WO2021085372A1

WO2021085372A1 - Resin composition, compound (z), optical filter, and use thereof

Info

Publication number: WO2021085372A1
Application number: PCT/JP2020/040085
Authority: WO
Inventors: 洋介内田; 勝也長屋; 仁視大崎; 泰典川部; 広幸下河; 一登中村
Original assignee: Jsr株式会社
Priority date: 2019-11-01
Filing date: 2020-10-26
Publication date: 2021-05-06
Also published as: JPWO2021085372A1; CN114616291A; TWI851844B; KR20220097889A; TW202118835A; CN114616291B

Abstract

An embodiment of the present invention pertains to a resin composition, a compound (Z), an optical filter, or a solid-state imaging device and optical sensor device using the optical filter. The resin composition contains a resin, and a compound (Z) represented by formula (I) and having a maximum absorption wavelength that falls within the wavelength range of 850-1100 nm.　(I): Cn⁺An^- [Cn⁺ represents a monovalent cation represented by formula (II), and An^- represents a monovalent anion.] [Y_A and Y_D each independently represent a hydrogen atom, a halogen atom, or a group having at least one selected from a carbon atom, a sulfur atom, an oxygen atom, a nitrogen atom, and a phosphorus atom, Z_A-Z_C and Y_B-Y_C each independently represent a hydrogen atom, a halogen atom, or a group having at least one selected from a carbon atom, a sulfur atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a silicon atom, or two adjacent ones of Z_A-Z_C may be linked together to form a ring, Y_B and Y_C are optionally linked together to form a ring, units A and B each independently represent a group having a complex aromatic ring, some groups in unit A may be linked to Y_A to form a ring, and some groups in unit B may be linked to Y_D to form a ring.]

Description

Resin composition, compound (Z), optical filter and its applications

One embodiment of the present invention relates to a resin composition, compound (Z), an optical filter, or a solid-state image sensor and an optical sensor device using the optical filter.

A CCD or CMOS image sensor, which is a solid-state image sensor for color images, is used in solid-state image sensors such as video cameras, digital still cameras, and mobile phones with camera functions. In these solid-state image sensors, a silicon photodiode having sensitivity to near infrared rays, which cannot be perceived by the human eye, is used in the light receiving portion. Silicon photodiodes and the like are also used in optical sensor devices. For example, in a solid-state image sensor, it is necessary to perform luminosity factor correction that makes the color tone natural to the human eye, and an optical filter that selectively transmits or cuts light rays in a specific wavelength region (for example, near infrared rays). Cut filter) is often used.

As such a near-infrared cut filter, those manufactured by various methods have been conventionally used. For example, a near-infrared cut filter in which a resin is used as a base material and a near-infrared absorbing dye is contained in the resin is known (see, for example, Patent Document 1). However, the near-infrared cut filter described in Patent Document 1 may not always have sufficient near-infrared absorption characteristics.

In addition, many mobile devices in recent years are equipped with a security authentication function (eg, iris authentication, face authentication) that uses near infrared rays with a wavelength of around 800 to 1000 nm, and the near infrared rays used for this authentication have appeared. In some cases, the camera image may be adversely affected by flare or ghost. For this reason, it is necessary to have a characteristic of cutting light rays in a relatively long wavelength region among near infrared rays.

Furthermore, in distance measurement technology using a laser, it is necessary to cut unnecessary light because it causes noise. However, as the wavelength of the light source of the laser becomes longer, a wide wavelength from the visible to the near infrared region is used. There is an increasing need to cut the area.

Conventionally, as the near-infrared absorbing dye, dyes such as polymethine-based, squarylium-based, porphyrin-based, dithiol metal complex-based, phthalocyanine-based, and diimonium-based dyes have been used. It is often used because of its high absorption capacity and high transparency in the visible light region.

Further, for example, the diimonium-based compound described in Patent Document 2 exhibits a wide and uniform absorption efficiency in the near-infrared region, and exhibits excellent transmission characteristics in the visible light region.

Japanese Unexamined Patent Publication No. 6-200113 Japanese Patent Application Laid-Open No. 2014-506252

However, it has been found that when an attempt is made to sufficiently cut light having a wavelength in the near-infrared region to be cut by using a diimonium-based dye, the visible light transmittance is lowered. Further, since the absorption waveform of the diimonium-based dye is gentle and the absorption band is wide, it is not suitable for selectively cutting light of a specific wavelength in the near infrared region.
On the other hand, as a dye having a steep waveform and selectively cutting light in the near infrared region having a wavelength of 850 nm or more, a polymethine dye such as cyanine or a croconium dye is suitable, but these dyes are heat or It did not have sufficient resistance to ultraviolet rays.

According to the present invention, it is possible to suppress a decrease in visible light transmittance while sufficiently cutting light having a wavelength in the near infrared region to be cut with a wavelength of 850 nm or more with a sharp absorption waveform, and to have sufficient resistance to heat and ultraviolet rays. Provided is a resin composition having.

The present inventors have diligently studied to solve the above-mentioned problems. A configuration example of the present invention is shown below.
In the present invention, the description of "A to B" or the like representing a numerical range is synonymous with "A or more and B or less", and A and B are included in the numerical range. Further, in the present invention, the wavelengths A to Bnm represent the characteristics at a wavelength resolution of 1 nm in a wavelength region having a wavelength of Anm or more and a wavelength of Bnm or less.

[1] Resin and
A resin composition represented by the following formula (I) and containing a compound (Z) having a maximum absorption wavelength in the wavelength range of 850 to 1100 nm.
Cn ⁺ An ^- (I)
[In formula (I), Cn ⁺ is a monovalent cation represented by the following formula (II), and An ^- is a monovalent anion. ]

[In Formula (II), the Y _A and Y _D are each independently, a carbon atom, a sulfur atom, an oxygen atom, a group having at least one selected from a nitrogen atom and a phosphorus atom, a hydrogen atom or a halogen atom,
Z _A to Z _C and Y _B to Y _C are independently groups having at least one selected from a carbon atom, a sulfur atom, an oxygen atom, a nitrogen atom, a phosphorus atom and a silicon atom, a hydrogen atom or a halogen atom, or a halogen atom. , Z _A to Z _C may be joined to each other to form a ring, or Y _B and Y _C may be joined to each other to form a ring.
Unit A and unit B are independent groups having a heteroaromatic ring.
Some groups in unit A may _{be bonded to Y A} to form a cyclic hydrocarbon group having 5 or 6 carbon atoms, and some groups in unit B may be bonded to _{Y D.} It may form a cyclic hydrocarbon group having 5 or 6 carbon atoms.
Z _B is a halogen atom or a group represented by any of the following formulas (A-1) to (A-2), and Y _B and Y _C are formed by being bonded to each other. When the 5-membered alicyclic hydrocarbon group is a 5-membered alicyclic hydrocarbon _{group and all the substituents other than Z B} in the 5-membered alicyclic hydrocarbon group are hydrogen atoms, the unit A is represented by the following formula (A-3). It is not a group represented, and unit B is not a group represented by the following formula (A-4).
Z _B is a chlorine atom and is a 6-membered alicyclic hydrocarbon group formed by mutual bonding of _{Y B} and Y _{C, and the 6-membered alicyclic hydrocarbon group.} When _{all the substituents other than Z B} are hydrogen atoms, the unit A is not a group represented by the following formula (A-5), and the unit B is a group represented by the following formula (A-6). not,
Z _B is a group represented by the following formula (A-7), and is a 5-membered alicyclic hydrocarbon group formed by bonding _{Y B} and Y _{C to each other, and} _{When all the substituents other than Z B} in the 5-membered alicyclic hydrocarbon group are hydrogen atoms, the unit A is not a group represented by the following formula (A-8), and the unit B is represented by the following formula. It is not a group represented by (A-9). ]

[In formulas (A-3) to (A-4), Y _a1 is an independently substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, and − * in the formula (A-3) is the above. It indicates that a single bond and carbon Y _a binds the formula (II), wherein = ** is the (a-4) in the carbon and to the double bond Y _D of the formula (II) are bound Is shown. ]

Wherein (A-5) ~ (A -6), Y a2 is a n- butyl group, the formula (A-5) in the - * is a carbon Y _A of the formula (II) are bound It indicates that a single bond is formed, and = ** in the formula (A-6) indicates that the Y _{D of the} formula (II) is double bonded to the carbon to which it is bonded. ]

[In formula (A-7), Rx and Ry are independently hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group. , Butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, cyclooctyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group, methoxy group, ethoxy group, propoxy group, fluoro group, chloro group, bromo Group, iodo group, cyano group or nitro group. ]

[In formulas (A-8) to (A-9), Y _a3 is an alkyl group having a linear or branched carbon number of 1 to 5 independently, and-* in the formula (A-8) is _{, Indicates that Y A of the} formula (II) is single-bonded to the carbon to which it is bonded, and = ** in the formula (A-9) is a double bond to the carbon to which _{Y D of the formula (II) is bonded.} Indicates to do. ]

[2] The unit A is a group represented by any of the following formulas (AI) to (A-III).
The unit B is a group represented by any of the following formulas (BI) to (B-III).
Y _A and Y _D are independently hydrogen atoms, halogen atoms, or hydrocarbon groups having 1 to 8 carbon atoms.
Z _A to Z _C and Y _B to Y _C are independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, -NR ^g R ^h group, amide group, imide group, cyano group, silyl group, -Q ¹ , -N = N-Q ¹ , -S-Q ² , -SSQ ² , or -SO ₂ Q ³ ,
_A 5- to 6-membered fat that may contain at least one aromatic hydrocarbon group, nitrogen atom, oxygen atom or sulfur atom having 6 to 14 carbon atoms, in which two adjacent two of Z A to Z _{C are bonded to each other.} It may form a ring group or a complex aromatic group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, and these alicyclic groups, aromatic hydrocarbon groups and complex. The aromatic group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.
A _{5- to 6-membered alicyclic group in which Y B} and Y _C are bonded to each other and may contain at least one aromatic hydrocarbon group having 6 to 14 carbon atoms, a nitrogen atom, an oxygen atom or a sulfur atom, or It may form a heteroaromatic group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, and these alicyclic groups, aromatic hydrocarbon groups and heteroaromatic groups may form. It may have an aliphatic hydrocarbon group or a halogen atom having 1 to 9 carbon atoms.
R ^g and R ^h are each independently a hydrogen atom, an −C (O) R ⁱ group or any of the following ^{L b} to L ^f ^{, and Q 1} is any of the following ^{L b} to L ^g. Q ² is a hydrogen atom or any of the following ^{L b} to L ^f ^{, Q 3} is either a hydroxyl group or the following L ^b to L ^f , and R ⁱ is any of the following ^{L b} to L ^f. is there,
The resin composition according to [1].

[Formula (A-I) ~ (A -III) in the - * indicates that the single bonds and carbon to which Y _A is attached of the formula (II),
= ** in formulas (BI) to (B-III) _{indicate that Y D of the} formula (II) is double bonded to the carbon to which it is bonded.
In formulas (AI)-(B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -N (R ⁸ )-.
R ¹ to R ⁶ are independently hydrogen atom, halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR ^g R ^h group, -SR ⁱ group, -SO ₂ R. It is either an ⁱ group, an -OSO ₂ R ⁱ group, an -C (O) R ⁱ group, or the following L ^b to L ^i.
Adjacent two of R ¹ to R ⁶ may be bonded to each other to form a cyclic hydrocarbon group having 5 or 6 carbon atoms.
R ¹ or R ⁴ in the formula (A-III), the formula in combination with Y _A in (II) may form a cyclic hydrocarbon group having 5 or 6 carbon atoms,
^{R 1} or R ⁴ in the formula (B-III) _{may be bonded to Y D} in the formula (II) to form a cyclic hydrocarbon group having 5 or 6 carbon atoms.
R ⁸ is a hydrogen atom, a halogen atom, an −C (O) R ⁱ group, or any of the following ^{L b} to Li ^i.
R ^g and R ^h are independently either a hydrogen atom, an −C (O) R ⁱ group, or L ^b to L ^f below.
R ⁱ is one of the following L ^b to L ^f ,
(L ^b ): aliphatic hydrocarbon group having 1 to 15 carbon atoms (L ^c ): halogen-substituted alkyl group (L ^d ): alicyclic hydrocarbon group (L ^e ): aromatic hydrocarbon group (L ^f ) : Heterocyclic group (L ^g ): -OR (R is a hydrocarbon group)
(L ^h ): Acyl group which may have a substituent L ( ^Li ): An alkoxycarbonyl group which may have a substituent L The substituent L is at least one selected from the ^{above L b} to L ^f. Is. ]

[3] The resin composition according to [1] or [2], wherein the compound (Z) satisfies the following requirement (A).
Requirement (A): In a transmission spectrum measured using a solution of the compound (Z) in dichloromethane (however, the transmission spectrum is a spectrum in which the transmittance at the absorption maximum wavelength is 10%). The average value of the light transmittance at a wavelength of 430 to 580 nm is 70% or more.

