CN117757205A

CN117757205A - Resin composition, compound, substrate, optical filter, solid-state imaging device, and optical sensor device

Info

Publication number: CN117757205A
Application number: CN202311778246.7A
Authority: CN
Inventors: 川部泰典; 长屋胜也; 内田洋介; 大崎仁视; 畠中创; 下河広幸; 面手真人; 大桥幸恵
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2020-02-21
Filing date: 2021-02-19
Publication date: 2024-03-26
Also published as: JP2021134350A; KR20210107545A; CN113292807A; TW202132473A

Abstract

The present invention provides a light source having a wavelength of 700nm to 750nm or a wavelength of 720nm to 900nmThere are 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, a high ratio of absorbance in the infrared region to absorbance in the visible region, and excellent light resistance (durability). A resin composition comprising: resin, and compound represented by formula (I) [ in formula (I), cn ⁺ Is a monovalent cation represented by the formula (II), an ^‑ Is a monovalent anion]。Cn ⁺ An ^‑ (I)

Description

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

The present invention is a divisional application of patent application of application number 202110188611.3, entitled "resin composition, compound, substrate, optical Filter, solid-state imaging device, and optical sensor device" filed on App. No. 2021, 02, and 19.

Technical Field

The present invention relates to a resin composition, a compound, a base material, an optical filter, and a solid-state imaging device and an optical sensor device using the optical filter.

Background

In solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions, a charge-coupled device (Charge Coupled Device, CCD) or a complementary metal oxide semiconductor (Complementary Metal Oxide Semiconductor, CMOS) image sensor (image sensor) having a solid-state imaging element as a color image is used. In these solid-state imaging devices, a silicon photodiode or the like having sensitivity to near infrared rays which cannot be perceived by the human eye is used in the light receiving portion. In addition, a silicon photodiode or the like is also used in the optical sensor device. For example, in a solid-state imaging device, it is often necessary to perform a visibility correction for displaying a natural color in the human eye, and to use an optical filter (for example, a near infrared cut filter) for selectively transmitting or cutting light in a specific wavelength region.

As such a near infrared cut filter, a filter manufactured by various methods has been used since the past. For example, a near infrared cut filter is known in which a resin is used as a base material and a near infrared absorbing dye is contained in the resin (for example, refer to patent document 1). However, the near infrared ray cut filter described in patent document 1 may not necessarily have sufficient near infrared ray absorption characteristics.

[ Prior Art literature ]

[ patent literature ]

Patent document 1 japanese patent laid-open publication No. 2008-303130

Disclosure of Invention

[ problem to be solved by the invention ]

As the near infrared absorbing dye, there have been conventionally used dyes such as polymethylene-based, squarylium-based, porphyrin-based, dithiol metal complex-based, phthalocyanine-based, and diimmonium-based, and among them, dyes such as polymethylene-based and squarylium-based have been used in many cases in terms of having sufficient resistance to heat.

However, these pigments which have been used before have room for improvement in at least any one of the following aspects:

since the absorption maximum wavelength is in the long wavelength region, it is required to have a compound having absorption maximum in the vicinity of the wavelength of 700nm to 750nm or in the vicinity of the wavelength of 720nm to 900 nm;

the ratio of absorbance in the infrared region to absorbance in the visible region is small;

the light resistance (durability) is not sufficient.

In the conventional near infrared cut filter, the reflected light from the filter may cause adverse effects on images such as flare and ghost, and in particular, when the reflection band of the near infrared cut filter overlaps with the wavelength band that can be photoelectrically converted by the sensor, the adverse effects may become more remarkable.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition which has an extremely high absorption in the vicinity of a wavelength of 700nm to 750nm or in the vicinity of a wavelength of 720nm to 900nm, has a high ratio of absorbance in the infrared region to absorbance in the visible region, and is excellent in light resistance (durability).

[ means of solving the problems ]

The present inventors have made diligent studies to solve the above-described problems, and as a result, have found that the above-described problems can be solved according to the following structural examples, and have completed the present invention. The following shows a structural example of the present invention.

In the present invention, the terms "a to B" and the like representing the numerical ranges are the same as those of the terms "a above and B below", and a and B are included in the numerical ranges. In the present invention, the wavelengths a to B nm are characteristics at 1nm, which indicate the wavelength resolution in the wavelength region of the wavelength a nm to the wavelength B nm.

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

Cn ⁺ An ^- (I)

[ in formula (I), cn ⁺ An is a monovalent cation represented by the following formula (II) ^- Is a monovalent anion]

[ chemical 1]

In the formula (II),

the unit A is any one of the following formulas (A-I) to (A-III),

The unit B is any one of the following formulas (B-I) to (B-III),

Y _A ～Y _E each independently is a hydrogen atom, a halogen atom, a hydroxy group, a carboxyl group, a nitro group, -NR ^g R ^h Group, amide group, imide group, cyano group, silane group, -Q ¹ 、-N＝N-Q ¹ 、-S-Q ² 、-SSQ ² or-SO ₂ Q ³ ，

Y _A And Y is equal to _C 、Y _B And Y is equal to _D 、Y _C And Y is equal to _E An aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-to 7-membered alicyclic group having at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and having at least one nitrogen atom, oxygen atom or sulfur atom, which may be bonded to each other, and may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and further, the alicyclic group may have =o,

Y _A and R in the following formula (A-III) ¹ Or R is ⁵ 、Y _E And R in the following formula (B-III) ⁵ Or R is ¹ Can be bonded to each other to form a 4-to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom,

R ^g r is R ^h Each independently is a hydrogen atom, -C (O) R ⁱ The radicals or L ^a ～L ^h Any of Q ¹ Is independently the following L ^a ～L ^h Any of Q ² Independently a hydrogen atom or L ^a ～L ^h Any of Q ³ Is hydroxy or L ^a ～L ^h Any of R ⁱ Is the following L ^a ～L ^h Any of (3)]

[ chemical 2]

[ formula (A-I) -formula (A-III) & lt- & gt represents Y with formula (II) _A The bonded carbon is subjected to single bonding,

in the formulae (B-I) to (B-III) = represents Y in the formula (II) _E The bonded carbon is double bonded,

in the formulas (A-I) to (B-III),

x is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or-NR ⁸ -，

R ¹ ～R ⁶ Each independently is a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -NR ^g R ^h Radical, -SR ⁱ Radicals, -SO ₂ R ⁱ Radical, -OSO ₂ R ⁱ Radical, -C (O) R ⁱ The radicals or L ^a ～L ^h Any one of the above-mentioned,

r adjacent to each other ¹ ～R ⁶ An aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-to 7-membered alicyclic group having at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and having at least one nitrogen atom, oxygen atom or sulfur atom, which may be bonded to each other, and may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and further, the alicyclic group may have =o,

R ⁸ independently a hydrogen atom, a halogen atom, -C (O) R ⁱ The radicals L ^a ～L ^h Any one of the above-mentioned,

R ^g r is R ^h Each independently is a hydrogen atom, -C (O) R ⁱ The radicals or L ^a ～L ^h Any one of the above-mentioned,

R ⁱ is independently the following L ^a ～L ^h Any one of the above-mentioned,

(L ^a ): aliphatic hydrocarbon group having 1 to 15 carbon atoms

(L ^b ): halogen-substituted alkyl of 1 to 15 carbon atoms

(L ^c ): alicyclic hydrocarbon group having 3 to 14 carbon atoms and optionally having substituent K

(L ^d ): aromatic hydrocarbon group having 6 to 14 carbon atoms and optionally substituted with K

(L ^e ): heterocyclic groups having 3 to 14 carbon atoms and optionally having substituent groups K

(L ^f ): -OR (R is a hydrocarbon group of 1 to 12 carbon atoms which may have a substituent L)

(L ^g ): acyl groups having 1 to 9 carbon atoms which may have a substituent L

(L ^h ): alkoxycarbonyl groups having 1 to 9 carbon atoms which may have a substituent L

The substituent K is selected from the group consisting of L ^a ～L ^b At least one of the substituents L is selected from the group consisting of L ^a ～L ^f At least one of (a)]。

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

essential condition (a): in a transmission spectrum measured using a solution obtained by dissolving the compound (Z) in methylene chloride, wherein the transmission spectrum is a spectrum having a transmittance of 10% at an absorption maximum wavelength, the average value of the transmittance at wavelengths of 430nm to 580nm is 93% or more.

[3]According to [1]]Or [2]]The resin composition, wherein R is ¹ ～R ⁶ At least one of (2) is the L ^a 、L ^c Or L ^d 。

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

essential condition (B-1): the absorption spectrum measured by using a solution obtained by dissolving the compound (Z) in methylene chloride has a maximum in the wavelength range of 720nm to 900 nm.

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

essential condition (B-2): the absorption spectrum measured by using a solution obtained by dissolving the compound (Z) in methylene chloride has a maximum in the wavelength range of 700nm to 750 nm.

[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 a cyclic (poly) olefin-based resin, an aromatic polyether-based resin, a polyimide-based resin, a polyester-based resin, a polycarbonate-based resin, a polyamide-based resin, a polyarylate-based resin, a polysulfone-based resin, a polyethersulfone-based resin, a poly-p-phenylene-based resin, a polyamideimide-based resin, a polyethylene naphthalate-based resin, a fluorinated aromatic polymer-based resin, a (modified) acrylic resin, an epoxy-based resin, an allyl ester-based curable resin, a silsesquioxane-based ultraviolet curable resin, an acrylic ultraviolet curable resin, and a vinyl ultraviolet curable resin.

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

[8] The substrate (i) according to [7], 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, wherein at least one of the two or more resin layers is a resin layer containing the compound (Z); or alternatively

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

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

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

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

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

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

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

Cn ⁺ An ^- (III)

[ in formula (III), cn ⁺ An is a monovalent cation represented by the following formula (IV) ^- Is a monovalent anion]

[ chemical 3]

In the formula (IV) shown in the specification,

the unit A is any one of the following formulas (A-I) to (A-III),

the unit B is any one of the following formulas (B-I) to (B-III),

R ^g r is R ^h Each independently is a hydrogen atom, -C (O) R ⁱ The radicals or L ^a ～L ^h Any of Q ¹ Is independently the following L ^a ～L ^h Any one of the above-mentioned,Q ² independently a hydrogen atom or L ^a ～L ^h Any of Q ³ Is hydroxy or L ^a ～L ^h Any of R ⁱ Is the following L ^a ～L ^h Any of (3)]

[ chemical 4]

In the formulas (A-I) to (B-III),

(L ^a ): aliphatic hydrocarbon group having 1 to 15 carbon atoms

(L ^b ): halogen-substituted alkyl of 1 to 15 carbon atoms

(L ^g ): acyl groups having 1 to 9 carbon atoms which may have a substituent L

[ Effect of the invention ]

According to the present invention, there can be provided a resin composition having a high absorption in the vicinity of 700nm to 750nm or in the vicinity of 720nm to 900nm, a high ratio of absorbance in the infrared region to absorbance in the visible region, and sufficient resistance to heat or light. Further, according to the present invention, an optical filter having these characteristics, particularly, light that sufficiently shields light in the infrared region and is capable of transmitting light in the visible region at a high rate can be provided. Therefore, according to the present invention, not only a near infrared cut filter (near infrared ray cut-off filter, NIR-CF) but also an optical filter such as a visible light-near infrared selective transmission filter (dual band pass filter (dual bandpass filter, DBPF)) or a near infrared transmission filter (infrared pass filter, IRPF) can be easily manufactured.

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 light.

As described above, according to the present invention, an optical filter having such characteristics can be provided, and therefore, an optical filter that can suppress reflected light of light in the vicinity of 700nm to 750nm or in the vicinity of 720nm to 900nm and can provide a good image with little flare or ghost can be easily obtained. In addition, the incidence angle dependence caused by the dielectric multilayer film can be suppressed when the optical filter is a filter having the dielectric multilayer film.

Drawings

FIG. 1 is a spectral transmittance spectrum of the substrate obtained in example 20.

FIG. 2 is a spectral transmittance spectrum of the substrate obtained in example 28.

Fig. 3 is a spectral transmittance spectrum of the optical filter obtained in example 20.

Fig. 4 is a spectral transmittance spectrum of the optical filter obtained in example 28.

FIG. 5 is a spectral transmittance spectrum of the substrate obtained in example 36.

Fig. 6 is a spectral transmittance spectrum of the optical filter obtained in example 36.

Detailed Description

Resin composition

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).

Examples of the form of such a resin composition include: a resin film (resin layer, resin substrate) containing the compound (Z); a resin film (resin layer) containing a compound (Z) formed on a support (for example, a resin support or a glass support); a liquid composition comprising a resin, a compound (Z) and a solvent.

The present composition may contain two or more resins, or may contain two or more compounds (Z).

< Compound (Z) >)

The compound (Z) is a compound represented by the following formula (I).

The compound (Z) has high near infrared ray cut-off performance and high visible light transmission performance at the absorption maximum of the wavelength of 700-750 nm or the wavelength of 720-900 nm, and has excellent optical characteristics and sufficient resistance to heat or light.

Cn ⁺ An ^- (I)

[ chemical 5]

In the formula (II),

the unit A is any one of the following formulas (A-I) to (A-III),

the unit B is any one of the following formulas (B-I) to (B-III),

Y _A and R in the following formula (A-III) ¹ Or R is ⁵ 、Y _E And R in the following formula (B-III) ⁵ Or R is ¹ Can be bonded to each other to form a polymer which can contain at least one nitrogen atom, oxygen atomA 4-to 7-membered alicyclic group of a child or sulfur atom,

[ chemical 6]

In the formulas (A-I) to (B-III),

(L ^a ): aliphatic hydrocarbon group having 1 to 15 carbon atoms

(L ^b ): halogen-substituted alkyl of 1 to 15 carbon atoms

(L ^g ): acyl groups having 1 to 9 carbon atoms which may have a substituent L

The substituent K is selected from the group consisting of L ^a ～L ^b At least one of the substituents L is selected from the group consisting of L ^a ～L ^f At least one of (a)]

The compound (Z) of the present invention is a compound represented by the following formula (III).

Cn ⁺ An ^- (III)

[ chemical 7]

In the formula (IV) shown in the specification,

the unit A is any one of the following formulas (A-I) to (A-III),

the unit B is any one of the following formulas (B-I) to (B-III),

[ chemical 8]

[ formula (A-I) to formula (A-III)* Represents Y of the formula (II) _A The bonded carbon is subjected to single bonding,

in the formulas (A-I) to (B-III),

(L ^a ): aliphatic hydrocarbon group having 1 to 15 carbon atoms

(L ^b ): halogen-substituted alkyl of 1 to 15 carbon atoms

(L ^g ): acyl groups having 1 to 9 carbon atoms which may have a substituent L

Furthermore, the-NR ⁸ -a group represented by the following formula (a), said-NR ^g R ^h The group is a group represented by the following formula (b), and the-SR group is a group represented by the following formula (b) ⁱ The radical is a radical represented by the following formula (c), the-SO ₂ R ⁱ The radical is a radical of the formula (d), the-OSO ₂ R ⁱ The radical is a radical of the formula (e), the radical-C (O) R ⁱ The group is a group represented by the following formula (f).

In addition, the-SSQ ² is-S-S-Q ² Represented radical, the-SO ₂ Q ³ R is represented by the following formula (d) ⁱ Take the place of Q ³ A base formed by the method.

[ chemical 9]

Furthermore, cn when the unit A is the formula (A-I) and the unit B is the formula (B-I) ⁺ Represented by the following formula (II-1). That is, the single bond (-) of "-" in the formulas (A-I) to (A-III) corresponds to Y in the formula (II) or (IV) _A A single bond between the bonded carbon atom and unit a, the double bond (= ") of" ×= "in the formulae (B-I) -formula (B-III) corresponds to Y in the formula (II) or formula (IV) _E Double bonds between the bonded carbon atoms and unit B.

[ chemical 10]

The Y is _B Y and Y _D More preferably each independently is a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, or Y _B Y and Y _D An alicyclic hydrocarbon group having 4 to 6 members (the alicyclic hydrocarbon group may have a substituent R selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a hydroxyl group, a halogen atom, =o) which are bonded to each other ⁹ )。

Further, at Y _B Y and Y _D In the case of a 4-to 6-membered alicyclic hydrocarbon group formed by bonding to each other, the formula (II) or the formula (IV) may be preferably represented by the following formulas (C-I) to (C-III), respectively.

