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

Abstract

The present invention provides a resin composition, a compound, a substrate, an optical filter, a solid-state imaging device, and an optical sensor device which have extremely high absorption at a wavelength near 700 nm to 750 nm or at a wavelength near 720 nm to 900 nm, have a large ratio of absorbance in the infrared region to absorbance in the visible light region, and have excellent light resistance (durability), a compound, a substrate, an optical filter, a solid-state imaging device, and an optical sensor device. A resin composition containing a resin and a compound represented by formula (I) [in formula (I), Cn + is a monovalent cation represented by formula (II), and An-is a monovalent anion]. Cn + A < n-I > # imgabs0 #

Description

[0001] The present invention is a divisional application of the invention patent application with application number 202110188611.3 filed on February 19, 2021, and invention name “Resin composition, compound, substrate, optical filter, solid-state imaging device and optical sensor device”. Technical Field

[0002] The present invention relates to a resin composition, a compound, a substrate, an optical filter, and a solid-state imaging device and an optical sensor device using the optical filter. Background Art

[0003] In solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions, charge coupled devices (CCD) or complementary metal oxide semiconductor (CMOS) image sensors are used as solid-state imaging elements for color images. In these solid-state imaging elements, silicon photodiodes that are sensitive to near-infrared rays that are not perceptible to the human eye are used in their light receiving parts. In addition, silicon photodiodes are also used in optical sensor devices. For example, in solid-state imaging elements, it is often necessary to perform visual sensitivity correction to present natural colors to the human eye, and use optical filters (for example, near-infrared cutoff filters) that selectively transmit or cut off light in a specific wavelength region.

[0004] As such near-infrared cut-off filters, filters manufactured by various methods have been used in the past. For example, there is known a near-infrared cut-off filter using a resin as a base material and containing a near-infrared absorbing pigment in the resin (see, for example, Patent Document 1). However, the near-infrared cut-off filter described in Patent Document 1 may not necessarily have sufficient near-infrared absorption characteristics.

[0005] [Prior art literature]

[0006] [Patent Document]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2008-303130 Summary of the invention

[0008] [Problems to be solved by the invention]

[0009] As the near-infrared absorbing dye, polymethine-based, squarylium-based, porphyrin-based, dithiol metal complex-based, phthalocyanine-based, diimmonium-based and other dyes have been conventionally used. Among them, polymethine-based and squarylium-based dyes are often used because they have sufficient resistance to heat.

[0010] However, these pigments that have been used previously have room for improvement in at least any of the following aspects:

[0011] Since the absorption maximum wavelength is in the long wavelength region, it is required to have a compound with an absorption maximum near the wavelength of 700nm to 750nm or near the wavelength of 720nm to 900nm;

[0012] The absorbance in the infrared region is smaller than that in the visible region.

[0013] The light resistance (durability) is not sufficient.

[0014] In addition, in previous near-infrared cutoff filters, reflected light from the filter sometimes causes adverse effects on images such as camera images in the form of flare 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.

[0015] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition having an absorption maximum near a wavelength of 700nm to 750nm or near a wavelength of 720nm to 900nm, a large ratio of absorbance in the infrared region to absorbance in the visible light region, and excellent light resistance (durability).

[0016] [Technical means to solve the problem]

[0017] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by the following structural examples, thereby completing the present invention. The structural examples of the present invention are shown below.

[0018] In the present invention, the description of "A to B" and the like indicating a numerical range has the same meaning as "A or more and B or less", and A and B are included in the numerical range. In the present invention, wavelength A nm to B nm refers to the characteristic of wavelength resolution at 1 nm in a wavelength region of wavelength A nm or more and wavelength B nm or less.

[0019] [1] A resin composition comprising: a resin and a compound (Z) represented by the following formula (I),

[0020] Cn + An -(I)

[0021] [In formula (I), Cn + is a monovalent cation represented by the following formula (II), An - is a monovalent anion]

[0022] [Chemistry 1]

[0023]

[0024] [In formula (II),

[0025] Unit A is any one of the following formulas (AI) to (A-III),

[0026] Unit B is any one of the following formulas (BI) to (B-III),

[0027] Y A ~Y E are independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, -NR g R h group, amide group, imide group, cyano group, silane group, -Q 1 、-N=NQ 1 、-SQ 2 ,-SSQ 2 , or -SO2Q 3 ,

[0028] Y A With Y C , Y B With Y D , Y C With Y E may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4- to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 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 a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom; and the alicyclic group may have =O,

[0029] Y A and R in the following formula (A-III) 1 or R 5 , Y E and R in the following formula (B-III) 5 or R 1 may be bonded to each other to form a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom,

[0030] R g and R hare independently a hydrogen atom, -C(O)R i Base or the following L a ~L h Any one of Q 1 Independently, the following L a ~L h Any one of Q 2 are independently a hydrogen atom or the following L a ~L h Any one of Q 3 is hydroxyl or the following L a ~L h Any one of R i For the following L a ~L h Any of]

[0031] [Chemistry 2]

[0032]

[0033] [-* in formula (AI) to formula (A-III) represents the same as Y in formula (II) A The carbon to which it is bonded is single-bonded.

[0034] =** in formula (BI) to formula (B-III) represents the same as Y in formula (II). E The carbons to which they are bonded are double bonded.

[0035] In formula (AI) to formula (B-III),

[0036] X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR 8 -,

[0037] R 1 ~R 6 are independently a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR g R h Base, -SR i Base, -SO2R i Base, -OSO2R i Base, -C(O)R i Base or the following L a ~L h Any one of

[0038] Adjacent R 1 ~R 6may be bonded to each other to form an aromatic hydrocarbon group having 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 having 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 a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom; and the alicyclic group may have =O,

[0039] R 8 are independently a hydrogen atom, a halogen atom, -C(O)R i Base, the following L a ~L h Any one of

[0040] R g and R h are independently a hydrogen atom, -C(O)R i Base or the following L a ~L h Any one of

[0041] R i Independently, the following L a ~L h Any one of

[0042] (L a ): an aliphatic hydrocarbon group having 1 to 15 carbon atoms

[0043] (L b ):C1-15 halogen-substituted alkyl

[0044] (L c ): an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K

[0045] (L d ): an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K

[0046] (L e ): a heterocyclic group having 3 to 14 carbon atoms which may have a substituent K

[0047] (L f ): -OR (R is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L)

[0048] (L g ): an acyl group having 1 to 9 carbon atoms which may have a substituent L

[0049] (L h ) : an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L

[0050] The substituent K is selected from L a ~L bAt least one of the substituents L is selected from the L a ~L f at least one of].

[0051] [2] The resin composition according to [1], wherein the compound (Z) satisfies the following requirement (A),

[0052] Requirement (A): In the transmission spectrum measured using a solution of the compound (Z) dissolved in dichloromethane (wherein the transmission spectrum is a spectrum with a transmittance of 10% at the absorption maximum wavelength), the average transmittance at a wavelength of 430 nm to 580 nm is 93% or more.

[0053] [3] The resin composition according to [1] or [2], wherein R 1 ~R 6 At least one of the L a , L c or L d .

[0054] [4] The resin composition according to any one of [1] to [3], wherein the compound (Z) satisfies the following requirement (B-1),

[0055] Requirement (B-1): In an absorption spectrum measured using a solution prepared by dissolving the compound (Z) in dichloromethane, the compound (Z) has a local maximum in a wavelength range of 720 nm to 900 nm.

[0056] [5] The resin composition according to any one of [1] to [3], wherein the compound (Z) satisfies the following requirement (B-2),

[0057] Requirement (B-2): In an absorption spectrum measured using a solution prepared by dissolving the compound (Z) in dichloromethane, the compound (Z) has a local maximum in a wavelength range of 700 nm to 750 nm.

[0058] [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, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curable resins, silsesquioxane UV curable resins, acrylic UV curable resins and vinyl UV curable resins.

[0059] [7] A substrate (i) comprising the resin composition according to any one of [1] to [6] and containing a compound (Z).

[0060] [8] The substrate (i) according to [7], wherein the substrate (i) is the following substrate:

[0061] A substrate comprising a resin layer containing the compound (Z);

[0062] A substrate comprising two or more resin layers, at least one of the two or more resin layers being a resin layer containing the compound (Z); or

[0063] A substrate comprising a glass support and a resin layer containing the compound (Z).

[0064] [9] An optical filter comprising the substrate (i) according to [7] or [8], and a dielectric multilayer film.

[0065]

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

[0066]

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

[0067]

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

[0068]

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

[0069]

[14] A compound (Z) represented by the following formula (III):

[0070] Cn + An - (III)

[0071] [In formula (III), Cn + is a monovalent cation represented by the following formula (IV), An - is a monovalent anion]

[0072] [Chemistry 3]

[0073]

[0074] [In formula (IV),

[0075] Unit A is any one of the following formulas (AI) to (A-III),

[0076] Unit B is any one of the following formulas (BI) to (B-III),

[0077] YA ~Y E are independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, -NR g R h group, amide group, imide group, cyano group, silane group, -Q 1 、-N=NQ 1 、-SQ 2 ,-SSQ 2 , or -SO2Q 3 ,

[0078] Y A With Y C , Y B With Y D , Y C With Y E may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4- to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 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 a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom; and the alicyclic group may have =O,

[0079] Y A and R in the following formula (A-III) 1 or R 5 , Y E and R in the following formula (B-III) 5 or R 1 may be bonded to each other to form a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom,

[0080] R g and R h are independently a hydrogen atom, -C(O)R i Base or the following L a ~L h Any one of Q 1 Independently, the following L a ~L h Any one of Q 2 are independently a hydrogen atom or the following L a ~L h Any one of Q 3 is hydroxyl or the following L a ~L h Any one of R i For the following L a ~L h Any of]

[0081] [Chemistry 4]

[0082]

[0083] [-* in formula (AI) to formula (A-III) represents the same as Y in formula (II) A The carbon to which it is bonded is single-bonded.

[0084] =** in formula (BI) to formula (B-III) represents the same as Y in formula (II). E The carbons to which they are bonded are double bonded.

[0085] In formula (AI) to formula (B-III),

[0086] X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR 8 -,

[0087] R 1 ~R 6 are independently a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR g R h Base, -SR i Base, -SO2R i Base, -OSO2R i Base, -C(O)R i Base or the following L a ~L h Any one of

[0088] Adjacent R 1 ~R 6 may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4- to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 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 a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom; and the alicyclic group may have =O,

[0089] R 8 are independently a hydrogen atom, a halogen atom, -C(O)R i Base, the following L a ~L h Any one of

[0090] R g and R h are independently a hydrogen atom, -C(O)R i Base or the following L a ~L h Any one of

[0091] R iIndependently, the following L a ~L h Any one of

[0092] (L a ): an aliphatic hydrocarbon group having 1 to 15 carbon atoms

[0093] (L b ):C1-15 halogen-substituted alkyl

[0094] (L c ): an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K

[0095] (L d ): an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K

[0096] (L e ): a heterocyclic group having 3 to 14 carbon atoms which may have a substituent K

[0097] (L f ): -OR (R is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L)

[0098] (L g ): an acyl group having 1 to 9 carbon atoms which may have a substituent L

[0099] (L h ) : an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L

[0100] The substituent K is selected from L a ~L b At least one of the substituents L is selected from the L a ~L f at least one of].

[0101] [Effects of the Invention]

[0102] According to the present invention, a resin composition having an absorption maximum near a wavelength of 700nm to 750nm or near a wavelength of 720nm to 900nm, a large ratio of the absorbance in the infrared region to the absorbance in the visible region, and sufficient resistance to heat or light can be provided. Furthermore, according to the present invention, an optical filter having these characteristics, in particular, fully shielding light in the infrared region and being able to transmit light in the visible region at a high ratio can be provided. Therefore, according to the present invention, not only a near infrared ray cut-off filter (NIR-CF) can be easily produced, but also an optical filter such as a visible light-near infrared selective transmission filter (dual bandpass filter (DBPF)) or a near infrared transmission filter (IRPF) can be easily produced.

[0103] In the present invention, sufficient resistance to heat or light means that the optical characteristics do not change significantly before and after application of heat or irradiation of light.

[0104] As described above, according to the present invention, an optical filter having the above characteristics can be provided, so that an optical filter that can suppress reflected light of light having a wavelength of about 700nm to 750nm or a wavelength of about 720nm to 900nm and can provide a good image with less flare or ghosting can be easily obtained. In addition, when the optical filter is a filter having a dielectric multilayer film, the incident angle dependency caused by the dielectric multilayer film can be suppressed. BRIEF DESCRIPTION OF THE DRAWINGS

[0105] Figure 1 This is the spectral transmittance spectrum of the substrate obtained in Example 20.

[0106] Figure 2 This is the spectral transmittance spectrum of the substrate obtained in Example 28.

[0107] Figure 3 This is the spectral transmittance spectrum of the optical filter obtained in Example 20.

[0108] Figure 4 This is the spectral transmittance spectrum of the optical filter obtained in Example 28.

[0109] Figure 5 This is the spectral transmittance spectrum of the substrate obtained in Example 36.

[0110] Figure 6 It is the spectral transmittance spectrum of the optical filter obtained in Example 36. DETAILED DESCRIPTION

[0111] 《Resin composition》

[0112] The resin composition of the present invention (hereinafter also referred to as "the present composition") is not particularly limited as long as it contains a resin and the compound (Z).

[0113] Examples of the form of such a resin composition include: a resin film (resin layer, resin substrate) containing a compound (Z); a resin film (resin layer) containing a compound (Z) formed on a support (e.g., a resin support, a glass support); and a liquid composition containing a resin, a compound (Z) and a solvent.

[0114] The present composition may contain two or more resins, and may contain two or more compounds (Z).

[0115] <Compound (Z)>

[0116] Compound (Z) is a compound represented by the following formula (I).

[0117] The compound (Z) has high near-infrared cutoff performance and high visible light transmittance at an absorption maximum near a wavelength of 700 nm to 750 nm or near a wavelength of 720 nm to 900 nm, is excellent in optical properties, and has sufficient resistance to heat and light.

[0118] Cn + An - (I)

[0119] [In formula (I), Cn + is a monovalent cation represented by the following formula (II), An - is a monovalent anion]

[0120] [Chemistry 5]

[0121]

[0122] [In formula (II),

[0123] Unit A is any one of the following formulas (AI) to (A-III),

[0124] Unit B is any one of the following formulas (BI) to (B-III),

[0125] Y A ~Y E are independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, -NR g R h group, amide group, imide group, cyano group, silane group, -Q 1 、-N=NQ 1 、-SQ2 ,-SSQ 2 , or -SO2Q 3 ,

[0126] Y A With Y C , Y B With Y D , Y C With Y E may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4- to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 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 a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom; and the alicyclic group may have =O,

[0127] Y A and R in the following formula (A-III) 1 or R 5 , Y E and R in the following formula (B-III) 5 or R 1 may be bonded to each other to form a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom,

[0128] R g and R h are independently a hydrogen atom, -C(O)R i Base or the following L a ~L h Any one of Q 1 Independently, the following L a ~L h Any one of Q 2 are independently a hydrogen atom or the following L a ~L h Any one of Q 3 is hydroxyl or the following L a ~L h Any one of R i For the following L a ~L h Any of]

[0129] [Chemistry 6]

[0130]

[0131] [-* in formula (AI) to formula (A-III) represents the same as Y in formula (II) A The carbon to which it is bonded is single-bonded.

[0132] =** in formula (BI) to formula (B-III) represents the same as Y in formula (II). E The carbons to which they are bonded are double bonded.

[0133] In formula (AI) to formula (B-III),

[0134] X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR 8 -,

[0135] R 1 ~R 6 are independently a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR g R h Base, -SR i Base, -SO2R i Base, -OSO2R i Base, -C(O)R i Base or the following L a ~L h Any one of

[0136] Adjacent R 1 ~R 6 may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4- to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 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 a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom; and the alicyclic group may have =O,

[0137] R 8 are independently a hydrogen atom, a halogen atom, -C(O)R i Base, the following L a ~L h Any one of

[0138] R g and R h are independently a hydrogen atom, -C(O)R i Base or the following L a ~L h Any one of

[0139] R i Independently, the following L a ~L h Any one of

[0140] (L a ): an aliphatic hydrocarbon group having 1 to 15 carbon atoms

[0141] (Lb ):C1-15 halogen-substituted alkyl

[0142] (L c ): an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K

[0143] (L d ): an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K

[0144] (L e ): a heterocyclic group having 3 to 14 carbon atoms which may have a substituent K

[0145] (L f ): -OR (R is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L)

[0146] (L g ): an acyl group having 1 to 9 carbon atoms which may have a substituent L

[0147] (L h ) : an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L

[0148] The substituent K is selected from L a ~L b At least one of the substituents L is selected from the L a ~L f At least one of]

[0149] In addition, the compound (Z) of the present invention is a compound represented by the following formula (III).

[0150] Cn + An - (III)

[0151] [In formula (III), Cn + is a monovalent cation represented by the following formula (IV), An - is a monovalent anion]

[0152] [Chemistry 7]

[0153]

[0154] [In formula (IV),

[0155] Unit A is any one of the following formulas (AI) to (A-III),

[0156] Unit B is any one of the following formulas (BI) to (B-III),

[0157] Y A ~Y Eare independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, -NR g R h group, amide group, imide group, cyano group, silane group, -Q 1 、-N=NQ 1 、-SQ 2 ,-SSQ 2 , or -SO2Q 3 ,

[0158] Y A With Y C , Y B With Y D , Y C With Y E may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4- to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 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 a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom; and the alicyclic group may have =O,

[0159] Y A and R in the following formula (A-III) 1 or R 5 , Y E and R in the following formula (B-III) 5 or R 1 may be bonded to each other to form a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom,

[0160] R g and R h are independently a hydrogen atom, -C(O)R i Base or the following L a ~L h Any one of Q 1 Independently, the following L a ~L h Any one of Q 2 are independently a hydrogen atom or the following L a ~L h Any one of Q 3 is hydroxyl or the following L a ~L h Any one of R i For the following L a ~L h Any of]

[0161] [Chemistry 8]

[0162]

[0163] [-* in formula (AI) to formula (A-III) represents the same as Y in formula (II) A The carbon to which it is bonded is single-bonded.

[0164] =** in formula (BI) to formula (B-III) represents the same as Y in formula (II). E The carbons to which they are bonded are double bonded.