[4] The resin composition according to any one of [1] to [3], wherein the compound (Z) satisfies the following requirements (C) and (D).
Requirement (C): In a transmission spectrum measured using a solution of the compound (Z) in dichloromethane (however, the transmission spectrum is a spectrum in which the transmittance at the absorption maximum wavelength is 10%). Having a wavelength in the wavelength range of 950 to 1150 nm and having a transmittance of 85% Requirement (D): A transmission spectrum measured using a solution of the compound (Z) in dichloromethane (however, the transmission spectrum is It is a spectrum in which the transmittance at the absorption maximum wavelength is 10%.) At a wavelength longer than the absorption maximum wavelength, the wavelength on the shortest wavelength side (Wa) at which the transmittance is 20% and the transmittance are 70%. The absolute value of the difference from the wavelength (Wb) on the shortest wavelength side is 10 to 60 nm.

[5] The resin is a cyclic (poly) olefin resin, an aromatic polyether resin, a polyimide resin, a polyester resin, a polycarbonate resin, a polyamide resin, a polyarylate resin, a polysulfone resin, or a polyether monkey. Hong resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester curable resin, silsesquioki The resin composition according to any one of [1] to [4], which is at least one resin selected from the group consisting of a sun-based ultraviolet curable resin, an acrylic-based ultraviolet curable resin, and a vinyl-based ultraviolet curable resin. ..

[6] Optical having a base material (i) containing a resin layer containing the compound (Z) formed from the resin composition according to any one of [1] to [5], and a dielectric multilayer film. filter.
[7] The base material (i) is
A substrate composed of a resin layer containing the compound (Z),
A base material containing two or more resin layers, wherein at least one of the two or more resin layers is a resin layer containing the compound (Z), or a base material.
The optical filter according to [6], which is a base material containing a glass support and a resin layer containing the compound (Z).

[8] The optical filter according to [6] or [7], wherein the optical filter is a near-infrared ray cut filter satisfying the following characteristics (a) and (b).
Characteristic (a): The average value of the transmittance measured from the vertical direction of the optical filter is 75% or more in the wavelength region of 430 to 580 nm. Characteristic (b): The vertical direction of the optical filter in the wavelength region of 850 to 1200 nm. The average value of transmittance measured from 5% or less

[9] The optical filter according to [6] or [7], wherein the optical filter is a visible light-near infrared selective transmission filter satisfying the following characteristics (c) and (d).
Characteristic (c): The average value of the transmittance measured from the vertical direction of the optical filter is 75% or more in the region of wavelength 430 to 580 nm. Characteristic (d): Light ray blocking band Za and light rays in the region of wavelength 650 nm or more. It has a transmission band Zb and a light blocking band Zc, and the center wavelength of each band is Za <Zb <Zc.
The minimum transmittances of Za and Zc measured from the vertical direction of the optical filter are 15% or less, respectively.
The maximum transmittance measured from the vertical direction of the optical filter in Zb is 55% or more.

[10] The optical filter according to [6] or [7], wherein the optical filter is a near-infrared ray transmitting filter satisfying the following characteristics (e) and (f).
Characteristic (e): The average value of the transmittance measured from the vertical direction of the optical filter is 10% or less in the region of wavelength 380 to 700 nm. Characteristic (f): The light transmission band Ya is provided in the region of wavelength 750 nm or more. However, in the light transmittance band Ya, the maximum transmittance ( _TIR ) measured from the vertical direction of the optical filter is 45% or more.

[11] The optical filter according to any one of [6] to [10], which is used for a solid-state image sensor.
[12] The optical filter according to any one of [6] to [10], which is used for an optical sensor device.

[13] A solid-state image sensor provided with the optical filter according to any one of [6] to [10].
[14] An optical sensor device including the optical filter according to any one of [6] to [10].

[15] A compound (Z) represented by the following formula (I) and having an absorption maximum wavelength in the wavelength range of 850 to 1100 nm.
Cn ⁺ An ^- (I)
[In formula (I), Cn ⁺ is a monovalent cation represented by the following formula (II), and An ^- is a monovalent anion. ]

[In formula (II), unit A is a group represented by any of the following formulas (AI) to (A-III).
Unit B is a group represented by any of the following formulas (BI) to (B-III).
Y _A and Y _D are independently hydrogen atoms, halogen atoms or hydrocarbon groups having 1 to 8 carbon atoms.
Z _A to Z _C and Y _B to Y _C are independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, -NR ^g R ^h group, amide group, imide group, cyano group, silyl group,- Q ¹ , -N = N-Q ¹ , -S-Q ² , -SSQ ² , or -SO ₂ Q ³ ,
_A 5- to 6-membered fat that may contain at least one aromatic hydrocarbon group, nitrogen atom, oxygen atom or sulfur atom having 6 to 14 carbon atoms, in which two adjacent two of Z A to Z _{C are bonded to each other.} It may form a ring group or a complex aromatic group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, and these alicyclic groups, aromatic hydrocarbon groups and complex. The aromatic group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.
A _{5- to 6-membered alicyclic group in which Y B} and Y _C are bonded to each other and may contain at least one aromatic hydrocarbon group having 6 to 14 carbon atoms, a nitrogen atom, an oxygen atom or a sulfur atom, or It may form a heteroaromatic group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, and these alicyclic groups, aromatic hydrocarbon groups and heteroaromatic groups may form. It may have an aliphatic hydrocarbon group or a halogen atom having 1 to 9 carbon atoms.
R ^g and R ^h are each independently a hydrogen atom, an −C (O) R ⁱ group or any of the following ^{L b} to L ^f ^{, and Q 1} is any of the following ^{L b} to L ^g. Q ² is a hydrogen atom or any of the following ^{L b} to L ^f ^{, Q 3} is either a hydroxyl group or the following L ^b to L ^f , and R ⁱ is any of the following ^{L b} to L ^f. Yes,
Z _B is a halogen atom or a group represented by any of the following formulas (A-1) to (A-2), and Y _B and Y _C are formed by being bonded to each other. When the 5-membered alicyclic hydrocarbon group is a 5-membered alicyclic hydrocarbon _{group and all the substituents other than Z B} in the 5-membered alicyclic hydrocarbon group are hydrogen atoms, the unit A is represented by the following formula (A-3). It is not a group represented, and unit B is not a group represented by the following formula (A-4).
Z _B is a chlorine atom and is a 6-membered alicyclic hydrocarbon group formed by mutual bonding of _{Y B} and Y _{C, and the 6-membered alicyclic hydrocarbon group.} When _{all the substituents other than Z B} are hydrogen atoms, the unit A is not a group represented by the following formula (A-5), and the unit B is a group represented by the following formula (A-6). not,
Z _B is a group represented by the following formula (A-7), and is a 5-membered alicyclic hydrocarbon group formed by bonding _{Y B} and Y _{C to each other, and} _{When all the substituents other than Z B} in the 5-membered alicyclic hydrocarbon group are hydrogen atoms, the unit A is not a group represented by the following formula (A-8), and the unit B is represented by the following formula. It is not a group represented by (A-9). ]

According to one embodiment of the present invention, it is possible to suppress a decrease in visible light transmittance while sufficiently cutting light having a wavelength in the near infrared region to be cut with a wavelength of 850 nm or more with a sharp absorption waveform, and with respect to heat and ultraviolet rays. It is possible to provide a resin composition having sufficient resistance (durability). Further, according to one embodiment of the present invention, it is possible to provide an optical filter having these characteristics.
In the present invention, having sufficient resistance to heat and ultraviolet rays means that the optical characteristics do not change significantly before and after applying heat or irradiating with ultraviolet rays.

Further, as described in Patent Document 2, since the diimonium dye exhibits a wide range of absorption characteristics in the near infrared region, the diimonium dye is used, for example, a visible light-near infrared selective transmission filter (DBPF) or near infrared. When trying to form a transmission filter (IRPF), it has not been easy to transmit only near infrared rays having a desired wavelength to be transmitted.
Further, for example, polymethine-based dyes have a sharp absorption peak in the near-infrared region (sharp), but the use of these conventional dyes has been restricted due to their poor durability.

On the other hand, the compound (Z) used in one embodiment of the present invention not only has sharp absorption in a wavelength region of 850 nm or more, but also has excellent durability. Therefore, according to one embodiment of the present invention. , Not only a near-infrared cut filter (NIR-CF) but also an optical filter such as DBPF or IRPF can be easily manufactured.

FIG. 1 is a diagram showing the spectral characteristics of the base material obtained in Example 1. FIG. 2 is a diagram showing the spectral characteristics of the optical filter obtained in Example 1. FIG. 3 is a diagram showing the spectral characteristics of the base material obtained in Comparative Example 2. FIG. 4 is a diagram showing the spectral characteristics of the optical filter obtained in Comparative Example 2.

≪Resin composition≫
The resin composition according to one embodiment of the present invention (hereinafter, also referred to as “the present composition”) is not particularly limited as long as it contains the resin and the compound (Z).
As a form of such a resin composition, for example, it is formed on a resin film (resin layer, resin substrate) containing the compound (Z); a support (eg, a resin support, a glass support). A resin film (resin layer) containing the compound (Z); a liquid composition containing a resin, the compound (Z) and a solvent can be mentioned.
The present composition may contain two or more kinds of resins, and may contain two or more kinds of compounds (Z).

<Compound (Z)>
The compound (Z) contained in the present composition and the compound (Z) according to one aspect of the present invention are represented by the following formula (I) and have a maximum absorption wavelength in the wavelength range of 850 to 1100 nm.
Such a compound (Z) has high near-infrared ray cutting performance and high visible light transmission performance in the vicinity of the absorption maximum at a wavelength of 850 nm or more, and has sufficient resistance to heat and ultraviolet rays. In addition, the compound (Z) has a sharp absorption peak (sharp absorption waveform).
Cn ⁺ An ^- (I)
[In formula (I), Cn ⁺ is a monovalent cation represented by the following formula (II), and An ^- is a monovalent anion. ]

The unit A is preferably a group represented by any of the following formulas (AI) to (A-III), and the unit B is preferably a group represented by the following formulas (BI) to (B-III). It is preferable that the group is represented by any of.

The -N (R ⁸ )-is a group represented by the following formula (a), the -NR ^g R ^h group is a group represented by the following formula (b), and the -SR ⁱ group is described. Table is a group represented by the following formula (c), the -SO ₂ R ⁱ groups are groups represented by the following formula (d), the -OSO ₂ R ⁱ groups by the following formula (e) The —C (O) R ⁱ group is a group represented by the following formula (f).

When the unit A has the formula (AI) and the unit B has the formula (BI), Cn ⁺ is represented by the following formula (II-1). That is, in Formula (A-I) ~ (A-III) - single bond "*" (-) is between the carbon atoms and the unit A Y _A in the formula (II) are attached the equivalent to a single bond, a double bond of the "** =" in the formula (B-I) ~ (B -III) (=) , the carbon to Y _D in the formula (II) are attached It corresponds to a double bond between an atom and unit B.

The "part of the groups in the unit A is combined with Y _A may form a cyclic hydrocarbon group having 5 or 6 carbon atoms" and, preferably, Formula (A-III) in the R ¹ or R ^4, combine with Y _a in the formula (II) indicates that may form a cyclic hydrocarbon group having 5 or 6 carbon atoms,
The above-mentioned "some groups in the unit B may _{be bonded to Y D} to form a cyclic hydrocarbon group having 5 or 6 carbon atoms" is preferably expressed in the formula (B-III). It is shown that R ¹ or R ⁴ _{may be bonded to Y D} in the above formula (II) to form a cyclic hydrocarbon group having 5 or 6 carbon atoms.

Y _A and Y _D are independent of each other, preferably a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom and a methyl group. (Me), ethyl group (Et), n-propyl group (n-Pr), isopropyl group (i-Pr), n-butyl group (n-Bu), sec-butyl group, tert-butyl group (t-) Bu), cyclohexyl group, phenyl group (Ph), more preferably hydrogen atom, chlorine atom, fluorine atom, bromine atom, methyl group, ethyl group, n-propyl group, isopropyl group, and particularly preferably hydrogen. It is an atom, a chlorine atom, a fluorine atom, a bromine atom, a methyl group, and an ethyl group.