[ chemical 11]

[ chemical 12]

[ chemical 13]

As substituent R ⁹ Preferably, the hydrogen atom, hydroxyl group, =o, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and cyclohexyl group, and more preferably, the hydrogen atom, hydroxyl group, =o, methyl, ethyl, and tert-butyl group.

The Y is _A 、Y _C Y and Y _E More preferably each independently is 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 methyl groupThio, phenylthio, -S- (4-tolyl) group (-S- (4-tolyl) group).

The L is ^a Preferably methyl (Me), ethyl (Et), n-propyl, isopropyl (i-Pr), n-butyl, sec-butyl, tert-butyl (tert-Bu), pentyl, hexyl, octyl, nonyl, decyl, dodecyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl.

The L is ^a The method can also be as follows: alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, butenyl, 1, 3-butadienyl, 2-methyl-1-propenyl, 2-pentenyl, hexenyl and the like; alkynyl groups such as ethynyl, propynyl, butynyl, 2-methyl-1-propynyl, hexynyl and the like.

As said L ^b Examples of the halogen-substituted alkyl group having 1 to 15 carbon atoms include a group in which at least one hydrogen atom of an alkyl group having 1 to 15 carbon atoms is substituted with a halogen atom, and trichloromethyl group, trifluoromethyl group, 1-dichloroethyl group, pentachloroethyl group, pentafluoroethyl group, heptachloropropyl group and heptafluoropropyl group are preferable.

As said L ^c The alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent K is preferably exemplified by: cycloalkyl groups such as cyclopropyl, cyclopropylmethyl, methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic alicyclic groups such as norbornyl and adamantyl.

As said 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), cumene, bis (trifluoromethyl) phenyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl, benzyl (CH) ₂ Ph)。

As said L ^e The heterocyclic group having 3 to 14 carbon atoms which may have a substituent K is preferably furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, morpholine or pyridine.

As said L ^f In (C) is preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, methoxymethyl, methoxyethyl, pentoxy, hexoseOxy, octyloxy, phenoxy (OPh), 4-methylphenoxy, cyclohexyloxy.

As said 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.

As said 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.

The X is preferably an oxygen atom, a sulfur atom, -NR ⁸ Particularly preferred is an oxygen atom.

In the formula (II) or (IV), the left and right units a and B may be the same or different, and in the same case, they are preferable because they are easy to synthesize.

Here again, the same combinations of units A and B are of the formulae (A-I) and (B-I), of the formulae (A-II) and (B-II), of the formulae (A-III) and (B-III).

The R is ¹ ～R ⁶ Each independently is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a 1, 1-dimethylbutyl group, a cyclopropyl group, a cyclopropylmethyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,4, 6-trimethylphenyl group, a 3, 5-bis (trifluoromethyl) phenyl group, a hydroxyl group, an amino group, a dimethylamino group (NMe) ₂ ) Diethylamino (NEt) ₂ ) Dibutylamino group (N (N-Bu) ₂ ) Cyano, nitro, acetylamino, propionylamino, N-methylacetylamino, trifluoroformylamino, pentafluoroacetylamino, t-butyrylamino, cyclohexylamino, N-butylsulfonyl, benzyl, diphenylmethyl, trifluoromethyl, difluoromethyl, methoxy, more preferably hydrogen, chlorine, fluorine, bromine, methyl, ethyl, N-propyl, isopropyl, N-butyl, sec-butyl, t-butyl, cyclohexyl, phenyl, amino, benzyl, diphenylmethyl, trifluoromethyl, difluoromethyl, methoxy.

The R is preferable in terms of easily obtaining a compound or the like having high near infrared ray cut-off performance and high visible light transmission performance at an absorption maximum in the vicinity of 700nm to 750nm or in the vicinity of 720nm to 900nm, and excellent optical characteristics and sufficient resistance to heat or light ¹ ～R ⁶ At least one of (2) is the L ^a 、L ^c Or L ^d . Furthermore, in the case where 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 (2) is L ^a 、L ^c Or L ^d "means" R ¹ 、R ² 、R ⁴ 、R ⁵ At least one of (2) is L ^a 、L ^c Or L ^d ”。

As said R ⁸ The hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, benzyl, n-pentyl, n-hexyl, and t-butyl are preferable, and the hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, and benzyl are more preferable.

As said An ^- The monovalent anions are not particularly limited, and examples thereof include: chloride, bromide, iodide, PF ₄ ^- In terms of perchlorate anions, tri-trifluoromethylsulfonyl methide anions, tetrafluoroborate anions, hexafluorophosphate anions, bis (trifluoromethylsulfonyl) imide anions, trifluoromethylsulfonate anions, tetrakis (pentafluorophenyl) borate anions, tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate anions and the like, bis (trifluoromethylsulfonyl) imide anions, trifluoromethylsulfonate anions, tris-trifluoromethylsulfonyl methide anions, tetrakis (pentafluorophenyl) borate anions, tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate anions and the like, bis (trifluoromethylsulfonyl) imide anions, tris-trifluoromethylsulfonyl methide anions, tetrakis (pentafluorophenyl) borate anions, tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate anions and the like are more preferable, and tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate anions are particularly preferable, and the tetrakis (pentafluorophenyl) borate anions are more preferable.

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

Specifically, these compounds (Z) can be synthesized by, for example, the methods described in the examples below.

TABLE 1

TABLE 2

Compounds of formula (I)

A，B

X

Y _A ，Y _E

Y _B ，Y _D

Y _C

R ¹

R ²

R ³

R ⁴

R ⁵

R ⁶

An

(z-51)

(A-I)，(B- I)

O

H

tert- Bu

H

PF ₄

(z-52)

(A-I)，(B- I)

O

H

tert- Bu

H

Cl

(z-53)

(A-I)，(B- I)

O

H

tert- Bu

H

Br

(z-54)

(A-I)，(B- I)

O

H

tert- Bu

H

I

(z-55)

(A-I)，(B- I)

O

H

Cl

H

tert- Bu

H

F

H

B(C ₆ F ₅ ) ₄

(z-56)

(A-I)，(B- I)

O

H

Cl

H

tert- Bu

H

Cl

H

B(C ₆ F ₅ ) ₄

(z-57)

(A-I)，(B- I)

O

H

Cl

H

tert- Bu

H

Br

H

B(C ₆ F ₅ ) ₄

(z-58)

(A-I)，(B- I)

O

H

Cl

H

tert- Bu

H

Me

H

B(C ₆ F ₅ ) ₄

(z-59)

(A-I)，(B- I)

O

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-60)

(A-I)，(B- I)

O

H

Cl

H

tert- Bu

H

OCH ₃

H

B(C ₆ F ₅ ) ₄

(z-61)

(A-I)，(B- I)

O

H

Cl

H

tert- Bu

H

NHCO CF ₃

H

B(C ₆ F ₅ ) ₄

(z-62)

(A-I)，(B- I)

O

H

i-Pr

H

F

H

B(C ₆ F ₅ ) ₄

(z-63)

(A-I)，(B- I)

O

H

i-Pr

H

Cl

H

B(C ₆ F ₅ ) ₄

(z-64)

(A-I)，(B- I)

O

H

i-Pr

H

Br

H

B(C ₆ F ₅ ) ₄

(z-65)

(A-I)，(B- I)

O

H

i-Pr

H

Me

H

B(C ₆ F ₅ ) ₄

(z-66)

(A-I)，(B- I)

O

H

i-Pr

H

i-Pr

H

B(C ₆ F ₅ ) ₄

(z-67)

(A-I)，(B- I)

O

H

i-Pr

H

OCH ₃

H

B(C ₆ F ₅ ) ₄

(z-68)

(A-I)，(B- I)

O

H

i-Pr

H

CF ₃

H

B(C ₆ F ₅ ) ₄

(z-69)

(A-I)，(B- I)

O

H

Ph

H

F

H

B(C ₆ F ₅ ) ₄

(z-70)

(A-I)，(B- I)

O

H

Ph

H

Cl

H

B(C ₆ F ₅ ) ₄

(z-71)

(A-I)，(B- I)

O

H

Ph

H

Br

H

B(C ₆ F ₅ ) ₄

(z-72)

(A-I)，(B- I)

O

H

Ph

H

Me

H

B(C ₆ F ₅ ) ₄

(z-73)

(A-I)，(B- I)

O

H

Ph

H

i-Pr

H

B(C ₆ F ₅ ) ₄

(z-74)

(A-I)，(B- I)

O

H

Ph

H

OCH ₃

H

B(C ₆ F ₅ ) ₄

(z-75)

(A-I)，(B- I)

O

H

Ph

H

NHCO CF ₃

H

B(C ₆ F ₅ ) ₄

(z-76)

(A-II)，(B- II)

N

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-77)

(A-II)，(B- II)

S

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-78)

(A-II)，(B- II)

O

CH ₃

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-79)

(A-II)，(B- II)

O

H

F

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-80)

(A-II)，(B- II)

O

H

Cl

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-81)

(A-II)，(B- II)

O

H

Br

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-82)

(A-II)，(B- II)

O

H

CH ₃

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-83)

(A-II)，(B- II)

O

H

OCH ₃

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-84)

(A-II)，(B- II)

O

H

OPh

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-85)

(A-II)，(B- II)

O

H

N(CH ₃ ) ₂

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-86)

(A-II)，(B- II)

O

H

NHPh

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-87)

(A-II)，(B- II)

O

H

NPh ₂

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-88)

(A-II)，(B- II)

O

H

SCH ₃

H

tert- Bu

H

B(C ₆ F ₅ ) ₄

(z-89)

(A-II)，(B- II)

O

H

SPh

H

tert- Bu

H

B(C ₆ F ₅ )4

(z-90)

(A-II)，(B- II)

O

H

Ph

H

B(C ₆ F ₅ )4

(z-91)

(A-II)，(B- II)

O

H

i-Pr

H

B(C ₆ F ₅ ) ₄

(z-92)

(A-II)，(B- II)

O

H

Cyclopropyl group

H

B(C ₆ F ₅ ) ₄

(z-93)

(A-II)，(B- II)

O

H

Cyclopropyl group Methyl group

H

B(C ₆ F ₅ ) ₄

(z-94)

(A-II)，(B- II)

O

H

Cyclohexyl group

H

B(C ₆ F ₅ ) ₄

(z-95)

(A-II)，(B- II)

O

H

Adamantane(s) Base group

H

B(C ₆ F ₅ ) ₄

(z-96)

(A-II)，(B- II)

O

H

2,4,6- Trimethyl Phenyl group

H

B(C ₆ F ₅ ) ₄

(z-97)

(A-II)，(B- II)

O

H

3, 5-bis (trifluoro) Methyl group) Phenyl group

H

B(C ₆ F ₅ ) ₄

(z-98)

(A-II)，(B- II)

O

H

tert- Bu

Cl

H

B(C ₆ F ₅ ) ₄

(z-99)

(A-II)，(B- II)

O

H

tert- Bu

Br

H

B(C ₆ F ₅ ) ₄

(z-100)

(A-II)，(B- II)

O

H

tert- Bu

Ph

H

B(C ₆ F ₅ ) ₄

TABLE 3

Compounds of formula (I)

A，B

X

Y _A ，Y _E

Y _B ，Y _D

Y _C

R ¹

R ²

R ³

R ⁴

R ⁵

R ⁶

An

(z-101)

(A-II)，(B-II)

O

H

tert-Bu

Me

H

B(C ₆ F ₅ ) ₄

(z-102)

(A-II)，(B-II)

O

H

tert-Bu

i-Pr

H

B(C ₆ F ₅ ) ₄

(z-103)

(A-II)，(B-II)

O

H

tert-Bu

NHCOC F ₃

H

B(C ₆ F ₅ ) ₄

(z-104)

(A-II)，(B-II)

O

H

tert-Bu

H

F

H

B(C ₆ F ₅ ) ₄

(z-105)

(A-II)，(B-II)

O

H

tert-Bu

H

Cl

H

B(C ₆ F ₅ ) ₄

(z-106)

(A-II)，(B-II)

O

H

tert-Bu

H

Br

H

B(C ₆ F ₅ ) ₄

(z-107)

(A-II)，(B-II)

O

H

tert-Bu

H

Me

H

B(C ₆ F ₅ ) ₄

(z-108)

(A-II)，(B-II)

O

H

tert-Bu

H

i-Pr

H

B(C ₆ F ₅ ) ₄

(z-109)

(A-II)，(B-II)

O

H

tert-Bu

H

OCH ₃

H

B(C ₆ F ₅ ) ₄

(z-110)

(A-II)，(B-II)

O

H

tert-Bu

H

CF ₃

H

B(C ₆ F ₅ ) ₄

(z-111)

(A-II)，(B-II)

O

H

tert-Bu

H

F

H

B(C ₆ F ₅ ) ₄

(z-112)

(A-II)，(B-II)

O

H

tert-Bu

H

Cl

H

B(C ₆ F ₅ ) ₄

(z-113)

(A-II)，(B-II)

O

H

tert-Bu

H

Br

H

B(C ₆ F ₅ ) ₄

(z-114)

(A-II)，(B-II)

O

H

tert-Bu

H

Me

H

B(C ₆ F ₅ ) ₄

(z-115)

(A-II)，(B-II)

O

H

tert-Bu

H

i-Pr

H

B(C ₆ F ₅ ) ₄

(z-116)

(A-II)，(B-II)

O

H

tert-Bu

H

OCH ₃

H

B(C ₆ F ₅ ) ₄

(z-117)

(A-II)，(B-II)

O

H

tert-Bu

H

NHCOCF ₃

H

B(C ₆ F ₅ ) ₄

(z-118)

(A-II)，(B-II)

O

H

tert-Bu

H

F

B(C ₆ F ₅ ) ₄

(z-119)

(A-II)，(B-II)

O

H

tert-Bu

H

Cl

B(C ₆ F ₅ ) ₄

(z-120)

(A-II)，(B-II)

O

H

tert-Bu

H

Br

B(C ₆ F ₅ ) ₄

(z-121)

(A-II)，(B-II)

O

H

tert-Bu

H

N(SO ₂ CF ₃ ) ₂

(z-122)

(A-II)，(B-II)

O

H

tert-Bu

H

C(SO ₂ CF ₃ ) ₃

(z-123)

(A-II)，(B-II)

O

H

tert-Bu

H

BF ₄

(z-124)

(A-II)，(B-II)

O

H

tert-Bu

H

ClO ₄

(z-125)

(A-II)，(B-II)

O

H

tert-Bu

H

PF ₄

(z-126)

(A-II)，(B-II)

O

H

tert-Bu

H

Cl

(z-127)

(A-II)，(B-II)

O

H

tert-Bu

H

Br

(z-128)

(A-II)，(B-II)

O

H

tert-Bu

H

I

(z-129)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

F

H

B(C ₆ F ₅ ) ₄

(z-130)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

Cl

H

B(C ₆ F ₅ ) ₄

(z-131)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

Br

H

B(C ₆ F ₅ ) ₄

(z-132)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

Me

H

B(C ₆ F ₅ ) ₄

(z-133)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

i-Pr

H

B(C ₆ F ₅ ) ₄

(z-134)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

OCH ₃

H

B(C ₆ F ₅ ) ₄

(z-135)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

NHCOCF ₃

H

B(C ₆ F ₅ ) ₄

(z-136)

(A-II)，(B-II)

O

H

i-Pr

H

F

H

B(C ₆ F ₅ ) ₄

(z-137)

(A-II)，(B-II)

O

H

i-Pr

H

Cl

H

B(C ₆ F ₅ ) ₄

(z-138)

(A-II)，(B-II)

O

H

i-Pr

H

Br

H

B(C ₆ F ₅ ) ₄

(z-139)

(A-II)，(B-II)

O

H

i-Pr

H

Me

H

B(C ₆ F ₅ ) ₄

(z-140)

(A-II)，(B-II)

O

H

i-Pr

H

i-Pr

H

B(C ₆ F ₅ ) ₄

(z-141)

(A-II)，(B-II)

O

H

i-Pr

H

OCH ₃

H

B(C ₆ F ₅ ) ₄

(z-142)

(A-II)，(B-II)

O

H

i-Pr

H

CF ₃

H

B(C ₆ F ₅ ) ₄

(z-143)

(A-II)，(B-II)

O

H

Ph

H

F

H

B(C ₆ F ₅ ) ₄

(z-144)

(A-II)，(B-II)

O

H

Ph

H

Cl

H

B(C ₆ F ₅ ) ₄

(z-145)

(A-II)，(B-II)

O

H

Ph

H

Br

H

B(C ₆ F ₅ ) ₄

(z-146)

(A-II)，(B-II)

O

H

Ph

H

Me

H

B(C ₆ F ₅ ) ₄

(z-147)

(A-II)，(B-II)

O

H

Ph

H

i-Pr

H

B(C ₆ F ₅ ) ₄

(z-148)

(A-II)，(B-II)

O

H

Ph

H

OCH ₃

H

B(C ₆ F ₅ ) ₄

(z-149)

(A-II)，(B-II)

O

H

Ph

H

NHCOCF ₃

H

B(C ₆ F ₅ ) ₄

(z-150)

(A-I)，(B-I)

O

H

tert-Bu

H

NMe ₂

H

B(C ₆ F ₅ ) ₄

TABLE 4

Further, R in Table 4 ³ R is R ⁴ "C-1, C-2" in a column means R in the formula (A-I) and the formula (B-I) ³ And R is R ⁴ Specifically, the aromatic hydrocarbon group having 6 carbon atoms bonded to each other means that the portion corresponding to the unit A and the unit B has the structure represented by the following formulas C-1 and C-2.

