condition (B-1) and the filter is an NIR-CF or DBPF, it is preferable to have a filter that satisfies the following characteristic (b-1). Characteristic (b-1): In the wavelength region of 700 nm to 800 nm, the average reflectivity of unpolarized light incident at an angle of 5° perpendicular to at least one side of the optical filter is preferably 25% or less, more preferably 15% or less. The average reflectivity is preferably low, so there is no particular limitation on its lower limit, and it can be 0%. By using this filter that satisfies the aforementioned characteristic (b-1), the intensity of reflected light in the wavelength region of 700 nm to 800 nm can be reduced, thereby eliminating image defects caused by the reflected light.

[0110] When the substrate (i) contains a compound that satisfies the necessary condition (B-2) and the filter is an NIR-CF or DBPF, it is preferable to have a filter that satisfies the following characteristic (b-2). Characteristic (b-2): In the wavelength region of 650 nm to 800 nm, the average reflectivity of unpolarized light incident at an angle of 5° perpendicular to at least one side of the optical filter is preferably 25% or less, more preferably 15% or less. The average reflectivity is preferably low, so there is no particular limitation on its lower limit, and it can be 0%. By using this filter that satisfies the aforementioned characteristic (b-2), the intensity of reflected light in the wavelength region of 650 nm to 800 nm can be reduced, thereby eliminating image defects caused by the reflected light.

[0111] Furthermore, in this invention, the average reflectance at wavelengths A nm to B nm is calculated by measuring the reflectance at each wavelength above A nm and below B nm in units of 1 nm and dividing the total value of the reflectance by the number of the measured reflectances (wavelength range, B-A+1). Measuring the reflectivity of unpolarized light incident from a vertical direction is extremely difficult. Therefore, in this invention, the reflectivity of unpolarized light incident from an angle 5° away from the vertical direction is measured.

[0112] "Unpolarized light" refers to light rays that do not have a polarization direction; it is a collection of waves whose electric field is distributed approximately uniformly in all directions. The "average transmittance of unpolarized light" can be calculated by averaging the "average transmittance of S-polarized light" and the "average transmittance of P-polarized light." The "average reflectance of unpolarized light" can be calculated by averaging the "average reflectance of S-polarized light" and the "average reflectance of P-polarized light."

[0113] By satisfying the characteristics (a) and (b-1) or (b-2) of this filter, the intensity of reflected light, especially in the wavelength region of 650 nm to 800 nm, can be reduced while maintaining good transmittance of visible light. Therefore, in recent years, in photographic devices such as high-performance digital still cameras, the reduction in sensitivity in the visible light region can be minimized, and image defects caused by the reflected light can be eliminated.

[0114] The thickness of this filter can be appropriately selected according to the desired application. In accordance with the recent trend of thinner and lighter solid-state imaging devices, the thickness of this filter is also preferably thin. Because this filter incorporates the substrate (i), it can be made thin.

[0115] The thickness of this filter is preferably 300 μm or less, more preferably 250 μm or less, even more preferably 200 μm or less, and particularly preferably 150 μm or less. There is no particular limitation on the lower limit; for example, 20 μm is ideal.

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

[0117] When using NIR-CF in solid-state imaging elements, low transmittance in the near-infrared wavelength region is preferable. In particular, solid-state imaging elements are known to have high light-receiving sensitivity in the 800 nm to 1200 nm wavelength region. By reducing transmittance in this wavelength region, effective correction of camera image quality and human visual perception can be achieved, resulting in excellent color reproduction. Furthermore, by reducing transmittance in the 850 nm to 1200 nm wavelength region, near-infrared light used in security authentication functions can be effectively prevented from reaching image sensors, etc.

[0118] Regarding NIR-CF, in the wavelength range of 850 nm to 1200 nm, the average transmittance measured from the vertical direction of the filter is preferably 5% or less, more preferably 4% or less, even more preferably 3% or less, and particularly preferably 2% or less. If the average transmittance of wavelengths from 850 nm to 1200 nm is within the specified range, near-infrared radiation can be sufficiently blocked, resulting in excellent color reproduction, and therefore this is preferred.

[0119] When NIR-CF is used in solid-state photographic elements, high visible light transmittance is preferred. Specifically, in the wavelength range of 430 nm to 580 nm, the average transmittance measured in the direction perpendicular to the filter is preferably 75% or more, more preferably 80% or more, and even more preferably 83% or more, particularly preferably 85% or more. If the average transmittance of wavelengths from 430 nm to 580 nm is within the specified range, excellent photographic sensitivity can be achieved.

[0120] <dbpf> There are no particular limitations if the DBPF is an optical filter that transmits visible light and light of desired wavelengths in the near-infrared region, and blocks light of desired wavelengths in the near-infrared region. The dielectric multilayer film used in the DBPF is preferably a film that transmits visible light and light of desired wavelengths in the near-infrared spectrum, and blocks light of desired wavelengths in the near-infrared spectrum.

[0121] Similar to NIR-CF, when DBPF is used in solid-state photographic elements, it is preferable to have high visible light transmittance. For the same reasons mentioned above, the average transmittance at wavelengths of 430 nm to 580 nm is preferably in the same range as that of NIR-CF.

[0122] <irpf> There are no particular restrictions on whether the IRFP is an optical filter that blocks visible light and allows light of the desired wavelength in the near-infrared range to pass through. The dielectric multilayer film used in the IRPF is preferably a film that blocks light of the wavelength to be blocked (a portion of visible light and / or near-infrared light). In addition, visible light absorbers can be used in IRPF to block visible light.

[0123] IRPFs are suitable for use in the optical systems of infrared surveillance cameras, vehicle-mounted infrared cameras, infrared communications, various sensing systems, infrared alarms, night vision devices, etc. In these applications, it is preferable that the transmittance of light wavelengths other than near-infrared light that are to be transmitted is low. In particular, in the wavelength range of 380 nm to 700 nm, the average transmittance measured in the vertical direction of the filter is preferably 10% or less, more preferably 5% or less.

[0124] Furthermore, regarding the IRPF, the transmittance of the near-infrared light to be transmitted is preferably high. Specifically, it has a light transmission band Ya in the region with a wavelength of 750 nm or more, and the maximum transmittance (TIR) ​​in the light transmission band Ya, when measured from the vertical direction of the filter, is preferably 45% or more, more preferably 50% or more.

[0125] <Dielectric Multilayer Film> This filter includes the substrate (i) and a dielectric multilayer film. Examples of the dielectric multilayer film include a laminate formed by alternating layers of high-refractive-index material and low-refractive-index material. The dielectric multilayer film can be disposed on one side or both sides of the substrate (i). When disposed on one side, the manufacturing cost or ease of manufacture is excellent; when disposed on both sides, an optical filter with high strength and resistance to warping or twisting can be obtained. When this filter is used in solid-state imaging elements, the warping or twisting of the filter is preferably small; therefore, it is preferable to dispose of the dielectric multilayer film on both sides of the substrate (i).

[0126] Materials constituting the high refractive index material layer include those with a refractive index of 1.7 or higher, and those typically with a refractive index of 1.7 to 2.5. Examples of such materials include those that contain titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as main components, and contain small amounts (e.g., 0% to 10% by mass relative to the main components) of titanium oxide, tin oxide, and / or cerium oxide.

[0127] As the material constituting the low refractive index material layer, a material with a refractive index of 1.6 or less can be used, and a material with a refractive index typically of 1.2 to 1.6 can be selected. Examples of such materials include: silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

[0128] Regarding the method of laminating the high-refractive-index material layer and the low-refractive-index material layer, there are no particular limitations as long as it is possible to form a dielectric multilayer film formed by laminating these material layers. For example, a dielectric multilayer film formed by alternating layers of high-refractive-index material layers can be directly formed on the substrate (i) using chemical vapor deposition (CVD), sputtering, vacuum evaporation, ion-assisted evaporation, or ion plating.

[0129] Typically, if the wavelength of the light to be blocked (e.g., near-infrared) is set as λ (nm), the thickness of each layer of the high-refractive-index material layer and the low-refractive-index material layer is preferably 0.1λ to 0.5λ. For NIR-CF, the value of λ (nm) is, for example, 700 nm to 1400 nm, preferably 750 nm to 1300 nm. If the thickness of each layer of the high-refractive-index material layer and the low-refractive-index material layer is within this range, the product of the refractive index (n) and the film thickness (d) (n×d), i.e., the optical film thickness, becomes approximately the same as λ / 4. Based on the relationship between reflection and refraction optical properties, there is a tendency to easily control the blocking-transmission of a specific wavelength.

[0130] Regarding the total number of layers of high-refractive-index material layers and low-refractive-index material layers in the dielectric multilayer film, for example in the case of NIR-CF, it is preferably 16 to 70 layers, more preferably 20 to 60 layers, based on the overall optical filter. If the thickness of each layer, the thickness of the dielectric multilayer film based on the overall optical filter, or the total number of layers is within the aforementioned range, sufficient manufacturing margin can be ensured, and warpage of the optical filter or cracking of the dielectric multilayer film can be reduced.

[0131] In this filter, by taking into account the absorption characteristics of compound (Z), the types of materials constituting the high refractive index material layer and the low refractive index material layer, the thickness of each layer of the high refractive index material layer and the low refractive index material layer, the order of layering, and the number of layers are appropriately selected. This ensures sufficient transmittance in the wavelength region to be transmitted (e.g., the visible region) and sufficient light cutoff characteristics in the wavelength region to be cut off (e.g., the near-infrared region), and reduces the reflectivity of light (e.g., near-infrared rays) incident from an oblique direction.

[0132] Here, to optimize the conditions of the dielectric multilayer film, parameters can be set in a way that balances the anti-reflection effect in the desired wavelength range (e.g., the visible region) and the light cutoff effect in the desired wavelength range (e.g., the near-infrared region) using optical thin film design software. For example, when forming a NIR-CF dielectric multilayer film, a parameter setting method could be used such as setting the target transmittance for wavelengths from 400 nm to 700 nm to be 100% and the target tolerance value to be 1, and setting the target transmittance for wavelengths from 705 nm to 950 nm to be 0% and the target tolerance value to be 0.5. These parameters can also be combined with various characteristics of the substrate (i) to further refine the wavelength range and change the target tolerance value.

[0133] <Other Functional Membranes> For purposes such as improving the surface hardness of the substrate (i) or the dielectric multilayer film, enhancing chemical resistance, antistatic properties, and eliminating damage, this filter may, without compromising the effects of the invention, suitably provide functional films such as antireflective films, hard coatings, or antistatic films between the substrate (i) and the dielectric multilayer film, on the side of the substrate (i) opposite to the side where the dielectric multilayer film is disposed, or on the side of the dielectric multilayer film opposite to the side where the substrate (i) is disposed.

[0134] This filter may include one layer of the functional membrane or two or more layers. If the filter includes two or more layers of the functional membrane, it may include two or more identical membranes or two or more different membranes.

[0135] There are no particular limitations on the method of laminating the functional film, and examples include: melt forming or casting forming on a substrate (i) or dielectric multilayer film, using coating agents such as antireflective agents, hard coating agents and / or antistatic agents as described above.