Y _B and Y _C are independent of each other, preferably hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, -NR ^g R ^h group, amide group, imide group, cyano group, silyl group, -Q ¹ , -N = N-Q ¹ , -S-Q ² , -SSQ ² , -SO ₂ Q ³ , or Y _B and Y _C are bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms. A 5- to 6-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom; or a heteroaromatic group having 3 to 14 carbon atoms which contains at least one nitrogen atom, oxygen atom or sulfur atom. Groups; may be formed, and these alicyclic groups, aromatic hydrocarbon groups and heteroaromatic groups may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.
R ^g and R ^h are each independently a hydrogen atom, an −C (O) R ⁱ group, or any of the above L ^b to L ^f , and Q ¹ is any of the above L ^b to L ^g . Q ² is a hydrogen atom or any of the ^{L b} to L ^f ^{, Q 3} is either a hydroxyl group or the L ^b to L ^f , and R ⁱ is any of the ^{L b} to L ^f. is there.

The -SSQ ² is a group represented by -S-S-Q ^2, wherein -SO ₂ Q ³ in the group represented by the formula (d), is a group obtained by replacing the R ⁱ to Q ³ ..

The Y _B and Y _C are independently, more preferably, hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-. A 5- or 6-membered alicyclic hydrocarbon group formed by mutual bonding of butyl groups, Y _B and Y _C (the alicyclic hydrocarbon group is an aliphatic group having a hydrogen atom and 1 to 9 carbon atoms. ^{It may have a substituent R 9} selected from a hydrocarbon group and a halogen atom), and particularly preferably, a hydrogen atom, a methyl group, a tert-butyl group, Y _B and Y _C are bonded to each other. It is a 5-membered alicyclic hydrocarbon group formed in the above manner, and a 6-membered alicyclic hydrocarbon group having ^{a substituent R 9} _{formed by bonding Y B} and Y _{C to each other.}
In the case of _{a 5- or 6-membered alicyclic hydrocarbon group formed by bonding Y B} and Y _{C to} each other, the formula (II) is preferably the following formulas (CI), ( It can be represented by C-II). When Y _B and Y _C are connected to each other and have a structure represented by the following formula (CI), in Tables 1 to 7 below, CI is described in the column of _{Y B.} The _{same applies to the case where Y B} and Y _C are bonded to each other and have a structure represented by the following formula (C-II).
_{The above-mentioned "case where all the substituents other than Z B} in the 5-membered alicyclic hydrocarbon group are hydrogen atoms" means the case represented by the following formula (C-II), and the above-mentioned "case". _{The case where all the substituents other than Z B} in the 6-membered alicyclic hydrocarbon group are hydrogen atoms ”means the case where R ⁹ is represented by a hydrogen atom in the following formula (CI). ..

In the formula (CI), R ⁹ is preferably a hydrogen 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, or a cyclohexyl group, preferably hydrogen. Atomic, methyl, ethyl, and tert-butyl groups are more preferred.

Z _A to Z _C are independent of each other, preferably hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, -NR ^g R ^h group, amide group, imide group, cyano group, silyl group, -Q ¹ ^{, -N = N-Q 1,} -S-Q 2, -SSQ 2, -SO 2 Q 3, or bonded to two mutual adjacent of Z _a ~ Z _C, 6 to 14 carbon atoms Aromatic hydrocarbon group; 5- to 6-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom; or 3 to 3 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom. 14 heteroaromatic groups; may be formed, and these alicyclic groups, aromatic hydrocarbon groups and heteroaromatic groups have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom. May
R ^g and R ^h are each independently a hydrogen atom, an −C (O) R ⁱ group, or any of the above L ^b to L ^f , and Q ¹ is any of the above L ^b to L ^g . Q ² is a hydrogen atom or any of the ^{L b} to L ^f ^{, Q 3} is either a hydroxyl group or the L ^b to L ^f , and R ⁱ is any of the ^{L b} to L ^f. is there.

The Z _A and Z _C are independent, more preferably hydrogen atoms.
The Z _B is more preferably a hydrogen atom, a chlorine atom, a dimethylamino group, a diethylamino group, a dibutylamino group, a diphenylamino group (NPh2), a methylphenylamino group, a methyl group, a phenyl group, a 4-methylphenoxy group ( O- (4-tolyl)), -S- (4-tolyl) group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3 -It is a thienyl group.

The L ^b is preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group (Pent), hexyl group (Hex), 1 , 1-Dimethylbutyl group, Octyl group (Oct), Nonyl group, Decyl group, Dodecyl group, more preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl Group, tert-butyl group, pentyl group, hexyl group, 1,1-dimethylbutyl group, octyl group.

The L ^b is an alkenyl group such as a vinyl group, a 1-propenyl group, a 2-propenyl group, a butenyl group, a 1,3-butadienyl group, a 2-methyl-1-propenyl group, a 2-pentenyl group, a hexenyl group; ethynyl. It may be an alkynyl group such as a group, a propynyl group, a butynyl group, a 2-methyl-1-propynyl group, or a hexynyl group.

Examples of the halogen-substituted alkyl group in L ^c, for example, include groups in which at least one hydrogen atom is substituted with a halogen atom an alkyl group having 1 to 15 carbon atoms, preferably, trichloromethyl group, trifluoromethyl group , 1,1-dichloroethyl group, pentachloroethyl group, pentafluoroethyl group, heptachloropropyl group, heptafluoropropyl group.

Examples of the alicyclic hydrocarbon group in L ^d include an alicyclic hydrocarbon group having 3 to 14 carbon atoms, preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a 4-pentylcyclohexyl group. , Cycloalkyl groups such as cycloheptyl group and cyclooctyl group; polycyclic alicyclic groups such as norbornan group, adamantyl group, 1-adamantylmethyl group and the like.

Examples of the aromatic hydrocarbon group for L ^e, for example, include an aromatic hydrocarbon group having 6 to 14 carbon atoms, preferably a phenyl group, a tolyl group, a xylyl group, mesityl group, cumenyl group, 1-naphthyl Group, 2-naphthyl group, anthracenyl group, phenanthryl group, benzyl group (CH ₂ Ph).

Examples of the heterocyclic group in L ^f include a heterocyclic group having 3 to 14 carbon atoms, preferably furan, thiophene, pyrrole, indole, indoline, indoline, benzofuran, benzothiophene, morpholine, and pyridine. is there.

Examples of the hydrocarbon group (R) in L ^g include a hydrocarbon group having 1 to 12 carbon atoms, and —OR is preferably a methoxy group (OMe), an ethoxy group, a propoxy group and an isopropoxy. Group, butoxy group (OBu), methoxymethyl group, methoxyethyl group, pentyloxy group, hexyloxy group, octyloxy group, phenoxy group, 4-methylphenoxy group, cyclohexyloxy group.

Examples of the acyl group that may have the substituent L at L ^h include an acyl group having 1 to 9 carbon atoms, preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, and the like. It is a 4-propylbenzoyl group and a trifluoromethylcarbonyl group.

As the alkoxycarbonyl group which may have a substituent L in L ^i, for example, include alkoxycarbonyl groups having 1-9 carbon atoms, preferably a methoxycarbonyl group, an ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl It is a propoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, and a 2-phenylethoxycarbonyl group.

The X is preferably an oxygen atom, a sulfur atom, —N (R ⁸ ) −, and the units A and B are of the formulas (AI), (A-III), (BI), (B). In the case of −III), it is particularly preferably an oxygen atom or a sulfur atom, and when the units A and B are of the formulas (A-II) and (B-II), it is particularly preferably −N (R ^8). )-.

In the formula (II), the left and right units A and B may be the same or different, but it is preferable that they are the same because it is easy to synthesize.
Here, the combinations in which the units A and B are the same are the formula (AI) and the formula (BI), the formula (A-II) and the formula (B-II), and the formula (A-III). And equation (B-III).

R ¹ to R ⁶ are independent of each other, preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl. Group, cyclohexyl group, 1,1-dimethylbutyl group, 1-adamantyl group, 1-adamantylmethyl group, 4-pentylcyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, diethylamino group (NET ₂ ), dibutyl Amino group (NBu ₂ ), cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, tert-butanoylamino group, cyclohexyl Sinoylamino group, n-butylsulfonyl group, benzyl group, diphenylmethyl group, trifluoromethyl group, difluoromethyl group, methoxy group, methoxy group, ethoxy group, propoxy group, butoxy group, more preferably hydrogen atom. , Chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, 1,1-dimethylbutyl group, 1-adamantyl Group, 1-adamantylmethyl group, 4-pentylcyclohexyl group, phenyl group, amino group, dimethylamino group, diethylamino group, dibutylamino group, benzyl group, diphenylmethyl group, trifluoromethyl group, difluoromethyl group, methoxy group, It is a butyl group.
Further, ^{two adjacent R 1} to R ⁶ may be bonded to each other to form a cyclic hydrocarbon group having 5 or 6 carbon atoms.

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

Wherein An ^- as it is not particularly limited as long as it is a monovalent anion, preferably chlorine ion, bromine ion, iodine ion, PF ₄ ^-, perchlorate anion, tris trifluoromethanesulfonyl methide anion, tetrafluoroborate Anions, hexafluorophosphate anions, bis (trifluoromethanesulfonyl) imide anions, trifluoromethanesulfonic acid anions, tetrakis (pentafluorophenyl) borate anions, tetrakis (3,5-bis (trifluoromethyl) phenyl) borate anions, etc. More preferably, bis (trifluoromethanesulfonyl) imide anion, trifluoromethanesulfonic acid anion, tristrifluoromethanesulfonylmethide anion, tetrakis (pentafluorophenyl) borate anion, tetrakis (3,5-bis (trifluoromethyl)). ) Phenyl) Borate anion, more preferably bis (trifluoromethanesulfonyl) imide anion, tristrifluoromethanesulfonylmethide anion, tetrakis, from the viewpoint that compound (Z), which is superior in heat resistance, can be easily obtained. It is a (pentafluorophenyl) borate anion, a tetrakis (3,5-bis (trifluoromethyl) phenyl) borate anion, and particularly preferably a tetrakis (pentafluorophenyl) borate anion.

Specific examples of the compound represented by the formula (I) include compounds (z-1) to (z-368) shown in Tables 1 to 7 below.
Specifically, these compounds (Z) can be synthesized, for example, by the method described in the following Examples.

The compound (Z) is preferably a compound soluble in an organic solvent, and particularly preferably a compound soluble in dichloromethane.
Here, the term "soluble in an organic solvent" means a case where 0.1 g or more of the compound (Z) is dissolved in 100 g of an organic solvent at 25 ° C.

The compound (Z) is preferably a compound that satisfies the following requirement (A).
Requirement (A): Transmission spectrum measured using a solution of compound (Z) in dichloromethane (however, the transmission spectrum is a spectrum in which the transmittance at the absorption maximum wavelength is 10%. Hereinafter, this transmission spectrum. Is also referred to as “transmission spectrum of compound (Z)”), the average value of the transmittance of light at a wavelength of 430 to 580 nm is preferably 70% or more, more preferably 85% or more, still more preferably 90% or more. Especially preferably, it is 93.0% or more. Since it is preferable that the average value of the transmittance is high, the upper limit thereof is not particularly limited and may be 100%.
When the compound (Z) satisfies this requirement (A), it is possible to further suppress a decrease in the visible light transmittance while sufficiently cutting the light having a wavelength in the near infrared region to be cut.

In the present invention, the average transmittance of wavelengths A to Bnm is obtained by measuring the transmittance at each wavelength of Annm or more and Bnm or less in 1 nm increments, and the total transmittance is the number of measured transmittances (wavelength range). , BA + 1), which is the value calculated by dividing by.

Compound (Z) is characterized by satisfying the following requirement (B).
Requirement (B): Absorption maximum wavelength is in the wavelength range of 850 to 1100 nm The absorption maximum wavelength of compound (Z) is preferably 855 to 1095 nm, more preferably 860 to 1090 nm.
The absorption maximum wavelength refers to the wavelength at which the value of the transmittance is the smallest in the transmission spectrum measured by using a solution of compound (Z) in dichloromethane.
When the absorption maximum wavelength of the compound (Z) is in the above range, it is possible to easily obtain an optical filter having a high light ray-cutting ability even in a relatively long wavelength region (a region having a wavelength of 850 nm or more) in the near infrared rays. .. In particular, an optical filter having an optical density (OD value) of about 4 or more can be easily obtained in a wavelength region of 900 nm or more, specifically, a wavelength of 940 nm.