In addition, Y of Table 4 _A 、Y _E 、R ¹ R is R ⁵ "D-1" in a column means Y _A And R in the formula (A-III) ¹ 、Y _E And R in the formula (B-III) ⁵ Specifically, the cation of the compound (z-163) is represented by the following formula D-1.

[ chemical 14]

[ 15]

The compound (Z) is preferably an organic solvent-soluble compound, particularly preferably a dichloromethane-soluble compound.

The term "soluble in an organic solvent" as used herein means that the compound (Z) is dissolved in an amount of 0.1g or more per 100g of the organic solvent at 25 ℃.

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

Essential condition (a): in the transmission spectrum measured using a solution in which the compound (Z) is dissolved in methylene chloride (wherein the transmission spectrum is a spectrum having a transmittance of 10% at the absorption maximum wavelength; hereinafter, the transmission spectrum is also referred to as "transmission spectrum of the compound (Z)"), the average value of the transmittance at the wavelength of 430nm to 580nm 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%.

If the compound (Z) satisfies the above-mentioned requirement (a), the light having a wavelength in the near infrared region to be cut off can be sufficiently cut off, and the decrease in the visible light transmittance can be further suppressed.

In the present invention, the average transmittance at wavelengths ase:Sub>A to B nm is ase:Sub>A value calculated by measuring the transmittance at each wavelength of 1nm or more at ase:Sub>A nm to B nm or less and dividing the total value of the transmittance by the number of the measured transmittances (wavelength range, B-a+1).

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

Essential condition (B-1): the absorption spectrum measured using a solution obtained by dissolving the compound (Z) in methylene chloride has a maximum value in a preferred range of 720nm to 900nm, more preferred range of 740nm to 880nm, and particularly preferred range of 740nm to 860 nm.

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

Suitable examples of the compound (Z) satisfying the above-mentioned requirement (B-1) include: the unit A is any one of the formulas (A-I) to (A-II), and the unit B is a compound of any one of the formulas (B-I) to (B-II).

Essential condition (B-2): in the absorption spectrum measured using a solution obtained by dissolving the compound (Z) in methylene chloride, the absorption spectrum has a maximum value in a preferable range of wavelengths from 700nm to 750nm, more preferably from 705nm to 748nm, and particularly preferably from 710nm to 745 nm.

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

Suitable examples of the compound (Z) satisfying the above-mentioned requirement (B-2) include: the unit A is the formula (A-III) and the unit B is the compound of the formula (B-III).

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

Essential condition (C): the retention rate D (=af×100/Ai) of absorbance Af at λa after the resin plate is irradiated with a fluorescent lamp for 30 days with respect to absorbance Ai at a maximum absorption wavelength at a wavelength in a range of 700nm to 1000nm of a resin plate containing the resin and the compound (Z) is preferably 95% or more, more preferably 97% or more. The retention rate D is preferably high, and therefore the upper limit thereof is not particularly limited and may be 100%.

Further, the resin plate has a thickness of 90 μm to 110 μm, and the compound (Z) is contained in an amount such that the absorbance Ai at the maximum absorption wavelength λa of the resin plate falls within a range of 0.5 to 1.5, relative to the resin, the resin is Artong (ARTON) manufactured using JSR (strands), and Yi Lunuo Sis (Irganox) 1010 (manufactured by Basf Japan (strands)) is contained in an amount of 0.3 parts by mass relative to 100 parts by mass of the resin in the resin plate.

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

Specifically, the retention rate D can be measured by the method described in the following examples.

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

Essential condition (D): in the spectroscopic absorption spectrum measured using a solution obtained by dissolving the compound (Z) in methylene chloride, when the absorbance at the longest wavelength of the maximum absorption wavelength is taken as epsilon a and the maximum value of absorbance at the wavelength of 430nm to 580nm is taken as epsilon bmax, epsilon a/epsilon bmax is preferably 20 or more, more preferably 25 or more, and still more preferably 27 or more. Since εa/εbmax is preferably large, the upper limit is not particularly limited and is, for example, 10000 or less.

When the compound (Z) satisfies the above-mentioned requirement (D), it can be said that the ratio of absorbance in the infrared region to absorbance in the visible region is large, and that the optical characteristics are excellent, and in an optical filter having a dielectric multilayer film, the dependence of the incident angle due to the multilayer film can be suppressed.

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, and particularly preferably 0.03 to 1.5 parts by mass, based on 100 parts by mass of the resin.

When the content of the compound (Z) is within the above range, a composition having excellent near infrared light transmittance and further excellent visible light transmittance, which can efficiently cut off the wavelength around 700nm to 750nm or around 720nm to 900nm, can be easily obtained.

< resin >)

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

The resins used in the present composition may be used singly or in combination.

The resin is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include resins having a glass transition temperature (Tg) of preferably 110 to 380 ℃, more preferably 110 to 370 ℃, and particularly preferably 120 to 360 ℃ in terms of excellent thermal stability, formability to a film (plate) shape, and the like, and being capable of easily obtaining a film that can be formed into a dielectric multilayer film by high-temperature vapor deposition at a vapor deposition temperature of 100 ℃ or higher. In addition, when the Tg of the resin is 140 ℃ or higher, a film which can be vapor deposited at a higher temperature to form a dielectric multilayer film can be obtained, and is particularly preferable.

As the resin, a resin having a total light transmittance (japanese industrial standard (Japanese Industrial Standards, JIS) K7375:2008) of 75% to 95%, more preferably 78% to 95%, and particularly preferably 80% to 95% of a resin plate having a thickness of 0.1mm containing the resin can be used.

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

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

Examples of the resin include: cyclic (poly) olefin-based resins, aromatic polyether-based resins, polyimide-based resins, polyester-based resins, polycarbonate-based resins, polyamide (aromatic polyamide-based) resins, polyarylate-based resins, polysulfone-based resins, polyethersulfone-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate (polyethylene naphthalate, PEN) -based resins, fluorinated aromatic polymer-based resins, (modified) acrylic resins, epoxy-based resins, allyl-ester-based curable resins, silsesquioxane-based ultraviolet curable resins, acrylic ultraviolet curable resins, vinyl-based ultraviolet curable resins.

Specific examples of such resins include resins described in International publication No. 2019/168890.

< other Components >)

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 matting agent, a metal complex compound, and the like, within a range that does not impair the effects of the present invention.

These other components may be used singly or in combination.

These other components may be mixed with the resin or the like at the time of preparing the present composition, or may be added at the time of synthesizing the resin. The amount to be added is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass, based on 100 parts by mass of the resin, as long as it is appropriately selected according to desired properties and the like.

[ Compound (X) ]

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

Examples of the compound (X) include: squarylium compounds, phthalocyanine compounds, polymethine compounds, naphthalocyanine compounds, ketone onium compounds, octaporphyrin (octaporphyrin) compounds, diimmonium compounds, perylene compounds, and metal dithioxide compounds.

The compound (X) preferably contains a squarylium compound, more preferably contains one or more squarylium compounds and other compounds (X '), and the other compounds (X') are particularly preferably phthalocyanine compounds and polymethine compounds.

The squarylium compound has a sharp absorption peak, and is excellent in visible light transmittance and a high molar absorptivity, but may generate fluorescence that causes scattered light when absorbing light. In this case, by using the squarylium compound in combination with the compound (X'), scattered light can be suppressed. In this way, when the optical filter obtained from the present composition is used in an imaging device or the like, the obtained camera image quality becomes better if the scattered light is suppressed.

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

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

[ ultraviolet absorber ]

Examples of the ultraviolet absorber include: azomethine compounds, indole compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, anthracene compounds, compounds described in Japanese patent application laid-open No. 2019-014707, and the like.

Particularly preferred are azomethine compounds, indole compounds, benzotriazole compounds and cyanoacrylate compounds. By containing these compounds, an optical filter having a small incident angle dependency in the near ultraviolet wavelength region can be easily obtained, and when the optical filter is used in an image pickup device or the like, the obtained camera image quality becomes better.

[ antioxidant ]

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

< additive >)

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

These additives may be used singly or in combination.

In particular, when the present composition is formulated into a liquid composition, an organic solvent is preferably used. As examples of the organic solvent, solvents in which the resin is soluble are preferable, and specifically, there can be mentioned: esters, ketones, aromatic hydrocarbons, halogen-containing compounds.

In addition, in the case of producing a resin layer by casting molding described later, the resin layer can be easily produced by using a leveling agent or an antifoaming agent.

Substrate (i)

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

The substrate (i) may be a single layer or a plurality of layers, and may have a resin layer (hereinafter also referred to as "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, in which case the two or more layers of the present resin may be the same or different.

When the base material (i) is a single layer, the base material (i) is composed of the present resin layer, that is, the present resin layer (resin substrate) is the base material (i).

In the case where the substrate (i) is a multilayer, examples of the substrate (i) include: a base material comprising two or more resin layers, wherein at least one of the two or more resin layers is the present resin layer; or a substrate comprising the present resin layer and a glass support, examples of suitable materials include: a substrate (A) comprising a laminate obtained by laminating the resin layer on a support such as a glass support or a resin support as a base; the base material (B) includes a laminate obtained by laminating a resin layer such as an overcoat layer containing a curable resin or the like on the present resin layer.

The substrate (i) is particularly preferably the substrate (B) in terms of manufacturing cost, ease of adjustment of optical characteristics, further effects of eliminating damage of the present resin layer, improvement of damage resistance of the substrate (i), and the like.

The resin layer such as the overcoat layer in the resin support or the base material (B) is a resin layer containing no compound (Z). The resin layer containing no compound (Z) is not particularly limited as long as it contains a resin, and examples of the resin include the same resins as those described in the column of the present composition. The resin layer containing no compound (Z) may be another functional film as described below.

The glass support is preferably a transparent glass support or an absorptive glass support. Among these, the use of an absorptive glass support is preferable because light having a wavelength in the near infrared region can be sufficiently blocked.

The thickness of the base material (i) is not particularly limited, and is preferably 10 μm to 250 μm, more preferably 15 μm to 230 μm, and particularly preferably 20 μm to 150 μm, depending on the intended use.

When the thickness of the base material (i) is within the above range, the optical filter using the base material (i) can be thinned and reduced in weight, and can be suitably used for various applications such as a solid-state imaging device. In particular, when the single-layer substrate (i) is used for a lens unit of a camera module or the like, the back of the lens unit can be reduced and the weight can be reduced.

[ method for producing substrate (i) ]

The resin layers such as the present resin layer, the resin support, and the overcoat layer may be formed by, for example, melt molding or cast molding, and if necessary, a coating agent such as an antireflective agent, a hard coat agent, and/or an antistatic agent may be applied after the molding.

In the case where the substrate (i) is the substrate (a), for example, the present composition is melt-molded or cast-molded on the support, and preferably, the substrate having the present resin layer formed on the support is produced by coating by spin coating, slit coating, ink jet or the like, drying and removing the solvent, and optionally further, irradiating with light or heating.

Melt forming

Specifically, the melt molding includes: a method of melt-molding the pellets obtained by melt-kneading the present composition; a method of melt forming the present composition; and a method of melt-molding particles obtained by removing the solvent from the liquid composition containing the solvent. As the melt molding method, there may be mentioned: injection molding, melt extrusion molding, blow molding, or the like.

Tape casting

As the casting, there may be mentioned: a method of removing the solvent by casting the liquid composition containing the solvent on a suitable support; and 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 cured by a suitable method such as ultraviolet irradiation or heating.

In the case where the substrate (i) is the single-layer substrate (i), the substrate (i) can be obtained by peeling off the coating film from the support after the casting molding, and in the case where the substrate (i) is the substrate (a), the substrate (i) can be obtained by not peeling off the coating film after the casting molding.

Examples of the suitable support include: glass plates, steel belts, steel cylinders, and supports made of resin (for example, polyester film or cycloolefin resin film).

Further, the present resin layer may be formed on the optical component by the following method: a method of applying the liquid composition to an optical part made of glass, quartz, plastic or the like, and drying the solvent; or a method of applying the curable composition, curing and drying.

In the case of forming the resin such as the resin support and the overcoat layer by melt molding or cast molding, a desired composition containing a resin (wherein the compound (Z) is not contained) may be used instead of the present composition in the column of the melt molding or cast molding.

The amount of residual solvent in the resin layer such as the present resin layer, the resin support, and the overcoat layer is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3 mass% or less, more preferably 1 mass% or less, and still more preferably 0.5 mass% or less, based on the weight of the present resin layer.

When the amount of the residual solvent is within the above range, a resin layer which is hardly deformed or has hardly changed in characteristics and which can easily exhibit a desired function can be obtained.

When the substrate (i) is used in an optical filter, the solvent content in the present resin layer, the resin support, the overcoat layer, and other resin layers is preferably suppressed to 100 mass ppm or less.

Optical Filter

The optical filter of the present invention (hereinafter also referred to as "present filter") has the above-described substrate (i) and a dielectric multilayer film.

In terms of further exhibiting the effects of the present invention, specific examples of such a filter include: a near infrared cut filter (NIR-CF), a visible light-near infrared selective transmission filter (DBPF), a near infrared transmission filter (IRPF). The filter may be used as a filter for a substitute light source (ALS: alternative Light Sources) used for scientific search or the like. These filters may have a conventional structure in addition to the base material (i).

In the case where the present filter is NIR-CF or DBPF, a filter satisfying the following characteristic (a) is preferable.

Characteristics (a): in the region of 430nm to 580nm, the average value of the transmittance when measured from 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, and therefore the upper limit thereof is not particularly limited and may be 100%.

If the present filter satisfies the above characteristic (a), the light having a wavelength in the near infrared region to be cut off can be sufficiently cut off, and the decrease in the visible light transmittance can be further suppressed, so that the present filter can be preferably used as an NIR-CF or DBPF.

When the substrate (i) contains a compound satisfying the above-mentioned requirement (B-1), and when the present filter is NIR-CF or DBPF, a filter satisfying the following characteristic (B-1) is preferable.

Characteristics (b-1): in the wavelength range of 700nm to 800nm, the average reflectance of the unpolarized light incident from an angle of 5 ° away 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 reflectance is preferably low, and thus the lower limit thereof is not particularly limited and may be 0%.

By using the present filter satisfying the above characteristic (b-1), the reflected light intensity in the wavelength region of 700nm to 800nm can be reduced, and thus, the image defect caused by the reflected light can be eliminated.