[0136] Alternatively, it can be manufactured by applying a curable composition containing a coating agent onto a substrate (i) or a dielectric multilayer film using a rod coater or similar device, and then curing it by ultraviolet irradiation or similar methods.

[0137] Examples of coating agents include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins. Specifically, examples include vinyl compounds, urethane resins, urethane acrylate resins, acrylate resins, epoxy resins, and epoxy acrylate resins. A single coating agent or two or more agents may be used. Examples of curable compositions comprising 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 also contain a polymerization initiator. Known photopolymerization initiators or thermal polymerization initiators may be used as the polymerization initiator, or a combination of both may be used. One polymerization initiator may be used alone, or two or more may be used.

[0139] In the curing composition, when the total amount of the curing composition is set to 100% by mass, the mixing ratio of the polymerization initiator is preferably 0.1% to 10% by mass, more preferably 0.5% to 10% by mass, and even more preferably 1% to 5% by mass. If the mixing ratio of the polymerization initiator is within the above range, a curing composition with excellent curing properties and processability can be easily obtained, and functional films such as antireflective films, hard coatings, or antistatic films with the desired hardness can be easily obtained.

[0140] Furthermore, an organic solvent may be added to the curable composition as a solvent. Known solvents may be used. Specific examples of organic solvents 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 can be used alone or in combination with more than one.

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

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

[0143] Applications of optical filters This filter excels in several aspects, including its ability to block light of the desired wavelength and its transmission capability of the desired wavelength. Therefore, it is useful for sensitivity correction applications in solid-state photographic elements such as CCD or CMOS image sensors in camera modules. In particular, it is useful in digital still cameras, smartphone cameras, mobile phone cameras, digital camcorders, wearable device cameras, personal computer (PC) cameras, surveillance cameras, automotive cameras, infrared cameras, televisions, car navigation systems, portable information terminals, video game consoles, portable game consoles, fingerprint authentication systems, digital music players, various sensing systems, and infrared communication systems. Furthermore, it is also useful as a heat ray blocking filter installed on glass panels in automobiles or buildings.

[0144] Solid-State Photographic Device The solid-state photography apparatus of the present invention includes this filter. Here, the solid-state photography apparatus is an apparatus that includes a solid-state photography element such as a CCD or CMOS image sensor, and specifically, it can be used in applications such as digital still cameras, smartphone cameras, mobile phone cameras, wearable device cameras, and digital video cameras.

[0145] Optical Sensor Devices There are no particular limitations on the optical sensor device of the present invention if it includes this filter, as long as it is set to a previously known structure. For example, an apparatus having a light receiving element and this filter can be listed; more specifically, an apparatus having a light receiving element (semiconductor substrate), a protective film, this filter and other filters can be listed. [Example]

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

[0147] [Synthesis example] The compounds (Z) and (X) used in the following examples were synthesized using commonly known synthetic methods. Compound (Z) can be synthesized, for example, by means of methods described in Japanese Patent Application Publication No. 2009-108267, Japanese Patent Application Publication No. Hei 5-59291, Japanese Patent Application Publication No. 2014-95007, Japanese Patent Application Publication No. 2011-52218, International Publication No. 2007 / 114398, Japanese Patent Application Publication No. 2003-246940, "Chemistry of Heterocyclic Compounds: The Cyanine Dyes and Related Compounds" (Vol. 18, Wiley, 1964), and "Near-Infrared Dyes for High Technology Applications" (Springer, 1997). Compound (X) can be found, for example, in Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Application Publication No. 60-228448, Japanese Patent Application Publication No. 1-146846, Japanese Patent Application Publication No. 1-228960, and Japanese Patent No. 4081149. The methods described in Japanese Patent Application Publication No. 63-124054, "Phalocyanines - Chemistry and Functions -" (IPC, 1997), Japanese Patent Application Publication No. 2007-169315, Japanese Patent Application Publication No. 2009-108267, Japanese Patent Application Publication No. 2010-241873, Japanese Patent No. 3699464, and Japanese Patent No. 4740631 are used to synthesize the phthalocyanines.

[0148] [Intermediate Synthesis Example 1] [Chemistry 16]

[0149] In a 200 mL pomegranate flask equipped with a stir bar, 8.33 g of compound a-1, synthesized using the method described in *Bioorganic and Medicinal Chemistry* (2013, vol. 21, #11, pp. 2826-2831), was added to 21.8 g of ethyl pivalate. After 5 minutes, 4.0 g of sodium hydride (60%, dispersed in paraffin liquid) was added, and the mixture was stirred at 80 °C for 3 hours. The mixture was then cooled to room temperature, neutralized with 100 mL of 1 N hydrochloric acid aqueous solution, and transferred to a separatory funnel. The organic phase was extracted with 150 mL of ethyl acetate. Subsequently, 15 g of magnesium sulfate was added to the extracted organic phase and stirred for 15 minutes. The magnesium sulfate was then removed by filtration, and the filtrate was transferred to a 300 mL pomegranate flask. The solvent was distilled off using an evaporator, yielding compound a-2.

[0150] A stir bar was placed in a flask containing compound a-2, and 20 mL of concentrated hydrochloric acid was added. The mixture was stirred at 40°C. After stirring for 1 hour, the reaction solution was cooled in an ice bath and neutralized with 200 mL of 1 N sodium hydroxide aqueous solution. The solution was then transferred to a separatory funnel, 150 mL of ethyl acetate was added, and the organic phase was extracted. 15 g of magnesium sulfate was then added, and the mixture was stirred for 15 minutes. The magnesium sulfate was removed by filtration, and the filtrate was transferred to a 300 mL flask. The solvent was distilled off using an evaporator. The remaining compound in the flask was then purified using silica gel chromatography to obtain 5.0 g of the target compound a-3. Furthermore, the compound was identified using liquid chromatography-mass spectroscopy (LC-MS) and 1H-nuclear magnetic resonance (1H-NMR) analysis.

[0151] [Intermediate Synthesis Example 2] [Chemistry 17]

[0152] In a 200 mL eggplant-shaped flask equipped with a stir bar, 3 g of compound a-3 and 30 mL of diethyl ether were added, and the mixture was cooled in an ice bath while stirring. After cooling in an ice bath for 5 minutes, 13.5 mL of a 1 mol / L solution of magnesium methyl iodide diethyl ether was added over a 10-minute period. The mixture was then heated to 35°C and stirred for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, and 30 mL of a 20% perchloric acid aqueous solution was added. The precipitated solid was filtered and separated, 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 then identified using 1H-NMR analysis.

[0153] [Example of the synthesis of compound (z-1)] [Chemistry 18]

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

[0155] In a 100 mL pear-shaped flask equipped with a stir bar, 0.1 g of compound a-5, 0.2 g of lithium tetra-pentafluorophenylborate, 20 mL of dichloromethane, and 10 mL of water were added and stirred at room temperature for 1 hour. The solution was then transferred to a separatory funnel to remove the aqueous phase. The organic phase was washed twice with 20 mL of water, and 1 g of sodium sulfate was added and stirred for 15 minutes. The sodium sulfate was then removed by filtration, and the filtrate was transferred to a 300 mL pear-shaped flask. The solvent was distilled off using an evaporator, and the solution was dried under reduced pressure at 50 °C to obtain 0.05 g of compound (z-1). The compound was then identified using LC-MS and 1H-NMR analysis.

[0156] [Intermediate Synthesis Example 3] [Chemistry 19]

[0157] In a 300 mL pear-shaped flask equipped with a stir bar, 5 g of flavonoid (compound a-6) and 50 mL of tetrahydrofuran (THF) were added, and the mixture was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 24.7 mL of a 1 mol / L magnesium methyl iodide diethyl ether solution was added over a 10-minute period. The mixture was then heated to 35°C and stirred for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, and 50 mL of a 20% perchloric acid aqueous solution was added. The precipitated solid was filtered and separated, washed with 50 mL of water, and dried under reduced pressure at 50°C to obtain 4.5 g of compound a-7. The compounds were then identified using 1H-NMR analysis.

[0158] [Synthesis example of compound (z-16)] [Chemistry 20]

[0159] In a 100 mL flask equipped with a stir bar, 0.7 g of compound a-7, 0.26 g of malondialdehyde diacetylaniline hydrochloride, 10 mL of acetonitrile, 5 mL of anhydrous acetic acid, and 0.2 mL of pyridine were added, and the mixture was heated under reflux for 2 hours. Afterward, the mixture was cooled to room temperature, and the precipitated solid was recovered by vacuum filtration. The solid was then washed with 10 mL of diethyl ether to obtain 0.6 g of compound a-8.

[0160] In a 100 mL pear-shaped flask equipped with a stir bar, 0.1 g of compound a-8, 0.2 g of lithium tetra-pentafluorophenylborate, 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 to remove the aqueous phase. The organic phase was then washed twice with 20 mL of water, and the solvent was removed by distillation 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 in an ice bath. The precipitated solid was recovered by suction filtration and dried under reduced pressure at 50 °C to obtain 0.07 g of compound (z-16). The compound was then identified using LC-MS and 1H-NMR analysis.

[0161] [Intermediate Synthesis Example 4] [Chemistry 21]

[0162] In a 200 mL pomelo flask equipped with a stir bar, 4 g of compound a-9 and 21.8 g of ethyl pivalate were added and stirred for 5 minutes. Then, 3.2 g of sodium hydride (60%, dispersed in liquid paraffin) was added, and the mixture was stirred at 80 °C for 3 hours. Afterward, the mixture was cooled to room temperature, neutralized with 30 mL of 1 N hydrochloric acid aqueous solution, and the organic phase was extracted with 150 mL of ethyl acetate. Subsequently, 15 g of magnesium sulfate was added to the organic phase and stirred for 15 minutes. The magnesium sulfate was then removed by filtration, and the filtrate was transferred to a 300 mL pomelo flask. The solvent was distilled off using an evaporator to obtain compound a-10.

[0163] A stir bar was placed in a round-bottom flask containing compound a-10, and 20 mL of concentrated hydrochloric acid was added. The mixture was stirred at 40°C. After stirring for 1 hour, the reaction solution was cooled in an ice bath and neutralized with 240 mL of 1 N sodium hydroxide aqueous solution. The solution was then transferred to a separatory funnel, 200 mL of ethyl acetate was added, and the organic phase was extracted. 15 g of magnesium sulfate was then added, and the mixture was stirred for 15 minutes. The magnesium sulfate was removed by filtration, and the filtrate was transferred to a 300 mL round-bottom flask. The solvent was distilled off using an evaporator. The remaining compound in the flask was then purified using silica gel chromatography to obtain 2.0 g of the target compound a-11. The compound was further identified using LC-MS and 1H-NMR analysis.

[0164] [Intermediate Synthesis Example 5] [Chemistry 22]

[0165] In a 200 mL eggplant-shaped flask equipped with a stir bar, 2.7 g of compound a-11 and 50 mL of diethyl ether were added, and the mixture was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 24.7 mL of a 1 mol / L solution of magnesium methyl iodide diethyl ether was added over a 10-minute period. The mixture was then heated to 35°C and stirred for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, and 50 mL of a 20% perchloric acid aqueous solution was added. The precipitated solid was filtered and separated, 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 then identified using 1H-NMR analysis.