The compound (Z) is preferably a compound that satisfies the following requirement (C).
Requirement (C): In the transmission spectrum of compound (Z), it is preferable to have a wavelength having a transmittance of 85%, and more preferably to have a wavelength having a transmittance of 90% in the wavelength range of 950 to 1150 nm. ..
A compound (Z) having an absorption maximum wavelength in the above range and satisfying this requirement (C) has a sharp absorption peak. Therefore, by using such a compound (Z), a near-infrared region to be cut is desired. It is possible to easily manufacture not only NIR-CF that can sufficiently cut light of the wavelength of the above, but also an optical filter such as DBPF or IRPF that transmits near infrared rays of a desired wavelength to be transmitted.

The compound (Z) is preferably a compound that satisfies the following requirement (D).
Requirement (D): At a wavelength longer than the absorption maximum wavelength of the transmission spectrum of the compound (Z), the shortest wavelength side wavelength (Wa) having a transmittance of 20% and the shortest wavelength side having a transmittance of 70%. The absolute value of the difference from the wavelength (Wb) of is preferably 10 to 60 nm, more preferably 15 to 58 nm, and particularly preferably 20 to 56 nm.
The fact that compound (Z) satisfies this requirement (D) indicates that the absorption peak of compound (Z) is sharp. By using the compound (Z) that satisfies this requirement (D), not only NIR-CF that can sufficiently cut light having a wavelength in the near-infrared region to be cut, but also DBPF that transmits near-infrared rays having a desired wavelength to be transmitted can be used. An optical filter such as IRPF can also be easily manufactured.

The content of the compound (Z) in the present composition is preferably 0.02 to 1.0 parts by mass, more preferably 0.02 to 0.80 parts by mass, and particularly preferably 0.02 to 0.80 parts by mass with respect to 100 parts by mass of the resin. It is 0.03 to 0.60 parts by mass.
When the content of the compound (Z) is in the above range, near infrared rays in the wavelength range of 850 to 1100 nm can be efficiently cut, and a composition having more excellent visible light transmittance can be easily obtained.

<Resin>
The resin used in this composition is not particularly limited, and conventionally known resins can be used.
The resin used in this composition may be one kind alone or two or more kinds.

The resin is not particularly limited as long as the effects of the present invention are not impaired, but for example, it is excellent in thermal stability and formability into a film (plate) shape, and is subjected to high-temperature vapor deposition at a vapor deposition temperature of about 100 ° C. or higher. The glass transition temperature (Tg) is preferably 110 to 380 ° C., more preferably 110 to 370 ° C., and particularly preferably 120 to 120 ° C. from the viewpoint that a film capable of forming a dielectric multilayer film can be easily obtained. Examples thereof include a resin having a temperature of 360 ° C. Further, when the Tg of the resin is 140 ° C. or higher, a film capable of forming a dielectric multilayer film by vapor deposition at a higher temperature can be obtained, which is particularly preferable.

As the resin, the total light transmittance (JIS K 7375: 2008) of a resin plate having a thickness of 0.1 mm made of the resin is preferably 75 to 95%, more preferably 78 to 95%, and particularly preferably 80. A resin having a value of up to 95% can be used.
When a resin having a total light transmittance in the above range is used, a resin composition or an optical filter having excellent transparency can be easily obtained.

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

Examples of the resin include cyclic (poly) olefin-based resin, aromatic polyether-based resin, polyimide-based resin, polyester-based resin, polycarbonate-based resin, polyamide (aramid) -based resin, polyarylate-based resin, and polysulfone-based resin. Polyether sulfone-based resin, polyparaphenylene-based resin, polyamideimide-based resin, polyethylene naphthalate (PEN) -based resin, fluorinated aromatic polymer-based resin, (modified) acrylic-based resin, epoxy-based resin, allyl ester-based curing Examples thereof include mold resins, silsesquioxane-based UV curable resins, acrylic UV curable resins, and vinyl UV curable resins.

[Cyclic (poly) olefin resin]
As the cyclic (poly) olefin resin, at least one monomer selected from the group consisting of a monomer represented by the following _{formula (X 0} ) and a monomer represented by the following formula (Y _0). The resin obtained by using the above and the resin obtained by hydrogenating the resin are preferable.

Wherein (X _0), in each of R ^x1 ~ R ^x4 independently represents an atom or a group selected from the following (i ') ~ (ix' ), k x, m x and p ^x are each independently 0 Represents an integer of ~ 4.
(I') Hydrogen atom (ii') Halogen atom (iii') Trialkylsilyl group (iv') Substituent or unsubstituted carbon number 1 having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. Hydrocarbon group (v') substituted or unsubstituted hydrocarbon group (vi') polar group having 1 to 30 carbon atoms (excluding (ii') and (iv')).
(Vii') Alkylidene groups formed by mutual bonding of ^{R x1} and R ^x2 or R ^x3 and R ^x4 ^{(however, R x1} to R ^x4 not involved in the bond are independently described in (i'). )-(Vi') represents an atom or group selected.)
(Viii') R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or heterocycle (however, R ^x1 to R not involved in the bond). ^x4 represents an atom or group independently selected from the above (i') to (vi').)
(Ix') A monocyclic hydrocarbon ring or heterocycle formed by bonding ^{R x2} and R ^x3 ^{to each other (however, R x1} and R ^x4 not involved in the bond are independently described in (i). Represents an atom or group selected from') to (vi').)

In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i') to (vi'), or R ^y1 and R ^y2 are bonded to each other. It represents a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocycle formed, and ^ky ^{and py} each independently represent an integer of 0 to 4.

[Aromatic polyether resin]
The aromatic polyether resin preferably has at least one structural unit selected from the group consisting of the structural unit represented by the following formula (1) and the structural unit represented by the following formula (2).

In the formula (1), R ¹ to R ⁴ independently represent monovalent organic groups having 1 to 12 carbon atoms, and a to d independently represent integers of 0 to 4.

In the formula (2), R ¹ to R ⁴ and a to d are independently ^{synonymous with R 1} to R ⁴ and a to d in the formula (1), and Y is a single bond, −SO ₂ -Or -CO-, R ⁷ and R ⁸ independently represent a halogen atom, a monovalent organic group or a nitro group having 1 to 12 carbon atoms, and g and h independently represent 0 to 4, respectively. It indicates an integer, and m indicates 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

Further, the aromatic polyether resin further has at least one structural unit selected from the group consisting of the structural unit represented by the following formula (3) and the structural unit represented by the following formula (4). You may be doing it.

In the formula (3), are each R ⁵ and R ⁶ independently represents a monovalent organic group having 1 to 12 carbon atoms, Z is a single bond, -O -, - S -, - SO 2 -, - It represents CO-, -CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms, where e and f independently represent an integer of 0 to 4, and n represents 0 or 1.

In the formula (4), R ⁷ , R ⁸ , Y, m, g and h are independently ^{synonymous with R 7} , R ⁸ , Y, m, g and h in the formula (2), respectively, and R ⁵ , R ⁶ , Z, n, e and f are independently ^{synonymous with R 5} , R ⁶ , Z, n, e and f in the above formula (3).

[Polyimide resin]
The polyimide resin is not particularly limited as long as it is a polymer compound containing an imide bond in the repeating unit. For example, it is synthesized by the methods described in JP-A-2006-199945 and JP-A-2008-163107. can do.

[Polyester resin]
The polyester-based resin is not particularly limited, and for example, it can be synthesized by the methods described in JP-A-2010-285505 and JP-A-2011-197450.

[Polycarbonate resin]
The polycarbonate-based resin is not particularly limited, and for example, it can be synthesized by the method described in JP-A-2008-163194.

[Fluorinated aromatic polymer resin]
The fluorinated aromatic polymer resin is not particularly limited, but at least selected from the group consisting of an aromatic ring having at least one fluorine atom and an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond. It is preferably a polymer containing a repeating unit containing one bond, and can be synthesized, for example, by the method described in JP-A-2008-181121.

[Acrylic UV curable resin]
The acrylic ultraviolet curable resin is not particularly limited, but is synthesized from a resin composition containing a compound having one or more acrylic groups or methacrylic groups in the molecule and a compound that is decomposed by ultraviolet rays to generate active radicals. Can be mentioned.
The acrylic ultraviolet curable resin can be suitably used as a curable resin that can be used when forming a resin layer such as the following resin layer and the following overcoat layer.

[Commercial goods]
Examples of commercially available products of the resin include the following commercially available products. Examples of commercially available cyclic (poly) olefin resins include Arton manufactured by JSR Corporation, Zeonoa manufactured by Zeon Corporation, APEL manufactured by Mitsui Chemicals Co., Ltd., and TOPAS manufactured by Polyplastics Corporation. Examples of commercially available products of the polyether sulfone-based resin include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available polycarbonate resins include Pure Ace manufactured by Teijin Limited, Panlite SP-3810 manufactured by Teijin Limited, and Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company. Examples of commercially available fluorene polyester-based resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include Acryviewer manufactured by Nippon Shokubai Co., Ltd. Examples of commercially available products of the silsesquioxane-based ultraviolet curable resin include Silplus manufactured by Nippon Steel Chemical & Materials Co., Ltd.

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

These other components may be mixed with a resin or the like when preparing the present composition, or may be added when synthesizing the resin. The amount to be added may be appropriately selected according to desired characteristics and the like, but is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the resin. Is.

[Compound (X)]
The present composition may contain one or more compounds (X) [absorbents other than ultraviolet absorbers] other than compound (Z).
Examples of the compound (X) include squarylium compounds, phthalocyanine compounds, polymethine compounds, naphthalocyanine compounds, croconium compounds, octaphyllin compounds, diimonium compounds, perylene compounds, and metal dithiolate compounds. Be done.

The compound (X) preferably contains a squarylium-based compound, more preferably one or more of each of the squarylium-based compound and the other compound (X'), and the other compound (X'). , Phthalocyanine compounds and polymethine compounds are particularly preferred.

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

The absorption maximum wavelength of the compound (X) is preferably 600 to 800 nm, more preferably 620 to 780 nm, still more preferably 650 to 760 nm, and particularly preferably 660 to 750 nm.
By using the compound (X) having the maximum absorption wavelength in the above range, the dependence of the color near red on the incident angle is improved, and an excellent optical filter can be easily obtained by correcting the luminosity factor.

[UV absorber]
Examples of the ultraviolet absorber include azomethine compounds, indol compounds, benzotriazole compounds, triazine compounds, anthracene compounds, and compounds described in JP-A-2019-014707.

[Antioxidant]
Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5'-dimethyldiphenylmethane, and the like. Tetrakiss [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane can be mentioned.

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

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

≪Optical filter≫
The optical filter according to an embodiment of the present invention (hereinafter, also referred to as “the present filter”) is a resin layer containing the compound (Z) formed from the present composition (hereinafter, also referred to as “the present resin layer”). It has a base material (i) containing the above and a dielectric multilayer film.
From the viewpoint that the effects of the present invention are more exhibited, specific examples of such a filter include a near-infrared cut filter (NIR-CF), a visible light-near infrared selective transmission filter (DBPF), and a near infrared filter. Infrared transmission filter (IRPF) can be mentioned. These filters may have a conventionally known configuration except that they have the present resin layer and a dielectric multilayer film.

The thickness of the present filter may be appropriately selected according to the desired application, but according to the recent trend of thinning and weight reduction of solid-state image sensors and the like, it is preferable that the thickness of the present filter is also thin.
Since this filter contains the base material (i), it can be made thinner.

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

<NIR-CF>
The NIR-CF is preferably an optical filter having excellent cutting performance in the wavelength region of 850 to 1200 nm and excellent transparency in the visible wavelength region.
The dielectric multilayer film used in this NIR-CF is preferably a near-infrared reflective film.

When NIR-CF is used for a solid-state image sensor or the like, it is preferable that the transmittance in the near infrared wavelength region is low. In particular, it is known that the light receiving sensitivity of the solid-state image sensor is relatively high in the wavelength region of 850 to 1200 nm, and by reducing the transmittance in this wavelength region, the visual sensitivity correction between the camera image and the human eye can be performed. It can be done effectively and excellent color reproducibility can be achieved. Further, by reducing the transmittance in the wavelength region of 850 to 1200 nm, it is possible to effectively prevent the near-infrared light used for the security authentication function from reaching the image sensor or the like.