In the case where the substrate (i) contains a compound satisfying the above-mentioned requirement (B-2), and the present filter is NIR-CF or DBPF, a filter satisfying the following characteristic (B-2) is preferable.

Characteristics (b-2): in the region of 650nm to 800nm, the average reflectance of the unpolarized light incident from an angle of 5 ° away 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 reflectance is preferably low, and thus the lower limit thereof is not particularly limited and may be 0%.

By using the present filter satisfying the above characteristic (b-2), the reflected light intensity in the wavelength region of 650nm to 800nm can be reduced, and thus, the image defect caused by the reflected light can be eliminated.

In the present invention, the average reflectance at wavelengths ase:Sub>A to B nm is ase:Sub>A value calculated by measuring the reflectance at each wavelength of 1nm or more at ase:Sub>A nm to B nm or less and dividing the total value of the reflectances by the number of the measured reflectances (wavelength range, B-a+1).

Since it is infinitely difficult to measure the reflectance of unpolarized light incident from the vertical direction, in the present invention, the reflectance characteristic of unpolarized light incident from an angle of 5 ° from the vertical direction is measured.

"unpolarized light" is light having no shift in polarization direction, and means an aggregate of waves in which an electric field is substantially uniformly distributed in all directions. The "average transmittance of unpolarized light" may be an average of the "average transmittance of S polarized light" and the "average transmittance of P polarized light". The "average reflectance of unpolarized light" may use an average of the "average reflectance of S polarized light" and the "average reflectance of P polarized light".

The present filter satisfies the above-described characteristics (a), (b-1) and (b-2), and can reduce the intensity of reflected light in a wavelength region of near infrared light, particularly 650nm to 800nm, while maintaining the transmittance of visible light satisfactorily, so that in recent years, in imaging devices such as digital still cameras and the like, the progress of the enhancement of performance has been made, the reduction in sensitivity in the visible light region can be suppressed to a minimum, and image defects due to the reflected light can be eliminated.

The thickness of the present filter may be appropriately selected depending on the intended use, and is also preferably thin in accordance with recent trends such as reduction in thickness and weight of solid-state imaging devices and the like.

The filter includes the base material (i), and thus can be thinned.

The thickness of the filter is preferably 300 μm or less, more preferably 250 μm or less, still more preferably 200 μm or less, particularly preferably 150 μm or less, and the lower limit is not particularly limited, and for example, 20 μm is preferable.

＜NIR-CF＞

The NIR-CF is preferably an optical filter excellent in cut-off performance in a wavelength region of 850nm to 1200nm and excellent in transmittance in a visible wavelength region.

The dielectric multilayer film used in the NIR-CF is preferably a near infrared ray reflection film.

In the case where NIR-CF is used in a solid-state imaging element or the like, 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 device is relatively high in a wavelength region of 800nm to 1200nm, and that the transmittance in the wavelength region is reduced, so that the visibility correction of the camera image and the human eye can be effectively performed, and excellent color reproducibility can be achieved. Further, by reducing the transmittance in the region of 850nm to 1200nm, near infrared light used for the security (security) authentication function can be effectively prevented from reaching the image sensor or the like.

In the NIR-CF, the average transmittance of the filter, as measured in the vertical direction of the filter, is preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, and particularly preferably 2% or less in the wavelength region of 850nm to 1200 nm.

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

In the case where NIR-CF is used in a solid-state imaging element or the like, the visible light transmittance is preferably high. Specifically, in the region of 430nm to 580nm, the average transmittance when measured from the vertical direction of the filter is preferably 75% or more, more preferably 80% or more, still more preferably 83% or more, and particularly preferably 85% or more.

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

＜DBPF＞

The DBPF is not particularly limited as long as it is an optical filter that transmits light of a wavelength to be transmitted in the visible light and the near infrared light and cuts off light of a wavelength to be cut off in the near infrared light.

The dielectric multilayer film used in the DBPF is preferably a film that transmits visible light, light having a wavelength to be transmitted in the near infrared, and cuts off light having a wavelength to be cut off in the near infrared.

In the case where the DBPF is used in a solid-state imaging device or the like, the visible light transmittance is preferably high, similarly to the NIR-CF, and for the same reason as described above, the average transmittance at a wavelength of 430nm to 580nm is preferably in the same range as the average transmittance of the NIR-CF.

＜IRPF＞

The IRPF is not particularly limited as long as it is an optical filter that cuts off visible light and transmits light of a wavelength to be transmitted in near infrared rays.

The dielectric multilayer film used in the IRPF is preferably a film that cuts off light (a part of visible light and/or near infrared rays) of a wavelength to be cut off.

In addition, IRPF may also use a visible light absorber to cut off visible light.

IRPF is suitably used in optical systems such as infrared monitoring cameras, in-vehicle infrared cameras, infrared communication, various sensor systems, infrared alarm devices, and night vision devices, and when used in these applications, it is preferable that the transmittance of light having a wavelength other than near infrared rays to be transmitted is low.

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

In addition, regarding IRPF, the transmittance of near infrared rays to be transmitted is preferably high, specifically, a light transmission band Ya having a wavelength of 750nm or more in which the maximum transmittance (T _IR ) Preferably 45% or more, more preferably 50% or more.

Dielectric multilayer film

The filter has 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.

The dielectric multilayer film may be provided on one side or both sides of the substrate (i). When the optical filter is provided on one side, the optical filter is excellent in manufacturing cost and manufacturing easiness, and when the optical filter is provided on both sides, the optical filter has high strength and is less likely to warp or twist. In the case where the present filter is used in a solid-state imaging element or the like, the warpage or distortion of the filter is preferably small, and therefore, it is preferable to provide dielectric multilayer films on both sides of the substrate (i).

The material constituting the high refractive index material layer may have a refractive index of 1.7 or more, and a material having a refractive index of usually 1.7 to 2.5 may be selected. Examples of such materials include: titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc sulfide, indium oxide, or the like is used as a main component, and a small amount (for example, 0 to 10 mass% relative to the main component) of titanium oxide, tin oxide, cerium oxide, or the like is contained.

As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less may be used, and a material having a refractive index of usually 1.2 to 1.6 may be selected. Examples of such materials include: silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

The method of stacking the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are stacked can be formed. For example, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated can be directly formed on the substrate (i) by a chemical vapor deposition (Chemical Vapor Deposition, CVD) method, a sputtering method, a vacuum evaporation method, an ion-assisted evaporation method, an ion plating method, or the like.

In general, when the wavelength of light to be blocked (for example, near infrared rays) is λ (nm), the thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ to 0.5λ. As a value of λ (nm), in the case of NIR-CF, for example, 700nm to 1400nm, preferably 750nm to 1300nm. When the thicknesses of the high refractive index material layer and the low refractive index material layer are within the above-described range, the product (n×d) of the refractive index (n) and the film thickness (d), that is, the optical film thickness becomes approximately the same value as λ/4, and the blocking-transmitting at a specific wavelength tends to be easily controllable in accordance with the relationship of the optical characteristics of reflection-refraction.

The total number of layers of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film is preferably 16 to 70 layers, more preferably 20 to 60 layers, in the case of NIR-CF, for example, based on the entire optical filter. When the thickness of each layer, the thickness of the dielectric multilayer film in the whole optical filter, or the total number of layers falls within the above range, a sufficient manufacturing margin (margin) can be secured, and warping of the optical filter or cracking of the dielectric multilayer film can be reduced.

In the present filter, by appropriately selecting the types of materials constituting the high refractive index material layer and the low refractive index material layer, the thicknesses of the layers of the high refractive index material layer and the low refractive index material layer, the order of lamination, and the number of layers, in combination with the absorption characteristics of the compound (Z), a sufficient transmittance can be ensured in a wavelength region to be transmitted (for example, a visible region), a sufficient light cut-off characteristic can be provided in a wavelength region to be cut off (for example, a near infrared region), and the reflectance when light (for example, near infrared) is incident from an oblique direction can be reduced.

Here, in order to optimize the conditions of the dielectric multilayer Film, for example, parameters may be set so that the antireflection effect in a wavelength region to be transmitted (for example, visible region) and the light blocking effect in a wavelength region to be blocked (for example, near infrared region) can be compatible with each other using optical Thin Film design software (for example, manufactured by core makinder (Essential Macleod), film Center (Thin Film Center)). In the case of the software, for example, there can be listed: in forming a dielectric multilayer film of NIR-CF, a parameter setting method is used in which the Target transmittance at a wavelength of 400nm to 700nm is set to 100%, the Target Tolerance (Target Tolerance) is set to 1, the Target transmittance at a wavelength of 705nm to 950nm is set to 0%, and the Target Tolerance is set to 0.5.

These parameters can also be used to more finely divide the wavelength range in combination with various characteristics of the substrate (i) and the like to change the value of the target tolerance.

< other functional films >)

The present filter may be provided with a functional film such as an antireflection film, a hard coat 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, as appropriate, within a range that does not impair the effects of the present invention, for the purpose of improving the surface hardness of the substrate (i) or the dielectric multilayer film, improving the chemical resistance, antistatic properties, eliminating damage, and the like.

The filter may comprise one layer of the functional film, or may comprise two or more layers. In the case where the present filter includes two or more functional films, the present filter may include two or more films that are the same or two or more films that are different from each other.

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

In addition, the manufacturing method can also be manufactured by the following steps: a curable composition containing a coating agent or the like is applied to the substrate (i) or the dielectric multilayer film by a bar coater or the like, and then cured by ultraviolet irradiation or the like.

The coating agent may be an Ultraviolet (UV)/Electron Beam (EB) curable resin, a thermosetting resin, or the like, and specifically, may be mentioned: vinyl compounds, urethane resins, urethane acrylate resins, acrylic esters, epoxy resins, and epoxy acrylate resins. The coating agent may be used singly or in combination of two or more.

Examples of the curable composition containing these coating agents include: vinyl, urethane acrylate, epoxy acrylate curable compositions, and the like.

The curable composition may also contain a polymerization initiator. As the polymerization initiator, a conventional photopolymerization initiator or a thermal polymerization initiator may be used, or a combination of a photopolymerization initiator and a thermal polymerization initiator may be used. The polymerization initiator may be used singly or in combination of two or more.

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

Further, an organic solvent may be added to the curable composition as a solvent, and a conventional solvent may be used as the organic solvent. Specific examples of the organic solvent include: alcohols such as methanol, ethanol, isopropanol, butanol, octanol, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, gamma-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; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

One kind of these solvents may be used alone, or two or more kinds may be used.

The thickness of the functional film is preferably 0.1 μm to 20. Mu.m, more preferably 0.5 μm to 10. Mu.m, particularly preferably 0.7 μm to 5. Mu.m.

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

[ use of optical Filter ]

The present filter is excellent in, for example, the blocking ability of light of a wavelength in a region to be blocked and the transmission ability of light of a wavelength to be transmitted. Therefore, the imaging device is useful for correcting the sensitivity of a solid-state imaging device such as a CCD or CMOS image sensor as a camera module. In particular, the present invention is useful in digital still cameras, smart phone cameras, mobile phone cameras, digital video cameras, wearable device cameras, personal computer (personal computer, PC) cameras, surveillance cameras, automobile cameras, infrared cameras, televisions, car navigation, portable information terminals, video game machines, portable game machines, fingerprint authentication systems, digital music players, various sensor systems, infrared communication, and the like. Further, the present invention is useful as a heat ray cut filter mounted on a glass plate or the like of an automobile, a building or the like.

Solid-state imaging device

The solid-state imaging device of the present invention includes the present filter. The solid-state imaging device is a device including a solid-state imaging element such as a CCD or CMOS image sensor, and is particularly useful for applications such as a digital still camera, a camera for a smart phone, a camera for a mobile phone, a camera for a wearable device, and a digital video camera.

Optical sensor device

The optical sensor device of the present invention is not particularly limited as long as it has a conventional structure, if it includes the filter.

For example, a device having a light receiving element and the present filter is exemplified, and specifically, a device having a light receiving element (semiconductor substrate), a protective film, the present filter, and other filters are exemplified.

Examples (example)

The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Synthesis example

The compound (Z) and the compound (X) used in the following examples were synthesized based on generally known synthesis methods.

The compound (Z) can be used, for example, in Japanese patent application laid-open No. 2009-108267, japanese patent application laid-open No. 5-59291, japanese patent application laid-open No. 2014-95007, japanese patent application laid-open No. 2011-52218, international publication No. 2007/114398, japanese patent application laid-open No. 2003-246940, and heterocyclic compound chemistry: cyanine dyes and related compounds (Chemistry of Heterocyclic Compounds: the Cyanine Dyes and Related Compounds) (volume 18 (Wiley, 1964)) and Near infrared dyes for high tech applications (Near-Infrared Dyes for High Technology Applications) (Springer, 1997).

The compound (X) can be synthesized by the methods described in, for example, japanese patent application No. 3366697, japanese patent application No. 2846091, japanese patent application No. 2864475, japanese patent application No. 3703869, japanese patent application No. 60-228448, japanese patent application No. 1-146846, japanese patent application No. 1-228960, japanese patent application No. 4081149, japanese patent application No. 63-124054, phthalocyanine-chemistry and function- (IPC, 1997), japanese patent application No. 2007-169315, japanese patent application No. 2009-108267, japanese patent application No. 2010-241873, japanese patent application No. 3699464, and Japanese patent application No. 4740631.

Synthesis example 1 of intermediate

[ 16]

To a 200mL eggplant-type flask equipped with a stirrer, 21.8g of ethyl pivalate was added to 8.33g of compound a-1.1 synthesized by the method described in "bioorganic and pharmaceutical chemistry (Bioorganic and Medicinal Chemistry) (2013, vol.21, #11, p.2826-2831), 5 minutes, and then 4.0g of sodium hydride (60% dispersed in paraffin liquid (dispersion in Paraffin Liquid)) was added, followed by stirring at 80℃for 3 hours. Thereafter, the mixture was cooled to room temperature, 100mL of a 1N aqueous hydrochloric acid solution was added thereto for neutralization, and then, the mixture was pipetted into a separating funnel, and an 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 the magnesium sulfate was removed by filtration through a filter, the filtrate was put into a 300mL eggplant-type flask, and the solvent was distilled off using an evaporator, thereby obtaining compound a-2.

A stirrer was placed in an eggplant-type flask in which the compound a-2 was placed, 20mL of concentrated hydrochloric acid was added thereto, and the mixture was stirred at 40 ℃. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 200mL of a 1N aqueous sodium hydroxide solution was added for neutralization. Then, the mixture was pipetted into a separating funnel, 150mL of ethyl acetate was added and the organic phase was extracted, after which 15g of magnesium sulfate was added and stirred for 15 minutes. Then, the magnesium sulfate was removed by filtration through a filter, and then the filtrate was put into a 300mL eggplant type flask, and the solvent was distilled off using an evaporator. Thereafter, the residue in the flask was purified by silica gel chromatographyThe compound was separated and purified, whereby 5.0g of the target compound a-3 was obtained. Furthermore, the compounds were identified by liquid chromatography-mass spectrometry (liquid chromatography-mass spectroscopy, LC-MS) ¹ H-Nuclear magnetic resonance ¹ H-nuclear magnetic resonance， ¹ H-NMR) analysis.

Synthesis example 2 of intermediate

[ chemical 17]

In a 200mL eggplant-type flask equipped with a stirrer, 30mL of diethyl ether and 3-3 g of Compound a were placed, and the flask was cooled in an ice bath while stirring. After cooling in an ice bath for 5 minutes, 13.5mL of 1mol/L methyl magnesium iodide diethyl ether solution was added over 10 minutes, followed by heating to 35℃and stirring for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, 30mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was separated by filtration, washed with 20mL of water, and dried under reduced pressure at 50℃to obtain 2.5g of Compound a-4. Furthermore, the identification of the compounds is by ¹ H-NMR analysis was performed.