[0166] [Synthesis example of compound (z-59)] [Chemistry 23]

[0167] In a 100 mL flask equipped with a stir bar, 0.5 g of compound a-12, 0.22 g of malondialdehyde diacetylaniline hydrochloride, 7.5 mL of acetonitrile, 2.5 mL of anhydrous acetic acid, and 0.2 mL of pyridine were added, and the mixture was heated under reflux for 2 hours. Afterward, the mixture was cooled to room temperature, and the precipitated solid was recovered by vacuum filtration. The solid was washed with 10 mL of acetic acid and 10 mL of acetonitrile, and then dried under reduced pressure at 50 °C to obtain 0.35 g of compound a-13.

[0168] In a 100 mL pear-shaped flask equipped with a stir bar, 0.3 g of compound a-13, 0.8 g of lithium tetra-pentafluorophenylborate, 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 to remove the aqueous phase. The organic phase was washed twice with 20 mL of water, and the solvent was distilled off from the organic phase using an evaporator. The residue was then dissolved in 20 mL of acetone, and 100 mL of water was added. 13 g of the solvent was distilled off using an evaporator, followed by ice bath cooling. The precipitated solid was then recovered by suction filtration, washed with 50 mL of methanol, and dried under reduced pressure at 50 °C to obtain 0.5 g of compound (z-59). The compound was then identified using LC-MS and 1H-NMR analysis.

[0169] [Intermediate Synthesis Example 6] [Chemistry 24]

[0170] In a 200 mL pear-shaped flask equipped with a stir bar, 4.5 g of compound a-14 and 21.8 g of ethyl isobutyrate were added and stirred for 5 minutes. Then, 3.2 g of sodium hydride (60%, dispersed in liquid paraffin) was added, and the mixture was stirred at 80 °C for 3 hours. Afterward, the mixture was cooled to room temperature, neutralized with 30 mL of 1 N hydrochloric acid aqueous solution, and the organic phase was extracted with 150 mL of ethyl acetate. Subsequently, 15 g of magnesium sulfate was added to the organic phase and stirred for 15 minutes. The magnesium sulfate was then removed by filtration, and the filtrate was transferred to a 300 mL pear-shaped flask. The solvent was distilled off using an evaporator, thus obtaining compound a-15.

[0171] A stir bar was placed in a flask containing compound a-15, and 20 mL of concentrated hydrochloric acid was added. The mixture was stirred at 40°C. After stirring for 1 hour, the reaction solution was cooled in an ice bath and neutralized with 240 mL of 1 N sodium hydroxide aqueous solution. The solution was then transferred to a separatory funnel, 200 mL of ethyl acetate was added, and the organic phase was extracted. 15 g of magnesium sulfate was then added, and the mixture was stirred for 15 minutes. The magnesium sulfate was removed by filtration, and the filtrate was transferred to a 300 mL flask. The solvent was distilled off using an evaporator. The remaining compound in the flask was then purified using silica gel chromatography to obtain 0.4 g of the target compound a-16. The compound was further identified using LC-MS and 1H-NMR analysis.

[0172] [Intermediate Synthesis Example 7] [Chemistry 25]

[0173] In a 100 mL eggplant-shaped flask equipped with a stir bar, 0.4 g of compound a-16 and 10 mL of diethyl ether were added, and the mixture was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 5.0 mL of a 1 mol / L diethyl ether solution of magnesium methyl iodide was added over a 10-minute period. The mixture was then heated to 35°C and stirred for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, and 10 mL of a 20% perchloric acid aqueous solution was added, followed by 20 mL of dichloromethane. The solution was 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, and 20 mL of diethyl ether was added, followed by stirring for 20 minutes. The solid component was then filtered by suction filtration and dried under reduced pressure at 50°C to obtain 0.5 g of compound a-17. The compound was then identified using 1H-NMR analysis.

[0174] [Synthesis example of compound (z-62)] [Chemistry 26]

[0175] In a 100 mL flask equipped with a stir bar, 0.4 g of compound a-17, 0.16 g of malondialdehyde diacetylaniline hydrochloride, 7.5 mL of acetonitrile, 2.5 mL of anhydrous acetic acid, and 0.2 mL of pyridine were added, and the mixture was heated under reflux for 2 hours. Afterward, the mixture was cooled to room temperature, and the precipitated solid was recovered by vacuum filtration. The solid was washed with 10 mL of diethyl ether and dried under reduced pressure at 50 °C to obtain 0.35 g of compound a-18.

[0176] In a 100 mL bowl-shaped flask equipped with a stir bar, 0.3 g of compound a-18, 0.8 g of lithium tetra-pentafluorophenylborate, 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 to remove the aqueous phase. The organic phase was washed twice with 20 mL of water, and the solvent was removed by distillation from the organic phase using an evaporator. The solid was then dried under reduced pressure at 50 °C to obtain 0.4 g of compound (z-62). The compound was identified using LC-MS and 1H-NMR analysis.

[0177] [Intermediate Synthesis Example 8] [Chemistry 27]

[0178] In a 200 mL flask equipped with a stir bar, 15 g of compound a-19 and 28.7 g of methyl 4,4-dimethyl-3-oxovalerate were added, and the mixture was stirred at 180 °C for 24 hours. Afterward, the mixture was cooled to room temperature, and 250 mL of hexane and 200 mL of 1 N hydrochloric acid aqueous solution were added. The liquid was transferred to a separatory funnel to remove the aqueous phase. Subsequently, the solvent was removed by distillation from the organic phase using an evaporator, and the remaining compound in the flask was separated and purified using silica gel chromatography, yielding 7 g of the target compound a-20. Furthermore, the compound was identified using LC-MS and 1H-NMR analysis.

[0179] [Intermediate Synthesis Example 9] [Chemistry 28]

[0180] In a 100 mL pear-shaped flask equipped with a stir bar, 3.5 g of compound a-20 and 20 mL of diethyl ether were added, and the mixture was cooled in an ice bath. After cooling in the ice bath for 5 minutes, 14.0 mL of a 1 mol / L solution of magnesium methyl iodide diethyl ether was added over a 10-minute period. The mixture was then heated to 35°C and stirred for 2 hours. Subsequently, the mixture was allowed to cool naturally to room temperature, and the resulting reaction solution was added over a 5-minute period to a beaker containing 100 mL of water and a stir bar. Then, 20 g of a 40% aqueous solution of boric acid fluoride was added over a 10-minute period, and the mixture was stirred for 30 minutes. The solution was then transferred to a separatory funnel. Next, 30 mL of dichloromethane was added, and the mixture was separated to remove the aqueous phase. The solvent was then removed by distillation from the organic phase using an evaporator. Subsequently, the residue was dissolved in 30 mL of dichloromethane, and 50 mL of diisopropyl ether was added. After removing 40 g of solvent using an evaporator, the mixture was cooled in an ice bath. The precipitated solid was then filtered by suction filtration and dried under reduced pressure at 50 °C to obtain 2.3 g of compound a-21. Furthermore, the compound was identified using 1H-NMR analysis.

[0181] [Synthesis example of compound (z-151)] [Chemistry 29]

[0182] In a 100 mL flask equipped with a stir bar, 0.5 g of compound a-21, 0.18 g of malondialdehyde diacetylaniline hydrochloride, and 15 mL of pyridine were added, and the mixture was 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 bowl-shaped flask equipped with a stir bar, 0.2 g of compound a-22, 0.8 g of lithium tetra-pentafluorophenylborate, 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 to remove the aqueous phase. The organic phase was washed twice with 20 mL of water, and the solvent was removed by distillation from the organic phase using an evaporator. Separation was performed using column chromatography to obtain 0.2 g of compound (z-151). The compound was then identified using LC-MS and 1H-NMR analysis.

[0184] [Intermediate Synthesis Example 10] [Chemistry 30]

[0185] In a 200 mL pomelo flask equipped with a stir bar, 1.9 g of compound a-23 and 2.0 g of ethyl pivalate were added and stirred for 5 minutes. Then, 0.3 g of sodium hydride (60%, dispersed in liquid paraffin) was added, and the mixture was stirred at 80 °C for 3 hours. Afterward, the mixture was cooled to room temperature, neutralized with 30 mL of 1 N hydrochloric acid aqueous solution, and the organic phase was extracted with 150 mL of ethyl acetate. Subsequently, 5 g of magnesium sulfate was added to the organic phase and stirred for 15 minutes. The magnesium sulfate was then removed by filtration, and the filtrate was transferred to a 300 mL pomelo flask. The solvent was distilled off using an evaporator, yielding 1.3 g of compound a-24.

[0186] A stir bar was placed in a round-bottom flask containing 1.3 g of compound a-24, and 20 mL of concentrated hydrochloric acid was added. The mixture was stirred at 40 °C. After stirring for 1 hour, the reaction solution was cooled in an ice bath and neutralized with 240 mL of 1 N sodium hydroxide aqueous solution. The solution was then transferred to a separatory funnel, 200 mL of ethyl acetate was added, and the organic phase was extracted. 5 g of magnesium sulfate was then added, and the mixture was stirred for 15 minutes. The magnesium sulfate was removed by filtration, and the filtrate was transferred to a 300 mL round-bottom flask. The solvent was distilled off using an evaporator. The remaining compound in the flask was then purified by silica gel chromatography to obtain 1.1 g of compound a-25. The compound was further identified using LC-MS and 1H-NMR analysis.

[0187] [Intermediate Synthesis Example 11] [Chemistry 31]

[0188] In a 200 mL eggplant-shaped flask equipped with a stir bar, 1.5 g of compound a-25 and 50 mL of diethyl ether were added, and the mixture was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 1.5 mL of a 1 mol / L solution of magnesium methyl iodide diethyl ether was added over a 10-minute period. The mixture was then heated to 35°C and stirred for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, and 50 mL of a 20% perchloric acid aqueous solution was added. The precipitated solid was filtered and separated, 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 then identified using 1H-NMR analysis.

[0189] [Synthesis example of compound (z-157)] [Chemistry 32]

[0190] In a 100 mL flask equipped with a stir bar, 7.0 g of compound a-26, 2.5 g of malondialdehyde diacetylaniline hydrochloride, 50 mL of acetonitrile, 10 mL of anhydrous acetic acid, and 10 mL of pyridine were added, and the mixture was heated under reflux for 2 hours. Afterward, the mixture was cooled to room temperature, and the precipitated solid was recovered by vacuum filtration. The solid was washed with 10 mL of acetic acid and 10 mL of acetonitrile, and then dried under reduced pressure at 50 °C to obtain 5.1 g of compound a-27.

[0191] In a 100 mL pear-shaped flask equipped with a stir bar, 0.6 g of compound a-27, 1.2 g of lithium tetra-pentafluorophenylborate, 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 to remove the aqueous phase. The organic phase was washed twice with 20 mL of water, and the solvent was distilled off from the organic phase using an evaporator. The residue was then dissolved in 20 mL of acetone, and 100 mL of water was added. 10 g of the solvent was distilled off using an evaporator, followed by ice bath cooling. The precipitated solid was then recovered by suction filtration, washed with 50 mL of methanol, and dried under reduced pressure at 50 °C to obtain 1.0 g of compound (z-157). The compound was then identified using LC-MS and 1H-NMR analysis.