[0165] In formula (AI) to formula (B-III),

[0166] X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR 8 -,

[0167] R 1 ~R 6 are independently a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR g R h Base, -SR i Base, -SO2R i Base, -OSO2R i Base, -C(O)R i Base or the following L a ~L h Any one of

[0168] Adjacent R 1 ~R 6 may be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4- to 7-membered alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 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 a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom; and the alicyclic group may have =O,

[0169] R 8 are independently a hydrogen atom, a halogen atom, -C(O)R i Base, the following L a ~L h Any one of

[0170] R g and R h are independently a hydrogen atom, -C(O)R i Base or the following L a ~L h Any one of

[0171] R i Independently, the following L a ~Lh Any one of

[0172] (L a ): an aliphatic hydrocarbon group having 1 to 15 carbon atoms

[0173] (L b ):C1-15 halogen-substituted alkyl

[0174] (L c ): an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K

[0175] (L d ): an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K

[0176] (L e ): a heterocyclic group having 3 to 14 carbon atoms which may have a substituent K

[0177] (L f ): -OR (R is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent L)

[0178] (L g ): an acyl group having 1 to 9 carbon atoms which may have a substituent L

[0179] (L h ) : an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L

[0180] The substituent K is selected from L a ~L b At least one of the substituents L is selected from the L a ~L f At least one of]

[0181] Furthermore, the -NR 8 - is a group represented by the following formula (a), wherein -NR g R h The group is a group represented by the following formula (b), wherein -SR i The group is a group represented by the following formula (c), wherein -SO2R i The group is a group represented by the following formula (d), wherein -OSO2R i The group is a group represented by the following formula (e), wherein -C(O)R i The group is a group represented by the following formula (f).

[0182] In addition, the -SSQ 2 For-SSQ 2 The group represented by -SO2Q 3 In the group represented by the following formula (d), R i Replaced by Q3 The basis formed.

[0183] [Chemistry 9]

[0184]

[0185] Furthermore, when the unit A is the formula (AI) and the unit B is the formula (BI), Cn + It is represented by the following formula (II-1). That is, the single bond (-) of "*-" in the above formula (AI) to formula (A-III) corresponds to Y in the above formula (II) or formula (IV). A The single bond between the carbon atom and the unit A, the double bond (=) of "**=" in the formula (BI) to (B-III) is equivalent to Y in the formula (II) or (IV) E Double bond between the bonded carbon atom and unit B.

[0186] [Chemistry 10]

[0187]

[0188] The Y B and Y D More preferably, each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, B and Y D A 4- to 6-membered alicyclic hydrocarbon group formed by bonding to each other (the alicyclic hydrocarbon group may have a substituent R selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a hydroxyl group, a halogen atom, and =O 9 ).

[0189] Furthermore, for Y B and Y D In the case of 4- to 6-membered alicyclic hydrocarbon groups bonded to each other, Formula (II) or Formula (IV) can be preferably represented by the following Formula (CI) to Formula (C-III), respectively.

[0190] [Chemistry 11]

[0191]

[0192] [Chemistry 12]

[0193]

[0194] [Chemistry 13]

[0195]

[0196] As a substituent R 9, preferably a hydrogen atom, a hydroxyl group, =O, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, or a cyclohexyl group, and more preferably a hydrogen atom, a hydroxyl group, =O, a methyl group, an ethyl group, or a tert-butyl group.

[0197] The Y A , Y C and Y E More preferably, each independently represents a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a hydroxyl group, a phenylamino group (NHPh), a diphenylamino group, a methylphenylamino group, a dimethylamino group, a methyl group, a methoxy group, a phenyl group, a phenoxy group, a 4-methylphenoxy group, a methylthio group, a phenylthio group, or an -S-(4-tolyl) group (-S-(4-tolyl) group).

[0198] The L a Preferred are methyl (Me), ethyl (Et), n-propyl, isopropyl (i-Pr), n-butyl, sec-butyl, tert-butyl (tert-Bu), pentyl, hexyl, octyl, nonyl, decyl and dodecyl, and more preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

[0199] The L a It may also be an alkenyl group such as vinyl, 1-propenyl, 2-propenyl, butenyl, 1,3-butadienyl, 2-methyl-1-propenyl, 2-pentenyl, and hexenyl; or an alkynyl group such as ethynyl, propynyl, butynyl, 2-methyl-1-propynyl, and hexynyl.

[0200] As the L b The halogen-substituted alkyl group having 1 to 15 carbon atoms in the alkyl group may be a group in which at least one hydrogen atom of the alkyl group having 1 to 15 carbon atoms is substituted with a halogen atom, preferably a trichloromethyl group, a trifluoromethyl group, a 1,1-dichloroethyl group, a pentachloroethyl group, a pentafluoroethyl group, a heptachloropropyl group, or a heptafluoropropyl group.

[0201] As the L c The alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K in the formula (I) may preferably include cycloalkyl groups such as cyclopropyl, cyclopropylmethyl, methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl and cyclooctyl; and polycyclic alicyclic groups such as norbornyl and adamantyl.

[0202] As the L d The aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K is preferably phenyl, tolyl, xylyl, mesityl (trimethylphenyl), cumyl, bis(trifluoromethyl)phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenanthryl, or benzyl (CH2Ph).

[0203] As the L eThe heterocyclic group having 3 to 14 carbon atoms which may have a substituent K is preferably furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, morpholine or pyridine.

[0204] As the L f The -OR in the above-mentioned group is preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a methoxymethyl group, a methoxyethyl group, a pentyloxy group, a hexyloxy group, an octyloxy group, a phenoxy group (OPh), a 4-methylphenoxy group or a cyclohexyloxy group.

[0205] As the L g The acyl group having 1 to 9 carbon atoms which may have a substituent L is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group, or a trifluoromethylcarbonyl group.

[0206] As the L h The alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group.

[0207] The X is preferably an oxygen atom, a sulfur atom, -NR 8 -, and an oxygen atom is particularly preferred.

[0208] In formula (II) or formula (IV), the left and right units A and B may be the same or different, but are preferably the same because synthesis is easy.

[0209] Here, the same combinations of unit A and unit B are formula (AI) and formula (BI), formula (A-II) and formula (B-II), and formula (A-III) and formula (B-III).

[0210] The R 1 ~R 6Preferably, each independently is a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a 1,1-dimethylbutyl group, a cyclopropyl group, a cyclopropylmethyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,4,6-trimethylphenyl group, a 3,5-bis(trifluoromethyl)phenyl group, a hydroxyl group, an amino group, a dimethylamino group (NMe2), a diethylamino group (NEt2), a dibutylamino group (N(n-Bu)2), a cyano group, a nitro group, Acetylamino, propionylamino, N-methylacetylamino, trifluoroformylamino, pentafluoroacetylamino, tert-butyrylamino, cyclohexanoylamino, n-butylsulfonyl, benzyl, diphenylmethyl, trifluoromethyl, difluoromethyl, methoxy, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclohexyl, phenyl, amino, benzyl, diphenylmethyl, trifluoromethyl, difluoromethyl, methoxy.

[0211] The above R is preferred in terms of being able to easily obtain a compound having high near-infrared cutoff performance and high visible light transmittance at an absorption maximum near a wavelength of 700 nm to 750 nm or near a wavelength of 720 nm to 900 nm, excellent optical properties, and sufficient resistance to heat or light. 1 ~R 6 At least one of the L a , L c or L d Furthermore, when the unit A is the formula (A-III) and the unit B is the formula (B-III), "R 1 ~R 6 At least one of L a , L c or L d ” means “R 1 , R 2 , R 4 , R 5 At least one of L a , L c or L d ”.

[0212] As the R 8 , preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, benzyl, n-pentyl, n-hexyl, or tert-butyl, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, or benzyl.

[0213] As the An - If it is a monovalent anion, there is no particular limitation, and preferably, the following may be mentioned: chloride ion, bromide ion, iodide ion, PF4 -, perchlorate anion, tris-trifluoromethanesulfonyl methide anion, tetrafluoroborate anion, hexafluorophosphate anion, bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonate anion, tetrakis(pentafluorophenyl)borate anion, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion, and the like, more preferably bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonate anion, tris-trifluoromethanesulfonyl methide anion, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion (pentafluorophenyl)borate anion, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion, and bis(trifluoromethanesulfonyl)imide anion, tris-trifluoromethanesulfonyl methide anion, tetrakis(pentafluorophenyl)borate anion, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion are more preferred from the perspective of easily obtaining a compound (Z) having better heat resistance, and tetrakis(pentafluorophenyl)borate anion is particularly preferred.

[0214] Specific examples of the compound represented by formula (I) or formula (III) include compounds (z-1) to (z-173) shown in Tables 1 to 4 below.

[0215] Specifically, these compounds (Z) can be synthesized, for example, by the method described in the following Examples.

[0216] [Table 1]

[0217] Compound A, B X <![CDATA[Y A ,AND E ]]> <![CDATA[Y B ,AND D ]]> <![CDATA[Y C ]]> <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> <![CDATA[R 6 ]]> An (z-1) (A-I), (B-I) O H H Cl H tert-Bu H H i-Pr H <![CDATA[B(C6F5)4]]> (z-2) (A-I), (B-I) N H H H H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-3) (A-I), (B-I) S H H H H tert-Bu H H H H <![CDATA[B(C6F5)4 <!-- 13 -->]]> (z-4) (A-I), (B-I) O <![CDATA[CH3]]> H H H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-5) (A-I), (B-I) O H H F H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-6) (A-I), (B-I) O H H Cl H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-7) (A-I), (B-I) O H H Br H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-8) (A-I), (B-I) O H H <![CDATA[CH3]]> H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-9) (A-I), (B-I) O H H <![CDATA[OCH3]]> H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-10) (A-I), (B-I) O H H OPh H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-11) (A-I), (B-I) O H H <![CDATA[N(CH3)2]]> H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-12) (A-I), (B-I) O H H NHPh H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-13) (A-I), (B-I) O H H <![CDATA[NPh2]]> H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-14) (A-I), (B-I) O H H <![CDATA[SCH3]]> H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-15) (A-I), (B-I) O H H SPh H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-16) (A-I), (B-I) O H H H H Ph H H H H <![CDATA[B(C6F5)4]]> (z-17) (A-I), (B-I) O H H H H i-Pr H H H H <![CDATA[B(C6F5)4]]> (z-18) (A-I), (B-I) O H H H H Cyclopropyl H H H H <![CDATA[B(C6F5)4]]> (z-19) (A-I), (B-I) O H H H H Cyclopropylmethyl H H H H <![CDATA[B(C6F5)4]]> (z-20) (A-I), (B-I) O H H H H Cyclohexyl H H H H <![CDATA[B(C6F5)4]]> (z-21) (A-I), (B-I) O H H H H Adamantyl H H H H <![CDATA[B(C6F5)4]]> (z-22) (A-I), (B-I) O H H H H 2,4,6-Trimethylphenyl H H H H <![CDATA[B(C6F5)4]]> (z-23) (A-I), (B-I) O H H H H 3,5-Bis(trifluoromethyl)phenyl H H H H <![CDATA[B(C6F5)4 <!-- 14 -->]]> (z-24) (A-I), (B-I) O H H H H tert-Bu Cl H H H <![CDATA[B(C6F5)4]]> (z-25) (A-I), (B-I) O H H H H tert-Bu Br H H H <![CDATA[B(C6F5)4]]> (z-26) (A-I), (B-I) O H H H H tert-Bu Ph H H H <![CDATA[B(C6F5)4]]> (z-27) (A-I), (B-I) O H H H H tert-Bu Me H H H <![CDATA[B(C6F5)4]]> (z-28) (A-I), (B-I) O H H H H tert-Bu i-Pr H H H <![CDATA[B(C6F5)4]]> (z-29) (A-I), (B-I) O H H H H tert-Bu <![CDATA[NHCOCF3]]> H H H <![CDATA[B(C6F5)4]]> (z-30) (A-I), (B-I) O H H H H tert-Bu H F H H <![CDATA[B(C6F5)4]]> (z-31) (A-I), (B-I) O H H H H tert-Bu H Cl H H <![CDATA[B(C6F5)4]]> (z-32) (A-I), (B-I) O H H H H tert-Bu H Br H H <![CDATA[B(C6F5)4]]> (z-33) (A-I), (B-I) O H H H H tert-Bu H Me H H <![CDATA[B(C6F5)4]]> (z-34) (A-I), (B-I) O H H H H tert-Bu H i-Pr H H <![CDATA[B(C6F5)4]]> (z-35) (A-I), (B-I) O H H H H tert-Bu H <![CDATA[OCH3]]> H H <![CDATA[B(C6F5)4]]> (z-36) (A-I), (B-I) O H H H H tert-Bu H <![CDATA[CF3]]> H H <![CDATA[B(C6F5)4]]> (z-37) (A-I), (B-I) O H H H H tert-Bu H H F H <![CDATA[B(C6F5)4]]> (z-38) (A-I), (B-I) O H H H H tert-Bu H H Cl H <![CDATA[B(C6F5)4]]> (z-39) (A-I), (B-I) O H H H H tert-Bu H H Br H <![CDATA[B(C6F5)4]]> (z-40) (A-I), (B-I) O H H H H tert-Bu H H Me H <![CDATA[B(C6F5)4]]> (z-41) (A-I), (B-I) O H H H H tert-Bu H H i-Pr H <![CDATA[B(C6F5)4]]> (z-42) (A-I), (B-I) O H H H H tert-Bu H H <![CDATA[OCH3]]> H <![CDATA[B(C6F5)4]]> (z-43) (A-I), (B-I) O H H H H tert-Bu H H <![CDATA[NHCOCF3]]> H <![CDATA[B(C6F5)4]]> (z-44) (A-I), (B-I) O H H H H tert-Bu H H H F <![CDATA[B(C6F5)4]]> (z-45) (A-I), (B-I) O H H H H tert-Bu H H H Cl <![CDATA[B(C6F5)4 <!-- 15 -->]]> (z-46) (A-I), (B-I) O H H H H tert-Bu H H H Br <![CDATA[B(C6F5)4]]> (z-47) (A-I), (B-I) O H H H H tert-Bu H H H H <![CDATA[N(SO2CF3)2]]> (z-48) (A-I), (B-I) O H H H H tert-Bu H H H H <![CDATA[C(SO2CF3)3]]> (z-49) (A-I), (B-I) O H H H H tert-Bu H H H H <![CDATA[BF4]]> (z-50) (A-I), (B-I) O H H H H tert-Bu H H H H <![CDATA[ClO4]]>

[0218] [Table 2]

[0219] Compound A, B X <![CDATA[Y A ,AND E ]]> <![CDATA[Y B ,AND D ]]> <![CDATA[Y C ]]> <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> <![CDATA[R 6 ]]> An (z-51) (A-I), (B-I) O H H H H tert-Bu H H H H <![CDATA[PF4]]> (z-52) (A-I), (B-I) O H H H H tert-Bu H H H H Cl (z-53) (A-I), (B-I) O H 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 <![CDATA[B(C6F5)4]]> (z-56) (A-I), (B-I) O H H Cl H tert-Bu H H Cl H <![CDATA[B(C6F5)4]]> (z-57) (A-I), (B-I) O H H Cl H tert-Bu H H Br H <![CDATA[B(C6F5)4]]> (z-58) (A-I), (B-I) O H H Cl H tert-Bu H H Me H <![CDATA[B(C6F5)4]]> (z-59) (A-I), (B-I) O H H H H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-60) (A-I), (B-I) O H H Cl H tert-Bu H H <![CDATA[OCH3]]> H <![CDATA[B(C6F5)4]]> (z-61) (A-I), (B-I) O H H Cl H tert-Bu H H <![CDATA[NHCOCF3]]> H <![CDATA[B(C6F5)4]]> (z-62) (A-I), (B-I) O H H H H i-Pr H F H H <![CDATA[B(C6F5)4]]> (z-63) (A-I), (B-I) O H H H H i-Pr H Cl H H <![CDATA[B(C6F5)4]]> (z-64) (A-I), (B-I) O H H H H i-Pr H Br H H <![CDATA[B(C6F5)4]]> (z-65) (A-I), (B-I) O H H H H i-Pr H Me H H <![CDATA[B(C6F5)4]]> (z-66) (A-I), (B-I) O H H H H i-Pr H i-Pr H H <![CDATA[B(C6F5)4 <!-- 16 -->]]> (z-67) (A-I), (B-I) O H H H H i-Pr H <![CDATA[OCH3]]> H H <![CDATA[B(C6F5)4]]> (z-68) (A-I), (B-I) O H H H H i-Pr H <![CDATA[CF3]]> H H <![CDATA[B(C6F5)4]]> (z-69) (A-I), (B-I) O H H H H Ph H H F H <![CDATA[B(C6F5)4]]> (z-70) (A-I), (B-I) O H H H H Ph H H Cl H <![CDATA[B(C6F5)4]]> (z-71) (A-I), (B-I) O H H H H Ph H H Br H <![CDATA[B(C6F5)4]]> (z-72) (A-I), (B-I) O H H H H Ph H H Me H <![CDATA[B(C6F5)4]]> (z-73) (A-I), (B-I) O H H H H Ph H H i-Pr H <![CDATA[B(C6F5)4]]> (z-74) (A-I), (B-I) O H H H H Ph H H <![CDATA[OCH3]]> H <![CDATA[B(C6F5)4]]> (z-75) (A-I), (B-I) O H H H H Ph H H <![CDATA[NHCOCF3]]> H <![CDATA[B(C6F5)4]]> (z-76) (A-II), (B-II) N H H H H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-77) (A-II), (B-II) S H H H H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-78) (A-II), (B-II) O <![CDATA[CH3]]> H H H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-79) (A-II), (B-II) O H H F H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-80) (A-II), (B-II) O H H Cl H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-81) (A-II), (B-II) O H H Br H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-82) (A-II), (B-II) O H H <![CDATA[CH3]]> H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-83) (A-II), (B-II) O H H <![CDATA[OCH3]]> H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-84) (A-II), (B-II) O H H OPh H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-85) (A-II), (B-II) O H H <![CDATA[N(CH3)2]]> H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-86) (A-II), (B-II) O H H NHPh H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-87) (A-II), (B-II) O H H <![CDATA[NPh2]]> H tert-Bu H H H H <![CDATA[B(C6F5)4 <!-- 17 -->]]> (z-88) (A-II), (B-II) O H H <![CDATA[SCH3]]> H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-89) (A-II), (B-II) O H H SPh H tert-Bu H H H H <![CDATA[B(C6F5)4]]> (z-90) (A-II), (B-II) O H H H H Ph H H H H <![CDATA[B(C6F5)4]]> (z-91) (A-II), (B-II) O H H H H i-Pr H H H H <![CDATA[B(C6F5)4]]> (z-92) (A-II), (B-II) O H H H H Cyclopropyl H H H H <![CDATA[B(C6F5)4]]> (z-93) (A-II), (B-II) O H H H H Cyclopropylmethyl H H H H <![CDATA[B(C6F5)4]]> (z-94) (A-II), (B-II) O H H H H Cyclohexyl H H H H <![CDATA[B(C6F5)4]]> (z-95) (A-II), (B-II) O H H H H Adamantyl H H H H <![CDATA[B(C6F5)4]]> (z-96) (A-II), (B-II) O H H H H 2,4,6-Trimethylphenyl H H H H <![CDATA[B(C6F5)4]]> (z-97) (A-II), (B-II) O H H H H 3,5-Bis(trifluoromethyl)phenyl H H H H <![CDATA[B(C6F5)4]]> (z-98) (A-II), (B-II) O H H H H tert-Bu Cl H H H <![CDATA[B(C6F5)4]]> (z-99) (A-II), (B-II) O H H H H tert-Bu Br H H H <![CDATA[B(C6F5)4]]> (z-100) (A-II), (B-II) O H H H H tert-Bu Ph H H H <![CDATA[B(C6F5)4]]>