[ Synthesis example of Compound (z-1) ]

[ chemical 18]

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.6g of compound a-4.5 g, N- [2-chloro-3- (phenylamino) -2-propenylidene ] -aniline monohydrochloride (N- [2-chloro-3- (phenolamino) -2-propenylidene ] -benzenamine monohydrochloride), 25mL of acetonitrile, 7.5mL of anhydrous acetic acid, and 0.6mL of pyridine, and the mixture was heated to reflux for 5 hours. Then, the mixture was cooled to room temperature, the solvent was distilled off by an evaporator, 5mL of acetic acid was added thereto, and the mixture was cooled and left to stand at 5℃for 2 days. Thereafter, the precipitated solid was filtered under reduced pressure, and washed with 5mL of acetic acid and 10mL of hexane, whereby 0.17g of Compound a-5 was obtained.

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.1g of Compound a-5, 0.2g of lithium tetrafluoro-phenylborate, 20mL of dichloromethane, and 10mL of water, and the mixture was stirred at room temperature for 1 hour. Then, the mixture was pipetted into a separating funnel, the aqueous phase was removed, and the organic phase was washed 2 times with 20mL of water, 1g of sodium sulfate was added, and stirred for 15 minutes. Then, sodium sulfate was removed by filtration through a filter, and the filtrate was put into a 300mL eggplant-type flask, the solvent was distilled off using an evaporator, and drying was performed under reduced pressure at 50 ℃. Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

[ intermediate Synthesis example 3]

[ chemical 19]

Into a 300mL eggplant-type flask equipped with a stirrer, 5g of flavone (compound a-6) and 50mL of Tetrahydrofuran (THF) were placed, and the flask was 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, followed by heating to 35℃and stirring for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, 50mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was separated by filtration, washed with 50mL of water, and dried under reduced pressure at 50℃to obtain 4.5g of compound a-7. Furthermore, the identification of the compounds is by ¹ H-NMR analysis was performed.

[ Synthesis example of Compound (z-16) ]

[ chemical 20]

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.7g of Compound a-7, 0.26g of malondialdehyde diamide hydrochloride, 10mL of acetonitrile, 5mL of anhydrous acetic acid, and 0.2mL of pyridine, and the mixture was heated under reflux for 2 hours. Thereafter, the mixture was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, followed by washing with 10mL of diethyl ether, whereby 0.6g of Compound a-8 was obtained.

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.1g of Compound a-8, 0.2g of lithium tetrafluorophenylborate, 20mL of dichloromethane, and 10mL of water, and the mixture was stirred at room temperature for 3 hours. Then, the solution was transferred to a separating funnel, and after the aqueous phase was removed, the organic phase was washed 2 times with 20mL of water, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, the residue was dissolved in 0.5mL of acetone, 10mL of methanol was added and ice-bath cooled, and the precipitated solid was recovered by suction filtration and dried under reduced pressure at 50℃to thereby obtain 0.07g of compound (z-16). Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

[ intermediate Synthesis example 4]

[ chemical 21]

Into a 200mL eggplant-type flask equipped with a stirrer, was added compound a-9 g and ethyl pivalate 21.8g, followed by stirring, 5 minutes later, 3.2g of sodium hydride (60% dispersed in paraffin liquid) was added, and then stirring was performed at 80℃for 3 hours. Thereafter, the mixture was cooled to room temperature, and after neutralization by adding 30mL of a 1N aqueous hydrochloric acid solution, the organic phase was extracted with 150mL of ethyl acetate. Then, 15g of magnesium sulfate was added to the organic phase and stirred for 15 minutes, after which the magnesium sulfate was removed by filtration through a filter, the filtrate was put into a 300mL eggplant-type flask, and the solvent was distilled off using an evaporator, thereby obtaining compound a-10.

A stirrer was placed in an eggplant-type flask in which the compound a-10 was placed, 20mL of concentrated hydrochloric acid was added thereto, and the mixture was stirred at 40 ℃. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 240mL of a 1N aqueous sodium hydroxide solution was added for neutralization. Then, the mixture was pipetted into a separating funnel, 200mL of ethyl acetate was added and the organic phase was extracted, after which 15g of magnesium sulfate was added and stirred for 15 minutes. Thereafter, magnesium sulfate was removed by filtration through a filter, and the filtrate was filteredPut into a 300mL eggplant-type flask, and the solvent was distilled off by using an evaporator. Thereafter, the compound remaining in the flask was separated and purified by silica gel chromatography, whereby 2.0g of the target compound a-11 was obtained. Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

Synthesis example 5 of intermediate

[ chemical 22]

Into a 200mL eggplant-type flask equipped with a stirrer, 50mL of diethyl ether and 2.7g of Compound a-11 were added, and the flask was 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, followed by heating to 35℃and stirring for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, 50mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was separated by filtration, washed with 50mL of water, and dried under reduced pressure at 50℃to obtain 0.7g of Compound a-12. Furthermore, the identification of the compounds is by ¹ H-NMR analysis was performed.

[ Synthesis example of Compound (z-59) ]

[ chemical 23]

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.5g of compound a-12, 0.22g of malonaldehyde diamide hydrochloride, 7.5mL of acetonitrile, 2.5mL of anhydrous acetic acid, and 0.2mL of pyridine, and the mixture was heated and refluxed for 2 hours. Thereafter, the mixture was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10mL of acetic acid and 10mL of acetonitrile, and dried under reduced pressure at 50℃to obtain 0.35g of Compound a-13.

Into a 100mL eggplant-type flask equipped with a stirrer, 0.3g of Compound a-13, 0.8g of lithium tetrafluorophenylborate, 50mL of dichloromethane, and 20mL of water were placed, and stirred at room temperature 3 hours. Then, the solution was transferred to a separating funnel, and after the aqueous phase was removed, the organic phase was washed 2 times with 20mL of water, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, the residue was dissolved in 20mL of acetone, 100mL of water was added, and the solvent was distilled off by an evaporator to an amount of 13g, followed by ice-bath cooling. Thereafter, the precipitated solid was recovered by suction filtration, washed with 50mL of methanol, and dried under reduced pressure at 50℃to obtain 0.5g of compound (z-59). Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

[ intermediate Synthesis example 6]

[ chemical 24]

Into a 200mL eggplant-type flask equipped with a stirrer, 4.5g of Compound a-14, 21.8g of ethyl isobutyrate were added and stirred, after 5 minutes, 3.2g of sodium hydride (60% dispersed in a paraffin liquid) was added, and then stirred at 80℃for 3 hours. Thereafter, the mixture was cooled to room temperature, and after neutralization by adding 30mL of a 1N aqueous hydrochloric acid solution, the organic phase was extracted with 150mL of ethyl acetate. Then, 15g of magnesium sulfate was added to the organic phase and stirred for 15 minutes, after which the magnesium sulfate was removed by filtration through a filter, the filtrate was put into a 300mL eggplant type flask, and the solvent was distilled off using an evaporator, thereby obtaining compound a-15.

A stirrer was placed in an eggplant-type flask in which the compound a-15 was placed, 20mL of concentrated hydrochloric acid was added thereto, and the mixture was stirred at 40 ℃. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 240mL of a 1N aqueous sodium hydroxide solution was added for neutralization. Thereafter, the mixture was pipetted into a separating funnel, 200mL of ethyl acetate was added and the organic phase was extracted, after which 15g of magnesium sulfate was added and stirred for 15 minutes. Then, the magnesium sulfate was removed by filtration through a filter, and the filtrate was placed in a 300mL eggplant type 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, whereby 0.4g of the target compound a-16 was obtained. Furthermore, the compoundsAuthentication is by LC-MS ¹ H-NMR analysis was performed.

[ intermediate Synthesis example 7]

[ chemical 25]

Into a 100mL eggplant-type flask equipped with a stirrer, 0.4g of compound a-16 and 10mL of diethyl ether were charged, and the flask was ice-cooled. After cooling in an ice bath for 5 minutes, 5.0mL of 1mol/L methyl magnesium iodide diethyl ether solution was added over 10 minutes, followed by heating to 35℃and stirring for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, 10mL of a 20% aqueous perchloric acid solution was added thereto, and then 20mL of methylene chloride was added thereto, followed by pipetting into a separating funnel, and the organic phase was recovered. The solvent was distilled off from the organic phase using an evaporator, and the solid residue was stirred, followed by addition of 20mL of diethyl ether and stirring for 20 minutes. Then, a solid component was collected by suction filtration and dried under reduced pressure at 50℃to thereby obtain 0.5g of Compound a-17. Furthermore, the identification of the compounds is by ¹ H-NMR analysis was performed.

[ Synthesis example of Compound (z-62) ]

[ chemical 26]

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.4g of compound a-17, 0.16g of malonaldehyde diamide hydrochloride, 7.5mL of acetonitrile, 2.5mL of anhydrous acetic acid, and 0.2mL of pyridine, and the mixture was heated and refluxed for 2 hours. Thereafter, it was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10mL of diethyl ether, and dried under reduced pressure at 50℃to thereby obtain 0.35g of Compound a-18.

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.3g of Compound a-18, 0.8g of lithium tetrafluoro-phenylborate, 50mL of dichloromethane, and 20mL of water, and the mixture was stirred at room temperature for 3 hours. Thereafter, the mixture was pipetted into a separating funnel to give a mixtureAfter the aqueous phase was removed, the organic phase was washed 2 times with 20mL of water, the solvent was distilled off from the organic phase using an evaporator, and the solid was dried under reduced pressure at 50 ℃. Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

Synthesis example 8 of intermediate

[ chemical 27]

Into a 200mL eggplant-type flask equipped with a stirrer were placed 28.7g of methyl 4, 4-dimethyl-3-oxopentanoate and 15g of compound a-19, followed by stirring at 180℃for 24 hours. Thereafter, the mixture was cooled to room temperature, 250mL of hexane and 200mL of 1N aqueous hydrochloric acid were added, and the mixture was pipetted into a separating funnel to remove the aqueous phase. Then, after the solvent was distilled off from the organic phase by using an evaporator, the compound remaining in the flask was separated and purified by silica gel chromatography, whereby 7g of the target compound a-20 was obtained. Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

[ intermediate Synthesis example 9]

[ chemical 28]

Into a 100mL eggplant-type flask equipped with a stirrer, 20mL of diethyl ether and 20.5 g of compound a-20 were added, and the flask was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 14.0mL of 1mol/L methyl magnesium iodide diethyl ether solution was added over 10 minutes, followed by heating to 35℃and stirring 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 a 40% aqueous solution of fluorinated boric acid was added over 10 minutes, followed by stirring for 30 minutes, and then transferred to a separating funnel. Then, 30mL of methylene chloride was added to conduct liquid separation, thereby removing the aqueous phase, and the organic phase was distilled off from the solvent using an evaporator. Thereafter, the residue was dissolved in twoTo 30mL of chloromethane, 50mL of diisopropyl ether was added, and after 40g of the solvent was removed by an evaporator, the solution was cooled in an ice bath, and the precipitated solid was collected by suction filtration and dried under reduced pressure at 50℃to obtain 2.3g of Compound a-21. Furthermore, the identification of the compounds is by ¹ H-NMR analysis was performed.

[ Synthesis example of Compound (z-151) ]

[ chemical 29]

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.5g of compound a-21, 0.18g of malonaldehyde diamide hydrochloride, and 15mL of pyridine, and the mixture was heated and refluxed for 2 hours. Thereafter, the mixture was cooled to room temperature, and then the solvent was distilled off by an evaporator, followed by separation by column chromatography, whereby 0.2g of compound a-22 was obtained.

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.2g of Compound a-22, 0.8g of lithium tetrafluoro-phenylborate, 50mL of dichloromethane, and 20mL of water, and the mixture was stirred at room temperature for 3 hours. Thereafter, the aqueous phase was removed by pipetting to a separating funnel, and the organic phase was washed 2 times with 20mL of water, the solvent was distilled off from the organic phase by using an evaporator, and separation was performed by column chromatography, whereby 0.2g of the compound (z-151) was obtained. Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

Synthesis example 10 of intermediate

[ chemical 30]

Into a 200mL eggplant-type flask equipped with a stirrer, 1.9g of Compound a-23.9 g and 2.0g of ethyl pivalate were added and stirred, after 5 minutes, 0.3g of sodium hydride (60% dispersed in a paraffin liquid) was added, and then stirred at 80℃for 3 hours. Thereafter, the mixture was cooled to room temperature, and after neutralization by adding 30mL of a 1N aqueous hydrochloric acid solution, the organic phase was extracted with 150mL of ethyl acetate. Then, 5g of magnesium sulfate was added to the organic phase and stirred for 15 minutes, after which the magnesium sulfate was removed by filtration through a filter, the filtrate was put into a 300mL eggplant-type flask, and the solvent was distilled off using an evaporator, whereby compound a-24.3 g was obtained.

An eggplant-type flask containing 1.3g of Compound a-24 was charged with a stirrer, and 20mL of concentrated hydrochloric acid was added thereto, followed by stirring at 40 ℃. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 240mL of a 1N aqueous sodium hydroxide solution was added for neutralization. Then, the mixture was pipetted into a separating funnel, 200mL of ethyl acetate was added and the organic phase was extracted, after which 5g of magnesium sulfate was added and stirred for 15 minutes. Thereafter, magnesium sulfate was removed by filtration through a filter, and the filtrate was placed in a 300mL eggplant type 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, whereby 1.1g of compound a-25 was obtained. Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

Synthesis example 11 of intermediate

[ 31]

Into a 200mL eggplant-type flask equipped with a stirrer, 50mL of diethyl ether and 1.5g of Compound a-25 were added, and the flask was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 1.5mL of 1mol/L methyl magnesium iodide diethyl ether solution was added over 10 minutes, followed by heating to 35℃and stirring for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, 50mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was separated by filtration, washed with 50mL of water, and dried under reduced pressure at 50℃to obtain 3.0g of compound a-26. Furthermore, the identification of the compounds is by ¹ H-NMR analysis was performed.

[ Synthesis example of Compound (z-157) ]

[ chemical 32]

Into a 100mL eggplant-type flask equipped with a stirrer were placed 7.0g of compound a-26, 2.5g of malonaldehyde diamide hydrochloride, 50mL of acetonitrile, 10mL of anhydrous acetic acid, and 10mL of pyridine, and the mixture was heated under reflux for 2 hours. Thereafter, the mixture was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10mL of acetic acid and 10mL of acetonitrile, and dried under reduced pressure at 50℃to obtain 5.1g of Compound a-27.

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.6g of Compound a-27.2 g of lithium tetrafluorophenylborate, 50mL of dichloromethane, and 50mL of water, and the mixture was stirred at room temperature for 3 hours. Then, the solution was transferred to a separating funnel, and after the aqueous phase was removed, the organic phase was washed 2 times with 20mL of water, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, the residue was dissolved in 20mL of acetone, 100mL of water was added, and the solvent was distilled off by an evaporator to an amount of 10g, followed by ice-bath cooling. Thereafter, the precipitated solid was recovered by suction filtration, washed with 50mL of methanol, and then dried under reduced pressure at 50℃to obtain 1.0g of the compound (z-157). Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

Synthesis example 12 of intermediate

[ 33]

Into a 200mL eggplant-type flask equipped with a stirrer were placed 22g of 1-adamantanecarbonyl chloride (compound a-28) and 5.2g of methylene cyclohexane, and after heating to 90 ℃, 10g of trifluoromethanesulfonic acid was added dropwise thereto and stirred for 10 minutes. Then, after cooling to 0 ℃, 150mL of hexane, 50mL of diethyl ether, and 50mL of water were added and stirred, and the precipitated solid was separated by filtration, and dried under reduced pressure at 50 ℃, whereby 4.2g of compound a-35 was obtained. Furthermore, the identification of the compounds is by ¹ H-NMR analysis was performed.

[ Synthesis example of Compound (z-163) ]

[ chemical 34]

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.5g of compound a-35, 0.1g of malonaldehyde diamide hydrochloride, 4mL of acetonitrile, 1mL of anhydrous acetic acid, and 1mL of pyridine, and the mixture was stirred at 90℃for 10 minutes. After cooling to 0 ℃, the precipitated solid was separated by filtration, washed with 2mL of acetonitrile, and dried under reduced pressure at 50 ℃, whereby 0.3g of compound a-36 was obtained. Furthermore, the identification of the compounds is by ¹ H-NMR analysis was performed.