[0192] [Intermediate Synthesis Example 12] [Chemistry 33]

[0193] In a 200 mL flask equipped with a stir bar, 22 g of 1-adamantane carbonyl chloride (compound a-28) and 5.2 g of methylenecyclohexane were added. The mixture was heated to 90°C, and then 10 g of trifluoromethanesulfonic acid was added dropwise while stirring for 10 minutes. After cooling to 0°C, 150 mL of hexane, 50 mL of diethyl ether, and 50 mL of water were added and stirred. The precipitated solid was separated by filtration and dried under reduced pressure at 50°C to obtain 4.2 g of compound a-35. The compound was then identified using 1H-NMR analysis.

[0194] [Synthesis example of compound (z-163)] [Chemistry 34]

[0195] In a 100 mL flask equipped with a stir bar, 0.5 g of compound a-35, 0.1 g of malondialdehyde diacetylaniline hydrochloride, 4 mL of acetonitrile, 1 mL of anhydrous acetic acid, and 1 mL of pyridine were added, and the mixture was stirred at 90 °C for 10 minutes. After cooling to 0 °C, the precipitated solid was separated by filtration, washed with 2 mL of acetonitrile, and dried under reduced pressure at 50 °C to obtain 0.3 g of compound a-36. Furthermore, the compound was identified using 1H-NMR analysis.

[0196] In a 100 mL pear-shaped flask equipped with a stir bar, 0.3 g of compound a-36, 0.4 g of lithium tetra-pentafluorophenylborate, 20 mL of dichloromethane, and 20 mL of water were added, and the mixture was stirred at room temperature for 4 hours. The aqueous phase was then transferred to a separatory funnel to remove it, followed by two washes of the organic phase with 20 mL of water. The solvent was then removed by distillation from the organic phase using an evaporator. The residue was then dissolved in dichloromethane, methanol was added, and the precipitated solid was recovered by suction filtration and dried under reduced pressure at 50 °C to obtain 0.4 g of compound (z-163). The compound was then identified using LC-MS and 1H-NMR analysis.

[0197] [Intermediate Synthesis Example 13] [Chemistry 35]

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

[0199] Subsequently, without further purification of compound a-38, 60 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40 °C. After 1 hour, the reaction solution was cooled in an ice bath and neutralized with 1 N sodium hydroxide aqueous solution. After separation and washing with ethyl acetate-water, sodium sulfate was added and the mixture was dried. The solvent was then distilled off using an evaporator. The resulting mixture was purified using silicone column chromatography to obtain compound a-39 (15.4 g). The compounds were identified using LC-MS and 1H-NMR analysis.

[0200] [Intermediate Synthesis Example 14] [Chemistry 36]

[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 mixture of 50 mL toluene and 50 mL water. The mixture was heated at 110 °C for 12 hours with vigorous stirring. After cooling to room temperature, the mixture was separated by toluene-water separation. Sodium sulfate was added to the organic layer, and the mixture was dried. The solvent was distilled off using an evaporator. The resulting mixture was purified by silicone column chromatography to obtain compound a-40 (12.4 g).

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

[0203] [Synthesis example of compound (z-156)] [Chemistry 37]

[0204] In a 100 mL flask equipped with a stir bar, 7.0 g of compound a-41, 2.5 g of malondialdehyde diacetylaniline hydrochloride, 50 mL of acetonitrile, 10 mL of anhydrous acetic acid, and 10 mL of pyridine were added, and the mixture was heated under reflux for 2 hours. Afterward, the mixture was cooled to room temperature, and the precipitated solid was recovered by vacuum filtration. The solid was washed with 10 mL of acetic acid and 10 mL of acetonitrile, and then dried under reduced pressure at 50 °C to obtain 5.0 g of compound a-42.

[0205] In a 100 mL pear-shaped flask equipped with a stir bar, 0.6 g of compound a-42, 1.2 g of lithium tetra-pentafluorophenylborate, 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 to remove the aqueous phase. The organic phase was washed twice with 20 mL of water, and the solvent was removed by distillation from the organic phase using an evaporator. The residue was then dissolved in 20 mL of acetone, and 100 mL of water was added. 10 g of the solvent was distilled off using an evaporator, followed by ice bath cooling. The precipitated solid was then recovered by suction filtration, washed with 50 mL of methanol, and dried under reduced pressure at 50 °C to obtain 1.0 g of compound (z-156). The compound was then identified using LC-MS and 1H-NMR analysis.

[0206] [Intermediate Synthesis Example 15] [Chemistry 38]

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

[0208] [Synthesis example of compound (z-161)] [Chemistry 39]

[0209] Ethyl tervastatin was replaced with compound a-44, and otherwise compound a-45 was obtained by the same method as in intermediate synthesis example 10.

[0210] Compound a-23 was changed to compound a-45, and malondialdehyde diacetylaniline hydrochloride was changed to N-[2-chloro-3-(phenylamino)-2-propenyne]-aniline monohydrochloride. Otherwise, compound (z-161) was obtained using the same method as in the synthesis examples of intermediate example 11 and compound (z-157). Furthermore, the compounds were identified using LC-MS and 1H-NMR analysis.

[0211] <Necessary Condition (A)> The necessary condition (A) was determined using a transmission spectrum (wherein the transmission spectrum is the spectrum with a transmittance of 10% at the wavelength of maximum absorption) obtained by dissolving either compound (Z) or compound (X) used in the following experiments in dichloromethane. The results are shown in Table 5. Furthermore, necessary conditions A through D in Table 5 represent necessary conditions (A), (B-1), (C), and (D) in the column for <compound (Z)>, respectively.

[0212] <Necessary Condition (B)> The necessary condition (B) was determined using the absorption spectrum obtained by dissolving either compound (Z) or compound (X) used in the following tests in dichloromethane and measuring it using a spectrophotometer (V-7200) manufactured by Nippon Spectrophotometer Co., Ltd. The results are shown in Table 5.

[0213] <Necessary Condition (C)> In a container, 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), compound (Z) or compound (X) used in the following experiment, and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass. Furthermore, when using compounds (z-1), (x-3), and (z-163), the amount used is set to 0.05 parts by mass; when using compound (z-16), the amount used is set to 0.06 parts by mass; when using compounds (z-59), (z-62), (z-156), (z-157), (z-158), (z-159), (z-160), (z-161), and (z-162), the amount used is set to 0.04 parts by mass; when using compound (z-151), the amount used is set to 0.08 parts by mass; and when using compound (x-4), the amount used is set to 0.03 parts by mass. The amounts of these compounds are adjusted based on the molar absorptivity of each compound, with the absorbance at the wavelength of maximum absorption of the obtained solution being approximately 1.

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

[0215] <Necessary Condition (D)> In the absorption spectra measured using a spectrophotometer (V-7200) manufactured by Nippon Spectrophotometer (Nippon Spectrophotometer Co., Ltd.), prepared by dissolving compound (Z) or compound (X) used in the following experiments in dichloromethane, the absorbance at the longest wavelength of maximum absorption is defined as εa, and the maximum absorbance in the wavelength range of 430 nm to 580 nm is defined as εbmax. εa / εbmax is then calculated. The results are shown in Table 5.

[0216] [Table 5] compound (z-1) (z-16) (z-59) (z-62) (z-151) (z-156) (z-157) (z-158) (z-159) (z-160) (z-161) (z-162) (z-163) (x-3) (x-4) Optical properties Necessary condition A (%) 99.5 98.7 99.8 99.5 94.7 99.5 99.0 99.3 98.6 99.5 99.3 98.6 99.1 97.5 99.4 Necessary condition B (nm) 787 825 770 757 824 785 788 790 800 791 800 810 760 931 760 Necessary condition D 69.0 27.9 167.6 181.2 25.5 82.5 86.5 66.6 35.0 49.0 78.5 30.0 93.5 38.5 65.3 Lightfastness evaluation Necessary condition C (%) 99.6 99.4 99.5 99.3 99.2 99.6 99.2 99.3 99.0 99.6 99.3 99.0 99.1 99.1 91

[0217] <Molecular weight> The molecular weight of the resin is determined by taking into account the solubility of each resin in the solvent, using the method described in (a) or (b) below. (a) Using a gel permeation chromatography (GPC) apparatus (Type 150C, Tosoh H-type column, developing solvent: o-dichlorobenzene) manufactured by Waters Corporation, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of standard polystyrene were determined. (b) Using a GPC apparatus (HLC-8220 type, column: TSKgel α-M, development solvent: THF) manufactured by Tosoh Co., Ltd., the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of standard polystyrene were determined.

[0218] Furthermore, regarding the resin synthesized in the resin synthesis example 3 described later, the molecular weight was not determined using the method described above, but rather the logarithmic viscosity was determined using the method (c) described below. (c) A portion of the polyimide solution was added to anhydrous methanol to precipitate the polyimide, which was then filtered to separate it from the unreacted monomer. The precipitated polyimide was then dried under vacuum at 80°C for 12 hours. 0.1 g of the obtained polyimide was dissolved in 20 mL of N-methyl-2-pyrrolidone (a dilute polyimide solution), and the logarithmic viscosity (μ) at 30°C was determined using a Cannon-Fenske viscometer and 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 (S., Ltd.) at a heating rate of 20°C per minute under a nitrogen flow.

[0220] [Resin Synthesis Example 1] 100 parts by mass of 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodecyl-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) as represented by formula (a) were loaded into a nitrogen-purged reaction vessel, and the solution was heated to 80°C. Then, 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 (0.025 mol / L) were added to the solution in the reaction vessel as a polymerization catalyst, and the solution was heated and stirred at 80°C for 3 hours to carry out a ring-opening polymerization reaction, thereby obtaining a ring-opening polymer solution. The polymerization conversion rate in the polymerization reaction was 97%.

[0221] [Chemistry 40]

[0222] 1,000 parts by mass of the obtained ring-opening polymer solution were loaded into an autoclave. 0.12 parts by mass of RuHCl(CO)[P(C6H5)3]3 were added to the ring-opening polymer solution. The reaction was carried out by heating and stirring for 3 hours under hydrogen pressure of 100 kg / cm² and reaction temperature of 165°C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. The obtained reaction solution was injected into a large amount of methanol, and the solidified material was separated and recovered. This solidified material was then dried to obtain the hydrogenated polymer (hereinafter referred to as "Resin A"). The obtained Resin A has 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 3 L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzyl nitrile, 87.60 g (0.250 mol) of 9,9-bis(4-hydroxyphenyl)fluorene, 41.46 g (0.300 mol) of potassium carbonate, 443 g of N,N-dimethylacetamide, and 111 g of toluene were added. A thermometer, stirrer, three-way stopcock with a nitrogen inlet, Dean-Stark tube, and cooling tube were then installed in the flask. After purging the flask with nitrogen, the resulting solution was reacted at 140 °C for 3 hours, with any water generated being removed from the Dean-Stark tube. Once it was confirmed that no water was being formed, the temperature was slowly increased to 160 °C, and the reaction was continued at this temperature for 6 hours. Subsequently, the solution was cooled to room temperature (25°C), and the generated salts were removed using filter paper. The filtrate was then added to methanol for reprecipitation, and the filter material (residue) was separated by filtration. The obtained filter material was vacuum dried overnight at 60°C to obtain a white powder (hereinafter also referred to as "Resin B") (yield 95%). The number average molecular weight (Mn) of the obtained Resin B was 75,000, the weight average molecular weight (Mw) was 188,000, and the glass transition temperature (Tg) was 285°C.