NIR-CF has an average transmittance of preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, particularly preferably 3% or less, when measured from the vertical direction of the filter in the wavelength region of 850 to 1200 nm. Is less than 2%.
When the average transmittance at a wavelength of 850 to 1200 nm is in this range, near infrared rays can be sufficiently cut and excellent color reproducibility can be achieved, which is preferable.

When NIR-CF is used for a solid-state image sensor or the like, it is preferable that the visible light transmittance is high. Specifically, in the region of wavelength 430 to 580 nm, 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, particularly preferably. Is 85% or more.
When the average transmittance at a wavelength of 430 to 580 nm is in this range, excellent imaging sensitivity can be achieved.

<DBPF>
The DBPF is not particularly limited as long as it is an optical filter that transmits visible light and light having a wavelength to be transmitted among near infrared rays and cuts light having a wavelength to be cut among near infrared rays.
The dielectric multilayer film used in the DBPF is preferably a film that transmits visible light and light having a wavelength that is desired to be transmitted among near infrared rays and cuts light having a wavelength that is desired to be cut among near infrared rays.

Similar to NIR-CF, when DBPF is used for a solid-state imaging device or the like, it is preferable that the visible light transmittance is high, and for the same reason as described above, the average transmittance at a wavelength of 430 to 580 nm is that of NIR-CF. It is preferably in the same range as the average transmittance.

In addition, DBPF has the following characteristics in that it can sufficiently transmit visible light and light having a wavelength of near infrared rays to be transmitted, and can sufficiently cut light of a wavelength of near infrared rays to be cut. It is preferable to satisfy (d).
Characteristic (d): A light blocking band Za, a light transmitting band Zb, and a light blocking band Zc are provided in a region having a wavelength of 650 nm or more, and the central wavelength of each band is Za <Zb <Zc.
The minimum transmittances of Za and Zc measured from the vertical direction of the filter are preferably 15% or less, more preferably 5% or less, respectively.
The maximum transmittance of the Zb measured from the vertical direction of the filter is preferably 55% or more, more preferably 60% or more.

Za has a wavelength of 650 nm or more and 900 nm or less, from the shortest wavelength Za1 in which the transmittance measured from the vertical direction of this filter is more than 20% to 20% or less, and the longest wavelength in which it is less than 20% to 20% or more. Refers to the wavelength band up to Za2. The central wavelength of Za is (Za1 + Za2) / 2 nm.

Zb has a wavelength of 750 nm or more and 1050 nm or less, from the shortest wavelength Zb1 in which the transmittance measured from the vertical direction of this filter is 40% or less to more than 40%, and the longest wavelength in which it is more than 40% to 40% or less. Refers to the wavelength band up to Zb2. The central wavelength of Zb is (Zb1 + Zb2) / 2 nm.

Zc refers to the wavelength band from the shortest wavelength Zc1 in which the transmittance measured from the vertical direction of this filter is more than 20% to 20% or less at a wavelength of 820 nm or more to the wavelength Zc2 of Zc1 + 200 nm. The central wavelength of Zc is (Zc1 + Zc2) / 2 nm.

<IRPF>
The IRPF is not particularly limited as long as it is an optical filter that cuts visible light and transmits light having a wavelength to be transmitted among near infrared rays.
The dielectric multilayer film used in this IRPF is preferably a film that cuts light having a wavelength to be cut (a part of visible light and / or near infrared rays).
In addition, IRPF may cut visible light by using a visible light absorber.

IRPF can be suitably used for optical systems such as infrared surveillance cameras, in-vehicle infrared cameras, infrared communication, various sensing systems, infrared alarms, and night vision devices. It is preferable that the light transmittance of the wavelength is low.
In particular, in the region of wavelength 380 to 700 nm, the average value of the transmittance when measured from the vertical direction of this filter is preferably 10% or less, more preferably 5% or less.

Further, the IRPF preferably has a high transmittance of near-infrared rays to be transmitted. Specifically, the IRPF has a light transmitting band Ya in a region having a wavelength of 750 nm or more, and the IRPF has a light transmitting band Ya in the light transmitting band Ya, which is vertical to the filter. _{The maximum transmittance (TIR} ) when measured from the direction is preferably 45% or more, more preferably 50% or more.

<Base material (i)>
The base material (i) may be a single layer or a multi-layer, and may have the present resin layer. The base material (i) may have two or more main resin layers, and in this case, the two or more main resin layers may be the same or different.
When the base material (i) is a single layer, the base material (i) is made of the present resin layer, that is, the present resin layer (resin substrate) is the base material (i).
When the base material (i) has multiple layers, the base material (i) is a base material containing two or more resin layers, and at least one of the two or more resin layers is the present resin layer. Examples thereof include a certain base material and a base material containing the present resin layer and a glass support. For example, a laminated body in which the present resin layer is laminated on a support such as a glass support or a resin support as a base. Examples thereof include a base material (A) containing the base material (A) and a base material (B) containing a laminate in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on the present resin layer.
The base material (i) is a base material because of the manufacturing cost, the ease of adjusting the optical characteristics, the ability to eliminate scratches on the resin layer, the improvement of the scratch resistance of the base material (i), and the like. (B) is particularly preferable.

The resin layer such as the overcoat layer in the resin support and the base material (B) refers to a resin layer that does not contain the compound (Z). The resin layer that does not contain the compound (Z) is not particularly limited as long as it contains a resin, and examples of the resin include resins similar to the resin described in the column of the present composition. Further, the resin layer containing no compound (Z) may be the following other functional film.

The thickness of the base material (i) can be appropriately selected depending on the desired application and is not particularly limited, but is preferably 10 to 250 μm, more preferably 15 to 230 μm, and particularly preferably 20 to 150 μm.
When the thickness of the base material (i) is within the above range, the filter using the base material (i) can be made thinner and lighter, and can be suitably used for various applications such as a solid-state image sensor. it can. In particular, when the single-layer base material (i) is used for a lens unit such as a camera module, it is preferable because the lens unit can be reduced in height and weight.

In the region of wavelength 850 to 1200 nm, the lowest transmittance (Ta) measured from the vertical direction of the base material (i) is preferably 0.1 to 40%, more preferably 0.5 to 35%, and particularly preferably. It is 1 to 30%.

In the wavelength region of 430 to 580 nm, the average transmittance (Tb) measured from the vertical direction of the base material (i) is preferably 80% or more, more preferably 81.0% or more.

When (Ta) and (Tb) of the base material (i) are in the above range, it is possible to easily obtain an optical filter exhibiting high visible light transmittance while sufficiently cutting light having a wavelength in the near infrared region to be cut. It is possible to easily obtain an optical filter that gives a good camera image with less flare and ghost.

[Manufacturing method of base material (i)]
The resin layer such as the present resin layer, the resin support, and the overcoat layer can be formed by, for example, melt molding or cast molding, and if necessary, an antistatic agent or a hard coating agent after molding. And / or a coating agent such as an antistatic agent may be coated.

When the base material (i) is the base material (A), for example, by melt-molding or casting the present composition on the support, a method such as spin coating, slit coating, or inkjet is preferable. After coating, the solvent is dried and removed, and if necessary, further light irradiation or heating is performed to produce a base material having the present resin layer formed on the support.

-Melting molding The melt molding specifically includes a method of melt-molding pellets obtained by melt-kneading the present composition; a method of melt-molding the present composition; a liquid present composition containing a solvent. Examples thereof include a method of melt-molding the pellets obtained by removing the solvent from the pellets. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding and the like.

-Cast molding The cast molding is a method of casting a liquid composition containing a solvent on an appropriate support to remove the solvent; the resin includes a photocurable resin and / or a thermosetting resin. Examples thereof include a method in which the present curable composition is cast on an appropriate support to remove the solvent, and then cured by an appropriate method such as ultraviolet irradiation or heating.
When the base material (i) is the single-layer base material (i), the base material (i) can be obtained by peeling the coating film from the support after cast molding. When the base material (i) is the base material (A), the base material (i) can be obtained by casting and molding without peeling the coating film.

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

Further, a method of coating an optical component such as a glass plate, quartz or plastic with the liquid present composition to dry the solvent, a method of coating the curable present composition and curing and drying, and the like. Therefore, the present resin layer can be formed on the optical component.

When the resin layer such as the resin support and the overcoat layer is formed by melt molding or cast molding, a desired composition containing a resin instead of the present composition in the column of melt molding or cast molding ( However, the compound (Z) is not included) may be used.

The amount of residual solvent in the resin layer such as the present resin layer, the resin support, and the overcoat layer should be as small as possible. Specifically, the amount of the residual solvent is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, based on the weight of the resin layer.
When the amount of the residual solvent is within the above range, a resin layer that is less likely to be deformed or changed in characteristics and can easily exhibit a desired function can be obtained.
When the base material (i) is used as an optical filter, it is preferable to suppress the solvent content in the resin layer such as the present resin layer, the resin support and the overcoat layer to 100 mass ppm or less.

<Dielectric multilayer film>
This filter has the base material (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 of the base material (i) or on both sides. When it is provided on one side, it is excellent in manufacturing cost and ease of manufacture, and when it is provided on both sides, it is possible to obtain an optical filter which has high strength and is less likely to warp or twist. When this filter is used for a solid-state image sensor or the like, it is preferable that the filter has a small warp or twist. Therefore, it is preferable to provide a dielectric multilayer film on both surfaces of the base material (i).

Examples of the material constituting the high refractive index material layer include a material having a refractive index of 1.7 or more, and a material having a refractive index of 1.7 to 2.5 is usually selected. Examples of such a material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide and the like as main components, and titanium oxide, tin oxide and /. Alternatively, those containing a small amount of cerium oxide or the like (for example, 0 to 10% by mass with respect to the main component) can be mentioned.

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

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

The thickness of each of the high refractive index material layer and the low refractive index material layer is usually preferably 0.1λ to 0.5λ, where λ (nm) is the near-infrared wavelength to be blocked. In the case of NIR-CF, the value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness of each layer of the high refractive index material layer and the low refractive index material layer is in this range, the optical film thickness, which is the product (n × d) of the refractive index (n) and the film thickness (d), becomes. The value is almost the same as λ / 4, and there is a tendency that the blocking / transmission of a specific wavelength can be easily controlled due to the relationship between the optical characteristics of reflection / refraction.

In the case of NIR-CF, for example, 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 as a whole, and 20 to 60 layers. More preferably. When the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of layers are within the above ranges, a sufficient manufacturing margin can be secured, and warpage of the optical filter and cracks of the dielectric multilayer film are reduced. can do.

In this filter, the material types constituting the high refractive index material layer and the low refractive index material layer, the thickness of each layer of the high refractive index material layer and the low refractive index material layer, according to the absorption characteristics of the compound (Z), etc. By appropriately selecting the stacking order and the number of stacks, sufficient light transmittance is secured in the wavelength range to be transmitted (example: visible range), and sufficient light ray cutting characteristics are provided in the near infrared wavelength range to be cut. In addition, it is possible to reduce the refractive index when near-infrared rays are incident from an oblique direction.

Here, in order to optimize the conditions of the dielectric multilayer film, for example, optical thin film design software (for example, Essential Macleod, manufactured by Thin Film Center) is used to prevent reflection in the wavelength range (eg, visible range) to be transmitted. The parameters may be set so that both the effect and the light ray cutting effect in the near infrared region to be cut can be achieved at the same time. In the case of the software, for example, when forming a NIR-CF dielectric multilayer film, the target transmittance at a wavelength of 400 to 700 nm is set to 100%, the target tolerance value is set to 1, and the wavelength is 705 to 950 nm. Parameter setting methods such as setting the target transmittance to 0% and the Target Tolerance value to 0.5 can be mentioned.
These parameters can also change the value of Target Tolerance by further dividing the wavelength range according to various characteristics of the base material (i) and the like.

<Other functional membranes>
In the present filter, the surface between the base material (i) and the dielectric multilayer film, the surface opposite to the surface on which the dielectric multilayer film of the base material (i) is provided, or the surface opposite to the surface provided with the dielectric multilayer film, or the surface opposite to the surface provided with the dielectric multilayer film, or On the surface opposite to the surface on which the base material (i) of the dielectric multilayer film is provided, the surface hardness of the base material (i) and the dielectric multilayer film is improved, the chemical resistance is improved, antistatic and scratch erasing are performed. For such purposes, functional films such as an antireflection film, a hard coat film, and an antistatic film can be appropriately provided.