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.3g of Compound a-36, 0.4g of lithium tetrafluoro-phenylborate, 20mL of dichloromethane, and 20mL of water, and the mixture was stirred at room temperature for 4 hours. Then, the solution was transferred to a separating funnel, and after the aqueous phase was removed, the organic phase was washed 2 times with 20mL of water, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, the residue was dissolved in methylene chloride, methanol was added, and the precipitated solid was recovered by suction filtration and dried under reduced pressure at 50℃to thereby obtain 0.4g of compound (z-163). Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

[ intermediate Synthesis example 13]

[ 35]

To a solution of compound a-37 (20.0 g) in t-BuOH (150 mL) was added ethyl pivalate (50.0 g), sodium hydride (60% dispersed in paraffin liquid) 5.5g, and then stirred at 80℃for 3 hours. Thereafter, the mixture was cooled to room temperature, and 20mL of concentrated hydrochloric acid was added. After 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.

Thereafter, the compound a-38 was not purified, 60mL of concentrated hydrochloric acid was added thereto, and the mixture was stirred at 40 ℃. After 1 hour, the reaction solution was cooled in an ice bath, and neutralized by adding a 1N aqueous sodium hydroxide solution. After 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, whereby compound a-39 (15.4 g) was obtained. Identification of the Compounds was performed by LC-MS ¹ H-NMR analysis was performed.

Synthesis example 14 of intermediate

[ 36]

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 50mL of toluene and 50mL of water, and the mixture was heated at 110℃for 12 hours while stirring vigorously. After cooling to room temperature, the organic layer was washed with toluene-water, added with sodium sulfate, dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography, whereby compound a-40 (12.4 g) was obtained.

While stirring compound a-40 (12.4 g) and 90mL of tetrahydrofuran, ice-bath cooling was performed. After cooling in an ice bath for 5 minutes, a solution of magnesium methyl iodide in diethyl ether (1 mol/L,50 mL) was added dropwise, and the mixture was heated to 35℃and stirred for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, 90mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was separated by filtration, washed with 60mL of water, and dried under reduced pressure at 50℃to obtain compound a-41 (10.4 g). Identification of the Compounds is by ¹ H-NMR analysis was performed.

[ Synthesis example of Compound (z-156) ]

[ 37]

Into a 100mL eggplant-type flask equipped with a stirrer were placed 7.0g of Compound a-41, 2.5g of malondialdehyde diamide hydrochloride, 50mL of acetonitrile, 10mL of anhydrous acetic acid, and 10mL of pyridine, and the mixture was heated under reflux for 2 hours. Thereafter, the mixture was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10mL of acetic acid and 10mL of acetonitrile, and dried under reduced pressure at 50℃to obtain 5.0g of Compound a-42.

Into a 100mL eggplant-type flask equipped with a stirrer were placed 0.6g of Compound a-42, 1.2g of lithium tetrafluorophenyl borate, 50mL of dichloromethane, and 50mL of water, and the mixture was stirred at room temperature for 3 hours. Then, the solution was transferred to a separating funnel, and after the aqueous phase was removed, the organic phase was washed 2 times with 20mL of water, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, the residue was dissolved in 20mL of acetone, 100mL of water was added, and the solvent was distilled off by an evaporator to an amount of 10g, followed by ice-bath cooling. Thereafter, the precipitated solid was recovered by suction filtration, washed with 50mL of methanol, and then dried under reduced pressure at 50℃to obtain 1.0g of the compound (z-156). Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

[ intermediate Synthesis example 15]

[ 38]

Compound a-43 (20.0 g), oxalyl chloride (oxalyl dichloride) (21.4 g), pyridine (13.4 g) and Dimethylformamide (DMF) (1 mL) were stirred in dichloromethane (100 mL) at room temperature for 1 hour. The methylene chloride was removed by an evaporator to obtain a mixture containing the compound a-44.

[ Synthesis example of Compound (z-161) ]

[ 39]

Compounds a to 45 were obtained in the same manner as in intermediate Synthesis example 10 except that ethyl pivalate was changed to compound a to 44.

Changing the compound a-23 to the compound a-45 and changing the malondialdehyde bisanilide hydrochloride to N- [ 2-chloro-3- (phenylamino) -2-propenylidene]Compound (z-161) was obtained in the same manner as in Synthesis example 11 of intermediate and in the same manner as in Synthesis example of Compound (z-157). Furthermore, the identification of the compounds was performed by LC-MS ¹ H-NMR analysis was performed.

< requirement (A) >)

The above-mentioned requirement (a) was measured using a transmission spectrum (wherein the transmission spectrum is a spectrum having a transmittance of 10% at an absorption maximum wavelength) measured using a spectrophotometer (V-7200) manufactured by japan spectroscopy (strand) using a solution obtained by dissolving the compound (Z) or the compound (X) used in the test described below in methylene chloride. The results are shown in table 5. The requirements A to D in Table 5 represent the requirements (A), the requirements (B-1), the requirements (C) and the requirements (D) in the columns < Compound (Z) > respectively.

< requirement (B) >)

The above-mentioned requirement (B) was measured by using an absorption spectrum measured by using a spectrophotometer (V-7200) manufactured by Japan Spectrophotometer (Strand) in which the compound (Z) or the compound (X) used in the test described below was dissolved in methylene chloride. The results are shown in table 5.

< requirement (C) >)

Into a container, 100 parts by mass of the resin A obtained in resin Synthesis example 1, 0.3 part by mass of Yi Lunuo (Irganox) 1010 (manufactured by BASF Japan (Str)), the compound (Z) or the compound (X) used in the following test, and methylene chloride were added to prepare a solution having a resin concentration of 20% by mass.

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

The obtained solution was cast on a smooth glass plate, dried at 20℃for 8 hours, and peeled from the glass plate. The peeled coating film was dried at 100℃under reduced pressure for 8 hours to obtain a resin layer for evaluation of light resistance having a thickness of 0.1mm, a longitudinal direction of 210mm and a transverse direction of 210 mm.

The absorbance of the resin layer for light resistance evaluation was measured using a spectrophotometer (V-7200) manufactured by Japan Spectrophotometer (Stra), 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 double bird (TWINBIRD) industry (Strand) was set up so as to be a distance of 30cm from directly above in the vertical direction with respect to the surface of the resin layer for light resistance evaluation, arm type touch inverter fluorescent lamp LK-H766B, total luminous flux: 1334 lm), and the fluorescent lamp was irradiated for 30 days. The absorbance Af at λa of the resin layer for evaluating light resistance after irradiation with the fluorescent lamp for 30 days was measured, and the retention ratio D (=af×100/Ai) of absorbance was calculated. The results are shown in table 5.

< requirement (D) >)

In an absorption spectrum measured by a spectrophotometer (V-7200) manufactured by Japan spectroscopy (Strand) using a solution obtained by dissolving the compound (Z) or the compound (X) used in the test described below in methylene chloride, εa/εbmax is calculated by taking the absorbance at the longest wavelength of the maximum absorption wavelength as εa and the absorbance at the wavelengths of 430nm to 580nm as εbmax. The results are shown in table 5.

< molecular weight >

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.

(a) The weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were measured using a Gel Permeation Chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh (Strand)) manufactured by Wotes (WATERS) company, developing solvent: o-dichlorobenzene.

(b) The weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were measured using a GPC apparatus (model HLC-8220, column: TSKgel. Alpha. -M, developing solvent: THF) manufactured by Tosoh (Stry).

The resin synthesized in resin synthesis example 3 described below was not subjected to the measurement of molecular weight by the above method, but was subjected to the measurement of logarithmic viscosity by the method (c) described below.

(c) A part of the polyimide solution was poured into absolute methanol to precipitate polyimide, and the polyimide was filtered to separate the polyimide from the unreacted monomers, followed by vacuum drying at 80 ℃ for 12 hours. The obtained polyimide (0.1 g) was dissolved in 20mL of N-methyl-2-pyrrolidone (thin polyimide solution), and the logarithmic viscosity (. Mu.) at 30℃was determined from the following formula using a Cannon-Fenske viscometer.

μ＝{ln(ts/t0)}/C

t0: flow time of solvent (N-methyl-2-pyrrolidone)

ts: flow time of thin polyimide solution

C：0.5g/dL

< glass transition temperature (Tg) >)

The glass transition temperature of the resin was measured using a differential scanning calorimeter (DSC 6200) manufactured by Hitachi High-Tech Science (Stra), at a temperature-increasing rate: the measurement was performed at 20℃per minute under a nitrogen stream.

Synthesis example 1 of resin

8-methyl-8-methoxycarbonyl tetracyclo [4.4.0.1 ] represented by the following formula (a) ^2,5 .1 ^7,10 ]100 parts by mass of dode-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) were charged into a reaction vessel replaced with nitrogen, and the solution was heated to 80 ℃. Then, 0.2 parts by mass of a toluene solution (0.6 mol/liter) of triethylaluminum as a polymerization catalyst and 0.9 parts by mass of a toluene solution (concentration 0.025 mol/liter) of methanol-modified tungsten hexachloride were added to the solution in the reaction vessel, and the solution was heated and stirred at 80 ℃ for 3 hours, thereby conducting ring-opening polymerization to obtain a ring-opening polymer solution. The polymerization conversion in the polymerization reaction was 97%.

[ 40]

1,000 parts by mass of the obtained ring-opening polymer solution, to which 0.12 parts by mass of RuHCl (CO) [ P (C) ₆ H ₅ ) ₃ ] ₃ Under a hydrogen pressure of 100kg/cm ² The hydrogenation reaction was carried out by stirring for 3 hours under heating at 165 ℃. After the obtained reaction solution (hydrogenated polymer solution) was cooled, hydrogen gas was pressurized. The obtained reaction solution was poured into a large amount of methanol, and then the coagulum was separated and recovered, which was dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin a"). The number average molecular weight (Mn) of the obtained resin A was 32,000, the weight average molecular weight (Mw) was 137,000, and the glass transition temperature (Tg) was 165 ℃.

Synthesis example 2 of resin

Into a 3L four-necked flask, 35.12g (0.253 mol) of 2, 6-difluorobenzonitrile, 87.60g (0.250 mol) of 9, 9-bis (4-hydroxyphenyl) fluorene, 41.46g (0.300 mol) of potassium carbonate, 443g of N, N-dimethylacetamide and 111g of toluene were charged. Then, a thermometer, a stirrer, a three-way cock with a nitrogen inlet tube, a Dean-Stark tube and a cooling tube were mounted in the four-necked flask. Then, after the flask was purged with nitrogen, the obtained solution was reacted at 140℃for 3 hours, and the water formed was removed from the dean-Stark tube as needed. When the formation of water was not confirmed, the temperature was gradually raised to 160℃and the reaction was carried out at the above-mentioned temperature for 6 hours. Thereafter, the mixture was cooled to room temperature (25 ℃) and the salt formed was removed by a filter paper, and the filtrate was taken into methanol to reprecipitate, and the filtrate (residue) was separated by filtration. The obtained filtrate was dried under vacuum at 60 ℃ overnight, whereby a white powder (hereinafter also referred to as "resin B") was obtained (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 ℃.

Synthesis example 3 of resin

In a 500mL 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, 27.66g (0.08 mol) of 1, 4-bis (4-amino-. Alpha.,. Alpha. -dimethylbenzyl) benzene and 7.38g (0.02 mol) of 4,4' -bis (4-aminophenoxy) biphenyl were placed under a nitrogen flow, and dissolved in 68.65g of γ -butyrolactone and 17.16g of N, N-dimethylacetamide. The obtained solution was cooled to 5℃using an ice-water bath, and 22.62g (0.1 mol) of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride and 0.50g (0.005 mol) of triethylamine as an imidization catalyst were added together while maintaining the same temperature. After the addition was completed, the temperature was raised to 180℃and the distillate was refluxed for 6 hours while being distilled off at any time. After the completion of the reaction, air cooling was performed until the internal temperature became 100 ℃, and 143.6g of N, N-dimethylacetamide was added to dilute the solution, followed by cooling with stirring, whereby 264.16g of a polyimide solution having a solid content of 20 mass% was obtained. A portion of the polyimide solution was injected into 1L of methanol and the polyimide was precipitated. After the polyimide separated by filtration was washed with methanol, it was dried in a vacuum drier at 100℃for 24 hours, thereby obtaining a white powder (hereinafter also referred to as "resin C"). As a result of measurement of Infrared (IR) spectrum of the obtained resin C, 1704cm unique to the imide group was observed ^-1 、1770cm ^-1 Is not limited to the absorption of (a). The glass transition temperature (Tg) of the resin C was 310℃and the logarithmic viscosity was 0.87.

Example 1

[ preparation of substrate ]

Into 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) (having an absorption maximum wavelength of 787nm in methylene chloride) as the compound (Z), 0.038 parts by mass of the following compound (X-1) (having an absorption maximum wavelength of 711nm in methylene chloride) as the compound (X), 0.075 parts by mass of the following compound (X-2) (having an absorption maximum wavelength of 738nm in methylene chloride) and methylene chloride were charged, and a solution having a resin concentration of 20% by mass was prepared. The obtained solution was cast on a smooth glass plate, dried at 20℃for 8 hours, and peeled from the glass plate. The peeled coating film was dried at 100℃under reduced pressure for 8 hours to obtain a resin layer (1) having a thickness of 0.1mm, a longitudinal direction of 210mm and a transverse direction of 210 mm.

Compounds (z-1)

[ chemical 41]

Compounds (x-1)

[ chemical 42]

Compounds (x-2)

[ chemical 43]

By means of a bar coater, the thickness of the obtained resin layer (2) was 3 μmThe resin composition (1) described below was applied to one side of the obtained resin layer (1), and the solvent was evaporated and removed by heating in an oven at 70℃for 2 minutes. Next, an exposure (exposure amount 500 mJ/cm) was performed using a UV conveyor type exposure machine (Ai Gufei (Eye graphics) (stock) manufactured, ai Yi (Eye) ultraviolet curing apparatus, model US2-X0405, 60 Hz) ² Illuminance: 200mW/cm ² ) The resin composition (1) is cured, and a resin layer (2) is formed on the resin layer (1). In the same manner, a resin layer (2) containing the resin composition (1) is also formed on the other surface of the resin layer (1). Thus, a substrate having a resin layer (2) containing no compound (Z) on both sides of the resin layer (1) containing the compound (Z) was obtained.

Resin composition (1): 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 (solvent used so that the solid content concentration in the obtained composition is 30% by mass)

(light resistance)

The obtained substrate was exposed to an indoor fluorescent lamp for 500 hours, and the light resistance of the near infrared ray absorbing pigment contained in the resin was evaluated. The light resistance is evaluated by calculating the residual rate (%) of the pigment from the change in absorbance before and after exposure of the fluorescent lamp at the wavelength at which the absorption intensity of the base material is highest (hereinafter referred to as "λa"; where λa is the wavelength at which the absorption intensity is highest in the case where the base material has a plurality of absorption maxima).

The residual rate of the pigment after 500 hours exposure to the fluorescent lamp was "o" and less than 95% was "x". The results are shown in table 8.

[ manufacture of optical Filter ]

A dielectric multilayer film (I) was formed on one surface of the substrate obtained in the production of the substrate, and a dielectric multilayer film (II) was further formed on the other surface of the substrate, whereby an optical filter having a thickness of about 0.110mm was obtained.

The dielectric multilayer film (I) is prepared by depositing silicon dioxide (SiO) ₂ ) Layer and titanium dioxide (TiO) ₂ ) A laminate (total of 26 layers) in which the layers were alternately laminated. The dielectric multilayer film (II) is prepared by depositing silicon dioxide (SiO) ₂ ) Layer and titanium dioxide (TiO) ₂ ) A laminate (22 layers in total) in which the layers were alternately laminated.

In both the dielectric multilayer film (I) and the dielectric multilayer film (II), the titanium oxide layer, the silicon oxide layer, the titanium oxide layer, the … silicon oxide layer, the titanium oxide layer, and the silicon oxide layer are alternately laminated in this order from the substrate side, and the outermost layer of the optical filter is the silicon oxide layer.

The thickness and the number of layers are optimized by using optical Thin Film design software (core maxwell (Essential Macleod), manufactured by Thin Film Center) in accordance with the wavelength dependent characteristic of the refractive index of the substrate, or the absorption characteristics of the compound (Z) and the compound (X) used, so that good transmittance in the visible region and reflection performance in the near infrared region can be achieved. In the present embodiment, the input parameters (Target) values for the software are set as shown in table 6 below in the optimization.