[0220] [Table 3]

[0221] Compound A, B X <![CDATA[Y A ,AND E ]]> <![CDATA[Y B ,AND D ]]> <![CDATA[Y C ]]> <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> <![CDATA[R 6 ]]> An (z-101) (A-II), (B-II) O H H H H tert-Bu Me H H H <![CDATA[B(C6F5)4]]> (z-102) (A-II), (B-II) O H H H H tert-Bu i-Pr H H H <![CDATA[B(C6F5)4]]> (z-103) (A-II), (B-II) O H H H H tert-Bu <![CDATA[NHCOCF3]]> H H H <![CDATA[B(C6F5)4]]> (z-104) (A-II), (B-II) O H H H H tert-Bu H F H H <![CDATA[B(C6F5)4]]> (z-105) (A-II), (B-II) O H H H H tert-Bu H Cl H H <![CDATA[B(C6F5)4]]> (z-106) (A-II), (B-II) O H H H H tert-Bu H Br H H <![CDATA[B(C6F5)4 <!-- 18 -->]]> (z-107) (A-II), (B-II) O H H H H tert-Bu H Me H H <![CDATA[B(C6F5)4]]> (z-108) (A-II), (B-II) O H H H H tert-Bu H i-Pr H H <![CDATA[B(C6F5)4]]> (z-109) (A-II), (B-II) O H H H H tert-Bu H <![CDATA[OCH3]]> H H <![CDATA[B(C6F5)4]]> (z-110) (A-II), (B-II) O H H H H tert-Bu H <![CDATA[CF3]]> H H <![CDATA[B(C6F5)4]]> (z-111) (A-II), (B-II) O H H H H tert-Bu H H F H <![CDATA[B(C6F5)4]]> (z-112) (A-II), (B-II) O H H H H tert-Bu H H Cl H <![CDATA[B(C6F5)4]]> (z-113) (A-II), (B-II) O H H H H tert-Bu H H Br H <![CDATA[B(C6F5)4]]> (z-114) (A-II), (B-II) O H H H H tert-Bu H H Me H <![CDATA[B(C6F5)4]]> (z-115) (A-II), (B-II) O H H H H tert-Bu H H i-Pr H <![CDATA[B(C6F5)4]]> (z-116) (A-II), (B-II) O H H H H tert-Bu H H <![CDATA[OCH3]]> H <![CDATA[B(C6F5)4]]> (z-117) (A-II), (B-II) O H H H H tert-Bu H H <![CDATA[NHCOCF3]]> H <![CDATA[B(C6F5)4]]> (z-118) (A-II), (B-II) O H H H H tert-Bu H H H F <![CDATA[B(C6F5)4]]> (z-119) (A-II), (B-II) O H H H H tert-Bu H H H Cl <![CDATA[B(C6F5)4]]> (z-120) (A-II), (B-II) O H H H H tert-Bu H H H Br <![CDATA[B(C6F5)4]]> (z-121) (A-II), (B-II) O H H H H tert-Bu H H H H <![CDATA[N(SO2CF3)2]]> (z-122) (A-II), (B-II) O H H H H tert-Bu H H H H <![CDATA[C(SO2CF3)3]]> (z-123) (A-II), (B-II) O H H H H tert-Bu H H H H <![CDATA[BF4]]> (z-124) (A-II), (B-II) O H H H H tert-Bu H H H H <![CDATA[ClO4]]> (z-125) (A-II), (B-II) O H H H H tert-Bu H H H H <![CDATA[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) O H H H H tert-Bu H H H H Br (z-128) (A-II), (B-II) O H H H H tert-Bu H H H H I (z-129) (A-II), (B-II) O H H Cl H tert-Bu H H F H <![CDATA[B(C6F5)4]]> (z-130) (A-II), (B-II) O H H Cl H tert-Bu H H Cl H <![CDATA[B(C6F5)4]]> (z-131) (A-II), (B-II) O H H Cl H tert-Bu H H Br H <![CDATA[B(C6F5)4]]> (z-132) (A-II), (B-II) O H H Cl H tert-Bu H H Me H <![CDATA[B(C6F5)4]]> (z-133) (A-II), (B-II) O H H Cl H tert-Bu H H i-Pr H <![CDATA[B(C6F5)4]]> (z-134) (A-II), (B-II) O H H Cl H tert-Bu H H <![CDATA[OCH3]]> H <![CDATA[B(C6F5)4]]> (z-135) (A-II), (B-II) O H H Cl H tert-Bu H H <![CDATA[NHCOCF3]]> H <![CDATA[B(C6F5)4]]> (z-136) (A-II), (B-II) O H H H H i-Pr H F H H <![CDATA[B(C6F5)4]]> (z-137) (A-II), (B-II) O H H H H i-Pr H Cl H H <![CDATA[B(C6F5)4]]> (z-138) (A-II), (B-II) O H H H H i-Pr H Br H H <![CDATA[B(C6F5)4]]> (z-139) (A-II), (B-II) O H H H H i-Pr H Me H H <![CDATA[B(C6F5)4]]> (z-140) (A-II), (B-II) O H H H H i-Pr H i-Pr H H <![CDATA[B(C6F5)4]]> (z-141) (A-II), (B-II) O H H H H i-Pr H <![CDATA[OCH3]]> H H <![CDATA[B(C6F5)4]]> (z-142) (A-II), (B-II) O H H H H i-Pr H <![CDATA[CF3]]> H H <![CDATA[B(C6F5)4]]> (z-143) (A-II), (B-II) O H H H H Ph H H F H <![CDATA[B(C6F5)4]]> (z-144) (A-II), (B-II) O H H H H Ph H H Cl H <![CDATA[B(C6F5)4]]> (z-145) (A-II), (B-II) O H H H H Ph H H Br H <![CDATA[B(C6F5)4]]> (z-146) (A-II), (B-II) O H H H H Ph H H Me H <![CDATA[B(C6F5)4]]> (z-147) (A-II), (B-II) O H H H H Ph H H i-Pr H <![CDATA[B(C6F5)4]]> (z-148) (A-II), (B-II) O H H H H Ph H H <![CDATA[OCH3]]> H <![CDATA[B(C6F5)4]]> (z-149) (A-II), (B-II) O H H H H Ph H H <![CDATA[NHCOCF3]]> H <![CDATA[B(C6F5)4]]> (z-150) (A-I), (B-I) O H H H H tert-Bu H <![CDATA[NMe2]]> H H <![CDATA[B(C6F5)4]]>

[0222] [Table 4]

[0223]

[0224] Furthermore, R in Table 4 3 and R 4 "C-1, C-2" in the column refers to R in the formula (AI) and the formula (BI). 3 With R 4 Specifically, the aromatic hydrocarbon group having 6 carbon atoms bonded to each other refers to a structure in which the parts corresponding to the unit A and the unit B are represented by the following formula C-1 and formula C-2.

[0225] In addition, Y in Table 4 A , Y E , R 1 and R 5The "D-1" in the column refers to Y A and R in the formula (A-III) 1 , Y E and R in the formula (B-III) 5 They are bonded to each other to form a 6-membered alicyclic group. Specifically, the cation of compound (z-163) is represented by the following formula D-1.

[0226] [Chemistry 14]

[0227]

[0228] [Chemistry 15]

[0229]

[0230] The compound (Z) is preferably a compound soluble in an organic solvent, and particularly preferably a compound soluble in dichloromethane.

[0231] Here, the term "soluble in an organic solvent" means that 0.1 g or more of the compound (Z) is dissolved in 100 g of the organic solvent at 25°C.

[0232] The compound (Z) is preferably a compound satisfying the following requirement (A).

[0233] Necessary condition (A): In the transmission spectrum measured using a solution obtained by dissolving compound (Z) in dichloromethane (wherein the transmission spectrum is a spectrum with a transmittance of 10% at the absorption maximum wavelength; hereinafter, the transmission spectrum is also referred to as the "transmission spectrum of compound (Z)"), the average value of the transmittance at a wavelength of 430 nm to 580 nm is preferably 93% or more, more preferably 95% or more. The average value of the transmittance is preferably high, and therefore the upper limit thereof is not particularly limited and may be 100%.

[0234] When the compound (Z) satisfies the above-mentioned requirement (A), it is possible to sufficiently block light having a wavelength in the near-infrared region to be blocked and further suppress a decrease in the visible light transmittance.

[0235] Furthermore, in the present invention, the average transmittance at wavelengths A nm to B nm is a value calculated by measuring the transmittance at each wavelength above A nm and below B nm in units of 1 nm and dividing the total value of the transmittance by the number of measured transmittances (wavelength range, B-A+1).

[0236] The compound (Z) is preferably a compound satisfying the following requirement (B-1) or requirement (B-2).

[0237] Necessary condition (B-1): In the absorption spectrum measured using a solution prepared by dissolving compound (Z) in dichloromethane, the absorption spectrum preferably has a maximum value in the 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.

[0238] When the absorption maximum wavelength of the compound (Z) is within the above range, an optical filter that can suppress reflected light of light having a wavelength of about 720 nm to 900 nm and provide a good image with less flare and ghost can be easily obtained.

[0239] Preferred examples of the compound (Z) satisfying the requirement (B-1) include compounds wherein the unit A is any one of the formulas (AI) to (A-II), and the unit B is any one of the formulas (BI) to (B-II).

[0240] Necessary condition (B-2): In the absorption spectrum measured using a solution prepared by dissolving compound (Z) in dichloromethane, the absorption spectrum preferably has a maximum value in the 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.

[0241] When the absorption maximum wavelength of the compound (Z) is within the above range, an optical filter that can suppress reflected light of light having a wavelength of about 700 nm to 750 nm and provide a good image with less flare and ghost can be easily obtained.

[0242] Preferred examples of the compound (Z) satisfying the requirement (B-2) include compounds wherein the unit A is of the formula (A-III) and the unit B is of the formula (B-III).

[0243] The compound (Z) is preferably a compound satisfying the following requirement (C).

[0244] Requirement (C): The retention rate D (=Af×100 / Ai) of the absorbance Af at the maximum absorption wavelength λa in the wavelength range of 700 nm to 1000 nm of the resin plate containing the resin and the compound (Z) after the resin plate is irradiated 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 the upper limit thereof is not particularly limited and may be 100%.

[0245] Furthermore, the thickness of the resin plate is in the range of 90 μm to 110 μm, the content of the compound (Z) relative to the resin is an amount such that the absorbance Ai of the resin plate at the maximum absorption wavelength λa is in the range of 0.5 to 1.5, the resin is ARTON manufactured by JSR (Co., Ltd.), and contains 0.3 parts by mass of Irganox 1010 (manufactured by BASF Japan (Co., Ltd.)) relative to 100 parts by mass of the resin in the resin plate.

[0246] The compound (Z) having a retention rate D within the above range can be said to be excellent in light resistance (durability), and by using such a compound (Z), an optical filter that exhibits desired optical characteristics for a long period of time can be easily obtained.

[0247] Specifically, the retention rate D can be measured by the method described in the following Examples.

[0248] The compound (Z) more preferably satisfies the following requirement (D).

[0249] Necessary condition (D): In a spectroscopic absorption spectrum measured using a solution obtained by dissolving compound (Z) in dichloromethane, when the absorbance at the longest wavelength among the maximum absorption wavelengths is εa and the maximum absorbance at wavelengths of 430 nm to 580 nm is εbmax, εa / εbmax is preferably 20 or more, more preferably 25 or more, and further preferably 27 or more. εa / εbmax is preferably large, and therefore the upper limit thereof is not particularly limited, and is, for example, 10,000 or less.

[0250] If compound (Z) satisfies the necessary condition (D), it can be said that the ratio of the absorbance in the infrared region to the absorbance in the visible light region is large, and it can be said that the optical properties are excellent. In an optical filter having a dielectric multilayer film, the incident angle dependence caused by the multilayer film can be suppressed.

[0251] The content of the compound (Z) in the present composition is preferably 0.02 to 2.0 parts by mass, more preferably 0.02 to 1.5 parts by mass, particularly preferably 0.03 to 1.5 parts by mass, relative to 100 parts by mass of the resin.

[0252] When the content of the compound (Z) is within the above range, a composition can be easily obtained which can efficiently cut off near infrared rays in the range of wavelengths around 700 nm to 750 nm or around 720 nm to 900 nm and has better visible light transmittance.

[0253] <Resin>

[0254] The resin used in the present composition is not particularly limited, and any existing resin can be used.

[0255] The resin used in the present composition may be a single type or two or more types.

[0256] The resin is not particularly limited as long as the effects of the present invention are not impaired. For example, in terms of excellent thermal stability and formability for film (plate) shape, and the ability to easily obtain a film that can form a dielectric multilayer film by high-temperature evaporation at a evaporation temperature of about 100°C or more, a resin having a glass transition temperature (Tg) of preferably 110°C to 380°C, more preferably 110°C to 370°C, and particularly preferably 120°C to 360°C can be cited. In addition, if the Tg of the resin is 140°C or more, a film that can form a dielectric multilayer film by evaporation at a higher temperature can be obtained, which is particularly preferred.

[0257] As the resin, a resin having a total light transmittance of a 0.1 mm thick resin plate containing the resin (Japanese Industrial Standards (JIS) K 7375: 2008) of preferably 75% to 95%, more preferably 78% to 95%, particularly preferably 80% to 95% can be used.

[0258] When a resin having a total light transmittance within the above range is used, a resin composition or an optical filter having excellent transparency can be easily obtained.

[0259] The weight average molecular weight (Mw) of the resin measured by gel permeation chromatography (GPC) in terms of polystyrene is usually 15,000 to 350,000, preferably 30,000 to 250,000, and the number average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.

[0260] Examples of the resin include cyclic (poly)olefin resins, aromatic polyether resins, polyimide resins, polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyamideimide 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.

[0261] Specific examples of these resins include resins described in International Publication No. 2019 / 168090.

[0262] <Other ingredients>

[0263] The present composition may further contain other components such as a compound (X) other than the compound (Z) [an absorber other than the ultraviolet absorber], an antioxidant, an ultraviolet absorber, a fluorescent matte agent, and a metal complex compound, within a range not impairing the effects of the present invention.

[0264] These other components may be used alone or in combination of two or more.

[0265] These other components can be mixed with resins etc. when preparing this composition, and can also be added when synthesizing resins. In addition, the addition amount can be appropriately selected according to the desired characteristics etc., and is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass, relative to 100 parts by mass of resin.

[0266] [Compound (X)]

[0267] The present composition may contain one or two or more compounds (X) other than the compound (Z) [absorbers other than the ultraviolet absorber].

[0268] Examples of the compound (X) include squarylium compounds, phthalocyanine compounds, polymethine compounds, naphthalocyanine compounds, crotonium compounds, octaphyrin compounds, diimmonium compounds, perylene compounds, and metal dithiolate compounds.

[0269] The compound (X) preferably contains a squarylium compound, and more preferably contains one or more squarylium compounds and other compounds (X'). The other compound (X') is particularly preferably a phthalocyanine compound and a polymethine compound.

[0270] The absorption peak of the squaric acid ylide compound is sharp, and has excellent visible light transmittance and high molar absorption coefficient, but sometimes generates fluorescence that causes scattered light when light is absorbed. In this case, by using the squaric acid ylide compound in combination with the compound (X'), scattered light can be suppressed. In this way, if scattered light is suppressed, when the optical filter obtained by the present composition is used in an imaging device, etc., the obtained camera image quality becomes better.

[0271] The absorption maximum wavelength of the compound (X) is preferably 650 nm to 1100 nm, more preferably 650 nm to 950 nm, further preferably 680 nm to 850 nm, particularly preferably 690 nm to 740 nm.

[0272] By using the compound (X) having an absorption maximum wavelength in the above range, an optical filter with more excellent visual sensitivity correction can be easily obtained.

[0273] [Ultraviolet light absorber]

[0274] Examples of the ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, anthracene compounds, and compounds described in Japanese Patent Application Laid-Open No. 2019-014707.

[0275] Particularly preferred are azomethine compounds, indole compounds, benzotriazole compounds, and cyanoacrylate compounds. By including these compounds, an optical filter having a small incidence angle dependency in the near-ultraviolet wavelength region can be easily obtained, and when the optical filter is used in an imaging device, etc., the obtained camera image quality becomes better.

[0276] [Antioxidant]

[0277] Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-tert-butyl-5,5′-dimethyldiphenylmethane, and tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane.

[0278] <Additives>

[0279] The present composition may further contain additives such as an organic solvent, a release agent, a surfactant, an antistatic agent, an adhesion aid, and a light diffusing material within a range that does not impair the effects of the present invention.

[0280] These additives may be used alone or in combination of two or more.

[0281] In particular, when the present composition is made into a liquid composition, it is preferable to use an organic solvent. Examples of the organic solvent are preferably solvents that can dissolve the resin, and specific examples thereof include esters, ketones, aromatic hydrocarbons, and halogen-containing compounds.

[0282] In addition, when the resin layer is produced by casting to be described later, the resin layer can be easily produced by using a leveling agent or a defoaming agent.

[0283] 《Base Material (i)》

[0284] The substrate (i) of the present invention is a substrate formed from the present composition and containing the compound (Z).

[0285] The substrate (i) may be a single layer or a multilayer, as long as it has a resin layer (hereinafter also referred to as "the present resin layer") formed from the present composition and containing the compound (Z). The substrate (i) may have two or more layers of the present resin layer, in which case the two or more layers of the present resin layer may be the same or different.

[0286] When the substrate (i) is a single layer, the substrate (i) is composed of the present resin layer, that is, the present resin layer (resin substrate) is the substrate (i).