This filter may contain one layer of the functional film or may contain two or more layers. When the present filter contains two or more layers of the functional film, the same film may be contained in two or more layers, or different films may be contained in two or more layers.

The method for laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melted on the base material (i) or the dielectric multilayer film in the same manner as described above. Examples thereof include a method of molding or cast molding.

It can also be produced by applying a curable composition containing the coating agent or the like on a base material (i) or a dielectric multilayer film with a bar coater or the like, and then curing by ultraviolet irradiation or the like.

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

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

The proportion of the polymerization initiator in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, when the total amount of the curable composition is 100% by mass. More preferably, it is 1 to 5% by mass. When the blending ratio of the polymerization initiator is within the above range, a curable composition having excellent curable properties, handleability, etc. can be easily obtained, and an antireflection film, a hard coat film, an antistatic film, etc. having a desired hardness can be easily obtained. Functional film can be easily obtained.

Further, an organic solvent may be added to the curable composition as a solvent, and a known solvent can be used as the organic solvent. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone and propylene. Esters such as 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; dimethylformamide, dimethylacetamide, N- Examples thereof include amides such as methylpyrrolidone.
These solvents may be used alone or in combination of two or more.

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

Further, for the purpose of improving the adhesion between the base material (i) and the functional film and / or the dielectric multilayer film and the adhesion between the functional film and the dielectric multilayer film, the base material (i), the functional film or the dielectric material is used. The surface of the multilayer film may be subjected to surface treatment such as corona treatment or plasma treatment.

[Use of optical filter]
This filter is excellent, for example, in the ability to cut light having a wavelength in a region to be cut and the ability to transmit light having a wavelength to be transmitted. Therefore, it is useful for correcting the luminosity factor of a solid-state image sensor such as a CCD or CMOS image sensor of a camera module. In particular, digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automobile cameras, infrared cameras, televisions, car navigation systems, mobile information terminals, video game machines, etc. It is useful for portable game machines, fingerprint authentication systems, digital music players, various sensing systems, infrared communications, etc. Further, it is also useful as a heat ray cut filter or the like attached to a glass plate or the like of an automobile or a building.

≪Solid image sensor≫
The solid-state image sensor according to an embodiment of the present invention includes the present filter. Here, the solid-state image sensor is a device provided with a solid-state image sensor such as a CCD or a CMOS image sensor, and specifically, a digital still camera, a smartphone camera, a mobile phone camera, a wearable device camera, or a digital video. Examples include cameras.

≪Optical sensor device≫
The optical sensor device according to the embodiment of the present invention is not particularly limited as long as it includes the present filter, and may have a conventionally known configuration.
For example, an apparatus having a light receiving element and the present filter can be mentioned, and specific examples thereof include an apparatus having a light receiving element (semiconductor substrate), a protective film, the present filter, another filter and the like.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent and the like.
(A) Using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by Waters Corp., weight equivalent to standard polystyrene. The average molecular weight (Mw) and the number average molecular weight (Mn) were measured.
(B) Using a GPC apparatus manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgelα-M, developing solvent: THF), the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were measured. ..

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

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

<Spectroscopic transmittance>
The transmittance of the base material and the optical filter in the near infrared region with a wavelength of 850 to 1200 nm and the visible light transmittance with a wavelength of 430 to 580 nm were measured using a spectrophotometer (V-7200) manufactured by Nippon Spectroscopy Co., Ltd. did. This transmittance is measured using the spectrophotometer under the condition that the light is vertically incident on the base material or the optical filter. The parameters measured using this device are as follows.

Xa: Wavelength of light having the lowest transmittance measured from the vertical direction of the base material at a wavelength of 850 to 1200 nm Ta: Minimum transmittance measured from the vertical direction of the base material at a wavelength of 850 to 1200 nm Tb: Base material Average transmittance of light with a wavelength of 430 to 580 nm measured from the vertical direction of Tc: Minimum transmittance of light with a wavelength of 850 to 1200 nm after the heating test measured from the vertical direction of the substrate Td: From the vertical direction of the substrate Measured average transmittance of light with a wavelength of 430 to 580 nm after the heating test Te: Minimum transmittance of light with a wavelength of 850 to 1200 nm after UV irradiation measured from the vertical direction of the substrate Tf: From the vertical direction of the substrate Measured average transmittance of light with a wavelength of 430 to 580 nm after UV irradiation Tg: Average transmittance of light with a wavelength of 850 to 1200 nm measured from the vertical direction of the optical filter Th: Wavelength measured from the vertical direction of the optical filter Average transmittance of light from 430 to 580 nm

[Example of compound synthesis]
The compounds (X) and (Z) used in the following examples were synthesized based on a generally known synthetic method.
Examples of the compound (X) include Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Application Laid-Open No. 60-228448, Japanese Patent Application Laid-Open No. 1-146846, and Japanese Patent Application Laid-Open No. Kaihei 1-2289960, Japanese Patent No. 4081149, Japanese Patent Application Laid-Open No. 63-124054, "Futarusinin-Chemistry and Function-" (IPC, 1997), Japanese Patent Application Laid-Open No. 2007-169315, Japanese Patent Application Laid-Open No. 2007-1693- It can be synthesized based on the methods described in Japanese Patent Application Laid-Open No. 108267, Japanese Patent Application Laid-Open No. 2010-241873, Japanese Patent No. 3699464, and Japanese Patent No. 4740631.

Examples of the compound (Z) include JP-A-2009-108267, JP-A-5-59291, JP-A-2014-95007, JP-A-2011-52218, International Publication No. 2007/114398, JP-A. 2003-246940, Chemistry of Heterocyclic Compounds: The Cyanine Days and Related Compounds, Volume 18 (Wiley, 1964), Near-Infre It can be synthesized, but specifically, it can be synthesized by the following method.

[Intermediate Synthesis Example 1]

Phosphoryl chloride (66.4 g) was added dropwise to DMF (250 mL) under ice-cooling, and the mixture was stirred as it was for 1 hour. Then, cyclohexanone (25.0 g) was added, and the mixture was heated at 80 ° C. for 3 hours. After allowing to cool to room temperature, ice water was added and the mixture was left overnight. The mixture was filtered to give the pale yellow target compound c-1 (37.4 g). NMR and LC-MS (Liquid Chromatography Mass Spectrometer) were used to identify the target compound.

[Intermediate Synthesis Example 2]

Under ice-cooling, a solution of phenylmagnesium bromide (PhMgBr) and tetrahydrofuran (1 mol / L, 330 mL) was added dropwise to a solution of cyclopentanone (25.4 g) in THF (200 mL), and the mixture was stirred at room temperature for 1 hour. Then methanol (10 mL) was added slowly, and then concentrated hydrochloric acid (10 mL) was added. Tetrahydrofuran was removed by an evaporator, separated by ethyl acetate and water, dried over sodium sulfate, and concentrated. The obtained solution was purified by silica gel column chromatography to obtain compound c-2 (29.6 g).
Phosphoryl chloride (54.7 g) was added dropwise to DMF (200 mL) under ice-cooling, and the mixture was stirred for 1 hour. Compound c-2 (29.6 g) was then added and heated at 80 ° C. for 3 hours. After allowing to cool at room temperature, ice water was added and the mixture was left overnight. The mixture was filtered to give the pale yellow target compound c-3 (35.7 g). NMR and LC-MS were used to identify the target compound.

[Intermediate Synthesis Example 3]

Phosphoryl chloride (81.1 g) was added dropwise to DMF (250 mL) under ice-cooling, and the mixture was stirred as it was for 1 hour. Then, cyclopentanone (25.0 g) was added, and the mixture was heated at 80 ° C. for 3 hours. After allowing to cool to room temperature, ice water was added and the mixture was left overnight. The mixture was filtered to give the pale yellow target compound c-4 (41.9 g). NMR and LC-MS were used to identify the target compound.

[Intermediate Synthesis Example 4]

Diphenylamine (25.1 g) and a 42% aqueous solution of tetrafluoroboric acid (46.6 g) were added to an acetonitrile solution (150 mL) of cyclopentanone (25.0 g), refluxed for 2 hours, and then allowed to cool. The precipitated solid was filtered and washed with cold methanol to obtain compound c-5 (82.6 g).
Compound c-5 (82.6 g) and ethyl N-phenylform imidate (80.1 g) were refluxed in butyronitrile (250 mL) for 2 hours and then allowed to cool to room temperature. The solid precipitated by adding diethyl ether (1 L) was filtered, dissolved in methanol (200 mL), and toluene was added (1 L) to precipitate the solid. This solid was filtered and dried to obtain the target compound c-6 (90.7 g). NMR and LC-MS were used to identify the target compound.

[Intermediate Synthesis Example 5]

Under ice-cooling, a solution of phenylmagnesium bromide and tetrahydrofuran (1 mol / L, 250 mL) was added dropwise to a solution of 4-methylcyclohexanone (25.0 g) in THF (100 mL), and the mixture was stirred at room temperature for 1 hour. Then methanol (10 mL) was added slowly, and then concentrated hydrochloric acid (10 mL) was added. Tetrahydrofuran was removed by an evaporator, separated by ethyl acetate and water, dried over sodium sulfate, and concentrated. The obtained solution was purified by silica gel column chromatography to obtain compound c-7 (26.1 g).
Phosphoryl chloride (33.0 g) was added dropwise to DMF under ice-cooling, and the mixture was stirred for 1 hour. Compound c-7 (26.1 g) was then added and heated at 80 ° C. for 3 hours. After allowing to cool to room temperature, ice water was added and the mixture was left overnight. The mixture was filtered to give the pale yellow target compound c-8 (24.6 g). NMR and LC-MS were used to identify the target compound.

[Intermediate Synthesis Example 6]

Phosphoryl chloride (89.0 g) was added dropwise to DMF (250 mL) under ice-cooling, and the mixture was stirred as it was for 1 hour. Then 3-pentanone (25.0 g) was added and heated at 80 ° C. for 3 hours. After allowing to cool to room temperature, ice water was added and the mixture was left overnight. The mixture was filtered to give the pale yellow target compound c-9 (9.3 g). NMR and LC-MS were used to identify the target compound.

[Intermediate Synthesis Example 7]

Phosphoryl chloride (45.0 g) was added dropwise to DMF (250 mL) under ice-cooling, and the mixture was stirred as it was for 1 hour. Then, 2,2,6,6-tetramethylheptane-4-one (25.0 g) was added, and the mixture was heated at 80 ° C. for 3 hours. After allowing to cool to room temperature, ice water was added and the mixture was left overnight. The mixture was filtered to give the pale yellow target compound c-10 (7.2 g). NMR and LC-MS were used to identify the target compound.

[Intermediate Synthesis Example 8]

Ethyl pivalate (52) in a t-BuOH (150 mL) solution of compound e-1 (20.0 g) synthesized by the method according to Bioorganic and Medicinal Chemistry, 2013, vol.21, # 11, p.2826-2831. After adding 9.0 g) and 9.6 g of sodium hydride (60%, dispersion in Paraffin Liquid), the mixture was stirred at 80 ° C. for 3 hours. Then, the mixture was cooled to room temperature, and 20 mL of concentrated hydrochloric acid was added. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator to obtain compound e-2.
Then, without purifying compound e-2, 15 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40 ° C. After 1 hour, the reaction solution was ice-cooled and neutralized by adding a 1N aqueous sodium hydroxide solution. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound e-3 (11.5 g). Compounds were identified by LC-MS and ^{1 1} H-NMR analysis.
Compound e-3 (11.5 g) and 90 mL of tetrahydrofuran were ice-cooled with stirring. After 5 minutes of ice cooling, a methyl magnesium iodide-diethyl ether solution (1 mol / L, 50 mL) was added dropwise, and the mixture was heated to 35 ° C. and stirred for 2 hours. Next, the reaction solution was ice-cooled, 90 mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was filtered off, washed with 60 mL of water, and dried under reduced pressure at 50 ° C. to obtain compound e-4 (10.5 g). ) Was obtained. Compounds were identified by ^{1 1} H-NMR analysis.