TABLE 6

As a result of optimization of the film structure, the dielectric multilayer film (I) was formed as a multilayer vapor-deposited film having 26 layers of a laminate in which a silica layer having a physical film thickness of about 37nm to 168nm and a titania layer having a physical film thickness of about 11nm to 104nm were alternately laminated, and the dielectric multilayer film (II) was formed as a multilayer vapor-deposited film having 22 layers of a laminate in which a silica layer having a physical film thickness of about 40nm to 191nm and a titania layer having a physical film thickness of about 10nm to 110nm were alternately laminated. An example of the optimized film structure is shown in table 7 below.

TABLE 7

The obtained optical filter was found to have an average value T of spectral transmittance measured in the vertical direction of the optical filter in the wavelength range of 430nm to 580nm and an average value R of spectral transmittance of unpolarized light incident from an angle of 5 DEG away from the vertical direction on the dielectric multilayer film (II) side in the wavelength range of 700nm to 800 nm. The spectral transmittance and spectral reflectance were measured using a spectrophotometer (V-7200) manufactured by japan spectroscopy (stock). The results are shown in table 8.

Example 2

In example 1, a substrate was obtained in the same manner as in example 1, except that 0.08 parts by mass of the following compound (z-16) (the absorption maximum wavelength in methylene chloride was 825 nm) was used in place of 0.2 parts by mass of the compound (z-1), and resin B was used in place of resin a.

The obtained substrate was evaluated for light resistance in the same manner as in example 1. The results are shown in table 8.

Compounds (z-16)

[ 44]

Then, in the same manner as in example 1, silica (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 26 layers of dielectric multilayer film (I) formed by alternately laminating layers, and further, silicon dioxide (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 22 layers of dielectric multilayer films (II) were alternately laminated to obtain an optical filter having a thickness of about 0.110 mm.

The design of the dielectric multilayer film was performed by taking into consideration the wavelength dependence of the refractive index of the substrate and the like in the same manner as in example 1, using the same design parameters as in example 1.

The obtained optical filter was subjected to average values T and R in the same manner as in example 1. The results are shown in table 8.

Example 3

In example 1, a substrate was obtained in the same manner as in example 1, except that 0.14 parts by mass of the following compound (z-59) (having an absorption maximum wavelength of 770nm in methylene chloride) was used in place of 0.2 parts by mass of the compound (z-1), and resin C was used in place of resin a.

Compounds (z-59)

[ 45]

Example 4

In example 1, a substrate was obtained in the same manner as in example 1, except that 0.2 parts by mass of the following compound (z-62) (the absorption maximum wavelength in methylene chloride was 757 nm) was used in place of 0.2 parts by mass of the compound (z-1), and that the subcritical (acryview) produced by japan catalyst (strand) was used in place of the resin a.

Compounds (z-62)

[ chemical 46]

Example 5

In example 1, a substrate was obtained in the same manner as in example 1, except that 0.08 parts by mass of the compound (z-151) (the absorption maximum wavelength in methylene chloride was 824 nm) was used instead of 0.2 parts by mass of the compound (z-1).

Compounds (z-151)

[ 47]

Then, in the same manner as in example 1, silica (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) Dielectric multilayer film (I) having 26 total layers formed by alternately laminating layers, and furtherOn the other surface of the substrate, silicon dioxide (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 22 layers of dielectric multilayer films (II) were alternately laminated to obtain an optical filter having a thickness of about 0.110 mm.

Example 6

In a vessel, 100 parts by mass of the resin A obtained in resin Synthesis example 1, 0.38 parts by mass of the compound (X-1) as the compound (X), 0.75 parts by mass of the compound (X-2) and methylene chloride were added to prepare a solution having a resin concentration of 20% by mass, and the solution was filtered by a microporous filter having a pore size of 5. Mu.m, to obtain a resin solution (E6-1).

In the same manner, 100 parts by mass of resin A, 2 parts by mass of the compound (Z-1) as the compound (Z) and methylene chloride were added to prepare a solution having a resin concentration of 20% by mass, and the solution was filtered by a microporous filter having a pore size of 5. Mu.m, to obtain a resin solution (E6-2).

The following resin composition (2) was applied to both surfaces of a transparent glass support "OA-10G" (thickness 200 μm) made of japan electric nitrate (strand) cut into a size of 200mm×200mm by a spin coater so that the film thickness after drying was about 1 μm, and then heated on a heating plate at 80 ℃ for 2 minutes to volatilize and remove the solvent, thereby forming an adhesive layer functioning as an adhesive layer between the glass support and the coating resin layer (1) and the coating resin layer (2) described later.

Next, a resin solution (E6-1) was applied to one surface of the glass support on which the adhesive layer was formed using a spin coater so that the film thickness after drying was 10 μm, and the solvent was volatilized and removed by heating on a heating plate at 80 ℃ for 5 minutes, thereby forming a coated resin layer (2).

Further, a resin solution (E6-2) was applied to the other surface of the glass support on which the adhesive layer was formed using a spin coater so that the film thickness after drying was 10. Mu.m, and the solvent was volatilized and removed by heating on a heating plate at 80℃for 5 minutes, thereby forming a coated resin layer (1).

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 the glass support and a resin layer containing no compound (Z) was laminated on the other surface.

The obtained substrate was evaluated for light resistance in the same manner as in example 1. The results are shown in table 9.

Resin composition (2): 30 parts by mass of isocyanuric acid ethylene oxide-modified triacrylate (trade name: luo Nisi (Aronix) M-315, manufactured by east Asia Synthesis (stock)), 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-glycidoxypropyl trimethoxysilane, 5 parts by mass of 1-hydroxycyclohexyl benzophenone (trade name: brilliant George (IRGACURE) 184, manufactured by BASF Japan (stock)), and 1 part by mass of Sang Aide (san-aid) SI-110 base (manufactured by Sanxinchem industry (stock)), and dissolved in propylene glycol monomethyl ether acetate in a solid content concentration of 50% by mass, and then filtered by a microporous filter having a pore size of 0.2 μm

Then, referring to example 1, on the surface of the coating resin layer (2), silica (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 26 layers of dielectric multilayer film (I) formed by alternately laminating layers, and further, silicon dioxide (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 22 layers of dielectric multilayer films (II) were alternately laminated to obtain an optical filter having a thickness of about 0.226 mm.

The obtained optical filter was subjected to average values T and R in the same manner as in example 1. The results are shown in table 9.

Example 7

A substrate was obtained in the same manner as in example 1, except that 0.01 part by mass of the following compound (x-3) (the maximum absorption wavelength in methylene chloride is 931 nm) was additionally used in example 1.

Compounds (x-3)

[ 48]

Example 8

A substrate was obtained in the same manner as in example 1, except that 0.03 parts by mass of the following compound (x-5) (the absorption maximum wavelength in methylene chloride is 1095 nm) was additionally used in example 1.

Compounds (x-5)

[ 49]

Example 9

In example 1, a substrate was obtained in the same manner as in example 1, except that 0.16 parts by mass of compound (z-16) (the maximum absorption wavelength in methylene chloride was 825 nm) and 0.12 parts by mass of compound (z-59) (the maximum absorption wavelength in methylene chloride was 770 nm) were used instead of 0.2 parts by mass of compound (z-1).

Example 10

A substrate was obtained in the same manner as in example 1, except that 0.17 parts by mass of the following compound (y-1) (the absorption maximum wavelength in methylene chloride is 394 nm) was additionally used in example 1.

Compounds (y-1)

[ 50]

Example 11

In example 6, a substrate was obtained in the same manner as in example 6, except that the near infrared absorbing glass substrate "BS-11" (thickness: 0.2 mm) manufactured by Songbo Nitro industries (Ltd.) was used instead of the transparent glass support "OA-10G" (thickness: 200 μm) manufactured by Nitro Japan.

Then, in the same manner as in example 6, on the surface of the coating resin layer (2), silica (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 26 layers of dielectric multilayer film (I) formed by alternately laminating layers, and further, silicon dioxide (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 22 layers of dielectric multilayer films (II) were alternately laminated to obtain an optical filter having a thickness of about 0.226 mm.

Example 12

In example 1, a substrate was obtained in the same manner as in example 1, except that 0.1 part by mass of the following compound (z-156) (the absorption maximum wavelength in methylene chloride was 785 nm) was used instead of 0.2 parts by mass of the compound (z-1).

Compounds (z-156)

[ 51]

Then, in the same manner as in example 1, silica (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 26 layers of dielectric multilayer film (I) formed by alternately laminating layers, and further, silicon dioxide (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) Dielectric material of 22 layers in total formed by alternately laminating layersMultilayer film (II) to obtain an optical filter having a thickness of about 0.110 mm.

Example 13

A substrate was obtained in the same manner as in example 12 except that 0.1 part by mass of the following compound (z-157) (having an absorption maximum wavelength of 788nm in methylene chloride) was used in place of 0.1 part by mass of the compound (z-156) in example 12.

Compounds (z-157)

[ 52]

Example 14

In example 12, a substrate was obtained in the same manner as in example 12 except that 0.1 part by mass of the following compound (z-158) (the absorption maximum wavelength in methylene chloride: 790 nm) was used instead of 0.1 part by mass of the compound (z-156).

Compounds (z-158)

[ 53]

Example 15

In example 12, a substrate was obtained in the same manner as in example 12 except that 0.1 part by mass of the following compound (z-159) (the absorption maximum wavelength in methylene chloride was 800 nm) was used instead of 0.1 part by mass of the compound (z-156).

Compounds (z-159)

[ 54]

Example 16

In example 12, a substrate was obtained in the same manner as in example 12 except that 0.1 part by mass of the following compound (z-160) (the absorption maximum wavelength in methylene chloride: 791 nm) was used instead of 0.1 part by mass of the compound (z-156).

Compounds (z-160)

[ 55]

Then, in the same manner as in example 1, silica (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 26 layers of dielectric multilayer film (I) formed by alternately laminating layers, and further, silicon dioxide (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 22 layers of dielectric multilayer film (II) formed by alternately laminating the layers, the thickness of which was about 0.110mm, was obtainedA filter.

Example 17

In example 12, a substrate was obtained in the same manner as in example 12 except that 0.1 part by mass of the following compound (z-161) (the absorption maximum wavelength in methylene chloride was 800 nm) was used instead of 0.1 part by mass of the compound (z-156).

Compounds (z-161)

[ 56]

Example 18

In example 12, a substrate was obtained in the same manner as in example 12, except that 0.1 part by mass of the following compound (z-162) (the absorption maximum wavelength in methylene chloride was 810 nm) was used instead of 0.1 part by mass of the compound (z-156).

Compounds (z-162)

[ 57]

Example 19

In example 12, a substrate was obtained in the same manner as in example 12, except that 0.1 part by mass of the following compound (z-163) (the absorption maximum wavelength in methylene chloride was 760 nm) was used instead of 0.1 part by mass of the compound (z-156).

Compounds (z-163)

[ 58]

Comparative example 1

A substrate was obtained in the same manner as in example 1, except that the compound (Z) was not used in example 1.

Comparative example 2

In example 1, a substrate was obtained in the same manner as in example 1, except that 0.038 parts by mass of compound (X-1), 0.075 parts by mass of compound (X-2), and 0.2 parts by mass of compound (X-3) (the maximum absorption wavelength in methylene chloride is 931 nm) were used instead of compound (Z).

Compounds (x-3)

[ 59]

Comparative example 3

In example 1, a substrate was obtained in the same manner as in example 1, except that 0.038 parts by mass of compound (X-1), 0.075 parts by mass of compound (X-2) and 0.08 parts by mass of compound (X-4) (the maximum absorption wavelength in methylene chloride was 760 nm) were used instead of compound (Z).

Compounds (x-4)

[ chemical 60]

TABLE 9

The optical filters obtained in examples 1 to 19 are useful in recent years because they can reduce the intensity of reflected light in a wavelength region of near infrared light, particularly 700 to 800nm, while maintaining good transmittance of visible light, and therefore can minimize the decrease in sensitivity in the visible light region and eliminate image defects caused by the reflected light in imaging devices such as digital still cameras and the like, which have advanced in high performance.

[ Synthesis example of Compound (z-164) ]

An eggplant-shaped flask was charged with acetyl chloride (2 equivalent) and tert-butyl alcohol (1 equivalent), and stirred while being heated by an oil bath adjusted to 85 ℃. To this, trifluoromethanesulfonic acid (1 equivalent) was added dropwise over 5 minutes, and after the completion of the addition, the oil bath was stirred for 30 minutes at a set temperature of 100 ℃. After cooling to room temperature, diethyl ether and water were added, and the precipitated solid was collected by filtration to obtain the following compound (m-1).

Compounds (m-1)

[ chemical 61]

The obtained compound (m-1) (1 equivalent) and malonaldehyde diamide tibetadine hydrochloride (0.5 equivalent) were charged into an eggplant-shaped flask, acetonitrile and anhydrous acetic acid were added thereto, and stirring was performed. Pyridine (1 equivalent) was then added dropwise and stirred at room temperature for 2 hours. Thereafter, acetonitrile, anhydrous acetic acid and pyridine were removed by an evaporator, and a liquid separation operation was performed by using methyl chloride/water. The organic phase was recovered, to which was added LiFeABA (lithium=tetrakis (pentafluorophenyl) borohydride) 1.5 equivalent and water, stirred vigorously for 3 hours. Thereafter, the organic phase was recovered, and methyl chloride was removed by an evaporator to obtain a compound (z-164).

Compound (z-164): the absorption maximum wavelength in methylene dichloride is 715nm

[ 62]

[ Synthesis example of Compound (z-165) ]

In the synthesis example of the compound (z-164), the compound (z-165) was obtained in the same manner as in the above synthesis example, except that acetyl chloride was changed to 1-methylcyclopropane carboxylic acid chloride.

Compound (z-165): the absorption maximum wavelength in methylene dichloride is 727nm

[ 63]

[ Synthesis example of Compound (z-166) ]

In the synthesis example of the compound (z-164), the compound (z-166) was obtained in the same manner as in the above synthesis example, except that acetyl chloride was changed to 1-methylcyclohexane carboxylic acid chloride.

Compound (z-166): the absorption maximum wavelength in methylene dichloride is 719nm

[ 64]

[ Synthesis example of Compound (z-167) ]

In the synthesis example of the compound (z-164), the compound (z-167) was obtained in the same manner as in the above synthesis example except that acetyl chloride was changed to 1-adamantanecarboxylic acid chloride.

Compound (z-167): the absorption maximum wavelength in methylene dichloride is 721nm

[ 65]

[ Synthesis example of Compound (z-168) ]

In the synthesis example of the compound (z-164), the compound (z-168) was obtained in the same manner as in the synthesis example except that malondialdehyde bisanilide hydrochloride was changed to the following compound (m-2).

Compounds (m-2)

[ chemical 66]

Compound (z-168): the absorption maximum wavelength in methylene dichloride is 720nm

[ 67]

[ Synthesis example of Compound (z-169) ]

In the synthesis example of the compound (z-167), the compound (z-169) was obtained in the same manner as in the synthesis example except that malondialdehyde bisanilide hydrochloride was changed to the compound (m-2).

Compound (z-169): the absorption maximum wavelength in methylene dichloride is 726nm

[ chemical 68]

[ Synthesis example of Compound (z-170) ]

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

Compounds (m-3)

[ 69]

Compound (z-170): the absorption maximum wavelength in methylene dichloride is 739nm

[ 70]

[ Synthesis example of Compound (z-171) ]

In a synthesis example of the compound (z-167), the compound (z-171) was obtained in the same manner as in the synthesis example except that the compound (m-1) was changed to the following compound (m-4).

Compounds (m-4)

[ chemical 71]

Compound (z-171): the absorption maximum wavelength in methylene dichloride is 734nm

[ chemical 72]

[ Synthesis example of Compound (z-172) ]

In a synthesis example of the compound (z-167), the compound (z-172) was obtained in the same manner as in the synthesis example except that the compound (m-1) was changed to the following compound (m-5).