[0287] When the substrate (i) is multilayer, examples of the substrate (i) include: a substrate comprising two or more resin layers, at least one of which is the present resin layer; or a substrate comprising the present resin layer and a glass support. Suitable examples include: a substrate (A), comprising a laminate formed by laminating the present resin layer on a support such as a glass support or a resin support serving as a base; and a substrate (B), comprising a laminate formed by laminating a resin layer such as an outer coating layer comprising a curing resin or the like on the present resin layer.

[0288] The substrate (i) is particularly preferably the substrate (B) in terms of production cost and ease of adjusting optical properties, and in turn, the effect of eliminating damage to the resin layer or improving the damage resistance of the substrate (i).

[0289] Furthermore, the resin layer such as the outer coating layer in the resin support or substrate (B) refers to a resin layer that does not contain the compound (Z). If the resin layer that does not contain the compound (Z) contains a resin, there is no particular limitation, and examples of the resin include the same resin as the resin described in the present composition column. In addition, the resin layer that does not contain the compound (Z) may also be the following other functional films.

[0290] As the glass support, a transparent glass support or an absorbing glass support is preferred. Among these, the absorbing glass support is preferred because it can sufficiently block light with a wavelength in the near infrared region.

[0291] The thickness of the substrate (i) can be appropriately selected depending on the intended use without particular limitation, but is preferably 10 μm to 250 μm, more preferably 15 μm to 230 μm, and particularly preferably 20 μm to 150 μm.

[0292] If the thickness of the substrate (i) is within the above range, the optical filter using the substrate (i) can be thinned and lightened, and can be suitably used in various applications such as solid-state imaging devices. In particular, when the single-layer substrate (i) is used in a lens unit of a camera module, the lens unit can be made low-profile and light-weight, which is preferred.

[0293] [Method for producing substrate (i)]

[0294] The resin layers such as the present resin layer, the resin support and the outer coating layer can be formed by, for example, melt molding or cast molding, and further, if necessary, a coating agent such as an antireflective agent, a hard coating agent and / or an antistatic agent can be applied after molding.

[0295] When the substrate (i) is the substrate (A), for example, the composition is melt-formed or cast on the support, and preferably the solvent is dried and removed after coating by spin coating, slit coating, ink jetting or the like, and then light irradiation or heating is performed as needed, thereby manufacturing a substrate having the resin layer formed on the support.

[0296] Melt forming

[0297] As the melt forming, specifically, there can be mentioned: a method of melt forming pellets obtained by melt kneading the present composition; a method of melt forming the present composition; a method of melt forming pellets obtained by removing a solvent from a liquid present composition containing a solvent, etc. Examples of the melt forming method include injection molding, melt extrusion molding, or blow molding.

[0298] ·Tape casting

[0299] Examples of the above-mentioned casting method include: a method in which a liquid composition containing a solvent is cast on a suitable support to remove the solvent; a method in which a curable composition containing a photocurable resin and / or a thermosetting resin as the resin is cast on a suitable support to remove the solvent, and then hardened by a suitable method such as ultraviolet irradiation or heating, etc.

[0300] When the substrate (i) is the single-layer substrate (i), the substrate (i) can be obtained by peeling off the coating film from the support body after the casting. In addition, when the substrate (i) is the substrate (A), the substrate (i) can be obtained by not peeling off the coating film after the casting.

[0301] Examples of the suitable support include a glass plate, a steel belt, a steel cylinder, and a support made of a resin (for example, a polyester film or a cyclic olefin-based resin film).

[0302] Furthermore, the present resin layer can also be formed on an optical component by a method such as applying the liquid present composition onto an optical component such as a glass plate, quartz or plastic and drying the solvent; or by applying the curable present composition and curing and drying.

[0303] When the resin support and the overcoat layer are formed by melt molding or casting, a desired composition containing a resin (but not containing compound (Z)) may be used instead of the present composition in the melt molding or casting column.

[0304] The amount of residual solvent in the resin layer such as the present resin layer, the resin support and the outer coating layer is preferably as small as possible. Specifically, the amount of residual solvent is preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less relative to the weight of the present resin layer.

[0305] When the residual solvent amount is within the above range, a resin layer that is unlikely to be deformed or have properties that are unlikely to change and that can easily exhibit a desired function can be obtained.

[0306] When the substrate (i) is used in an optical filter, the solvent content in the resin layer such as the present resin layer, the resin support, and the overcoat layer is preferably suppressed to 100 ppm by mass or less.

[0307] Optical Filters

[0308] The optical filter of the present invention (hereinafter also referred to as "the present filter") comprises the substrate (i) and a dielectric multilayer film.

[0309] In terms of further exerting the effects of the present invention, as such filters, specifically, near infrared cut-off filters (NIR-CF), visible light-near infrared selective transmission filters (DBPF), near infrared transmission filters (IRPF) can be listed. In addition, the present filter can also be used as a filter for alternative light sources (ALS: Alternative Light Sources) used in scientific searches, etc. In addition to having the substrate (i), these filters can be set to the existing structure.

[0310] When the present filter is NIR-CF or DBPF, it is preferably a filter satisfying the following characteristic (a).

[0311] Characteristic (a): In the wavelength region of 430 nm to 580 nm, the average value of the transmittance when measured in the vertical direction of the optical filter is preferably 75% or more, more preferably 80% or more. The average value of the transmittance is preferably high, so the upper limit is not particularly limited and can be 100%.

[0312] If the present filter satisfies the characteristic (a), it can fully cut off light of a wavelength in the near-infrared region to be cut off while further suppressing a decrease in visible light transmittance, and can therefore be more preferably used as an NIR-CF or DBPF.

[0313] When the substrate (i) contains a compound satisfying the requirement (B-1), and the filter is NIR-CF or DBPF, it is preferably a filter satisfying the following characteristic (b-1).

[0314] Characteristic (b-1): In the region of wavelengths of 700 nm to 800 nm, the average reflectivity of unpolarized light incident at an angle of 5° from the vertical direction of at least one surface of the optical filter is preferably 25% or less, more preferably 15% or less. The average reflectivity is preferably low, so its lower limit is not particularly limited and may be 0%.

[0315] By using the present filter satisfying the 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.

[0316] When the substrate (i) contains a compound satisfying the requirement (B-2), and the filter is NIR-CF or DBPF, it is preferably a filter satisfying the following characteristic (b-2).

[0317] Characteristic (b-2): In the region of wavelength 650nm to 800nm, the average reflectivity of unpolarized light incident at an angle of 5° from the vertical direction of 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 its lower limit is not particularly limited and can be 0%.

[0318] By using the present filter satisfying the 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.

[0319] Furthermore, in the present invention, the average reflectivity at wavelengths A nm to B nm is a value calculated by measuring the reflectivity at each wavelength above A nm and below B nm in units of 1 nm and dividing the total value of the reflectivity by the number of measured reflectivities (wavelength range, B-A+1).

[0320] It is extremely difficult to measure the reflectivity of non-polarized light incident from a vertical direction. Therefore, in the present invention, the reflectivity characteristics of non-polarized light incident from an angle of 5° deviating from the vertical direction are measured.

[0321] “Non-polarized light” is light that does not have a deviation in the polarization direction, and refers to a collection of waves whose electric field is roughly uniformly distributed in all directions. The average value of “the average transmittance of S-polarized light” and “the average transmittance of P-polarized light” can be used as the “average reflectivity of non-polarized light”. The average value of “the average reflectivity of S-polarized light” and “the average reflectivity of P-polarized light” can be used as the “average reflectivity of non-polarized light”.

[0322] By satisfying the above-mentioned characteristics (a) and characteristics (b-1) or characteristics (b-2), the present filter can reduce the intensity of reflected light in the near-infrared region, especially in the wavelength region of 650nm to 800nm, while maintaining good transmittance of visible light. Therefore, in recent years, in imaging devices such as digital still cameras that have been progressing in high performance, the reduction in sensitivity in the visible light region can be suppressed to a minimum, and image defects caused by the above-mentioned reflected light can be eliminated.

[0323] The thickness of the present filter may be appropriately selected according to the desired application, and the thickness of the present filter is preferably thin in accordance with the recent trend of thinning and weight reduction of solid-state imaging devices and the like.

[0324] Since the filter includes the substrate (i), it can be made thinner.

[0325] The thickness of the filter is preferably 300 μm or less, more preferably 250 μm or less, further preferably 200 μm or less, and particularly preferably 150 μm or less. The lower limit is not particularly limited, and is ideally 20 μm, for example.

[0326] <NIR-CF>

[0327] The NIR-CF is preferably an optical filter having excellent cutoff performance in the wavelength region of 850 nm to 1200 nm and excellent transmittance in the visible wavelength region.

[0328] The dielectric multilayer film used in the NIR-CF is preferably a near-infrared reflective film.

[0329] When NIR-CF is used in a solid-state imaging element, the transmittance in the near-infrared wavelength region is preferably low. In particular, it is known that the light receiving sensitivity of the solid-state imaging element in the wavelength region of 800nm ​​to 1200nm is relatively high. By reducing the transmittance in the wavelength region, the visual sensitivity of the camera image and the human eye can be effectively corrected, and excellent color reproducibility can be achieved. In addition, by further reducing the transmittance in the wavelength region of 850nm to 1200nm, the near-infrared light used in the security authentication function can be effectively prevented from reaching the image sensor, etc.

[0330] Regarding NIR-CF, in the wavelength region of 850 nm to 1200 nm, the average transmittance when measured in the perpendicular direction of the filter is preferably 5% or less, more preferably 4% or less, further preferably 3% or less, and particularly preferably 2% or less.

[0331] When the average transmittance at a wavelength of 850 nm to 1200 nm is within the above range, near infrared rays can be sufficiently cut off and excellent color reproducibility can be achieved, which is preferred.

[0332] When the NIR-CF is used in a solid-state imaging element, the visible light transmittance is preferably high. Specifically, in the wavelength region of 430 nm to 580 nm, the average transmittance when measured in the vertical direction of the filter is preferably 75% or more, more preferably 80% or more, further preferably 83% or more, and particularly preferably 85% or more.

[0333] When the average transmittance at a wavelength of 430 nm to 580 nm is within the above range, excellent imaging sensitivity can be achieved.

[0334] <DBPF>

[0335] The DBPF is not particularly limited as long as it is an optical filter that transmits visible light and light of a desired wavelength among near-infrared rays and cuts off light of a desired wavelength among near-infrared rays.

[0336] The dielectric multilayer film used in the DBPF is preferably a film that transmits visible light and light of a wavelength to be transmitted among near-infrared rays, and blocks light of a wavelength to be blocked among near-infrared rays.

[0337] Similar to NIR-CF, when DBPF is used in solid-state imaging elements, etc., its visible light transmittance is preferably high. For the same reasons as described above, its average transmittance at wavelengths of 430nm to 580nm is preferably in the same range as the average transmittance of NIR-CF.

[0338] <IRPF>

[0339] The IRPF is not particularly limited as long as it is an optical filter that cuts off visible light and transmits light of a desired wavelength among near-infrared rays.

[0340] The dielectric multilayer film used in the IRPF is preferably a film that cuts off light of a desired wavelength (part of visible light and / or near infrared light).

[0341] In addition, IRPF can also use visible light absorbers to cut off visible light.

[0342] IRPF can be suitably used in optical systems such as infrared surveillance cameras, vehicle-mounted infrared cameras, infrared communications, various sensor systems, infrared alarms, night vision devices, etc. When used in these applications, it is preferred that the transmittance of light of wavelengths other than near-infrared rays to be transmitted is low.

[0343] In particular, in the wavelength region of 380 nm to 700 nm, the average value of the transmittance when measured in the vertical direction of the present filter is preferably 10% or less, and more preferably 5% or less.

[0344] In addition, the IRPF preferably has a high transmittance of near infrared light to be transmitted, and specifically has a light transmission band Ya in a region with a wavelength of 750 nm or more, in which the maximum transmittance (T IR ) is preferably 45% or more, more preferably 50% or more.

[0345] <Dielectric multilayer film>

[0346] The filter comprises the substrate (i) and a dielectric multilayer film. Examples of the dielectric multilayer film include a laminate in which high-refractive index material layers and low-refractive index material layers are alternately laminated.

[0347] The dielectric multilayer film may be disposed on a single surface of the substrate (i) or on both surfaces. When disposed on a single surface, the manufacturing cost or ease of manufacturing is excellent, and when disposed on both surfaces, an optical filter having high strength and being difficult to warp or twist can be obtained. When the present filter is used in a solid-state imaging element, etc., the warping or twisting of the filter is preferably small, and therefore it is preferred that the dielectric multilayer film is disposed on both surfaces of the substrate (i).

[0348] As materials constituting the high refractive index material layer, materials with a refractive index of 1.7 or more can be cited, and materials with a refractive index of 1.7 to 2.5 can be selected. As such materials, for example, materials having titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide or indium oxide as main components and containing a small amount (for example, 0 mass % to 10 mass % relative to the main component) of titanium oxide, tin oxide and / or cerium oxide can be cited.

[0349] As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index of generally 1.2 to 1.6 can be selected. Examples of such a material include silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

[0350] There is no particular limitation on the method for stacking the high refractive index material layer and the low refractive index material layer as long as a dielectric multilayer film formed by stacking these material layers can be formed. For example, a dielectric multilayer film formed by alternately stacking high refractive index material layers and low refractive index material layers can be directly formed on the substrate (i) by chemical vapor deposition (CVD), sputtering, vacuum evaporation, ion-assisted evaporation or ion plating.

[0351] Generally, if the wavelength of the light to be blocked (e.g., near infrared light) is set to 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. As the value of λ (nm), in the case of NIR-CF, for example, it is 700nm to 1400nm, preferably 750nm to 1300nm. If the thickness of each layer of the high refractive index material layer and the low refractive index material layer is within the range, the product (n×d) of the refractive index (n) and the film thickness (d), that is, the optical film thickness, becomes a value approximately the same as λ / 4, and according to the relationship between the optical characteristics of reflection-refraction, there is a tendency to easily control the blocking-transmission of specific wavelengths.

[0352] Regarding the total number of stacked 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 stacked layers is within the above range, sufficient manufacturing margin can be ensured, and warping of the optical filter or cracking of the dielectric multilayer film can be reduced.

[0353] In the present filter, 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 stacking, and the number of stacking layers are appropriately selected in combination with the absorption characteristics of the compound (Z), thereby ensuring sufficient transmittance in the wavelength region to be transmitted (e.g., visible region), and having sufficient light cutting properties in the wavelength region to be cut off (e.g., near-infrared region), and reducing the reflectivity when light (e.g., near-infrared light) is incident from an oblique direction.

[0354] Here, in order to optimize the conditions of the dielectric multilayer film, for example, it is sufficient to use optical thin film design software (e.g., Essential Macleod, manufactured by Thin Film Center) to set parameters in a manner that takes into account both the anti-reflection effect in the wavelength region to be transmitted (e.g., visible region) and the light cutoff effect in the wavelength region to be cutoff (e.g., near infrared region). In the case of the software, for example, when forming a dielectric multilayer film of NIR-CF, the target transmittance of the wavelength of 400nm to 700nm is set to 100%, the target tolerance (TargetTolerance) value is set to 1, and the target transmittance of the wavelength of 705nm to 950nm is set to 0%, and the target tolerance value is set to 0.5.

[0355] These parameters can also be combined with various characteristics of the substrate (i) to further divide the wavelength range to change the value of the target tolerance.

[0356] <Other functional films>

[0357] In order to increase the surface hardness of the substrate (i) or the dielectric multilayer film, improve chemical resistance, resist static electricity and eliminate damage, the present filter can be appropriately provided with a functional film such as an anti-reflective film, a hard coating film or an antistatic film between the substrate (i) and the dielectric multilayer film, on the surface of the substrate (i) opposite to the surface on which the dielectric multilayer film is provided, or on the surface of the dielectric multilayer film opposite to the surface on which the substrate (i) is provided, within the range that does not impair the effects of the present invention.

[0358] The filter may include one layer of the functional film or two or more layers. When the filter includes two or more layers of the functional film, the filter may include two or more layers of the same film or two or more layers of different films.

[0359] The method for laminating the functional film is not particularly limited, and examples thereof include a method of melt-molding or casting a coating agent such as an antireflective agent, a hard coating agent and / or an antistatic agent on the substrate (i) or the dielectric multilayer film in the same manner as described above.

[0360] Alternatively, the film can be produced by applying a curable composition containing a coating agent or the like onto the substrate (i) or the dielectric multilayer film using a bar coater or the like, and then curing the film by irradiating ultraviolet rays or the like.

[0361] Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins, and specifically, vinyl compounds, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate resins, etc. The coating agent may be used alone or in combination of two or more.

[0362] Examples of the curable composition containing these coating agents include vinyl-based, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based, and epoxy acrylate-based curable compositions.

[0363] The curable composition may also contain a polymerization initiator. As the polymerization initiator, an existing photopolymerization initiator or a thermal polymerization initiator may be used, or a photopolymerization initiator and a thermal polymerization initiator may be used in combination. The polymerization initiator may be used alone or in combination of two or more.

[0364] In the curable composition, when the total amount of the curable composition is 100 mass %, the blending ratio of the polymerization initiator is preferably 0.1 mass % to 10 mass %, more preferably 0.5 mass % to 10 mass %, and further preferably 1 mass % to 5 mass %. If the blending ratio of the polymerization initiator is within the above range, a curable composition having excellent curing characteristics and handling properties can be easily obtained, and a functional film such as an antireflective film, a hard coating film, or an antistatic film having a desired hardness can be easily obtained.

[0365] Furthermore, an organic solvent may be added to the curable composition as a solvent, and an existing solvent may be used as the organic solvent. Specific examples of the organic solvent include: alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; and amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0366] These solvents may be used alone or in combination of two or more.

[0367] The thickness of the functional film 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.

[0368] In addition, in order to improve 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, the surface of the substrate (i), the functional film or the dielectric multilayer film may be subjected to surface treatment such as corona treatment or plasma treatment.

[0369] [Application of optical filters]

[0370] Regarding this filter, for example, the cutoff ability of the wavelength of the light in the area to be cut off and the transmittance of the wavelength of the light to be transmitted are excellent. Therefore, it is useful for the correction of the visual sensitivity of solid-state imaging elements such as CCD or CMOS image sensors of camera modules. In particular, it is useful in digital still cameras, cameras for smart phones, cameras for mobile phones, digital cameras, cameras for wearable devices, personal computers (personal computers, PC) cameras, surveillance cameras, automotive cameras, infrared cameras, televisions, car navigation, portable information terminals, video game consoles, portable game consoles, fingerprint authentication systems, digital music players, various sensor systems, infrared communications, etc. Furthermore, it is also useful as a heat ray cutoff filter installed on a glass plate of a car or building, etc.