[0224] [Resin Synthesis Example 3] In a 500 mL five-necked flask containing a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean-Stark tube, and cooling tube, under a nitrogen stream, 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 added 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 acid dianhydride and 0.50 g (0.005 mol) of triethylamine as a acetylation catalyst were added. After the addition was complete, the temperature was raised to 180°C, and the distillate was continuously distilled off while refluxing for 6 hours. After the reaction was complete, the mixture was air-cooled until the internal temperature reached 100°C. Then, 143.6 g of N,N-dimethylacetamide was added for dilution while stirring and cooling, thereby obtaining 264.16 g of a polyimide solution with a solid content of 20% by mass. A portion of the polyimide solution was injected into 1 L of methanol to precipitate the polyimide. After washing the filtered polyimide with methanol, it was dried in a vacuum dryer at 100°C for 24 hours to obtain a white powder (hereinafter referred to as "resin C"). The infrared (IR) spectrum of the obtained resin C was measured, and the characteristic absorptions of the acetamide group at 1704 cm⁻¹ and 1770 cm⁻¹ were observed. The glass transition temperature (Tg) of resin C is 310℃, and the logarithmic viscosity is 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 compound (z-1) (with a maximum absorption wavelength of 787 nm in dichloromethane), 0.038 parts by mass of compound (x-1) (with a maximum absorption wavelength of 711 nm in dichloromethane), 0.075 parts by mass of compound (x-2) (with a maximum absorption wavelength of 738 nm in dichloromethane), and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass. The obtained solution was cast onto a smooth glass plate and dried at 20°C for 8 hours, then peeled off from the glass plate. The peeled coating was then dried at 100°C under reduced pressure for 8 hours to obtain a resin layer (1) with a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm.

[0226] Compound (z-1) [Chemistry 41]

[0227] Compound (x-1) [Chemistry 42]

[0228] Compound (x-2) [Chemistry 43]

[0229] Using a bar coater, the resin composition (1) was coated onto one side of the obtained resin layer (1) to a thickness of 3 μm. The solvent was evaporated and removed by heating at 70°C for 2 minutes in an oven. Next, the resin composition (1) was cured using a UV conveyor type exposure machine (manufactured by Eyegraphics, Inc., Eye UV curing apparatus, model US2-X0405, 60 Hz) to form a resin layer (2) on the resin layer (1). Similarly, a resin layer (2) containing the resin composition (1) was also formed on the other side of the resin layer (1). Thus, a substrate having a resin layer (2) without compound (Z) on both sides of the resin layer (1) containing compound (Z) was obtained.

[0230] Resin composition (1): a composition comprising 60 parts by weight of tricyclodecanedimethyl acrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexylphenyl ketone, and methyl ethyl ketone (solvent, used such that the concentration of solid components in the obtained composition is 30% by weight).

[0231] (Lightfastness) The obtained substrate was exposed to indoor fluorescent light for 500 hours to evaluate the lightfastness of the near-infrared absorbing pigment contained in the resin. Lightfastness was evaluated by calculating the pigment retention rate (%) based on the change in absorbance before and after fluorescent light exposure at the wavelength with the highest absorption intensity of the substrate (hereinafter referred to as "λa"; in the case of multiple absorption maxima of the substrate, λa is the wavelength with the highest absorption intensity). A "○" is set to a pigment retention rate of 95% or higher after 500 hours of exposure to fluorescent light, and a "×" is set to a pigment retention rate of less than 95%. The results are shown in Table 8.

[0232] [Fabrication of Optical Filters] In the fabrication of the substrate, a dielectric multilayer film (I) is formed on one side of the substrate, and then a dielectric multilayer film (II) is formed on the other side of the substrate to obtain an optical filter with a thickness of about 0.110 mm.

[0233] Dielectric multilayer film (I) is a laminate (totaling 26 layers) formed by alternating deposition of silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers at a deposition temperature of 100°C. Dielectric multilayer film (II) is a laminate (totaling 22 layers) formed by alternating deposition of silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers at a deposition temperature of 100°C. In either the dielectric multilayer film (I) or the dielectric multilayer film (II), silicon dioxide layers and titanium dioxide layers are alternately deposited in the order of titanium dioxide layer, silicon dioxide layer, titanium dioxide layer, ... silicon dioxide layer, titanium dioxide layer, silicon dioxide layer, starting from the substrate side, and the outermost layer of the optical filter is set as a silicon dioxide layer.

[0234] Regarding the thickness and number of layers, optimization was performed using optical thin film design software (manufactured by Essential Macleod, Thin Film Center) to achieve good transmittance in the visible region and reflectivity in the near-infrared region, based on the wavelength-dependent characteristics of the substrate's refractive index and the absorption characteristics of the compounds (Z) and (X) used. In this embodiment, the input parameters (target values) for the software were set as shown in Table 6 below during optimization.

[0235] [Table 6] Dielectric Multilayer film Wavelength (nm) Input parameters for the software Angle of incidence Required angle Target tolerance type (I) 420 20 100 1 Transmission rate 430~450 20 100 0.8 Transmission rate 451~561 20 100 1 Transmission rate 562~650 15 100 1 Transmission rate 651~700 0 100 1 Transmission rate 800~949 0 0 1 Transmission rate (II) 350~410 0 0 1 Transmission rate 420 0 50 1 Transmission rate 430~700 0 100 1 Transmission rate

[0236] The result of the optimized film structure is that the dielectric multilayer film (I) is a 26-layer evaporated film formed by alternating layers of silicon dioxide with a physical film thickness of approximately 37 nm to 168 nm and titanium dioxide with a physical film thickness of approximately 11 nm to 104 nm, and the dielectric multilayer film (II) is a 22-layer evaporated film formed by alternating layers of silicon dioxide with a physical film thickness of approximately 40 nm to 191 nm and titanium dioxide with a physical film thickness of approximately 10 nm to 110 nm. An example of the optimized film structure is shown in Table 7 below.

[0237] [Table 7] Dielectric multilayer film layer Layer material Physical film thickness (nm) Optical film thickness(nd) (I) 1 SiO2 83.6 0.236 2 TiO2 93.0 0.450 3 SiO2 161.3 0.455 4 TiO2 92.8 0.449 5 SiO2 157.0 0.442 6 TiO2 86.1 0.416 7 SiO2 155.0 0.437 8 TiO2 85.1 0.412 9 SiO2 154.2 0.435 10 TiO2 84.4 0.408 11 SiO2 153.6 0.433 12 TiO2 84.0 0.406 13 SiO2 153.1 0.431 14 TiO2 83.6 0.405 15 SiO2 152.7 0.430 16 TiO2 83.6 0.405 17 SiO2 152.7 0.430 18 TiO2 83.8 0.406 19 SiO2 153.3 0.432 20 TiO2 85.0 0.411 21 SiO2 158.1 0.446 22 TiO2 88.3 0.427 23 SiO2 168.3 0.474 24 TiO2 103.9 0.503 25 SiO2 37.0 0.104 26 TiO2 10.6 0.051 Substrate (II) 27 TiO2 10.1 0.046 28 SiO2 39.7 0.107 29 TiO2 109.9 0.503 30 SiO2 185.4 0.498 31 TiO2 108.6 0.497 32 SiO2 190.4 0.512 33 TiO2 110.2 0.504 34 SiO2 190.8 0.513 35 TiO2 110.1 0.503 36 SiO2 190.5 0.512 37 TiO2 109.5 0.501 38 SiO2 190.8 0.513 39 TiO2 109.3 0.500 40 SiO2 188.8 0.507 41 TiO2 108.5 0.496 42 SiO2 183.7 0.493 43 TiO2 103.0 0.471 44 SiO2 174.3 0.468 45 TiO2 95.6 0.437 46 SiO2 171.3 0.460 47 TiO2 94.9 0.434 48 SiO2 83.6 0.224

[0238] Regarding the obtained optical filter, the average value T of the spectral transmittance measured in the direction perpendicular to the optical filter in the wavelength range of 430 nm to 580 nm, and the average value R of the spectral reflectance of unpolarized light incident at a 5° angle perpendicular to the side of the self-polarizing dielectric multilayer film (II) in the wavelength range of 700 nm to 800 nm were calculated. Furthermore, the spectral transmittance and spectral reflectance were measured using a spectrophotometer (V-7200) manufactured by Nippon Spectrophotometer Co., Ltd. The results are shown in Table 8.

[0239] [Implementation Example 2] In Example 1, 0.08 parts by mass of compound (z-16) (with a maximum absorption wavelength of 825 nm in dichloromethane) were used instead of 0.2 parts by mass of compound (z-1), and resin B was used instead of resin A. Otherwise, the same procedure as in Example 1 was followed to obtain the substrate. The lightfastness 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) [Chemistry 44]

[0241] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0242] [Example 3] In Example 1, 0.14 parts by mass of compound (z-59) (with a maximum absorption wavelength of 770 nm in dichloromethane) were used instead of 0.2 parts by mass of compound (z-1), and resin C was used instead of resin A. Otherwise, the same procedure as in Example 1 was followed to obtain the substrate. The lightfastness 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) [Chemistry 45]

[0244] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0245] [Example 4] In Example 1, 0.2 parts by mass of compound (z-62) (with a maximum absorption wavelength of 757 nm in dichloromethane) were used instead of 0.2 parts by mass of compound (z-1), and Acryviewa manufactured by Nippon Catalyst Co., Ltd. was used instead of resin A. Otherwise, the same procedure as in Example 1 was followed to obtain the substrate. The lightfastness 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) [Chemistry 46]

[0247] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0248] [Example 5] In Example 1, 0.08 parts by mass of compound (z-151) (with a maximum absorption wavelength of 824 nm in dichloromethane) were used instead of 0.2 parts by mass of compound (z-1), and the substrate was otherwise obtained in the same manner as in Example 1. The lightfastness 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) [Chemistry 47]

[0250] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0251] [Example 6] In a container, 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 were added to prepare a resin solution with a resin concentration of 20% by mass. The solution was then filtered using a microporous filter with 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 using a microporous filter with a pore size of 5 μm to obtain a resin solution (E6-2).

[0252] Using a spin coater, the following resin composition (2) was applied to both sides of a transparent glass support "OA-10G" (200 μm thick) manufactured by Nippon Electric Glass Co., Ltd., which was cut to a size of 200 mm × 200 mm. Then, the solvent was evaporated and removed by heating at 80°C for 2 minutes on a heating plate, 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 later.