Compounds (m-5)

[ 73]

Compound (z-172): the absorption maximum wavelength in methylene dichloride is 738nm

[ chemical 74]

[ Synthesis example of Compound (z-173) ]

A compound (z-173) was obtained in the same manner as in the above-described synthesis example, except that the compound (m-2) was changed to the following compound (m-6) in the synthesis example of the compound (z-169).

Compounds (m-6)

[ 75]

Compound (z-173): the absorption maximum wavelength in methylene dichloride is 724nm

[ chemical 76]

Examples 20 to 32 and comparative examples 4 to 7

[ preparation of substrate ]

Specifically, a substrate was produced in the same manner as in example 1.

In the proportions shown in Table 12, a solution having a resin concentration of 20% by mass was prepared by adding the resin, the compound (Z), the compound (X), the compound (Y) and methylene chloride. The obtained solution was cast on a smooth glass plate, dried at 20℃for 8 hours, and peeled from the glass plate. The peeled coating film was dried at 100℃under reduced pressure for 8 hours to obtain a resin layer (1) having a thickness of 0.1mm, a longitudinal direction of 210mm and a transverse direction of 210 mm.

The numerical values shown in the columns of compound (Z), compound (X) and compound (Y) in table 12 represent the content (parts by mass) of each compound per 100 parts by mass of the resin.

The compound (x-6) in Table 12 is a compound represented by the following formula (the absorption maximum wavelength in methylene chloride is 717 nm).

[ chemical 77]

The resin composition (1) described below was applied to one side of the obtained resin layer (1) by a bar coater so that the thickness of the obtained resin layer (2) was 3. Mu.m, and the solvent was evaporated and removed by heating at 70℃for 2 minutes in an oven. Next, an exposure (exposure amount 500 mJ/cm) was performed using a UV conveyor type exposure machine (Ai Gufei (Eye graphics) (stock) manufactured, ai Yi (Eye) ultraviolet curing apparatus, model US2-X0405, 60 Hz) ² Illuminance: 200mW/cm ² )，The resin composition (1) is cured, thereby forming a resin layer (2) on the resin layer (1). In the same manner, a resin layer (2) containing the resin composition (1) is also formed on the other surface of the resin layer (1).

< spectral transmittance >

The transmittance in the near infrared region of 650nm to 800nm and the visible light transmittance in 430nm to 580nm of the obtained substrate were measured using a spectrophotometer (V-7200) manufactured by Japan Spectrophotometer (Strand). The transmittance is measured by using the spectrophotometer under the condition that light is perpendicularly incident to the surface of the substrate. The parameters measured by the present apparatus are as follows. The results are shown in table 12.

The spectral transmittance spectra of the substrates obtained in examples 20 and 28 are shown in fig. 1 to 2, respectively.

Further, regarding Tc and Td described below, the obtained substrate was heated in an oven preheated to 155 ℃ for 7 hours, and the transmittance (heat resistance evaluation) of the substrate after the heating test was measured.

In addition, regarding Te and Tf, a UV exposure machine (manufactured by Kikuaki electric (stock)), ai Yi (Eye) ultraviolet curing device US2-KO4501, illuminance: 180mW/cm was used ² Irradiation amount: 560mJ/cm ² ) The obtained substrate was irradiated with UV, and the transmittance of the substrate after the UV irradiation was measured (UV resistance evaluation).

Xa: the wavelength of light having the lowest transmittance measured in the vertical direction of the substrate is 650nm to 800nm

Ta: the lowest transmittance measured in the vertical direction of the substrate at a wavelength of 650nm to 800nm

Tb: average transmittance of light having a wavelength of 430nm to 580nm measured in a direction perpendicular to the substrate

Tc: minimum transmittance of light having a wavelength of 650nm to 800nm after a heat test, measured in a direction perpendicular to the substrate

Td: average transmittance of light having a wavelength of 430nm to 580nm after a heat test, measured in a direction perpendicular to the substrate

Te: the minimum transmittance of light having a wavelength of 650nm to 800nm after UV irradiation, measured from the vertical direction of the substrate

Tf: average transmittance of light having a wavelength of 430nm to 580nm after UV irradiation, measured from the vertical direction of the substrate

[ manufacture of optical Filter ]

A dielectric multilayer film (III) was formed on one surface of the substrate obtained in the production of the substrate, and a dielectric multilayer film (IV) was further formed on the other surface of the substrate, thereby obtaining an optical filter having a thickness of about 0.110 mm.

The dielectric multilayer film (III) is prepared by depositing silicon dioxide (SiO) ₂ ) Layer and titanium dioxide (TiO) ₂ ) A laminate (total of 28 layers) in which the layers were alternately laminated. The dielectric multilayer film (IV) is prepared by depositing silicon dioxide (SiO) at 100 DEG C ₂ ) Layer and titanium dioxide (TiO) ₂ ) A laminate (total 24 layers) in which the layers were alternately laminated.

In both the dielectric multilayer film (III) and the dielectric multilayer film (IV), the titanium oxide layer, the silicon oxide layer, the titanium oxide layer, the … silicon oxide layer, the titanium oxide layer, and the silicon oxide layer are alternately laminated in this order from the substrate side, and the outermost layer of the optical filter is the silicon oxide layer.

The thickness and the number of layers are optimized by using optical Thin Film design software (core maxwell (Essential Macleod), manufactured by Thin Film Center) in accordance with the wavelength dependent characteristic of the refractive index of the substrate, or the absorption characteristics of the compound (Z) and the compound (X) used, so that good transmittance in the visible region and reflection performance in the near infrared region can be achieved. In the present embodiment, the input parameters (target values) for the software are set as shown in table 10 below in the optimization.

TABLE 10

As a result of optimization of the film structure, the dielectric multilayer film (III) was formed as a multilayer vapor-deposited film having 28 layers of a laminate in which a silica layer having a physical film thickness of about 32nm to 159nm and a titania layer having a physical film thickness of about 9nm to 94nm were alternately laminated, and the dielectric multilayer film (IV) was formed as a multilayer vapor-deposited film having 24 layers of a laminate in which a silica layer having a physical film thickness of about 39nm to 193nm and a titania layer having a physical film thickness of about 12nm to 117nm were alternately laminated. An example of the optimized film structure is shown in table 11 below.

TABLE 11

< spectral transmittance >

The transmittance in the near infrared region of the obtained optical filter at a wavelength of 650nm to 800nm and the transmittance in the visible light at a wavelength of 430nm to 580nm were measured using a spectrophotometer (V-7200) manufactured by Japan Spectrophotometer (Strand). The transmittance is a transmittance measured using the spectrophotometer under a condition that light is perpendicularly incident to the optical filter. The parameters measured by the present apparatus are as follows. The results are shown in table 12.

The spectral transmittance spectra of the optical filters obtained in examples 20 and 28 are shown in fig. 3 to 4, respectively.

Tg: average transmittance of light having a wavelength of 650nm to 800nm measured from a vertical direction of the optical filter

Th: average transmittance of light having a wavelength of 430nm to 580nm measured in a direction perpendicular to the optical filter

Examples 33 to 43 and comparative example 8

Specifically, a substrate was produced in the same manner as in example 6.

Resin A, compound (X), compound (Y) and methylene chloride were added in the proportions shown in Table 13 to prepare a solution having a resin concentration of 20% by mass, and the solution was filtered through a microporous filter having a pore size of 5. Mu.m, to obtain a resin solution (E-1).

Resin A, compound (Z) and methylene chloride were added in the proportions shown in Table 13 to prepare a solution having a resin concentration of 20% by mass, and the solution was filtered through a microporous filter having a pore size of 5. Mu.m, to obtain a resin solution (E-2).

Further, only example 39 was used in place of "OA-10G" using a near infrared absorbing glass substrate "BS-11" (thickness 200 μm) manufactured by Songbo Nitro industries (stock) cut into a size of 200mm by 200 mm.

Next, the resin solution (E-1) was applied to one surface of the glass support on which the adhesive layer was formed using a spin coater so that the film thickness after drying was 10 μm, and the solvent was volatilized and removed by heating on a heating plate at 80 ℃ for 5 minutes, thereby forming a coated resin layer (2).

Further, a resin solution (E-2) was applied to the other surface of the glass support on which the adhesive layer was formed using a spin coater so that the film thickness after drying was 10. Mu.m, and the solvent was volatilized and removed by heating on a heating plate at 80℃for 5 minutes, thereby forming a coated resin layer (1).

The values shown in the compounds z-164 to z-173 in Table 13 indicate the content (parts by mass) of each compound with respect to 100 parts by mass of the resin in the resin layer (1), and the values shown in the compounds x-1, x-2 and y-1 in Table 13 indicate the content (parts by mass) of each compound with respect to 100 parts by mass of the resin in the resin layer (2).

The substrates Xa, ta to Tf were measured in the same manner as in example 20. The results are shown in Table 13.

The spectral transmittance spectrum of the substrate obtained in example 36 is shown in fig. 5.

Then, in the same manner as in example 20, on one surface of the obtained substrate, silica (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 28 layers of dielectric multilayer films (III) formed by alternately laminating the layers, and further, silicon dioxide (SiO ₂ ) Layer and titanium dioxide (TiO) ₂ ) A total of 24 layers of dielectric multilayer films (IV) were alternately laminated to obtain an optical filter having a thickness of about 0.226 mm.

The design of the dielectric multilayer film was performed by using the same design parameters as in example 20, taking into consideration the wavelength dependence of the refractive index of the substrate, and the like, as in example 20.

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

The spectral transmittance spectrum of the optical filter obtained in example 36 is shown in fig. 6.

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The optical filters obtained in examples 20 to 43 are useful in recent years because they can reduce the intensity of reflected light in the near-infrared light, particularly in the wavelength region of 700 to 750nm, while maintaining the transmittance of visible light satisfactorily, and therefore can minimize the decrease in sensitivity in the visible light region and eliminate image defects caused by the reflected light in imaging devices such as digital still cameras and the like, which have advanced in terms of higher performance.

Claims

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

Cn ⁺ An ^- (I)

in the formula (I), cn ⁺ An is a monovalent cation represented by the following formula (II) ^- Is a monovalent anion;

in the formula (II) of the present invention,

unit a is of the formula (a-I),

unit B is of the formula (B-I),

Y _A And Y is equal to _C 、Y _B And Y is equal to _D And Y _C And Y is equal to _E An aromatic hydrocarbon group having 6 to 14 carbon atoms, an alicyclic group having 4 to 7 carbon atoms which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms which contains at least one nitrogen atom, oxygen atom or sulfur atom, which may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and further, the alicyclic group may have =o,

R ^g r is R ^h Each independently is a hydrogen atom, -C (O) R ⁱ The radicals or L ^a ～L ^e Any of Q ¹ Is independently the following L ^a ～L ^e Any of Q ² Independently a hydrogen atom or L ^a ～L ^e Any of Q ³ Is hydroxy or L ^a ～L ^e Any of R ⁱ Is the following L ^a ～L ^e Any of (2);

in formula (A-I) — represents Y with formula (II) _A The bonded carbon is subjected to single bonding,

in formula (B-I) = x represents Y with formula (II) _E The bonded carbon is double bonded,

In the formulas (A-I) and (B-I),

R ¹ ～R ⁶ Each independently is a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group, -SR ⁱ Radicals, -SO ₂ R ⁱ Radical, -OSO ₂ R ⁱ Radical, -C (O) R ⁱ The radicals or L ^a ～L ^h Any one of the above-mentioned,

r adjacent to each other ¹ ～R ⁶ An aromatic hydrocarbon group having 6 to 14 carbon atoms which may be bonded to each other and may contain at least one nitrogen atom or oxygenAn alicyclic group having 4 to 7 members of an atom or a sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom, and 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 further, the alicyclic group may have =o,

R ⁸ independently a hydrogen atom, a halogen atom, -C (O) R ⁱ The radicals or L ^a ～L ^h Any one of the above-mentioned,

L ^a : aliphatic hydrocarbon group having 1 to 15 carbon atoms

L ^b : halogen-substituted alkyl of 1 to 15 carbon atoms

L ^c : alicyclic hydrocarbon group having 3 to 14 carbon atoms and optionally having substituent K

L ^d : aromatic hydrocarbon group having 6 to 14 carbon atoms and optionally substituted with K

L ^e : heterocyclic groups having 3 to 14 carbon atoms and optionally having substituent groups K

The substituent K is selected from the group consisting of L ^a ～L ^b At least one of them.

2. The resin composition of claim 1, wherein the R ¹ ～R ⁶ Is represented by the following groups,

R ¹ : hydrogen atom

R ² : the L is ^a 、L ^c Or L ^d Any of (3)

R ³ : a hydrogen atom, the L ^d Any of (3)

R ⁴ : any of hydrogen atoms, halogen atoms

R ⁵ : a hydrogen atom, the L ^a Any of (3)

R ⁶ : hydrogen atom

R ³ 、R ⁴ Can be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms.

3. The resin composition according to claim 2, wherein the compound Z satisfies the following requirement A,

essential condition a: in a transmission spectrum measured using a solution obtained by dissolving the compound Z in methylene chloride, the average value of the transmission at a wavelength of 430nm to 580nm is 93% or more, and the transmission spectrum is a spectrum having a transmission of 10% at the absorption maximum wavelength.

4. A resin composition according to any one of claims 1 to 3, wherein the R ¹ ～R ⁶ At least one of (2) is the L ^a 、L ^c Or L ^d 。

5. A resin composition according to any one of claim 1 to 3, wherein said compound Z satisfies the following requirement B-1,

essential condition B-1: the absorption spectrum measured using a solution obtained by dissolving the compound Z in methylene chloride has a maximum in the wavelength range of 720nm to 900 nm.

6. A resin composition according to any one of claim 1 to 3, wherein said compound Z satisfies the following requirement B-2,

essential condition B-2: the absorption spectrum measured using a solution obtained by dissolving the compound Z in methylene chloride has a maximum in the wavelength range of 700nm to 750 nm.

7. The resin composition according to any one of claims 1 to 3, wherein the resin is at least one resin selected from the group consisting of a cyclic (poly) olefin-based resin, an aromatic polyether-based resin, a polyimide-based resin, a polyester-based resin, a polycarbonate-based resin, a polyamide-based resin, a polyarylate-based resin, a polysulfone-based resin, a polyethersulfone-based resin, a poly-p-phenylene-based resin, a polyamideimide-based resin, a polyethylene naphthalate-based resin, a fluorinated aromatic polymer-based resin, a (modified) acrylic resin, an epoxy-based resin, an allyl ester-based curable resin, a silsesquioxane-based ultraviolet curable resin, an acrylic ultraviolet curable resin, and a vinyl-based ultraviolet curable resin.

8. A substrate i formed from the resin composition according to claim 7 and containing the compound Z.

9. The substrate i according to claim 8, 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, wherein at least one of the two or more resin layers is a resin layer containing the compound Z; or alternatively

A substrate comprising a glass support and a resin layer containing the compound Z.

10. An optical filter having the substrate i as claimed in claim 8 or 9, and a dielectric multilayer film.

11. The optical filter according to claim 10, which is used for a solid-state imaging device.

12. The optical filter of claim 10 for use in an optical sensor device.

13. A solid-state imaging device comprising the optical filter according to claim 10.

14. An optical sensor device comprising the optical filter of claim 10.

15. A compound Z represented by the following formula (III),

Cn ⁺ An ^- (III)

in the formula (III), cn ⁺ An is a monovalent cation represented by the following formula (IV) ^- Is a monovalent anionA seed;

in the formula (IV) of the present invention,

unit a is of the formula (a-I),

unit B is of the formula (B-I),

in the formulas (A-I) and (B-I),

r adjacent to each other ¹ ～R ⁶ An aromatic hydrocarbon group having 6 to 14 carbon atoms, an alicyclic group having 4 to 7 carbon atoms which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group having 3 to 14 carbon atoms which contains at least one nitrogen atom, oxygen atom or sulfur atom, which may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and further, the alicyclic group may have =o,

L ^a : aliphatic hydrocarbon group having 1 to 15 carbon atoms

L ^b : halogen-substituted alkyl of 1 to 15 carbon atoms