[Intermediate Synthesis Example 9]

Ethyl isobutyrate (50) in a t-BuOH (150 mL) solution of compound e-1 (20.0 g) synthesized by the method according to Bioorganic and Medicinal Chemistry, 2013, vol.21, # 11, p.2826-2831. After adding 9.0 g) and 9.6 g of sodium hydride (60%, dispersion in Paraffin Liquid), the mixture was stirred at 80 ° C. for 3 hours. Then, the mixture was cooled to room temperature, and 20 mL of concentrated hydrochloric acid was added. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator to obtain compound e-5.
Then, the compound e-5 was not purified, 15 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40 ° C. After 1 hour, the reaction solution was ice-cooled and neutralized by adding a 1N aqueous sodium hydroxide solution. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound e-6 (10.4 g). Compounds were identified by LC-MS and ^{1 1} H-NMR analysis.
Compound e-6 (10.4 g) and 90 mL of tetrahydrofuran were ice-cooled with stirring. After 5 minutes of ice cooling, a methyl magnesium iodide-diethyl ether solution (1 mol / L, 50 mL) was added dropwise, and the mixture was heated to 35 ° C. and stirred for 2 hours. Next, the reaction solution was ice-cooled, 90 mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was filtered off, washed with 60 mL of water, and dried under reduced pressure at 50 ° C. to obtain compound e-7 (8.3 g). ) Was obtained. Compounds were identified by ^{1 1} H-NMR analysis.

[Intermediate Synthesis Example 10]

Compound e-8 can be synthesized by using the method described in Organic Letters, 2015, vol.17, # 13, p.3306-3309.

[Intermediate Synthesis Example 11]

Compound e-9 can be synthesized by using the method described in European Journal of Organic Chemistry, 2018, vol.2018, # 2, p.240-246.

[Intermediate Synthesis Example 12]

Compound e-10 can be synthesized by using the method described in Journal of Organic Chemistry, 2000, vol.65, # 7, p.2236-2238, PF6.

[Intermediate Synthesis Example 13]

Ethyl pivalate (45.0 g) was added to a t-BuOH (150 mL) solution of compound e-11 (20.0 g), and 9.6 g of sodium hydride (60%, dispersion in Paraffin Liquid) was added. The mixture was stirred at 80 ° C. for 3 hours. Then, the mixture was cooled to room temperature, and 20 mL of concentrated hydrochloric acid was added. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator to obtain compound e-12.
Then, the compound e-12 was not purified, 15 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40 ° C. After 1 hour, the reaction solution was ice-cooled and neutralized by adding a 1N aqueous sodium hydroxide solution. After separating and washing with ethyl acetate and 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 (hexane / ethyl acetate = 4/1) to obtain compound e-13 (19.1 g). Compounds were identified by LC-MS and ^{1 1} H-NMR analysis.
Compound e-13 (19.1 g) and 90 mL of tetrahydrofuran were ice-cooled with stirring. After 5 minutes of ice cooling, a methyl magnesium iodide-diethyl ether solution (1 mol / L, 50 mL) was added dropwise, and the mixture was heated to 35 ° C. and stirred for 2 hours. Next, the reaction solution was ice-cooled, 30 mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was filtered off, washed with 60 mL of water, and dried under reduced pressure at 50 ° C. to obtain compound e-14 (16.8 g). ) Was obtained. Compounds were identified by ^{1 1} H-NMR analysis.

[Intermediate Synthesis Example 14]

Compound e-15 can be synthesized by using the method described in Journal of the American Chemical Society, 2015, vol.137, # 14, p.4759-4765.

[Intermediate Synthesis Example 15]

Compound e-16 can be synthesized by using the method described in Journal of the Chemical Society. Perkin Transactions 1 (2001), 2000, # 4, p.599-603.

[Intermediate Synthesis Example 16]

In dichloromethane (100 mL), compound e-17 (20.0 g), oxalyl dichloride (22.0 g), pyridine (13.7 g) and DMF (1 mL) were stirred at room temperature for 1 hour. Dichloromethane was removed by an evaporator to give a mixture containing compound e-18.
The resulting mixture, acetonitrile (200 mL), 5-methyl-2-hydroxyacetophenone (21.3 g) and triethylamine (15.1 g) were added and stirred at room temperature. Acetonitrile was removed with an evaporator, the mixture was separated with ethyl acetate and water, and the organic layer was dried over sodium sulfate. Ethyl acetate in the organic layer was removed by an evaporator to obtain compound e-19.
This was dissolved in t-BuOH (100 mL) without purification, 6.3 g of sodium hydride (60%, dispersion in Paraffin Liquid) was added, and the mixture was stirred at 80 ° C. for 3 hours. Then, the mixture was cooled to room temperature, and 20 mL of concentrated hydrochloric acid was added. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator to obtain compound e-20.
Then, 20 mL of concentrated hydrochloric acid was added without purifying compound e-20, and the mixture was stirred at 40 ° C. After 1 hour, the reaction solution was ice-cooled and neutralized by adding a 1N aqueous sodium hydroxide solution. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound e-21 (27.3 g). Compounds were identified by LC-MS and ^{1 1} H-NMR analysis.
Compound e-21 (27.3 g) and 90 mL of tetrahydrofuran were ice-cooled with stirring. After 5 minutes of ice cooling, a methyl magnesium iodide-diethyl ether solution (1 mol / L, 50 mL) was added dropwise, and the mixture was heated to 35 ° C. and stirred for 2 hours. Next, the reaction solution was ice-cooled, 90 mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was filtered off, washed with 60 mL of water, and dried under reduced pressure at 50 ° C. to obtain compound e-22 (16.2 g). Got Compounds were identified by ^{1 1} H-NMR analysis.

[Intermediate Synthesis Example 17]

In dichloromethane (100 mL), compound e-23 (20.0 g), oxalyl dichloride (21.4 g), pyridine (13.4 g) and DMF (1 mL) were stirred at room temperature for 1 hour. Dichloromethane was removed by an evaporator to give a mixture containing compound e-24.
The resulting mixture, acetonitrile (200 mL), 5-methyl-2-hydroxyacetophenone (20.8 g) and triethylamine (14.8 g) were added and stirred at room temperature. Acetonitrile was removed with an evaporator, the mixture was separated with ethyl acetate and water, and the organic layer was dried over sodium sulfate. Ethyl acetate in the organic layer was removed by an evaporator to obtain compound e-25.
This was dissolved in t-BuOH (100 mL) without purification, 6.1 g of sodium hydride (60%, dispersion in Paraffin Liquid) was added, and the mixture was stirred at 80 ° C. for 3 hours. Then, the mixture was cooled to room temperature, and 20 mL of concentrated hydrochloric acid was added. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried. The solvent was distilled off using an evaporator to obtain compound e-26.
Then, compound e-26 was not purified, 30 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40 ° C. After 1 hour, the reaction solution was ice-cooled and neutralized by adding a 1N aqueous sodium hydroxide solution. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound e-27 (27.0 g). Compounds were identified by LC-MS and ^{1 1} H-NMR analysis.
Compound e-27 (27.0 g) and 90 mL of tetrahydrofuran were ice-cooled with stirring. After 5 minutes of ice cooling, a methyl magnesium iodide-diethyl ether solution (1 mol / L, 50 mL) was added dropwise, and the mixture was heated to 35 ° C. and stirred for 2 hours. Next, the reaction solution was ice-cooled, 90 mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was filtered off, washed with 60 mL of water, and dried under reduced pressure at 50 ° C. to obtain compound e-28 (15.9 g). ) Was obtained. Compounds were identified by ^{1 1} H-NMR analysis.

[Intermediate Synthesis Example 18]

Ethyl pivalate (50.0 g) was added to a t-BuOH (150 mL) solution of compound e-29 (25.0 g), and 6.7 g of sodium hydride (60%, dispersion in Paraffin Liquid) was added. The mixture was stirred at 80 ° C. for 3 hours. Then, the mixture was cooled to room temperature, and 15 mL of concentrated hydrochloric acid was added. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator to obtain compound e-30.
Then, 30 mL of concentrated hydrochloric acid was added without purifying compound e-30, and the mixture was stirred at 40 ° C. After 1 hour, the reaction solution was ice-cooled and neutralized by adding a 1N aqueous sodium hydroxide solution. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound e-31 (16.2 g). Compounds were identified by LC-MS and ^{1 1} H-NMR analysis.
Compound e-31 (16.2 g) and 90 mL of tetrahydrofuran were ice-cooled with stirring. After 5 minutes of ice cooling, a methyl magnesium iodide-diethyl ether solution (1 mol / L, 50 mL) was added dropwise, and the mixture was heated to 35 ° C. and stirred for 2 hours. Next, the reaction solution was ice-cooled, 90 mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was filtered off, washed with 60 mL of water, and dried under reduced pressure at 50 ° C. to obtain compound e-32 (12.9 g). ) Was obtained. Compounds were identified by ^{1 1} H-NMR analysis.

[Intermediate Synthesis Example 19]

Ethyl isobutyrate (52.0 g) was added to a t-BuOH (150 mL) solution of compound e-11 (25.0 g), and 7.3 g of sodium hydride (60%, dispersion in Paraffin Liquid) was added. The mixture was stirred at 80 ° C. for 3 hours. Then, the mixture was cooled to room temperature, and 20 mL of concentrated hydrochloric acid was added. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator to obtain compound e-33.
Then, 20 mL of concentrated hydrochloric acid was added without purifying compound e-33, and the mixture was stirred at 40 ° C. After 1 hour, the reaction solution was ice-cooled and neutralized by adding a 1N aqueous sodium hydroxide solution. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound e-34 (17.1 g). Compounds were identified by LC-MS and ^{1 1} H-NMR analysis.
Compound e-34 (17.1 g) and 90 mL of tetrahydrofuran were ice-cooled with stirring. After 5 minutes of ice cooling, a methyl magnesium iodide-diethyl ether solution (1 mol / L, 50 mL) was added dropwise, and the mixture was heated to 35 ° C. and stirred for 2 hours. Next, the reaction solution was ice-cooled, 90 mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was filtered off, washed with 60 mL of water, and dried under reduced pressure at 50 ° C. to obtain compound e-35 (14.6 g). ) Was obtained. Compounds were identified by ^{1 1} H-NMR analysis.

[Intermediate Synthesis Example 20]

Ethyl 2-methylbutyrate (55.0 g) was added to a t-BuOH (150 mL) solution of compound e-36 (25.0 g), and 6.0 g of sodium hydride (60%, dispersion in Paraffin Liquid) was added. Then, the mixture was stirred at 80 ° C. for 3 hours. Then, the mixture was cooled to room temperature, and 20 mL of concentrated hydrochloric acid was added. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator to obtain compound e-37.
Then, compound e-37 was not purified, 60 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40 ° C. After 1 hour, the reaction solution was ice-cooled and neutralized by adding a 1N aqueous sodium hydroxide solution. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound e-38 (15.9 g). Compounds were identified by LC-MS and ^{1 1} H-NMR analysis.
Compound e-38 (15.9 g) and 90 mL of tetrahydrofuran were ice-cooled with stirring. After 5 minutes of ice cooling, a methyl magnesium iodide-diethyl ether solution (1 mol / L, 50 mL) was added dropwise, and the mixture was heated to 35 ° C. and stirred for 2 hours. Next, the reaction solution was ice-cooled, 90 mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was filtered off, washed with 60 mL of water, and dried under reduced pressure at 50 ° C. to obtain compound e-39 (13.8 g). Got Compounds were identified by ^{1 1} H-NMR analysis.

[Intermediate Synthesis Example 21]

Aluminum chloride anhydride (29.1 g) was added to compound e-40 (25.0 g) synthesized by the method described in Helvetica Chimica Acta, 1981, vol. 64, # 5, p.1672-1681, and 130 It was heated at ° C. for 2 hours. Then, the mixture was allowed to cool to room temperature, and ice water and 1 L of ethyl acetate were added under ice cooling. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound e-41 (20.0 g).
Ethyl pivalate (50.0 g) was added to a solution of compound e-41 (20.0 g) in t-BuOH (150 mL), and 5.5 g of sodium hydride (60%, dispersion in Paraffin Liquid) was added. The mixture was stirred at 80 ° C. for 3 hours. Then, the mixture was cooled to room temperature, and 20 mL of concentrated hydrochloric acid was added. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator to obtain compound e-42.
Then, compound e-42 was not purified, 60 mL of concentrated hydrochloric acid was added, and the mixture was stirred at 40 ° C. After 1 hour, the reaction solution was ice-cooled and neutralized by adding a 1N aqueous sodium hydroxide solution. After separating and washing with ethyl acetate and water, sodium sulfate was added and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound e-43 (15.4 g). Compounds were identified by LC-MS and ^{1 1} H-NMR analysis.
Compound e-43 (15.4 g), phenylboronic acid (11.7 g), tetrakis (triphenylphosphine) palladium (1.0 g), potassium carbonate (60.0 g) in a mixed solution of 50 mL of toluene and 50 mL of water. It was dissolved and heated at 110 ° C. for 12 hours with vigorous stirring. After allowing to cool to room temperature, the mixture was separated and washed with toluene and water, sodium sulfate was added to the organic layer and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound e-44 (12.4 g).
Compound e-44 (12.4 g) and 90 mL of tetrahydrofuran were ice-cooled with stirring. After 5 minutes of ice cooling, a methyl magnesium iodide-diethyl ether solution (1 mol / L, 50 mL) was added dropwise, and the mixture was heated to 35 ° C. and stirred for 2 hours. Next, the reaction solution was ice-cooled, 90 mL of a 20% aqueous perchloric acid solution was added, the precipitated solid was filtered off, washed with 60 mL of water, and dried under reduced pressure at 50 ° C. to obtain compound e-45 (10.4 g). Got Compounds were identified by ^{1 1} H-NMR analysis.