[0253] Next, using a spin coater, the resin solution (E6-1) was applied to one side of the glass support on which the adhesive layer was formed, with a dried film thickness of 10 μm. The solvent was evaporated and removed by heating at 80°C for 5 minutes on a heating plate, thereby forming a coated resin layer (2). Then, using a spin coater, the resin solution (E6-2) is coated onto the other side of the glass support on which the adhesive layer is formed, with a dried film thickness of 10 μm. The solvent is evaporated and removed by heating at 80°C for 5 minutes on a heating plate, thereby forming a coated resin layer (1). Thus, a substrate with a thickness of 222 μm is obtained, which is formed by depositing a resin layer containing compound (Z) on one side of a glass support and depositing a resin layer without compound (Z) on the other side. The lightfastness 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 weight of ethylene oxide-modified triacrylate isocyanurate (trade name: Aronix M-315, manufactured by Toa Gosei Co., Ltd.), 20 parts by weight of 1,9-nonanediol diacrylate, 20 parts by weight of methacrylic acid, 30 parts by weight of glycidyl methacrylate, 5 parts by weight of 3-glycidoxypropyltrimethoxysilane, 5 parts by weight of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by BASF Japan Co., Ltd.), and 1 part by weight of San-Aid SI-110 main agent (manufactured by San-Shin Chemical Industry Co., Ltd.) were mixed and dissolved in propylene glycol monomethyl ether acetate at a solid content of 50% by weight. The mixture was then filtered through a microporous filter with a pore size of 0.2 μm.

[0255] Subsequently, referring to Example 1, a dielectric multilayer film (I) with a total of 26 layers, consisting of alternating layers of silicon dioxide (SiO2) and titanium dioxide (TiO2), was formed on the surface of the coated resin layer (2). Then, a dielectric multilayer film (II) with a total of 22 layers, consisting of alternating layers of silicon dioxide (SiO2) and titanium dioxide (TiO2), was formed on the surface of the coated resin layer (1), thereby obtaining an optical filter with a thickness of approximately 0.226 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 9.

[0256] [Example 7] In Example 1, 0.01 parts by mass of the following compound (x-3) (with a maximum absorption wavelength of 931 nm in dichloromethane) were added, and the substrate was obtained in the same manner as in Example 1. The lightfastness 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) [Chemistry 48]

[0258] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0259] [Example 8] In Example 1, 0.03 parts by mass of the following compound (x-5) (with a maximum absorption wavelength of 1095 nm in dichloromethane) were added, and the substrate was obtained in the same manner as in Example 1. The lightfastness 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) [Chemistry 49]

[0261] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0262] [Example 9] In Example 1, 0.16 parts by mass of compound (z-16) (with a maximum absorption wavelength of 825 nm in dichloromethane) and 0.12 parts by mass of compound (z-59) (with a maximum absorption wavelength of 770 nm in dichloromethane) were used instead of 0.2 parts by mass of compound (z-1). Otherwise, the same procedure as in Example 1 was followed to obtain the substrate. The lightfastness of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0263] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0264] [Example 10] In Example 1, 0.17 parts by mass of the following compound (y-1) (with a maximum absorption wavelength of 394 nm in dichloromethane) were added, and the substrate was obtained in the same manner as in Example 1. The lightfastness 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) [Transformation 50]

[0266] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

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

[0268] Subsequently, similar to Example 6, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the surface of the coated resin layer (2). Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the surface of the coated resin layer (1), thereby obtaining an optical filter with a thickness of approximately 0.226 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 9.

[0269] [Example 12] In Example 1, 0.1 parts by mass of compound (z-156) (with a maximum absorption wavelength of 785 nm in dichloromethane) was used instead of 0.2 parts by mass of compound (z-1), and the substrate was otherwise obtained in the same manner as in Example 1. The lightfastness 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) [Chemistry 51]

[0271] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0272] [Example 13] In Example 12, 0.1 parts by mass of compound (z-157) (with a maximum absorption wavelength of 788 nm in dichloromethane) were used instead of 0.1 parts by mass of compound (z-156), and the substrate was otherwise obtained in the same manner as in Example 12. The lightfastness 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) [Chemistry 52]

[0274] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0275] [Example 14] In Example 12, 0.1 parts by mass of compound (z-156) was used instead of 0.1 parts by mass of compound (z-156), and the substrate was otherwise obtained in the same manner as in Example 12. The lightfastness 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) [Chemistry 53]

[0277] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0278] [Example 15] In Example 12, 0.1 parts by mass of compound (z-159) (with a maximum absorption wavelength of 800 nm in dichloromethane) were used instead of 0.1 parts by mass of compound (z-156), and the substrate was otherwise obtained in the same manner as in Example 12. The lightfastness 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) [Chemistry 54]

[0280] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0281] [Example 16] In Example 12, 0.1 parts by mass of compound (z-160) (with a maximum absorption wavelength of 791 nm in dichloromethane) were used instead of 0.1 parts by mass of compound (z-156), and the substrate was otherwise obtained in the same manner as in Example 12. The lightfastness 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) [Chemistry 55]

[0283] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0284] [Example 17] In Example 12, 0.1 parts by mass of compound (z-161) (with a maximum absorption wavelength of 800 nm in dichloromethane) was used instead of 0.1 parts by mass of compound (z-156), and the substrate was otherwise obtained in the same manner as in Example 12. The lightfastness 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) [Chemistry 56]

[0286] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0287] [Example 18] In Example 12, 0.1 parts by mass of compound (z-162) (with a maximum absorption wavelength of 810 nm in dichloromethane) were used instead of 0.1 parts by mass of compound (z-156), and the substrate was otherwise obtained in the same manner as in Example 12. The lightfastness 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) [Chemistry 57]

[0289] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0290] [Example 19] In Example 12, 0.1 parts by mass of compound (z-163) (with a maximum absorption wavelength of 760 nm in dichloromethane) were used instead of 0.1 parts by mass of compound (z-156), and the substrate was otherwise obtained in the same manner as in Example 12. The lightfastness 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) [Chem.58]

[0292] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0293] [Comparative Example 1] In Example 1, compound (Z) was not used; otherwise, the same procedure as in Example 1 was followed to obtain the substrate. The lightfastness of the obtained substrate was evaluated in the same manner as in Example 1. The results are shown in Table 8.

[0294] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0295] [Comparative Example 2] In Example 1, instead of using compound (Z), 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) (with a maximum absorption wavelength of 931 nm in dichloromethane) were used as compound (X). Otherwise, the same procedure as in Example 1 was followed to obtain the substrate. The lightfastness 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) [Chemistry 59]

[0297] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0298] [Comparative Example 3] In Example 1, instead of using compound (Z), 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) (which has a maximum absorption wavelength of 760 nm in dichloromethane) were used as compound (X). Otherwise, the same procedure as in Example 1 was followed to obtain the substrate. The lightfastness 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) [Transformation 60]

[0300] Subsequently, similar to Example 1, a dielectric multilayer film (I) consisting of 26 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (II) consisting of 22 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm. Regarding the design of the dielectric multilayer film, similar to Example 1, the same design parameters as in Example 1 were used after taking into account the wavelength dependence of the substrate's refractive index. Regarding the obtained optical filter, the average values ​​T and R were calculated in the same manner as in Example 1. The results are shown in Table 8.

[0301] [Table 8] Example 1 Example 2 Example 3 Example 4 Example 5 Example 7 Example 8 Example 9 Example 10 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Comparative example 1 Comparative example 2 Comparative example 3 substrate resin Layer (1) resin Resin A Resin B Resin C Yakuribiya (acryviewa) Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Compound (Z) (parts by weight) (z-1) 0.2 - - - - 0.2 0.2 - 0.2 - - - - - - - - - - - (z-16) - 0.08 - - - - - 0.16 - - - - - - - - - - - - (of-59) - - 0.14 - - - - 0.12 - - - - - - - - - - - - (of-62) - - - 0.2 - - - - - - - - - - - - - - - - (of-151) - - - - 0.08 - - - - - - - - - - - - - - - (from-156) - - - - - - - - - 0.1 - - - - - - - - - - (z-157) - - - - - - - - - - 0.1 - - - - - - - - - (from-158) - - - - - - - - - - - 0.1 - - - - - - - - (from-159) - - - - - - - - - - - - 0.1 - - - - - - - (z-160) - - - - - - - - - - - - 0.1 - - - - - - (from-161) - - - - - - - - - - - - - - 0.1 - - - - - (z-162) - - - - - - - - - - - - - - - 0.1 - - - - (z-163) - - - - - - - - - - - - - - - - 0.1 - - - Compound (X) (parts by weight) (x-1) 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 0.038 (x-2) 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 (x-3) - - - - - 0.01 - - - - - - - - - - - - 0.2 - (x-4) - - - - - - - - - - - - - - - - - - - 0.08 (x-5) - - - - - - 0.03 - - - - - - - - - - - - - Compound (Y) (parts by weight) (y-1) - - - - - - - - 0.17 - - - - - - - - - - - substrate Lightfastness ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × Optics filter Dielectric multilayer film (I) 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 Dielectric multilayer film (II) twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two Optical properties R(%) 8.7 10.4 8.7 9.5 10.8 9.0 9.0 9.0 9.0 8.7 9.0 8.8 10.0 8.7 8.8 10.0 10.8 26.5 11.5 8.7 T(%) 90.4 90.8 91.2 91.8 82.9 87.0 88.2 87.0 89.7 91.4 90.0 91.0 84.0 91.4 91.0 84.0 82.9 93.3 80.7 87.9

[0302] [Table 9] Implementation Example 6 Implementation Example 11 substrate Support body OA-10G BS-11 Resin layer(1) Resin Resin A Resin A (z-1) 2 2 (z-16) - - (z-59) - - (z-62) - - (x-177) - - Resin layer (2) resin Resin A Resin A (x-1) 0.38 0.38 (x-2) 0.75 0.75 (x-3) - - (x-4) - - (x-5) - - Lightfastness ○ ○ Optics filter Dielectric multilayer film (I) 26 26 Dielectric multilayer film (II) twenty two twenty two Optical properties R(%) 8.6 9.0 T(%) 90.3 86.6

[0303] The optical filters obtained in Examples 1 to 19 can reduce the intensity of reflected light, especially in the wavelength region of 700 nm to 800 nm, while maintaining good visible light transmittance. Therefore, in recent years, in photographic devices such as high-performance digital still cameras, the reduction in sensitivity in the visible light region can be minimized, and image defects caused by the reflected light can be eliminated, which is useful.

[0304] [Synthesis example of compound (z-164)] In a flask, acetyl chloride (2 equal volumes) and tert-butyl alcohol (1 equal volume) were added. The mixture was heated in an oil bath at 85°C while stirring. Trifluoromethanesulfonic acid (1 equal volume) was added dropwise over 5 minutes. After the addition was complete, the oil bath temperature was set to 100°C, and the mixture was 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) [Chemistry 61]

[0306] In a flask, the obtained compound (m-1) (1 equal volume) and malondialdehyde diacetylaniline hydrochloride (0.5 equal volume) were added. Acetonitrile and anhydrous acetic acid were then added and the mixture was stirred. Pyridine (1 equal volume) was then added dropwise, and the mixture was stirred at room temperature for 2 hours. Subsequently, acetonitrile, anhydrous acetic acid, and pyridine were removed using an evaporator, and the mixture was separated using methyl chloride / water. The organic phase was recovered, and 1.5 equal volume of LiFABA (lithium = tetra(pentafluorophenyl)borohydride) and water were added, followed by vigorous stirring for 3 hours. The organic phase was then recovered, and methyl chloride was removed using an evaporator to obtain compound (z-164).