[0371] Solid-state imaging device

[0372] The solid-state imaging device of the present invention includes the present filter. Here, the solid-state imaging device is a device including a solid-state imaging element such as a CCD or CMOS image sensor, and specifically can be used in digital still cameras, cameras for smartphones, cameras for mobile phones, cameras for wearable devices, digital video cameras, and the like.

[0373] 《Optical sensor device》

[0374] The optical sensor device of the present invention is not particularly limited as long as it includes the present filter, and may be configured as a conventional structure.

[0375] For example, a device including a light receiving element and the present filter can be cited. Specifically, a device including a light receiving element (semiconductor substrate), a protective film, the present filter, another filter, and the like can be cited.

[0376] [Example]

[0377] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples at all.

[0378] [Synthesis example]

[0379] The compound (Z) and the compound (X) used in the following examples were synthesized based on a generally known synthesis method.

[0380] Compound (Z) can be synthesized, for example, by referring to the methods described in JP-A-2009-108267, JP-A-5-59291, JP-A-2014-95007, JP-A-2011-52218, International Publication No. 2007 / 114398, JP-A-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).

[0381] Compound (X) can be found in, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Unexamined Publication No. 60-228448, Japanese Patent Unexamined Publication No. 1-146846, Japanese Patent Unexamined Publication No. 1-228960, Japanese Patent No. 4081149. , Japanese Patent Laid-Open No. 63-124054, "Phthalocyanine - Chemistry and Function -" (IPC, 1997), Japanese Patent Laid-Open No. 2007-169315, Japanese Patent Laid-Open No. 2009-108267, Japanese Patent Laid-Open No. 2010-241873, Japanese Patent No. 3699464, and Japanese Patent No. 4740631 are used for synthesis.

[0382] [Intermediate Synthesis Example 1]

[0383] [Chemistry 16]

[0384]

[0385] In a 200mL eggplant flask with a stirrer, 8.33g of compound a-1 synthesized by the method described in "Bioorganic and Medicinal Chemistry" (2013, vol.21, #11, p.2826-2831) was added, 21.8g of ethyl pivalate was added, and 4.0g of sodium hydride (60%, dispersed in paraffin liquid) was added after 5 minutes, and stirred at 80°C for 3 hours. Thereafter, it was cooled to room temperature, 100mL of 1N hydrochloric acid aqueous solution was added for neutralization, and then the liquid was transferred to a separatory funnel, and the organic phase was extracted with 150mL of ethyl acetate. Then, 15g of magnesium sulfate was added to the extracted organic phase and stirred for 15 minutes, after which magnesium sulfate was removed by filtering through a filter, and the filtrate was placed in a 300mL eggplant flask, and the solvent was distilled off using an evaporator to obtain compound a-2.

[0386] A stirring bar was placed in the eggplant-shaped flask containing compound a-2, and 20 mL of concentrated hydrochloric acid was added, followed by stirring at 40°C. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 200 mL of 1N sodium hydroxide aqueous solution was added for neutralization. Then, the liquid was transferred to a separatory funnel, 150 mL of ethyl acetate was added and the organic phase was extracted, and then 15 g of magnesium sulfate was added and stirred for 15 minutes. Then, the magnesium sulfate was removed by filtering through a filter, and then the filtrate was placed in a 300 mL eggplant-shaped flask, and the solvent was distilled off using an evaporator. Thereafter, the residual compound in the flask was separated and purified by silica gel chromatography, thereby obtaining 5.0 g of the target compound a-3. Furthermore, the identification of the compound was performed by liquid chromatography-mass spectrometry (LC-MS) and 1 H-NMR ( 1 H-nuclear magnetic resonance, 1 H-NMR) analysis was performed.

[0387] [Intermediate Synthesis Example 2]

[0388] [Chemistry 17]

[0389]

[0390] In a 200 mL eggplant-shaped flask with a stirrer, 3 g of compound a-3 and 30 mL of diethyl ether were placed, 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 methyl magnesium iodide diethyl ether solution was added over a period of 10 minutes, and then the mixture was heated to 35°C and stirred for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, 30 mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was separated by filtration, washed with 20 mL of water, and dried under reduced pressure at 50°C to obtain 2.5 g of compound a-4. Furthermore, the compound was identified using 1 H-NMR analysis was performed.

[0391] [Synthesis Example of Compound (z-1)]

[0392] [Chemistry 18]

[0393]

[0394] In a 100mL eggplant flask with a stirrer, add compound a-4 1.5g, N-[2-chloro-3-(phenylamino)-2-propenylidene]-benzenamine monohydrochloride 0.6g, acetonitrile 25mL, anhydrous acetic acid 7.5mL, and pyridine 0.6mL, and heat to reflux for 5 hours. Then, cool to room temperature, distill the solvent using an evaporator, then add acetic acid 5mL, and cool and stand at 5°C for 2 days. Thereafter, the precipitated solid is filtered under reduced pressure, washed with acetic acid 5mL and hexane 10mL, thereby obtaining 0.17g of compound a-5.

[0395] In a 100mL eggplant-shaped flask with a stirrer, add 0.1g of compound a-5, 0.2g of lithium tetrakis-pentafluorophenylborate, 20mL of dichloromethane, and 10mL of water, and stir at room temperature for 1 hour. Then, transfer the liquid to a separatory funnel, remove the aqueous phase, wash the organic phase twice with 20mL of water, add 1g of sodium sulfate and stir for 15 minutes. Thereafter, filter through a filter to remove the sodium sulfate, place the filtrate in a 300mL eggplant-shaped flask, use an evaporator to distill off the solvent, and dry under reduced pressure at 50°C to obtain 0.05g of compound (z-1). Furthermore, the compound was identified using LC-MS and 1 H-NMR analysis was performed.

[0396] [Intermediate Synthesis Example 3]

[0397] [Chemistry 19]

[0398]

[0399] In a 300mL eggplant-shaped flask with a stirrer, 5g of flavonoids (compound a-6) and 50mL of tetrahydrofuran (THF) were added and cooled in an ice bath. After cooling in an ice bath for 5 minutes, 24.7mL of 1mol / L methyl magnesium iodide diethyl ether solution was added over 10 minutes, and then heated to 35°C and stirred for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, 50mL of 20% aqueous perchloric acid solution was added, the precipitated solid was filtered and separated, washed with 50mL of water, and dried under reduced pressure at 50°C to obtain 4.5g of compound a-7. Furthermore, the compound was identified using 1 H-NMR analysis was performed.

[0400] [Synthesis Example of Compound (z-16)]

[0401] [Chemistry 20]

[0402]

[0403] In a 100 mL eggplant-shaped flask with a stirrer, 0.7 g of compound a-7, 0.26 g of malondialdehyde dianilide hydrochloride, 10 mL of acetonitrile, 5 mL of anhydrous acetic acid, and 0.2 mL of pyridine were added and heated to reflux for 2 hours. Thereafter, the mixture was cooled to room temperature, and the precipitated solid was recovered by vacuum filtration and washed with 10 mL of diethyl ether to obtain 0.6 g of compound a-8.

[0404] In a 100 mL eggplant-shaped flask with a stirrer, add 0.1 g of compound a-8, 0.2 g of lithium tetrakis-pentafluorophenylborate, 20 mL of dichloromethane, and 10 mL of water, and stir at room temperature for 3 hours. Then, transfer the liquid to a separatory funnel, remove the aqueous phase, wash the organic phase twice with 20 mL of water, and use an evaporator to distill the solvent from the organic phase. Thereafter, dissolve the residue in 0.5 mL of acetone, add 10 mL of methanol and cool in an ice bath, recover the precipitated solid by suction filtration, and dry under reduced pressure at 50°C to obtain 0.07 g of compound (z-16). Furthermore, the compound was identified by LC-MS and 1 H-NMR analysis was performed.

[0405] [Intermediate Synthesis Example 4]

[0406] [Chemistry 21]

[0407]

[0408] In a 200mL eggplant flask with a stirrer, add 4g of compound a-9 and 21.8g of ethyl pivalate and stir. After 5 minutes, add 3.2g of sodium hydride (60%, dispersed in paraffin liquid), and then stir at 80°C for 3 hours. Thereafter, cool to room temperature, add 30mL of 1N hydrochloric acid aqueous solution for neutralization, and extract the organic phase with 150mL of ethyl acetate. Then, in the organic phase, add 15g of magnesium sulfate and stir for 15 minutes, then filter and remove magnesium sulfate through a filter, put the filtrate into a 300mL eggplant flask, and use an evaporator to distill the solvent to obtain compound a-10.

[0409] A stirring bar was placed in the eggplant-shaped flask containing compound a-10, and 20 mL of concentrated hydrochloric acid was added, followed by stirring at 40°C. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 240 mL of 1N sodium hydroxide aqueous solution was added for neutralization. Subsequently, the liquid was transferred to a separatory funnel, 200 mL of ethyl acetate was added and the organic phase was extracted, and then 15 g of magnesium sulfate was added and stirred for 15 minutes. Thereafter, the magnesium sulfate was removed by filtering through a filter, and the filtrate was placed in a 300 mL eggplant-shaped flask, and the solvent was distilled off using an evaporator. Thereafter, the compound remaining in the flask was separated and purified by silica gel chromatography, thereby obtaining 2.0 g of the target compound a-11. Furthermore, the identification of the compound was performed using LC-MS and 1 H-NMR analysis was performed.

[0410] [Intermediate Synthesis Example 5]

[0411] [Chemistry 22]

[0412]

[0413] In a 200mL eggplant-shaped flask with a stirrer, add 2.7g of compound a-11 and 50mL of diethyl ether, and cool in an ice bath. After cooling in an ice bath for 5 minutes, add 24.7mL of 1mol / L methyl magnesium iodide diethyl ether solution over 10 minutes, then heat to 35°C and stir for 2 hours. Then, cool the reaction solution in an ice bath, add 50mL of 20% perchloric acid aqueous solution, filter and separate the precipitated solid, wash with 50mL of water, and dry under reduced pressure at 50°C to obtain 0.7g of compound a-12. Furthermore, the compound was identified using 1 H-NMR analysis was performed.

[0414] [Synthesis Example of Compound (z-59)]

[0415] [Chemistry 23]

[0416]

[0417] In a 100 mL eggplant-shaped flask with a stirrer, 0.5 g of compound a-12, 0.22 g of malondialdehyde dianilide hydrochloride, 7.5 mL of acetonitrile, 2.5 mL of anhydrous acetic acid, and 0.2 mL of pyridine were added and heated to reflux for 2 hours. Thereafter, the mixture was cooled to room temperature, and the precipitated solid was recovered by vacuum filtration, washed with 10 mL of acetic acid and 10 mL of acetonitrile, and dried under reduced pressure at 50° C., thereby obtaining 0.35 g of compound a-13.

[0418] In a 100 mL eggplant-shaped flask with a stirrer, add 0.3 g of compound a-13, 0.8 g of lithium tetrakis-pentafluorophenylborate, 50 mL of dichloromethane, and 20 mL of water, and stir at room temperature for 3 hours. Then, transfer the liquid to a separatory funnel, remove the aqueous phase, wash the organic phase twice with 20 mL of water, and use an evaporator to distill the solvent from the organic phase. Thereafter, dissolve the residue in 20 mL of acetone, add 100 mL of water, and use an evaporator to distill 13 g of the solvent, and then cool in an ice bath. Thereafter, recover the precipitated solid by suction filtration, wash it with 50 mL of methanol, and dry the solid under reduced pressure at 50°C, thereby obtaining 0.5 g of compound (z-59). Furthermore, the compound was identified by LC-MS and 1 H-NMR analysis was performed.

[0419] [Intermediate Synthesis Example 6]

[0420] [Chemistry 24]

[0421]

[0422] In a 200mL eggplant flask with a stirrer, add 4.5g of compound a-14 and 21.8g of ethyl isobutyrate and stir. After 5 minutes, add 3.2g of sodium hydride (60%, dispersed in paraffin liquid), and then stir at 80°C for 3 hours. Thereafter, cool to room temperature, add 30mL of 1N hydrochloric acid aqueous solution for neutralization, and extract the organic phase with 150mL of ethyl acetate. Then, add 15g of magnesium sulfate to the organic phase and stir for 15 minutes, then filter and remove magnesium sulfate through a filter, put the filtrate into a 300mL eggplant flask, and use an evaporator to distill the solvent to obtain compound a-15.

[0423] A stirring bar was placed in the eggplant-shaped flask containing compound a-15, and 20 mL of concentrated hydrochloric acid was added, followed by stirring at 40°C. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 240 mL of 1N sodium hydroxide aqueous solution was added for neutralization. Thereafter, the liquid was transferred to a separatory funnel, 200 mL of ethyl acetate was added and the organic phase was extracted, and then 15 g of magnesium sulfate was added and stirred for 15 minutes. Subsequently, the magnesium sulfate was removed by filtering through a filter, and the filtrate was placed in a 300 mL eggplant-shaped flask, and the solvent was distilled off using an evaporator. Thereafter, the compound remaining in the flask was separated and purified by silica gel chromatography, thereby obtaining 0.4 g of the target compound a-16. Furthermore, the identification of the compound was performed using LC-MS and 1 H-NMR analysis was performed.

[0424] [Intermediate Synthesis Example 7]

[0425] [Chemistry 25]

[0426]

[0427] In a 100-mL eggplant-shaped flask with a stirrer, add 0.4 g of compound a-16 and 10 mL of diethyl ether, and cool in an ice bath. After cooling in an ice bath for 5 minutes, add 5.0 mL of a 1 mol / L methyl magnesium iodide diethyl ether solution over 10 minutes, then heat to 35°C and stir for 2 hours. Next, cool the reaction solution in an ice bath, add 10 mL of a 20% perchloric acid aqueous solution, then add 20 mL of dichloromethane, transfer to a separatory funnel, and recover the organic phase. Use an evaporator to distill off the solvent from the organic phase, stir the solid residue, add 20 mL of diethyl ether, and stir for 20 minutes. Next, filter out the solid component by suction filtration, and dry under reduced pressure at 50°C to obtain 0.5 g of compound a-17. Furthermore, the identification of the compound is performed using 1 H-NMR analysis was performed.

[0428] [Synthesis Example of Compound (z-62)]

[0429] [Chemistry 26]

[0430]

[0431] In a 100 mL eggplant-shaped flask with a stirrer, 0.4 g of compound a-17, 0.16 g of malondialdehyde dianilide hydrochloride, 7.5 mL of acetonitrile, 2.5 mL of anhydrous acetic acid, and 0.2 mL of pyridine were added and heated to reflux for 2 hours. Thereafter, the mixture was cooled to room temperature, and the precipitated solid was recovered by vacuum filtration, washed with 10 mL of diethyl ether, and dried under reduced pressure at 50° C., thereby obtaining 0.35 g of compound a-18.

[0432] In a 100 mL eggplant flask with a stirrer, add 0.3 g of compound a-18, 0.8 g of lithium tetrakis-pentafluorophenylborate, 50 mL of dichloromethane, and 20 mL of water, and stir at room temperature for 3 hours. Then, transfer the liquid to a separatory funnel, remove the aqueous phase, wash the organic phase twice with 20 mL of water, use an evaporator to distill the solvent from the organic phase, and dry the solid under reduced pressure at 50°C to obtain 0.4 g of compound (z-62). In addition, the identification of the compound was performed using LC-MS and 1 H-NMR analysis was performed.

[0433] [Intermediate Synthesis Example 8]

[0434] [Chemistry 27]

[0435]

[0436] In a 200 mL eggplant-shaped flask with a stirrer, add 15 g of compound a-19 and 28.7 g of methyl 4,4-dimethyl-3-oxopentanoate, and stir at 180°C for 24 hours. Thereafter, cool to room temperature, add 250 mL of hexane and 200 mL of 1N hydrochloric acid aqueous solution, transfer to a separatory funnel, and remove the aqueous phase. Subsequently, after using an evaporator to distill off the solvent from the organic phase, the compound remaining in the flask is separated and purified by silica gel chromatography, thereby obtaining 7 g of the target compound a-20. Furthermore, the identification of the compound is performed by LC-MS and 1 H-NMR analysis was performed.

[0437] [Intermediate Synthesis Example 9]

[0438] [Chemistry 28]

[0439]

[0440] In a 100mL eggplant-shaped flask with a stirrer, 3.5g of compound a-20 and 20mL of diethyl ether were added and cooled in an ice bath. After cooling in an ice bath for 5 minutes, 14.0mL of 1mol / L methyl iodide magnesium diethyl ether solution was added over 10 minutes, then heated to 35°C and stirred for 2 hours. Then, after naturally cooling to room temperature, the obtained reaction solution was added to a beaker containing 100mL of water and a stirrer over 5 minutes. Thereafter, 20g of 40% fluorinated boric acid aqueous solution was added over 10 minutes, stirred for 30 minutes, and then transferred to a separatory funnel. Then, 30mL of dichloromethane was added for liquid separation, thereby removing the aqueous phase, and using an evaporator to distill the solvent from the organic phase. Thereafter, the residue was dissolved in 30 mL of dichloromethane, 50 mL of diisopropyl ether was added, 40 g of the solvent was removed by an evaporator, and then the mixture was cooled in an ice bath. The precipitated solid component was collected by suction filtration and dried under reduced pressure at 50° C., thereby obtaining 2.3 g of compound a-21. 1 H-NMR analysis was performed.

[0441] [Synthesis Example of Compound (z-151)]

[0442] [Chemistry 29]

[0443]

[0444] In a 100 mL eggplant-shaped flask with a stirrer, 0.5 g of compound a-21, 0.18 g of malondialdehyde dianilide hydrochloride, and 15 mL of pyridine were added and heated under reflux for 2 hours. After cooling to room temperature, the solvent was distilled off using an evaporator and separated using column chromatography to obtain 0.2 g of compound a-22.

[0445] In a 100 mL eggplant flask with a stirrer, add 0.2 g of compound a-22, 0.8 g of lithium tetrakis-pentafluorophenylborate, 50 mL of dichloromethane, and 20 mL of water, and stir at room temperature for 3 hours. Thereafter, transfer the liquid to a separatory funnel, remove the aqueous phase, wash the organic phase twice with 20 mL of water, use an evaporator to distill the solvent from the organic phase, and separate by column chromatography to obtain 0.2 g of compound (z-151). Furthermore, the identification of the compound was performed by LC-MS and 1 H-NMR analysis was performed.