[0307] Compound (z-164): exhibits maximum absorption in dichloromethane at a wavelength of 715 nm. [Chemistry 62]

[0308] [Synthesis example of compound (z-165)] In the synthesis example of compound (z-164), acetyl chloride was replaced with 1-methylcyclopropanecarboxylic acid acetyl chloride, and otherwise compound (z-165) was obtained by the same method as in the synthesis example described above. Compound (z-165): exhibits a maximum absorption wavelength of 727 nm in dichloromethane.

[0309] [Chemistry 63]

[0310] [Synthesis example of compound (z-166)] In the synthesis example of compound (z-164), acetyl chloride was replaced with 1-methylcyclohexanecarboxylic acid acetyl chloride, and otherwise compound (z-166) was obtained by the same method as in the synthesis example described above.

[0311] Compound (z-166): exhibits a maximum absorption wavelength of 719 nm in dichloromethane. [Chemistry 64]

[0312] [Synthesis example of compound (z-167)] In the synthesis example of compound (z-164), acetyl chloride was replaced with 1-adamantanecarboxylic acid acetyl chloride, and otherwise compound (z-167) was obtained by the same method as in the synthesis example described above.

[0313] Compound (z-167): exhibits a maximum absorption wavelength of 721 nm in dichloromethane. [Chemistry 65]

[0314] [Synthesis example of compound (z-168)] In the synthesis example of compound (z-164), malondialdehyde diacetylaniline hydrochloride was replaced with the following compound (m-2), and otherwise compound (z-168) was obtained by the same method as in the synthesis example described above.

[0315] • Compound (m-2) [Chemistry 66]

[0316] Compound (z-168): exhibits maximum absorption in dichloromethane at a wavelength of 720 nm. [Chemistry 67]

[0317] [Synthesis example of compound (z-169)] In the synthesis example of compound (z-167), malondialdehyde diacetylaniline hydrochloride was replaced with the compound (m-2), and otherwise, compound (z-169) was obtained by the same method as in the synthesis example.

[0318] Compound (z-169): exhibits a maximum absorption wavelength of 726 nm in dichloromethane. [Chemistry 68]

[0319] [Synthesis example of compound (z-170)] In the synthesis example of compound (z-169), compound (m-2) was changed to compound (m-3), and otherwise compound (z-170) was obtained by the same method as in the synthesis example.

[0320] Compound (m-3) [Chemistry 69]

[0321] Compound (z-170): exhibits maximum absorption in dichloromethane at a wavelength of 739 nm. [Chemistry 70]

[0322] [Synthesis example of compound (z-171)] In the synthesis example of compound (z-167), compound (m-1) was changed to compound (m-4), and otherwise compound (z-171) was obtained by the same method as in the synthesis example.

[0323] Compound (m-4) [Chemistry 71]

[0324] Compound (z-171): exhibits maximum absorption in dichloromethane at a wavelength of 734 nm. [Chemistry 72]

[0325] [Synthesis example of compound (z-172)] In the synthesis example of compound (z-167), compound (m-1) was changed to compound (m-5), and otherwise compound (z-172) was obtained by the same method as in the synthesis example.

[0326] Compound (m-5) [Chemistry 73]

[0327] Compound (z-172): exhibits a maximum absorption wavelength of 738 nm in dichloromethane. [Chemistry 74]

[0328] [Synthesis example of compound (z-173)] In the synthesis example of compound (z-169), compound (m-2) was changed to compound (m-6), and otherwise compound (z-173) was obtained by the same method as in the synthesis example.

[0329] Compound (m-6) [Chemistry 75]

[0330] Compound (z-173): exhibits maximum absorption in dichloromethane at a wavelength of 724 nm. [Chemistry 76]

[0331] [Examples 20-32 and Comparative Examples 4-7] [Preparation of substrate] The same procedure as in Example 1 was followed, specifically, the substrate was prepared in the following manner. 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 listed in Table 12. 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 was then dried at 100°C under reduced pressure for 8 hours to obtain a resin layer (1) with a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm. Furthermore, the values ​​recorded in the columns for compound (Z), compound (X) and compound (Y) in Table 12 represent the content (parts by mass) of each compound relative to 100 parts by mass of the resin.

[0332] Furthermore, the compound (x-6) in Table 12 is the compound represented by the following formula (with a maximum absorption wavelength of 717 nm in dichloromethane). [Chemistry 77]

[0333] Using a bar coater, the resin composition (1) was coated onto one side of the obtained resin layer (1) to a thickness of 3 μm. The solvent was evaporated and removed by heating at 70°C for 2 minutes in an oven. Next, the resin composition (1) was cured by exposure using a UV conveyor type exposure machine (manufactured by Eyegraphics, Inc., Eye UV curing device, model US2-X0405, 60 Hz) (exposure dose: 500 mJ / cm2, illuminance: 200 mW / cm2), thereby forming a resin layer (2) on the resin layer (1). Similarly, a resin layer (2) containing the resin composition (1) was also formed on the other side of the resin layer (1).

[0334] Resin composition (1): a composition comprising 60 parts by weight of tricyclodecanedimethyl acrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexylphenyl ketone, and methyl ethyl ketone (solvent, used such that the concentration of solid components in the obtained composition is 30% by weight).

[0335] <Spectrophotometric transmittance> The transmittance of the substrate in the near-infrared region (650 nm to 800 nm) and the transmittance of the substrate in the visible light region (430 nm to 580 nm) were measured using a spectrophotometer (V-7200) manufactured by Nippon Spectrophotometer Co., Ltd. The transmittance was measured using the spectrophotometer under conditions where light was incident perpendicularly to the surface of the substrate. The parameters measured using this apparatus are as follows. The results are shown in Table 12. The spectral transmittance spectra of the substrates obtained in Examples 20 and 28 are shown in Figures 1 and 2, respectively. Furthermore, regarding Tc and Td, the obtained substrate was heated in an oven preheated to 155°C for 7 hours, and the transmittance of the substrate after the heating test was measured (heat resistance evaluation). In addition, regarding Te and Tf, the obtained substrate was irradiated with UV using a UV exposure machine (manufactured by Iwasaki Electric Co., Ltd., Eye UV curing device US2-KO4501, illuminance: 180 mW / cm2, irradiation dose: 560 mJ / cm2), and the transmittance of the substrate after UV irradiation was measured (UV resistance evaluation).

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

[0337] [Fabrication of Optical Filters] In the fabrication of the substrate, a dielectric multilayer film (III) is formed on one side of the substrate, and then a dielectric multilayer film (IV) is formed on the other side of the substrate to obtain an optical filter with a thickness of about 0.110 mm.

[0338] Dielectric multilayer film (III) is a laminate (totaling 28 layers) formed by alternating deposition of silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers at a deposition temperature of 100°C. Dielectric multilayer film (IV) is a laminate (totaling 24 layers) formed by alternating deposition of silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers at a deposition temperature of 100°C. In either the dielectric multilayer film (III) or the dielectric multilayer film (IV), silicon dioxide layers and titanium dioxide layers are alternately deposited in the order of titanium dioxide layer, silicon dioxide layer, titanium dioxide layer, ... silicon dioxide layer, titanium dioxide layer, silicon dioxide layer, starting from the substrate side, and the outermost layer of the optical filter is set as a silicon dioxide layer.

[0339] Regarding the thickness and number of layers, optimization was performed using optical thin film design software (manufactured by Essential Macleod, Thin Film Center) to achieve good transmittance in the visible region and reflectivity in the near-infrared region, based on the wavelength-dependent characteristics of the substrate's refractive index and the absorption characteristics of the compounds (Z) and (X) used. In this embodiment, the input parameters (target values) for the software were set as shown in Table 10 below during optimization.

[0340] [Table 10] Dielectric Multilayer film Wavelength (nm) Input parameters for the software Angle of incidence Required angle Target tolerance type (III) 400~450 20 100 0.2 Transmission rate 390~700 0 100 1 Transmission rate 710~1000 0 0 1 Transmission rate (IV) 480~540 25 100 0.15 Transmission rate 420~840 0 100 1 Transmission rate 950~1260 0 0 1 Transmission rate

[0341] The optimized membrane structure resulted in the following: the dielectric multilayer film (III) was fabricated as a 28-layer vapor-deposited film consisting of alternating layers of silicon dioxide with a physical film thickness of approximately 32 nm to 159 nm and titanium dioxide with a physical film thickness of approximately 9 nm to 94 nm; and the dielectric multilayer film (IV) was fabricated as a 24-layer vapor-deposited film consisting of alternating layers of silicon dioxide with a physical film thickness of approximately 39 nm to 193 nm and titanium dioxide with a physical film thickness of approximately 12 nm to 117 nm. An example of the optimized membrane structure is shown in Table 11 below.

[0342] [Table 11] Dielectric multilayer film layer Layer material Physical film thickness (nm) Optical film thickness(nd) (III) 1 SiO2 78.5 0.208 2 TiO2 88.4 0.400 3 SiO2 158.7 0.421 4 TiO2 86.9 0.393 5 SiO2 152.9 0.406 6 TiO2 84.1 0.381 7 SiO2 151.9 0.403 8 TiO2 82.4 0.373 9 SiO2 149.8 0.398 10 TiO2 81.1 0.367 11 SiO2 148.0 0.393 12 TiO2 80.1 0.362 13 SiO2 147.3 0.391 14 TiO2 79.7 0.361 15 SiO2 147.3 0.391 16 TiO2 80.3 0.363 17 SiO2 148.0 0.393 18 TiO2 81.1 0.367 19 Silicon dioxide 149.4 0.397 20 Titanium dioxide 81.3 0.368 21 Silicon dioxide 150.7 0.400 22 Titanium dioxide 82.5 0.373 23 Silicon dioxide 149.8 0.398 24 Titanium dioxide 86.4 0.391 25 Silicon dioxide 159.2 s 0.423 26 Titanium dioxide 93.7<000513s5> 0.424 27 Silicon dioxide 32.2 0.085 28 Titanium dioxide 9.4 0.042 Substrate (IV) 29 Titanium dioxide 11.5 0.052 30 Silicon dioxide 38.7 0.103 31 Titanium dioxide 116.7 0.528 32 Silicon dioxide 190.4 0.508 33 TiO2 111.2 0.503 34 SiO2 192.1 0.512 35 TiO2 112.3 0.508 36 SiO2 192.0 0.512 37 TiO2 111.9 0.506 38 SiO2 191.9 0.512 39 TiO2 111.8 0.506 40 SiO2 192.7 0.514 41 TiO2 111.7 0.505 42 SiO2 193.2 0.515 43 TiO2 111.9 0.506 44 SiO2 193.1 0.515 45 TiO2 112.0 0.507 46 SiO2 192.5 0.513 47 TiO2 112.6 0.509 48 SiO2 192.6 0.513 49 TiO2 111.9 0.506 50 SiO2 191.3 0.510 51 TiO2 111.0 0.502 52 SiO2 95.4 0.254

[0343] <Spectrophotometric transmittance> The transmittance of the optical filter in the near-infrared region (650 nm to 800 nm) and the transmittance of the optical filter in the visible light region (430 nm to 580 nm) were measured using a spectrophotometer (V-7200) manufactured by Nippon Spectrophotometer Co., Ltd. The transmittance was measured using the spectrophotometer under conditions where light was incident perpendicularly to the optical filter. The parameters measured using this apparatus are as follows. The results are shown in Table 12. The spectral transmittance spectra of the optical filters obtained in Examples 20 and 28 are shown in Figures 3 and 4, respectively.