[0446] [Intermediate Synthesis Example 10]

[0447] [Chemistry 30]

[0448]

[0449] In a 200mL eggplant flask with a stirrer, add 1.9g of compound a-23 and 2.0g of ethyl pivalate and stir. After 5 minutes, add 0.3g of sodium hydride (60%, dispersed in paraffin liquid), and then stir at 80°C for 3 hours. Thereafter, cool to room temperature, add 30mL of 1N hydrochloric acid aqueous solution for neutralization, and extract the organic phase with 150mL of ethyl acetate. Then, in the organic phase, add 5g of magnesium sulfate and stir for 15 minutes, then filter and remove magnesium sulfate through a filter, put the filtrate into a 300mL eggplant flask, and use an evaporator to distill the solvent to obtain 1.3g of compound a-24.

[0450] A stirring bar was placed in an eggplant-shaped flask containing 1.3 g of compound a-24, and 20 mL of concentrated hydrochloric acid was added, followed by stirring at 40°C. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 240 mL of 1N sodium hydroxide aqueous solution was added for neutralization. Subsequently, the solution was transferred to a separatory funnel, 200 mL of ethyl acetate was added, and the organic phase was extracted. Thereafter, 5 g of magnesium sulfate was added and stirred for 15 minutes. Thereafter, the magnesium sulfate was removed by filtering through a filter, and the filtrate was placed in a 300 mL eggplant-shaped flask, and the solvent was distilled off using an evaporator. Thereafter, the compound remaining in the flask was separated and purified by silica gel chromatography, thereby obtaining 1.1 g of compound a-25. Furthermore, the compound was identified by LC-MS and 1 H-NMR analysis was performed.

[0451] [Intermediate Synthesis Example 11]

[0452] [Chemistry 31]

[0453]

[0454] In a 200 mL eggplant-shaped flask with a stirrer, add 1.5 g of compound a-25 and 50 mL of diethyl ether, and cool in an ice bath. After cooling in an ice bath for 5 minutes, add 1.5 mL of 1 mol / L methyl magnesium iodide diethyl ether solution over 10 minutes, then heat to 35°C and stir for 2 hours. Next, cool the reaction solution in an ice bath, add 50 mL of 20% aqueous perchloric acid solution, filter and separate the precipitated solid, wash with 50 mL of water, and dry under reduced pressure at 50°C to obtain 3.0 g of compound a-26. Furthermore, the compound was identified using 1 H-NMR analysis was performed.

[0455] [Synthesis Example of Compound (z-157)]

[0456] [Chemistry 32]

[0457]

[0458] In a 100 mL eggplant flask with a stirrer, add 7.0 g of compound a-26, 2.5 g of malondialdehyde dianilide hydrochloride, 50 mL of acetonitrile, 10 mL of anhydrous acetic acid, and 10 mL of pyridine, and heat under reflux for 2 hours. Thereafter, cool to room temperature, and recover the precipitated solid by vacuum filtration, wash with 10 mL of acetic acid and 10 mL of acetonitrile, and dry under reduced pressure at 50° C. to obtain 5.1 g of compound a-27.

[0459] In a 100-mL eggplant-shaped flask with a stirrer, add 0.6 g of compound a-27, 1.2 g of lithium tetrakis-pentafluorophenylborate, 50 mL of dichloromethane, and 50 mL of water, and stir at room temperature for 3 hours. Then, transfer the liquid to a separatory funnel, remove the aqueous phase, wash the organic phase twice with 20 mL of water, and use an evaporator to distill off the solvent from the organic phase. Thereafter, dissolve the residue in 20 mL of acetone, add 100 mL of water, and use an evaporator to distill off 10 g of the solvent, followed by cooling in an ice bath. Thereafter, recover the precipitated solid by suction filtration, wash it with 50 mL of methanol, and then dry the solid under reduced pressure at 50°C to obtain 1.0 g of compound (z-157). Furthermore, the compound was identified using LC-MS and 1 H-NMR analysis was performed.

[0460] [Intermediate Synthesis Example 12]

[0461] [Chemistry 33]

[0462]

[0463] In a 200 mL eggplant flask with a stirrer, 22 g of 1-adamantanecarbonyl chloride (compound a-28) and 5.2 g of methylenecyclohexane were added, heated to 90°C, and stirred for 10 minutes while dropping 10 g of trifluoromethanesulfonic acid. Then, after cooling to 0°C, 150 mL of hexane, 50 mL of diethyl ether, and 50 mL of water were added and stirred, and the precipitated solid was filtered and separated, and dried under reduced pressure at 50°C to obtain 4.2 g of compound a-35. In addition, the identification of the compound was performed using 1 H-NMR analysis was performed.

[0464] [Synthesis Example of Compound (z-163)]

[0465] [Chemistry 34]

[0466]

[0467] In a 100 mL eggplant flask with a stirrer, add 0.5 g of compound a-35, 0.1 g of malondialdehyde dianilide hydrochloride, 4 mL of acetonitrile, 1 mL of anhydrous acetic acid, and 1 mL of pyridine, and stir at 90°C for 10 minutes. After cooling to 0°C, the precipitated solid was filtered and separated, washed with 2 mL of acetonitrile, and dried under reduced pressure at 50°C to obtain 0.3 g of compound a-36. The compound was identified by 1 H-NMR analysis was performed.

[0468] In a 100 mL eggplant-shaped flask with a stirrer, add 0.3 g of compound a-36, 0.4 g of lithium tetrakis-pentafluorophenylborate, 20 mL of dichloromethane, and 20 mL of water, and stir at room temperature for 4 hours. Then, transfer the liquid to a separatory funnel, remove the aqueous phase, wash the organic phase twice with 20 mL of water, and use an evaporator to distill the solvent from the organic phase. Thereafter, dissolve the residue in dichloromethane, add methanol, recover the precipitated solid by suction filtration, and dry under reduced pressure at 50°C to obtain 0.4 g of compound (z-163). Furthermore, the compound was identified by LC-MS and 1 H-NMR analysis was performed.

[0469] [Intermediate Synthesis Example 13]

[0470] [Chemistry 35]

[0471]

[0472] To a solution of compound a-37 (20.0 g) in t-BuOH (150 mL), ethyl pivalate (50.0 g) was added, and 5.5 g of sodium hydride (60%, dispersed in paraffin liquid) was added, followed by stirring at 80° C. for 3 hours. Thereafter, the mixture was cooled to room temperature, and 20 mL of concentrated hydrochloric acid was added. After separation and washing with ethyl acetate-water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator to obtain compound a-38.

[0473] Afterwards, without refining compound a-38, 60 mL of concentrated hydrochloric acid was added and stirred at 40°C. After 1 hour, the reaction solution was cooled in an ice bath and neutralized by adding 1N sodium hydroxide aqueous solution. After separation and washing with ethyl acetate-water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound a-39 (15.4 g). The compound was identified by LC-MS and 1 H-NMR analysis was performed.

[0474] [Intermediate Synthesis Example 14]

[0475] [Chemistry 36]

[0476]

[0477] Compound a-39 (15.4 g), phenylboronic acid (11.7 g), tetrakis(triphenylphosphine)palladium (1.0 g), and potassium carbonate (60.0 g) were dissolved in a mixed solution of 50 mL of toluene and 50 mL of water, and heated at 110 ° C for 12 hours while vigorously stirring. After cooling to room temperature, toluene-water was used for liquid separation and washing, sodium sulfate was added to the organic layer and dried, and the solvent was distilled off using an evaporator. The obtained mixture was refined by silica gel column chromatography to obtain compound a-40 (12.4 g).

[0478] Compound a-40 (12.4 g) and 90 mL of tetrahydrofuran were stirred while being cooled in an ice bath. After cooling in an ice bath for 5 minutes, methyl magnesium iodide diethyl ether solution (1 mol / L, 50 mL) was added dropwise, heated to 35°C, and stirred for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, 90 mL of a 20% aqueous perchloric acid 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 compound was identified using 1 H-NMR analysis was performed.

[0479] [Synthesis Example of Compound (z-156)]

[0480] [Chemistry 37]

[0481]

[0482] In a 100 mL eggplant flask with a stirrer, add 7.0 g of compound a-41, 2.5 g of malondialdehyde dianilide hydrochloride, 50 mL of acetonitrile, 10 mL of anhydrous acetic acid, and 10 mL of pyridine, and heat under reflux for 2 hours. Thereafter, cool to room temperature, and recover the precipitated solid by vacuum filtration, wash with 10 mL of acetic acid and 10 mL of acetonitrile, and dry under reduced pressure at 50° C. to obtain 5.0 g of compound a-42.

[0483] In a 100-mL eggplant-shaped flask with a stirrer, add 0.6 g of compound a-42, 1.2 g of lithium tetrakis-pentafluorophenylborate, 50 mL of dichloromethane, and 50 mL of water, and stir at room temperature for 3 hours. Then, transfer the liquid to a separatory funnel, remove the aqueous phase, wash the organic phase twice with 20 mL of water, and use an evaporator to distill off the solvent from the organic phase. Thereafter, dissolve the residue in 20 mL of acetone, add 100 mL of water, and use an evaporator to distill off 10 g of the solvent, followed by cooling in an ice bath. Thereafter, recover the precipitated solid by suction filtration, wash it with 50 mL of methanol, and then dry the solid under reduced pressure at 50°C to obtain 1.0 g of compound (z-156). Furthermore, the compound was identified using LC-MS and 1 H-NMR analysis was performed.

[0484] [Intermediate Synthesis Example 15]

[0485] [Chemistry 38]

[0486]

[0487] Compound a-43 (20.0 g), oxalyldichloride (21.4 g), pyridine (13.4 g) and dimethylformamide (DMF) (1 mL) were stirred in dichloromethane (100 mL) at room temperature for 1 hour. Dichloromethane was removed by evaporator to obtain a mixture containing compound a-44.

[0488] [Synthesis Example of Compound (z-161)]

[0489] [Chemistry 39]

[0490]

[0491] Compound a-45 was obtained by the same method as Intermediate Synthesis Example 10 except that ethyl pivalate was changed to compound a-44.

[0492] Compound (z-161) was obtained by the same method as in Intermediate Synthesis Example 11 and Compound (z-157), except that compound a-23 was changed to compound a-45 and malonaldehyde dianilide hydrochloride was changed to N-[2-chloro-3-(phenylamino)-2-propenyl]-aniline monohydrochloride. Compound (z-161) was obtained by the same method as in Intermediate Synthesis Example 11 and Compound (z-157). Compounds were identified by LC-MS and 1 H-NMR analysis was performed.

[0493] <Required conditions (A)>

[0494] The required condition (A) was measured using a solution prepared by dissolving the compound (Z) or compound (X) used in the following test in dichloromethane and measuring the transmission spectrum using a spectrophotometer (V-7200) manufactured by JASCO Corporation (wherein the transmission spectrum is a spectrum with a transmittance of 10% at the absorption maximum wavelength). The results are shown in Table 5. In Table 5, required conditions A to D respectively represent required condition (A), required condition (B-1), required condition (C) and required condition (D) in the <Compound (Z)> column.

[0495] <Required conditions (B)>

[0496] The requirement (B) was measured using an absorption spectrum obtained by dissolving the compound (Z) or compound (X) used in the following test in dichloromethane and measuring it using a spectrophotometer (V-7200) manufactured by JASCO Corporation. The results are shown in Table 5.

[0497] <Required conditions (C)>

[0498] In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.3 parts by mass of Irganox 1010 (manufactured by BASF Japan Co., Ltd.), the compound (Z) or compound (X) used in the following test, and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass.

[0499] Furthermore, when the following compounds (z-1), (x-3), and (z-163) are used, the amount used is 0.05 parts by mass, when the following compound (z-16) is used, the amount used is 0.06 parts by mass, when the following compounds (z-59), (z-62), (z-156), (z-157), (z-158), (z-159), (z-160), (z-161), and (z-162) are used, the amount used is 0.04 parts by mass, when the following compound (z-151) is used, the amount used is 0.08 parts by mass, and when the following compound (x-4) is used, the amount used is 0.03 parts by mass. The amount of each of these compounds is adjusted according to the molar absorption coefficient of each compound so that the absorbance at the absorption maximum wavelength of the obtained solution is about 1.

[0500] The obtained solution was cast on a smooth glass plate, dried at 20°C for 8 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100°C for 8 hours under reduced pressure to obtain a light resistance evaluation resin layer having a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm.

[0501] The absorbance of the resin layer for light resistance evaluation was measured using a spectrophotometer (V-7200) manufactured by JASCO Corporation, and the absorbance Ai at the maximum absorption wavelength λa in the wavelength range of 700nm to 1000nm was measured. Thereafter, a fluorescent lamp (manufactured by TWINBIRD Industries, arm-type touch inverter fluorescent lamp LK-H766B, total beam: 1334lm) was set at a distance of 30cm from directly above the surface of the resin layer for light resistance evaluation in the vertical direction, and the fluorescent lamp was irradiated for 30 days. The absorbance Af at the λa of the resin layer for light resistance evaluation after irradiation with the fluorescent lamp for 30 days was measured, and the retention rate D of the absorbance (=Af×100 / Ai) was calculated. The results are shown in Table 5.

[0502] <Required conditions (D)>

[0503] In the absorption spectrum measured using a solution obtained by dissolving the compound (Z) or compound (X) used in the following test in dichloromethane and using a spectrophotometer (V-7200) manufactured by JASCO Corporation, εa was used as the absorbance at the longest wavelength among the maximum absorption wavelengths, and εbmax was used as the maximum absorbance at wavelengths of 430 nm to 580 nm, and εa / εbmax was calculated. The results are shown in Table 5.

[0504]

[0505] <Molecular weight>

[0506] The molecular weight of the resin is measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent and the like.

[0507] (a) Using a gel permeation chromatography (GPC) apparatus manufactured by Waters (Model 150C, column: H-type column manufactured by Tosoh Co., Ltd., developing solvent: o-dichlorobenzene), the weight average molecular weight (Mw) and number average molecular weight (Mn) converted to standard polystyrene were measured.

[0508] (b) Using a GPC apparatus manufactured by Tosoh Co., Ltd. (HLC-8220 model, column: TSK gel α-M, developing solvent: THF), the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured.

[0509] In addition, regarding the resin synthesized in Resin Synthesis Example 3 described later, the molecular weight was not measured by the above method, but the logarithmic viscosity was measured by the following method (c).

[0510] (c) A portion of the polyimide solution was poured into anhydrous methanol to precipitate polyimide, which was separated from the unreacted monomer by filtration, and then vacuum dried at 80° C. for 12 hours. 0.1 g of the obtained polyimide was dissolved in 20 mL of N-methyl-2-pyrrolidone (dilute polyimide solution), and the logarithmic viscosity (μ) at 30° C. was calculated using a Cannon-Fenske viscometer by the following formula.

[0511] μ={ln(ts / t0)} / C

[0512] t0: Flow time of solvent (N-methyl-2-pyrrolidone)

[0513] ts: Flow time of dilute polyimide solution

[0514] C: 0.5 g / dL

[0515] <Glass transition temperature (Tg)>

[0516] The glass transition temperature of the resin was measured using a differential scanning calorimeter (DSC6200) manufactured by Hitachi High-Tech Science Co., Ltd. at a heating rate of 20° C. per minute under a nitrogen flow.

[0517] [Resin Synthesis Example 1]

[0518] 8-methyl-8-methoxycarbonyltetracyclic [4.4.0.1 2,5 .1 7,10 ] 100 parts by mass of 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 reaction) were loaded into a nitrogen-substituted 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 / liter) as a polymerization catalyst and 0.9 parts by mass of a toluene solution of tungsten hexachloride modified with methanol (concentration 0.025 mol / liter) were added to the solution in the reaction vessel, and the solution was heated and stirred at 80°C for 3 hours to perform a ring-opening polymerization reaction and obtain a ring-opening polymer solution. The polymerization conversion rate in the polymerization reaction was 97%.

[0519] [Chemistry 40]

[0520]

[0521] 1,000 parts by mass of the obtained ring-opening polymer solution was placed in an autoclave, and 0.12 parts by mass of RuHCl(CO)[P(C6H5)3]3 was added to the ring-opening polymer solution. 2 , reaction temperature 165 ° C, heating and stirring for 3 hours to carry out hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas is depressurized. After injecting the obtained reaction solution into a large amount of methanol, the solidified product is separated and recovered, and dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The number average molecular weight (Mn) of the obtained resin A is 32,000, the weight average molecular weight (Mw) is 137,000, and the glass transition temperature (Tg) is 165 ° C.

[0522] [Resin Synthesis Example 2]

[0523] In a 3L four-necked flask, 35.12g (0.253mol) of 2,6-difluorobenzonitrile, 87.60g (0.250mol) of 9,9-bis(4-hydroxyphenyl)fluorene, 41.46g (0.300mol) of potassium carbonate, 443g of N,N-dimethylacetamide and 111g of toluene were added. Then, a thermometer, a stirrer, a three-way stopcock with a nitrogen inlet tube, a Dean-Stark tube and a cooling tube were installed in the four-necked flask. Then, after nitrogen substitution in the flask, the obtained solution was reacted at 140°C for 3 hours, and the generated water was removed from the Dean-Stark tube at any time. When the generation of water was not confirmed, the temperature was slowly raised to 160°C, and the reaction was carried out for 6 hours at the temperature of the state. Thereafter, the mixture was cooled to room temperature (25°C), the generated salt was removed by filter paper, the filtrate was put into methanol for reprecipitation, and the filtrate (residue) was separated by filtration. The obtained filtrate was vacuum dried at 60°C for one night 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.

[0524] [Resin Synthesis Example 3]

[0525] In a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a dropping funnel with a side tube, a Dean-Stark tube, and a cooling tube, 27.66 g (0.08 mol) of 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene and 7.38 g (0.02 mol) of 4,4'-bis(4-aminophenoxy)biphenyl were placed under a nitrogen stream and dissolved in 68.65 g of γ-butyrolactone and 17.16 g of N,N-dimethylacetamide. The obtained solution was cooled to 5°C using an ice-water bath, and 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 0.50 g (0.005 mol) of triethylamine as an imidization catalyst were added while maintaining the same temperature. After the addition was completed, the temperature was raised to 180°C, and the distillate was removed as needed while refluxed for 6 hours. After the reaction is completed, air cooling is performed until the internal temperature reaches 100°C, and then 143.6 g of N,N-dimethylacetamide is added for dilution, and the mixture is cooled while being stirred to obtain 264.16 g of a polyimide solution having a solid content concentration of 20% by mass. A portion of the polyimide solution is injected into 1 L of methanol to precipitate the polyimide. After the filtered and separated polyimide is washed with methanol, it is dried in a vacuum dryer at 100°C for 24 hours to obtain a white powder (hereinafter also referred to as "resin C"). The infrared (IR) spectrum of the obtained resin C was measured, and the result showed that the 1704 cm-1 peculiar to the imide group -1 、1770cm -1 The glass transition temperature (Tg) of resin C is 310°C, and the logarithmic viscosity is measured to be 0.87.

[0526] [Example 1]

[0527] 〔Making of base material〕

[0528] In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.20 parts by mass of the following compound (z-1) as the compound (Z) (absorption maximum wavelength in dichloromethane is 787 nm), 0.038 parts by mass of the following compound (x-1) as the compound (X) (absorption maximum wavelength in dichloromethane is 711 nm), 0.075 parts by mass of the following compound (x-2) (absorption maximum wavelength in dichloromethane is 738 nm), and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 20°C for 8 hours, and then peeled from the glass plate. Furthermore, the peeled coating film was dried at 100°C under reduced pressure for 8 hours to obtain a resin layer (1) having a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm.

[0529] Compound (z-1)

[0530] [Chemistry 41]

[0531]

[0532] Compound (x-1)

[0533] [Chemistry 42]

[0534]

[0535] Compound (x-2)

[0536] [Chemistry 43]

[0537]

[0538] The following resin composition (1) was applied to one side of the obtained resin layer (1) using a bar coater so that the thickness of the obtained resin layer (2) was 3 μm, and the solvent was evaporated and removed by heating at 70° C. in an oven for 2 minutes. Next, exposure (exposure amount 500 mJ / cm 2 , illumination: 200mW / cm 2 ), the resin composition (1) is cured to form a resin layer (2) on the resin layer (1). Similarly, a resin layer (2) containing the resin composition (1) is also formed on the other side of the resin layer (1). Thus, a substrate having a resin layer (2) not containing the compound (Z) on both sides of the resin layer (1) containing the compound (Z) is obtained.

[0539] Resin composition (1): a composition comprising 60 parts by mass of tricyclodecane dimethanol acrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, and methyl ethyl ketone (a solvent used so that the solid content concentration in the obtained composition is 30% by mass)

[0540] (Lightfastness)

[0541] The obtained substrate was exposed to indoor fluorescent light for 500 hours, and the light resistance of the near infrared absorbing pigment contained in the resin was evaluated. The light resistance was evaluated by calculating the pigment residual rate (%) based on the change in absorbance before and after exposure to fluorescent light at the wavelength with the highest absorption intensity of the substrate (hereinafter referred to as "λa"; when the substrate has multiple absorption maxima, λa is the wavelength with the highest absorption intensity).

[0542] The case where the pigment remaining rate after exposure to the fluorescent light for 500 hours was 95% or more was rated as "○", and the case where it was less than 95% was rated as "×".

[0543] [Fabrication of optical filters]

[0544] A dielectric multilayer film (I) is formed on one surface of the substrate obtained in the preparation of the substrate, and a dielectric multilayer film (II) is further formed on the other surface of the substrate to obtain an optical filter with a thickness of about 0.110 mm.

[0545] The dielectric multilayer film (I) is a laminated body (total 26 layers) formed by alternately laminating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers at a vapor deposition temperature of 100°C. The dielectric multilayer film (II) is a laminated body (total 22 layers) formed by alternately laminating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers at a vapor deposition temperature of 100°C.

[0546] In either the dielectric multilayer film (I) or the dielectric multilayer film (II), silicon dioxide layers and titanium dioxide layers are alternately stacked in the order of titanium dioxide layer, silicon dioxide layer, titanium dioxide layer, ... silicon dioxide layer, titanium dioxide layer, silicon dioxide layer from the substrate side, and the outermost layer of the optical filter is set as a silicon dioxide layer.

[0547] The thickness and number of layers of each layer were optimized using optical thin film design software (Essential Macleod, manufactured by ThinFilm Center) in order to achieve good transmittance in the visible region and reflective performance in the near-infrared region, based on the wavelength dependence of the refractive index of the substrate or the absorption characteristics of the compound (Z) and compound (X) used. When optimizing, in this embodiment, the input parameters (target values) for the software were set as shown in Table 6 below.

[0548] [Table 6]

[0549]

[0550] As a result of the film structure optimization, the dielectric multilayer film (I) is made into a multilayer vapor-deposited film with 26 layers in which silicon dioxide layers with a physical film thickness of about 37nm to 168nm and titanium dioxide layers with a physical film thickness of about 11nm to 104nm are alternately stacked, and the dielectric multilayer film (II) is made into a multilayer vapor-deposited film with 22 layers in which silicon dioxide layers with a physical film thickness of about 40nm to 191nm and titanium dioxide layers with a physical film thickness of about 10nm to 110nm are alternately stacked. An example of the optimized film structure is shown in Table 7 below.

[0551] [Table 7]

[0552]

[0553] The obtained optical filter was obtained by obtaining the average value T of the spectral transmittance measured in the vertical direction of the optical filter in the wavelength of 430nm to 580nm and the average value R of the spectral reflectance of the non-polarized light incident at an angle of 5° from the vertical direction of the dielectric multilayer film (II) side in the wavelength of 700nm to 800nm. Furthermore, the spectral transmittance and spectral reflectance were measured using a spectrophotometer (V-7200) manufactured by JASCO Corporation. The results are shown in Table 8.

[0554] [Example 2]

[0555] In Example 1, the substrate was obtained in the same manner as in Example 1 except that 0.08 mass parts of the following compound (z-16) (absorption maximum wavelength in dichloromethane is 825 nm) was used instead of 0.2 mass parts of compound (z-1), and resin B was used instead of resin A.

[0556] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0557] Compound (z-16)

[0558] [Chemistry 44]

[0559]

[0560] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0561] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0562] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0563] [Example 3]

[0564] In Example 1, the substrate was obtained in the same manner as in Example 1, except that 0.14 mass parts of the following compound (z-59) (absorption maximum wavelength in dichloromethane is 770 nm) was used instead of 0.2 mass parts of compound (z-1), and resin C was used instead of resin A.

[0565] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0566] Compound (z-59)

[0567] [Chemistry 45]

[0568]

[0569] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0570] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0571] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0572] [Example 4]

[0573] In Example 1, 0.2 mass parts of the following compound (z-62) (absorption maximum wavelength in dichloromethane is 757 nm) is used instead of 0.2 mass parts of compound (z-1), and Acryviewa manufactured by Nippon Catalyst Co., Ltd. is used instead of resin A. Except for this, the substrate is obtained in the same manner as in Example 1.

[0574] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0575] Compound (z-62)

[0576] [Chemistry 46]

[0577]

[0578] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0579] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0580] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0581] [Example 5]

[0582] In Example 1, a substrate was obtained in the same manner as in Example 1 except that 0.08 mass parts of compound (z-151) (absorption maximum wavelength in dichloromethane: 824 nm) was used instead of 0.2 mass parts of compound (z-1).

[0583] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0584] Compound (z-151)

[0585] [Chemistry 47]

[0586]

[0587] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0588] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0589] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0590] [Example 6]

[0591] 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 are added to prepare a solution with a resin concentration of 20% by mass, and the solution is filtered using a microporous filter with a pore size of 5 μm to obtain a resin solution (E6-1).

[0592] In the same manner, 100 parts by mass of resin A, 2 parts by mass of the compound (z-1) as compound (Z), and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass, and the solution was filtered using a microporous filter having a pore size of 5 μm to obtain a resin solution (E6-2).

[0593] The following resin composition (2) was applied on both sides of a transparent glass support "OA-10G" (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd. and cut into a size of 200 mm × 200 mm using a spin coater in such a way that the film thickness after drying was about 1 μm. Thereafter, the film was heated on a hot plate at 80°C for 2 minutes to evaporate and remove the solvent, thereby forming an adhesive layer that functions as an adhesive layer between the glass support and the coating resin layer (1) and the coating resin layer (2) described later.

[0594] Next, the resin solution (E6-1) was applied to one surface of the glass support having the adhesive layer formed thereon using a spin coater so that the film thickness after drying was 10 μm, and the solution was heated on a hot plate at 80° C. for 5 minutes to volatilize and remove the solvent, thereby forming a coating resin layer (2).

[0595] Furthermore, the resin solution (E6-2) was applied to the other surface of the glass support body having the adhesive layer formed thereon using a spin coater so that the film thickness after drying was 10 μm, and the solution was heated on a hot plate at 80° C. for 5 minutes to volatilize and remove the solvent, thereby forming a coating resin layer (1).

[0596] Thus, a substrate having a thickness of 222 μm was obtained in which a resin layer containing the compound (Z) was laminated on one surface of a glass support and a resin layer not containing the compound (Z) was laminated on the other surface.

[0597] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 9 shows the results.

[0598] Resin composition (2): 30 parts by mass of isocyanuric acid ethylene oxide-modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.), 20 parts by mass of 1,9-nonanediol diacrylate, 20 parts by mass of methacrylic acid, 30 parts by mass of glycidyl methacrylate, 5 parts by mass of 3-glycidyloxypropyltrimethoxysilane, 5 parts by mass of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by BASF Japan Co., Ltd.) and 1 part by mass of San-Aid SI-110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed, dissolved in propylene glycol monomethyl ether acetate so as to have a solid content concentration of 50% by mass, and then filtered using a microporous filter having a pore size of 0.2 μm.

[0599] Next, referring to Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the surface of the coating resin layer (2), and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the surface of the coating resin layer (1), thereby obtaining an optical filter with a thickness of approximately 0.226 mm.

[0600] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0601] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 9 shows the result.

[0602] [Example 7]

[0603] In Example 1, a substrate was obtained in the same manner as in Example 1 except that 0.01 parts by mass of the following compound (x-3) (absorption maximum wavelength in dichloromethane: 931 nm) was additionally used.

[0604] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0605] Compound (x-3)

[0606] [Chemistry 48]

[0607]

[0608] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0609] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0610] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0611] [Example 8]

[0612] In Example 1, a substrate was obtained in the same manner as in Example 1 except that 0.03 parts by mass of the following compound (x-5) (absorption maximum wavelength in dichloromethane: 1095 nm) was additionally used.

[0613] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0614] Compound (x-5)

[0615] [Chemistry 49]

[0616]

[0617] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0618] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0619] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0620] [Example 9]

[0621] In Example 1, the substrate was obtained in the same manner as in Example 1, except that 0.16 mass parts of compound (z-16) (the absorption maximum wavelength in dichloromethane is 825 nm) and 0.12 mass parts of compound (z-59) (the absorption maximum wavelength in dichloromethane is 770 nm) were used to replace 0.2 mass parts of compound (z-1).

[0622] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0623] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0624] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0625] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0626] [Example 10]

[0627] In Example 1, a substrate was obtained in the same manner as in Example 1 except that 0.17 parts by mass of the following compound (y-1) (absorption maximum wavelength in dichloromethane: 394 nm) was additionally used.

[0628] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0629] Compound (y-1)

[0630] [Chemistry 50]

[0631]

[0632] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0633] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0634] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0635] [Example 11]

[0636] In Example 6, the substrate was obtained in the same manner as in Example 6, except that a near-infrared absorbing glass substrate "BS-11" (thickness 0.2 mm) manufactured by Matsunami Glass Industries Co., Ltd. was used instead of a transparent glass support "OA-10G" (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd.

[0637] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 9 shows the results.

[0638] Subsequently, in the same manner as in Example 6, a dielectric multilayer film (I) comprising 26 layers in total, in which silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers are alternately stacked, is formed on the surface of the coating resin layer (2), and further, a dielectric multilayer film (II) comprising 22 layers in total, in which silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers are alternately stacked, is formed on the surface of the coating resin layer (1), thereby obtaining an optical filter having a thickness of approximately 0.226 mm.

[0639] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0640] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 9 shows the result.

[0641] [Example 12]

[0642] In Example 1, a substrate was obtained in the same manner as in Example 1 except that 0.1 parts by mass of the following compound (z-156) (absorption maximum wavelength in dichloromethane: 785 nm) was used instead of 0.2 parts by mass of the compound (z-1).

[0643] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0644] Compound (z-156)

[0645] [Chemistry 51]

[0646]

[0647] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0648] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0649] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0650] [Example 13]

[0651] In Example 12, a substrate was obtained in the same manner as in Example 12 except that 0.1 mass part of the following compound (z-157) (absorption maximum wavelength in dichloromethane: 788 nm) was used instead of 0.1 mass part of the compound (z-156).

[0652] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0653] Compound (z-157)

[0654] [Chemistry 52]

[0655]

[0656] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0657] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0658] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0659] [Example 14]

[0660] In Example 12, a substrate was obtained in the same manner as in Example 12 except that 0.1 mass part of the following compound (z-158) (absorption maximum wavelength in dichloromethane: 790 nm) was used instead of 0.1 mass part of the compound (z-156).

[0661] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0662] Compound (z-158)

[0663] [Chemistry 53]

[0664]

[0665] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0666] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0667] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0668] [Example 15]

[0669] In Example 12, a substrate was obtained in the same manner as in Example 12 except that 0.1 mass part of the following compound (z-159) (absorption maximum wavelength in dichloromethane: 800 nm) was used instead of 0.1 mass part of the compound (z-156).

[0670] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0671] Compound (z-159)

[0672] [Chemistry 54]

[0673]

[0674] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0675] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0676] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0677] [Example 16]

[0678] In Example 12, a substrate was obtained in the same manner as in Example 12 except that 0.1 mass part of the following compound (z-160) (absorption maximum wavelength in dichloromethane: 791 nm) was used instead of 0.1 mass part of the compound (z-156).

[0679] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0680] Compound (z-160)

[0681] [Chemistry 55]

[0682]

[0683] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0684] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0685] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0686] [Example 17]

[0687] In Example 12, a substrate was obtained in the same manner as in Example 12 except that 0.1 mass part of the following compound (z-161) (absorption maximum wavelength in dichloromethane: 800 nm) was used instead of 0.1 mass part of the compound (z-156).

[0688] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0689] Compound (z-161)

[0690] [Chemistry 56]

[0691]

[0692] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0693] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0694] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0695] [Example 18]

[0696] In Example 12, a substrate was obtained in the same manner as in Example 12 except that 0.1 mass part of the following compound (z-162) (absorption maximum wavelength in dichloromethane: 810 nm) was used instead of 0.1 mass part of the compound (z-156).

[0697] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0698] Compound (z-162)

[0699] [Chemistry 57]

[0700]

[0701] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0702] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0703] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0704] [Example 19]

[0705] In Example 12, a substrate was obtained in the same manner as in Example 12 except that 0.1 mass part of the following compound (z-163) (absorption maximum wavelength in dichloromethane: 760 nm) was used instead of 0.1 mass part of the compound (z-156).

[0706] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0707] Compound (z-163)

[0708] [Chemistry 58]

[0709]

[0710] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0711] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0712] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0713] [Comparative Example 1]

[0714] In Example 1, except not using compound (Z), it carried out similarly to Example 1, and obtained the base material.

[0715] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0716] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0717] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0718] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0719] [Comparative Example 2]

[0720] In Example 1, instead of using compound (Z), 0.038 mass parts of compound (x-1), 0.075 mass parts of compound (x-2), and 0.2 mass parts of compound (x-3) (absorption maximum wavelength in dichloromethane is 931 nm) are used as compound (X). The substrate is obtained in the same manner as in Example 1, except that the above-mentioned steps are repeated.

[0721] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0722] Compound (x-3)

[0723] [Chemistry 59]

[0724]

[0725] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0726] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0727] About the obtained optical filter, the average value T and the average value R were calculated|required similarly to Example 1. Table 8 shows the result.

[0728] [Comparative Example 3]

[0729] In Example 1, instead of using compound (Z), 0.038 mass parts of compound (x-1), 0.075 mass parts of compound (x-2), and 0.08 mass parts of compound (x-4) (absorption maximum wavelength in dichloromethane is 760 nm) are used as compound (X). The substrate is obtained in the same manner as in Example 1, except that the above-mentioned steps are repeated.

[0730] The light resistance of the obtained substrate was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0731] Compound (x-4)

[0732] [Chemistry 60]

[0733]

[0734] Then, in the same manner as in Example 1, a dielectric multilayer film (I) with a total of 26 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on one side of the obtained substrate, and further, a dielectric multilayer film (II) with a total of 22 layers consisting of alternately stacked silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.110 mm.

[0735] The design of the dielectric multilayer film was performed similarly to Example 1 by taking into account the wavelength dependency of the refractive index of the substrate and the like and using the same design parameters as in Example 1.

[0736] The average value T and the average value R were obtained for the obtained optical filter in the same manner as in Example 1. The results are shown in FIG.

[0737] Table 8.

[0738]

[0739] [Table 9]

[0740]

[0741] The optical filters obtained in Examples 1 to 19 can reduce the intensity of reflected light in the near-infrared region, especially in the wavelength region of 700nm to 800nm, while maintaining good transmittance of visible light. Therefore, in recent years, in imaging devices such as digital still cameras that have been progressing in high performance, the reduction in sensitivity in the visible light region can be suppressed to a minimum, and image defects caused by the reflected light can be eliminated, which is useful.

[0742] [Synthesis Example of Compound (z-164)]

[0743] Acetyl chloride (2 equivalents) and tert-butyl alcohol (1 equivalent) were placed in an eggplant-shaped flask and stirred while heating in an oil bath adjusted to 85°C. Trifluoromethanesulfonic acid (1 equivalent) was added dropwise over 5 minutes. After the addition was completed, the temperature of the oil bath was set to 100°C and stirred for 30 minutes. After cooling to room temperature, diethyl ether and water were added, and the precipitated solid was filtered to obtain the following compound (m-1).

[0744] Compound (m-1)

[0745] [Chemistry 61]

[0746]

[0747] In an eggplant-shaped flask, the obtained compound (m-1) (1 equivalent) and malondialdehyde dianilide hydrochloride (0.5 equivalent) are placed, and acetonitrile and anhydrous acetic acid are added thereto and stirred. Subsequently, pyridine (1 equivalent) is added dropwise and stirred at room temperature for 2 hours. Thereafter, acetonitrile, anhydrous acetic acid and pyridine are removed by an evaporator, and liquid separation operation is performed using methyl chloride / water. The organic phase is recovered, and 1.5 equivalents of LiFABA (lithium = tetrakis(pentafluorophenyl) borohydride) and water are added thereto, and the mixture is stirred vigorously for 3 hours. Thereafter, the organic phase is recovered, and the methyl chloride is removed by an evaporator to obtain compound (z-164).

[0748] Compound (z-164): The absorption maximum wavelength in dichloromethane is 715 nm

[0749] [Chemistry 62]

[0750]

[0751] [Synthesis Example of Compound (z-165)]

[0752] Compound (z-165) was obtained by the same method as in the Synthesis Example of Compound (z-164), except that acetyl chloride was changed to 1-methylcyclopropanecarboxylic acid chloride.