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

[0345] [Examples 33-43 and Comparative Example 8] The same procedure as in Example 6 was followed, specifically, the substrate was prepared in the following manner. According to the proportions recorded in Table 13, resin A, compound (X), compound (Y) and dichloromethane were added to prepare a resin solution with a resin concentration of 20% by mass. The solution was then filtered using a microporous filter with a pore size of 5 μm to obtain the resin solution (E-1). According to the proportions recorded in Table 13, resin A, compound (Z) and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass. The solution was then filtered using a microporous filter with a pore size of 5 μm to obtain the resin solution (E-2).

[0346] Using a spin coater, the following resin composition (2) was applied to both sides of a transparent glass support "OA-10G" (200 μm thick) manufactured by Nippon Electric Glass Co., Ltd., which was cut to a size of 200 mm × 200 mm. Then, the solvent was evaporated and removed by heating at 80°C for 2 minutes on a heating plate, 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 later. Furthermore, in Example 39, a near-infrared absorbing glass substrate "BS-11" (200 μm thick) 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, the resin solution (E-1) is coated onto one side of the glass support on which the adhesive layer is formed, with a dried film thickness of 10 μm. The solvent is evaporated and removed by heating at 80°C for 5 minutes on a heating plate, thereby forming a coated resin layer (2). Then, using a spin coater, the resin solution (E-2) is coated onto the other side of the glass support on which the adhesive layer is formed, with a dried film thickness of 10 μm. The solvent is evaporated and removed by heating at 80°C for 5 minutes on a heating plate, thereby forming a coated resin layer (1). Thus, a substrate with a thickness of 222 μm is obtained, which is formed by depositing a resin layer containing compound (Z) on one side of a glass support and depositing a resin layer without compound (Z) on the other side. Furthermore, the values ​​recorded in compounds z-164 to z-173 in Table 13 represent the content (parts by mass) of each compound relative to 100 parts by mass of resin in resin layer (1), and the values ​​recorded in compounds x-1, x-2 and y-1 in Table 13 represent the content (parts by mass) of each compound relative to 100 parts by mass of resin in resin layer (2). The same procedure was performed as in Example 20, and the Xa, Ta~Tf of the substrate were measured. The results are shown in Table 13. The spectral transmittance spectrum of the substrate obtained in Example 36 is shown in Figure 5.

[0348] Resin composition (2): 30 parts by weight of ethylene oxide-modified triacrylate isocyanurate (trade name: Aronix M-315, manufactured by Toa Gosei Co., Ltd.), 20 parts by weight of 1,9-nonanediol diacrylate, 20 parts by weight of methacrylic acid, 30 parts by weight of glycidyl methacrylate, 5 parts by weight of 3-glycidoxypropyltrimethoxysilane, 5 parts by weight of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by BASF Japan Co., Ltd.), and 1 part by weight of San-Aid SI-110 main agent (manufactured by San-Shin Chemical Industry Co., Ltd.) were mixed and dissolved in propylene glycol monomethyl ether acetate at a solid content of 50% by weight. The mixture was then filtered through a microporous filter with a pore size of 0.2 μm.

[0349] Subsequently, similar to Example 20, a dielectric multilayer film (III) consisting of 28 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on one side of the obtained substrate. Then, a dielectric multilayer film (IV) consisting of 24 layers of alternating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers was formed on the other side of the substrate to obtain an optical filter with a thickness of approximately 0.226 mm. Regarding the design of the dielectric multilayer film, similar to Example 20, the same design parameters as in Example 20 were used after taking into account the wavelength dependence of the substrate's refractive index. The same procedure was performed as in Example 20, measuring the Tg and Th of the optical filter. The results are shown in Table 13. The spectral transmittance spectrum of the optical filter obtained in Example 36 is shown in Figure 6.

[0350] [Table 12] Example Comparative example 20 twenty one twenty two twenty three twenty four 25 26 27 28 29 30 31 32 4 5 6 7 resin layer resin (parts by weight) Resin A 100 100 100 100 100 100 - - 100 100 100 100 100 100 - - 100 Resin B - - - - - - 100 - - - - - - - 100 - - Resin C - - - - - - - 100 - - - - - - - 100 - Compound (Z) (parts by weight) z-164 0.1 - - - - - - - 0.1 - - - - - - - - z-165 - 0.13 - - - - - - - - - - - - - - - z-166 - - 0.13 - - - - - - - - - - - - - - z-167 - - - 0.13 - - 0.13 0.13 - - - - - - - - - z-168 - - - - 0.13 - - - - - - - - - - - - z-169 - - - - - z-170 - 0.13 - - - z-171 - - 0.13 - - z-172 - - - 0.13 - z-173 - - - - - 0.13 - - - - - - 0.13 - - - - Compound (X) (parts by weight) x-1 0.035 0.04 0.027 0.03 0.03 0.04 0.03 0.03 0.035 0.03 0.03 0.03 0.03 0.07 0.07 0.07 0.03 x-2 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.08 0.08 0.08 0.01 x-6 - - - - - - - - - - - - - - - - 0.08 Compound (Y) (parts by weight) y-1 - - - - - - - - 0.17 - - - - - - - - optical properties of substrate Xa(nm) 715 719 718 718 718 719 722 719 714 743 738 740 725 712 718 713 717 Ta(%) 0.015 0.014 0.015 0.014 0.014 0.014 0.015 0.018 0.015 0.014 0.015 0.015 0.015 0.015 0.015 0.019 0.021 Tb(%) 88.5 88.4 88.5 89.2 88.4 88.9 89.5 88.8 88.1 89.4 88.7 88.0 88.5 87.2 87.6 86.9 87.6 Tc(%) 0.017 0.016 0.017 0.015 0.017 0.015 0.017 0.019 0.016 0.013 0.014 0.015 0.016 0.017 0.017 0.021 0.025 Td(%) 88.7 88.6 88.7 89.2 88.6 89 89.5 88.9 88.2 89.3 89.1 89.0 88.5 87.1 87.5 86.9 87.4 Te(%) 0.019 0.017 0.019 0.017 0.019 0.017 0.019 0.023 0.017 0.015 0.017 0.017 0.019 0.019 0.019 0.024 0.13 Tf(%) 87.9 87.9 88.1 88.6 88.1 88.4 88.7 88.1 88.1 88.5 88.2 88.0 87.9 86.5 86.9 86.1 85.4 Optics Filter Dielectric multilayer film (III) 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 - Dielectric multilayer (IV) twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four - Optical properties Tg(%) 5.02 4.82 5.02 4.83 4.99 4.83 4.86 4.89 5.00 4.80 4.95 4.90 4.85 5.00 5.03 5.07 - Th(%) 91.2 91.1 91.6 91.6 91.1 91.4 91.6 91.3 91.3 91.5 91.1 91.0 90.9 89.6 89.6 89.2 -

[0351] [Table 13] Example Comparative example 33 34 35 36 37 38 39 40 41 42 43 8 resin layer Resin layer (1) resin Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A z-164 1.0 - - - - - 1.0 - - - - - z-165 - 1.3 - - - - - - - - - - z-166 - - 1.3 - - - - - - - - - z-167 - - - 1.3 - - - - - - - - z-168 - - - - 1.3 - - - - - - - z-169 - - - - - 1.3 - - - - - - z-170 - - - - - - - 1.3 - - - - z-171 - - - - - - - - 1.3 - - - z-172 - - - - - - - - - 1.3 - - z-173 - - - - - - - - - - 1.3 - Resin layer (2) resin Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A Resin A x-1 0.35 0.4 0.27 0.4 0.4 0.4 0.35 0.4 0.4 0.4 0.4 0.7 x-2 0.2 0.1 0.1 0.1 0.1 0.1 0.2 0.1 0.1 0.1 0.1 0.8 y-1 - - - - - - 1.7 - - - - - optical properties of substrate Xa(nm) 715 719 718 718 718 719 714 743 738 740 725 712 Ta(%) 0.015 0.014 0.015 0.014 0.014 0.014 0.012 0.014 0.015 0.015 0.015 0.015 Tb(%) 88.3 88.6 88.3 89.1 88.5 88.8 88.0 89.3 88.6 87.9 88.4 87.1 Tc(%) 0.017 0.016 0.017 0.015 0.017 0.015 0.013 0.013 0.014 0.015 0.016 0.017 Td(%) 88.4 88.5 88.5 89.2 88.3 88.9 88 89.2 89 88.9 88.4 86.9 Te(%) 0.019 0.017 0.019 0.017 0.019 0.017 0.014 0.015 0.017 0.017 0.019 0.019 Tf(%) 88.1 88.1 88.2 88.9 88.2 88.7 88.0 88.4 88.1 87.9 87.8 86.4 Optics filter Dielectric multilayer film (III) 28 28 28 28 28 28 28 28 28 28 28 28 Dielectric multilayer (IV) twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four twenty four Optical properties Tg(%) 5.02 5.01 4.99 4.86 4.97 4.85 4.38 4.80 4.95 4.90 4.85 5.02 Th(%) 91.1 91.2 91.4 91.7 91.2 91.6 90.5 91.4 91.0 90.9 90.8 89.8

[0352] The optical filters obtained in Examples 20 to 43 can reduce the intensity of reflected light, especially in the wavelength region of 700 nm to 750 nm, while maintaining good visible light transmittance. Therefore, in recent years, in photographic devices such as high-performance digital still cameras, the reduction in sensitivity in the visible light region can be minimized, and image defects caused by the reflected light can be eliminated, which is useful.

[0353] none< / irpf> < / dbpf>

Claims

1. A resin composition comprising: a resin, and any one of the compounds represented by the following formulas (z-1), (z-16), (z-62), (z-151), (z-156), (z-157) to (z-163), wherein: Formula (z-1) Formula (z-16) Formula (z-62) Formula (z-151) Formula (z-156) Formula (z-157) Formula (z-158) Formula (z-159) Formula (z-160) Formula (z-161) Formula (z-162) Formula (z-163).

2. A substrate (i) formed from a resin composition as described in claim 1 and containing a compound (Z).

3. The substrate (i) as claimed in claim 2, wherein the substrate (i) is a substrate comprising a resin layer containing the compound (Z); a substrate comprising two or more resin layers, wherein at least one of the two or more resin layers is a resin layer containing the compound (Z); or a substrate comprising a glass support and a resin layer containing the compound (Z).

4. An optical filter having a substrate (i) as described in claim 2 or claim 3, and a dielectric multilayer film.

5. The optical filter as described in claim 4, used in a solid-state imaging device.

6. The optical filter as described in claim 4, used in an optical sensor device.

7. A solid-state imaging apparatus comprising an optical filter as described in claim 4.

8. An optical sensor device comprising an optical filter as described in claim 4.

9. A compound represented by any one of the following formulas (z-1), (z-16), (z-62), (z-151), (z-156), (z-157) to (z-163), where: Formula (z-1) Formula (z-16) Formula (z-62) Formula (z-151) Formula (z-156) Formula (z-157) Formula (z-158) Formula (z-159) Formula (z-160) Formula (z-161) Formula (z-162) Formula (z-163).

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