[0753] Compound (z-165): The absorption maximum wavelength in dichloromethane is 727 nm

[0754] [Chemistry 63]

[0755]

[0756] [Synthesis Example of Compound (z-166)]

[0757] Compound (z-166) was obtained by the same method as in the Synthesis Example of Compound (z-164), except that acetyl chloride was changed to 1-methylcyclohexanecarboxylic acid chloride.

[0758] Compound (z-166): The absorption maximum wavelength in dichloromethane is 719 nm

[0759] [Chemistry 64]

[0760]

[0761] [Synthesis Example of Compound (z-167)]

[0762] Compound (z-167) was obtained by the same method as in the Synthesis Example of Compound (z-164), except that acetyl chloride was replaced with 1-adamantanecarboxylic acid chloride.

[0763] Compound (z-167): The absorption maximum wavelength in dichloromethane is 721 nm

[0764] [Chemistry 65]

[0765]

[0766] [Synthesis Example of Compound (z-168)]

[0767] Compound (z-168) was obtained by the same method as in the synthesis example of compound (z-164), except that malonaldehyde dianilide hydrochloride was changed to the following compound (m-2).

[0768] Compound (m-2)

[0769] [Chemistry 66]

[0770]

[0771] Compound (z-168): The absorption maximum wavelength in dichloromethane is 720nm

[0772] [Chemistry 67]

[0773]

[0774] [Synthesis Example of Compound (z-169)]

[0775] Compound (z-169) was obtained by the same method as in the above Synthesis Example except that malonaldehyde dianilide hydrochloride was changed to the above Compound (m-2).

[0776] Compound (z-169): The absorption maximum wavelength in dichloromethane is 726 nm

[0777] [Chemistry 68]

[0778]

[0779] [Synthesis Example of Compound (z-170)]

[0780] In the synthesis example of compound (z-169), compound (z-170) was obtained by the same method as in the synthesis example except that compound (m-2) was changed to the following compound (m-3).

[0781] Compound (m-3)

[0782] [Chemistry 69]

[0783]

[0784] Compound (z-170): The absorption maximum wavelength in dichloromethane is 739 nm

[0785] [Chemistry 70]

[0786]

[0787] [Synthesis Example of Compound (z-171)]

[0788] In the synthesis example of compound (z-167), compound (z-171) was obtained by the same method as in the synthesis example except that compound (m-1) was changed to the following compound (m-4).

[0789] Compound (m-4)

[0790] [Chemistry 71]

[0791]

[0792] Compound (z-171): The absorption maximum wavelength in dichloromethane is 734 nm

[0793] [Chemistry 72]

[0794]

[0795] [Synthesis Example of Compound (z-172)]

[0796] In the synthesis example of compound (z-167), compound (z-172) was obtained by the same method as in the synthesis example except that compound (m-1) was changed to the following compound (m-5).

[0797] Compound (m-5)

[0798] [Chemistry 73]

[0799]

[0800] Compound (z-172): The absorption maximum wavelength in dichloromethane is 738 nm

[0801] [Chemistry 74]

[0802]

[0803] [Synthesis Example of Compound (z-173)]

[0804] In the synthesis example of compound (z-169), compound (z-173) was obtained by the same method as in the synthesis example except that compound (m-2) was changed to the following compound (m-6).

[0805] Compound (m-6)

[0806] [Chemistry 75]

[0807]

[0808] Compound (z-173): The absorption maximum wavelength in dichloromethane is 724 nm

[0809] [Chemistry 76]

[0810]

[0811] [Example 20 to Example 32 and Comparative Example 4 to Comparative Example 7]

[0812] 〔Making of base material〕

[0813] The same procedure as in Example 1 was carried out, and specifically, a substrate was prepared as follows.

[0814] Resin, compound (Z), compound (X), compound (Y) and dichloromethane were added in the proportions shown in Table 12 to prepare a solution having a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 20°C for 8 hours, and then peeled from the glass plate. Furthermore, the peeled coating film was dried at 100°C for 8 hours under reduced pressure to obtain a resin layer (1) having a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm.

[0815] In addition, the numerical values ​​described in the columns of 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.

[0816] In addition, the compound (x-6) in Table 12 is a compound represented by the following formula (the absorption maximum wavelength in dichloromethane is 717 nm).

[0817] [Chemistry 77]

[0818]

[0819] The following resin composition (1) was applied to one side of the obtained resin layer (1) using a bar coater so that the thickness of the obtained resin layer (2) was 3 μm, and the solvent was evaporated and removed by heating at 70° C. in an oven for 2 minutes. Next, exposure (exposure amount 500 mJ / cm 2 , illumination: 200mW / cm 2 ), the resin composition (1) is cured to form a resin layer (2) on the resin layer (1). Similarly, a resin layer (2) containing the resin composition (1) is also formed on the other side of the resin layer (1).

[0820] Resin composition (1): a composition comprising 60 parts by mass of tricyclodecane dimethanol acrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone, and methyl ethyl ketone (a solvent used so that the solid content concentration in the obtained composition is 30% by mass)

[0821] <Spectral transmittance>

[0822] The transmittance of the obtained substrate in the near-infrared region of 650nm to 800nm ​​wavelength and the visible light transmittance of 430nm to 580nm wavelength are measured using a spectrophotometer (V-7200) manufactured by JASCO Corporation. The transmittance is measured using the spectrophotometer under the condition that the light is incident perpendicularly to the surface of the substrate. The parameters measured using this device are as follows. The results are shown in Table 12.

[0823] The spectral transmittance spectra of the substrates obtained in Example 20 and Example 28 are shown in Figures 1 - 2 middle.

[0824] In addition, regarding the following Tc and Td, the obtained substrate was heated for 7 hours in an oven preheated to 155° C., and the transmittance of the substrate after the heating test was measured (heat resistance evaluation).

[0825] In addition, regarding Te and Tf, a UV exposure machine (manufactured by Iwasaki Electric Co., Ltd., Eye UV curing device US2-KO4501, illumination: 180 mW / cm 2 , irradiation dose: 560mJ / cm 2 ) The obtained substrate is irradiated with UV, and the transmittance of the substrate after the UV irradiation is measured (UV resistance evaluation).

[0826] Xa: The wavelength of light with the lowest transmittance measured in the direction perpendicular to the substrate in the wavelength range of 650 nm to 800 nm

[0827] Ta: The minimum transmittance measured in the direction perpendicular to the substrate at a wavelength of 650nm to 800nm

[0828] Tb: Average transmittance of light with a wavelength of 430 nm to 580 nm measured in the direction perpendicular to the substrate

[0829] Tc: The minimum transmittance of light with a wavelength of 650nm to 800nm ​​after the heating test, measured in the vertical direction of the substrate

[0830] Td: Average transmittance of light with a wavelength of 430 nm to 580 nm after the heating test, measured in the direction perpendicular to the substrate

[0831] Te: Minimum transmittance of light with a wavelength of 650nm to 800nm ​​after UV irradiation, measured in the vertical direction of the substrate

[0832] Tf: Average transmittance of light with a wavelength of 430 nm to 580 nm after UV irradiation, measured in the vertical direction of the substrate

[0833] [Fabrication of optical filters]

[0834] A dielectric multilayer film (III) is formed on one surface of the substrate obtained in the preparation of the substrate, and a dielectric multilayer film (IV) is formed on the other surface of the substrate to obtain an optical filter with a thickness of about 0.110 mm.

[0835] The dielectric multilayer film (III) is a laminated body (total 28 layers) formed by alternately laminating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers at a vapor deposition temperature of 100°C. The dielectric multilayer film (IV) is a laminated body (total 24 layers) formed by alternately laminating silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers at a vapor deposition temperature of 100°C.

[0836] In either the dielectric multilayer film (III) or the dielectric multilayer film (IV), silicon dioxide layers and titanium dioxide layers are alternately stacked in the order of titanium dioxide layer, silicon dioxide layer, titanium dioxide layer, ... silicon dioxide layer, titanium dioxide layer, and silicon dioxide layer from the substrate side, and the outermost layer of the optical filter is set as a silicon dioxide layer.

[0837] The thickness and number of layers of each layer were optimized using optical thin film design software (Essential Macleod, manufactured by ThinFilm Center) in order to achieve good transmittance in the visible region and reflective performance in the near-infrared region, based on the wavelength dependence of the refractive index of the substrate or the absorption characteristics of the compound (Z) and compound (X) used. When optimizing, in this embodiment, the input parameters (target values) for the software were set as shown in Table 10 below.

[0838] [Table 10]

[0839]

[0840] As a result of the film structure optimization, the dielectric multilayer film (III) is made into a multilayer vapor-deposited film with 28 layers in which silicon dioxide layers with a physical film thickness of about 32nm to 159nm and titanium dioxide layers with a physical film thickness of about 9nm to 94nm are alternately stacked, and the dielectric multilayer film (IV) is made into a multilayer vapor-deposited film with 24 layers in which silicon dioxide layers with a physical film thickness of about 39nm to 193nm and titanium dioxide layers with a physical film thickness of about 12nm to 117nm are alternately stacked. An example of the optimized film structure is shown in Table 11 below.

[0841] [Table 11]

[0842]

[0843] <Spectral transmittance>

[0844] The transmittance of the near-infrared region of the obtained optical filter, the wavelength of 650nm to 800nm, and the visible light transmittance of the wavelength of 430nm to 580nm are measured using a spectrophotometer (V-7200) manufactured by Nippon Spectroscopy (stock). The transmittance is the transmittance measured using the spectrophotometer under the condition that light is incident perpendicularly to the optical filter. The parameters measured using this device are as follows. The results are shown in Table 12.

[0845] The spectral transmittance spectra of the optical filters obtained in Example 20 and Example 28 are shown in Figures 3 - 4 middle.

[0846] Tg: Average transmittance of light with a wavelength of 650nm to 800nm ​​measured in the vertical direction of the optical filter

[0847] Th: Average transmittance of light with a wavelength of 430nm to 580nm measured in the vertical direction of the optical filter

[0848] [Examples 33 to 43 and Comparative Example 8]

[0849] The same procedure as in Example 6 was carried out, and specifically, a substrate was prepared as follows.

[0850] Resin A, compound (X), compound (Y) and dichloromethane were added in the ratios shown in Table 13 to prepare a solution having a resin concentration of 20% by mass, which was then filtered through a microporous filter with a pore size of 5 μm to obtain a resin solution (E-1).

[0851] Resin A, compound (Z) and dichloromethane were added in the ratios shown in Table 13 to prepare a solution having a resin concentration of 20 mass %, which was then filtered through a microfilter having a pore size of 5 μm to obtain a resin solution (E-2).

[0852] The following resin composition (2) was applied on both sides of a transparent glass support "OA-10G" (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd. and cut into a size of 200 mm × 200 mm using a spin coater in such a way that the film thickness after drying was about 1 μm. Thereafter, the film was heated on a hot plate at 80°C for 2 minutes to evaporate and remove the solvent, thereby forming an adhesive layer that functions as an adhesive layer between the glass support and the coating resin layer (1) and the coating resin layer (2) described later.

[0853] In addition, only in Example 39, a near-infrared absorbing glass substrate "BS-11" (thickness 200 μm) manufactured by Matsunami Glass Industries Co., Ltd. cut into a size of 200 mm×200 mm was used instead of "OA-10G".

[0854] Next, the resin solution (E-1) was applied on one surface of the glass support having the adhesive layer formed thereon using a spin coater so that the film thickness after drying was 10 μm, and the solution was heated on a hot plate at 80° C. for 5 minutes to volatilize and remove the solvent, thereby forming a coating resin layer (2).

[0855] Furthermore, the resin solution (E-2) was applied on the other surface of the glass support having the adhesive layer formed thereon using a spin coater so that the film thickness after drying was 10 μm, and the solution was heated on a hot plate at 80° C. for 5 minutes to volatilize and remove the solvent, thereby forming a coating resin layer (1).

[0856] Thus, a substrate having a thickness of 222 μm was obtained in which a resin layer containing the compound (Z) was laminated on one surface of a glass support and a resin layer not containing the compound (Z) was laminated on the other surface.

[0857] Furthermore, the numerical values ​​recorded in compounds z-164 to compound z-173 in Table 13 represent the content (mass parts) of each compound relative to 100 mass parts of resin in the resin layer (1), and the numerical values ​​recorded in compounds x-1, compound x-2 and compound y-1 in Table 13 represent the content (mass parts) of each compound relative to 100 mass parts of resin in the resin layer (2).

[0858] Xa, Ta to Tf of the substrate were measured in the same manner as in Example 20. The results are shown in Table 13.

[0859] The spectral transmittance spectrum of the substrate obtained in Example 36 is shown in Figure 5 middle.

[0860] Resin composition (2): 30 parts by mass of isocyanuric acid ethylene oxide-modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.), 20 parts by mass of 1,9-nonanediol diacrylate, 20 parts by mass of methacrylic acid, 30 parts by mass of glycidyl methacrylate, 5 parts by mass of 3-glycidyloxypropyltrimethoxysilane, 5 parts by mass of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by BASF Japan Co., Ltd.) and 1 part by mass of San-Aid SI-110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed, dissolved in propylene glycol monomethyl ether acetate so as to have a solid content concentration of 50% by mass, and then filtered using a microporous filter having a pore size of 0.2 μm.

[0861] Then, in the same manner as in Example 20, a dielectric multilayer film (III) consisting of 28 layers in total, in which silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers are alternately stacked, is formed on one side of the obtained substrate, and further, a dielectric multilayer film (IV) consisting of 24 layers in total, in which silicon dioxide (SiO2) layers and titanium dioxide (TiO2) layers are alternately stacked, is formed on the other side of the substrate, thereby obtaining an optical filter with a thickness of approximately 0.226 mm.

[0862] The design of the dielectric multilayer film is performed similarly to Example 20, taking into account the wavelength dependence of the refractive index of the substrate and the like, and using the same design parameters as in Example 20.

[0863] Tg and Th of the optical filter were measured in the same manner as in Example 20. The results are shown in Table 13.

[0864] The spectral transmittance spectrum of the optical filter obtained in Example 36 is shown in Figure 6 middle.

[0865]

[0866]

[0867] The optical filters obtained in Examples 20 to 43 can reduce the intensity of reflected light in the near-infrared region, especially in the wavelength region of 700nm to 750nm, while maintaining good transmittance of visible light. Therefore, in recent years, in imaging devices such as digital still cameras that have progressed in high performance, the reduction in sensitivity in the visible light region can be suppressed to a minimum, and image defects caused by the reflected light can be eliminated, which is useful.

Claims

1. An optical filter comprising a substrate i and a dielectric multilayer film, wherein the substrate i is formed from a resin composition according to the following and contains a compound Z, The resin composition comprises: a resin and a compound Z represented by the following formula (I): Cn + The - (I) In formula (I), Cn + is a monovalent cation represented by the following formula (II), An - It is a monovalent anion; In formula (II), Unit A is the following formula (A-III), Unit B is the following formula (B-III), Y A ~Y E are independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, -NR g R h group, amide group, imide group, cyano group, silane group, -Q 1 、-N=NQ 1 、-SQ 2 ,-SSQ 2 , or -SO2Q 3 , Y A With Y C , Y B With Y D , and Y C With Y E not bonded to each other or bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4- to 7-membered alicyclic group containing no or at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, wherein these aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups have no or have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group has no or has =O, Y A and R in the following formula (A-III) 1 or R 5 , and Y E and R in the following formula (B-III) 5 or R 1 are not bonded to each other or are bonded to each other to form a 4- to 7-membered alicyclic group containing no or at least one nitrogen atom, oxygen atom or sulfur atom, R g and R h are independently a hydrogen atom, -C(O)R i Base or the following L a ~L h Any one of Q 1 Independently, the following L a ~L h Any one of Q 2 are independently a hydrogen atom or the following L a ~L h Any one of Q 3 is hydroxyl or the following L a ~L h Any one of R i For the following L a ~L h any of; -* in formula (A-III) represents the same as Y of formula (II). A The bonded carbon is single bonded. =** in formula (B-III) represents the same as Y of formula (II) E The carbons to which they are bonded are double bonded. In formula (A-III) and formula (B-III), X is independently an oxygen atom, a selenium atom or a tellurium atom, R 1 , R 2 , R 4 , R 5 are independently a hydrogen atom, a halogen atom, a sulfone group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR g R h Base, -SR i Base, -SO2R i Base, -OSO2R i Base, -C(O)R i Base or the following L a ~L c , L e ~L h Any one of Adjacent R 1 , R 2 , R 4 , R 5 Not bonded to each other, R g and R h are independently a hydrogen atom, -C(O)R i Base or the following L a ~L h Any one of R i Independently, the following L a ~L h Any one of L a : Aliphatic hydrocarbon group having 1 to 15 carbon atoms L b : Alkyl group having 1 to 15 carbon atoms and substituted by halogen L c : An alicyclic hydrocarbon group having 3 to 14 carbon atoms and having no or a substituent K L d : An aromatic hydrocarbon group having 6 to 14 carbon atoms and having no or a substituent K L e : A heterocyclic group having 3 to 14 carbon atoms and having no or a substituent K L f :-OR, R is a hydrocarbon group having 1 to 12 carbon atoms and having no substituent L L g : an acyl group having 1 to 9 carbon atoms and having no or a substituent L L h : Alkoxycarbonyl having 1 to 9 carbon atoms and having no or a substituent L The substituent K is selected from L a ~L b At least one of the substituents L is selected from the L a ~L e At least one of .

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

3. The optical filter according to claim 1 or 2, wherein the R 1 ~R 6 At least one of the L a , L c or L d .

4. The optical filter according to claim 1 or 2, wherein the compound Z satisfies the following requirement B-1, Requirement B-1: In an absorption spectrum measured using a solution prepared by dissolving the compound Z in dichloromethane, the compound Z has a local maximum in a wavelength range of 720 nm to 900 nm.

5. The optical filter according to claim 1 or 2, wherein the compound Z satisfies the following requirement B-2, Requirement B-2: In an absorption spectrum measured using a solution prepared by dissolving the compound Z in dichloromethane, the compound has a local maximum in a wavelength range of 700 nm to 750 nm.

6. An optical filter according to claim 1 or 2, 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, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene 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.

7. The optical filter according to claim 1, wherein the substrate i is the following substrate: A substrate comprising a resin layer containing the compound Z; A substrate comprising two or more resin layers, at least one of the two or more resin layers being a resin layer containing the compound Z; or A substrate comprising a glass support and a resin layer containing the compound Z. The optical filter according to claim 1 , which is used in a solid-state imaging device.

9. The optical filter according to claim 1, which is used in an optical sensor device. 10 . A solid-state imaging device comprising the optical filter according to claim 1 .

11. An optical sensor device comprising the optical filter according to claim 1.

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