[Intermediate Synthesis Example 22]

Trifluoromethanesulfonic acid (10 g) was added to a mixed solution of methylenecyclohexane (5.2 g) and 1-adamantane carbonyl chloride (Ad-COCl, 22 g) at 0 ° C., and then heated at 90 ° C. for 10 minutes. Then, the reaction solution was cooled to 0 ° C., 150 mL of hexane, 50 mL of ether and 50 mL of water were added and stirred. The precipitated solid was filtered, washed with hexane, and dried under reduced pressure to give compound e-46 (4.2 g). Compounds were identified by ^{1 1} H-NMR analysis.

[Dye synthesis example 1]

Compound e-4 (5.0 g) and compound c-1 (1.0 g) were heated in toluene (20 mL) / methanol (20 mL) at 70 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-1 (2.7 g). Identification of compound d-1 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-1 (2.7 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (3.8 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-25 (4.4 g). Identification of compound z-25 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 2]

Compound e-7 (5.0 g) and compound c-3 (1.2 g) were heated in toluene (20 mL) / methanol (20 mL) at 70 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-2 (2.6 g). Identification of compound d-2 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-2 (2.6 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (3.7 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and silica gel is used. Purification by column chromatography (mobile phase: dichloromethane) gave compound z-130 (4.2 g). Identification of compound z-130 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 3]

Compound e-8 (5.0 g) and compound c-4 (1.1 g) were heated in toluene (20 mL) / methanol (20 mL) at 90 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-3 (2.6 g). Identification of compound d-3 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-3 (2.6 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.3 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and are stirred on a silica gel column. Purification by chromatography (mobile phase: dichloromethane) gave compound z-184 (4.5 g). Identification of compound z-184 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 4]

Compound e-9 (5.0 g) and compound c-1 (1.1 g) were heated in toluene (20 mL) / methanol (20 mL) at 60 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-4 (3.2 g). Identification of compound d-4 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-4 (3.2 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.9 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-191 (4.9 g). Identification of compound z-191 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 5]

Compound e-10 (5.0 g) and compound c-4 (0.98 g) were heated in toluene (20 mL) / methanol (20 mL) at 50 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-5 (3.5 g). Identification of compound d-5 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-5 (3.5 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.7 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z- 211 (5.3 g). Identification of compound z-211 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 6]

Compound e-14 (5.0 g), compound c-6 (3.5 g) and sodium acetate (1.4 g) were heated in acetic anhydride (30 mL) at 100 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: methanol) to obtain compound d-6 (3.7 g). Identification of compound d-6 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-6 (3.7 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.9 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-273 (5.5 g). Identification of compound z-273 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 7]

Compound e-15 (5.0 g), compound c-6 (2.8 g) and sodium acetate (1.1 g) were heated in acetic anhydride (30 mL) at 100 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: methanol) to obtain compound d-7 (3.7 g). Identification of compound d-7 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-7 (3.7 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex were stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and silica gel column chromatography (mobile phase) was performed. : Purification with dichloromethane) gave compound z-277 (5.4 g). Identification of compound z-277 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 8]

Compound e-16 (5.0 g), compound c-6 (4.0 g) and sodium acetate (1.5 g) were heated in acetic anhydride (30 mL) at 100 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: methanol) to obtain compound d-8 (3.5 g). Identification of compound d-8 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-8 (3.5 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (5.1 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-298 (5.6 g). Identification of compound z-298 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 9]

Compound e-22 (5.0 g) and compound c-1 (1.0 g) were heated in toluene (20 mL) / methanol (20 mL) at 60 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-9 (2.9 g). Identification of compound d-9 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-9 (2.9 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.0 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-311 (4.5 g). Identification of compound z-311 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 10]

Compound e-28 (5.0 g) and compound c-1 (1.0 g) were heated in toluene (20 mL) / methanol (20 mL) at 60 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-10 (3.0 g). Identification of compound d-10 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-10 (3.0 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.1 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-332 (4.1 g). Identification of compound z-332 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 11]

Compound e-32 (5.0 g) and compound c-1 (1.1 g) were heated in toluene (20 mL) / methanol (20 mL) at 60 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-11 (3.0 g). Identification of compound d-11 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-11 (3.0 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.5 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-359 (4.8 g). Identification of compound z-359 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 12]

Compound e-35 (5.0 g) and compound c-4 (1.1 g) were heated in toluene (20 mL) / methanol (20 mL) at 60 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-12 (2.6 g). Identification of compound d-12 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-12 (2.6 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.4 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and silica gel is used. Purification by column chromatography (mobile phase: dichloromethane) gave compound z-128 (4.6 g). Identification of compound z-128 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 13]

Compound e-9 (5.0 g) and compound c-4 (1.1 g) were heated in toluene (20 mL) / methanol (20 mL) at 60 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-13 (3.1 g). Identification of compound d-13 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-13 (3.1 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.8 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-199 (4.9 g). Identification of compound z-199 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 14]

Compound e-8 (5.0 g) and compound c-1 (1.0 g) were heated in toluene (20 mL) / methanol (20 mL) at 90 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-14 (3.0 g). Identification of compound d-14 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-14 (3.0 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.7 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-153 (5.0 g). Identification of compound z-153 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 15]

Compound e-39 (5.0 g) and compound c-8 (2.5 g) were heated in toluene (20 mL) / methanol (20 mL) at 90 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-15 (3.5 g). Identification of compound d-15 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-15 (3.5 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (4.7 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-72 (5.3 g). Identification of compound z-72 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 16]

Compound e-45 (5.0 g) and compound c-1 (0.9 g) were heated in toluene (20 mL) / methanol (20 mL) at 90 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-16 (6.0 g). Identification of compound d-16 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-16 (6.0 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (7.3 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-360 (8.7 g). Identification of compound z-360 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 17]

Compound e-28 (5.0 g), glutaconaldehyde dianyl hydrochloride (5.4 g) and sodium acetate (1.2 g) were heated in acetic anhydride (30 mL) at 100 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: methanol) to obtain compound d-17 (5.4 g). Identification of compound d-17 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-17 (5.4 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (8.4 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-362 (8.7 g). Identification of compound z-362 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 18]

Compound e-45 (5.0 g), glutaconaldehyde dianyl hydrochloride (4.7 g) and sodium acetate (1.1 g) were heated in acetic anhydride (30 mL) at 100 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: methanol) to obtain compound d-18 (4.7 g). Identification of compound d-18 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-18 (4.7 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (6.3 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-363 (7.0 g). Identification of compound z-363 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 19]

Compound e-46 (5.0 g) and compound c-4 (0.6 g) were heated in toluene (20 mL) / methanol (20 mL) at 90 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-19 (6.0 g). Identification of compound d-19 was performed by 1H-NMR and LC-MS.
Compound d-19 (6.1 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (5.6 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-364 (8.5 g). Identification of compound z-364 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 20]

Compound e-28 (5.0 g) and compound c-9 (0.9 g) were heated in toluene (20 mL) / methanol (20 mL) at 90 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-20 (6.7 g). Identification of compound d-20 was performed by 1H-NMR and LC-MS.
Compound d-20 (6.7 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (9.5 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and are stirred on a silica gel column. Purification by chromatography (mobile phase: dichloromethane) gave compound z-365 (11.1 g). Identification of compound z-365 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 21]

Compound e-45 (5.0 g) and compound c-9 (0.8 g) were heated in toluene (20 mL) / methanol (20 mL) at 90 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-21 (5.9 g). Identification of compound d-21 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-21 (5.9 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (7.3 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-366 (8.5 g). Identification of compound z-366 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 22]

Compound e-28 (5.0 g) and compound c-10 (1.4 g) were heated in toluene (20 mL) / methanol (20 mL) at 90 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-22 (5.3 g). Identification of compound d-22 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-22 (5.3 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (6.8 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-376 (8.4 g). Identification of compound z-376 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Dye synthesis example 23]

Compound e-45 (5.0 g) and compound c-10 (1.3 g) were heated in toluene (20 mL) / methanol (20 mL) at 90 ° C. for 1 hour. After allowing to cool at room temperature, the solvent was removed by an evaporator, and purification was performed by silica gel column chromatography (mobile phase: hexane / ethyl acetate = 3/1) to obtain compound d-23 (4.3 g). Identification of compound d-23 was performed by ^{1 1} H-NMR and LC-MS.
Compound d-23 (4.3 g) and lithium tetrakis (pentafluorophenyl) borate diethyl ether complex (5.4 g) are stirred in dichloromethane (30 mL) / water (30 mL) at room temperature for 8 hours, and the silica gel column is used. Purification by chromatography (mobile phase: dichloromethane) gave compound z-368 (6.7 g). Identification of compound z-368 was performed by ^{1 1} H-NMR, ¹⁹ F-NMR and LC-MS.

[Resin Synthesis Example 1]
8-Methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-ene (hereinafter also referred to as "DNM") 100 parts by mass, 1-hexene (molecular weight modifier) 18 parts by mass and toluene (solvent for ring-opening polymerization reaction) 300 parts by mass, nitrogen. It was placed in a replaced reaction vessel and the solution was heated to 80 ° C. Next, 0.2 parts by mass of a toluene solution of triethylaluminum (0.6 mol / liter) and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) 0 were added to the solution in the reaction vessel as a polymerization catalyst. .9 parts by mass was added, and the solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts by mass of the ring-opening polymer solution obtained above was charged into an autoclave, and 0.12 parts by mass of _{RuHCl (CO) [P (C 6} H ₅ ) ₃ ] _{3 was added to the ring-opening polymer solution.} Then, under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C., the hydrogenation reaction was carried out by heating and stirring for 3 hours. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released. The obtained reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter, also referred to as "resin A"). The obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.

[Resin Synthesis Example 2]
35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g of potassium carbonate in a 3 L four-necked flask. (0.300 mol), 443 g of N, N-dimethylacetamide and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask. Then, after nitrogen substitution in the flask, the obtained solution was reacted at 140 ° C. for 3 hours, and the water produced was removed from the Dean-Stark apparatus at any time. When the formation of water was no longer observed, the temperature was gradually raised to 160 ° C., and the reaction was carried out at the same temperature for 6 hours. Then, the mixture was cooled to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filter medium was vacuum dried at 60 ° C. overnight to obtain a white powder (hereinafter, also referred to as “resin B”) (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.

[Resin Synthesis Example 3]
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen introduction tube, dripping funnel with side tube, Dean Stark tube and cooling tube, 1,4-bis (4-amino-α, 27.66 g (0.08 mol) of α-dimethylbenzyl) benzene and 7.38 g (0.02 mol) of 4,4′-bis (4-aminophenoxy) biphenyl were added, and 68.65 g of γ-butyrolactone and N, It was dissolved in 17.16 g of N-dimethylacetamide. The resulting solution was cooled to 5 ° C. using an ice-water bath and kept at the same temperature with 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and an imidization catalyst. 0.50 g (0.005 mol) of triethylamine was added all at once. After completion of the addition, the temperature was raised to 180 ° C., and the distillate was refluxed for 6 hours while being distilled off as needed. After completion of the reaction, the mixture is air-cooled until the internal temperature reaches 100 ° C., then 143.6 g of N, N-dimethylacetamide is added to dilute the reaction, and the mixture is cooled with stirring to obtain a polyimide solution 264 having a solid content concentration of 20% by mass. .16 g was obtained. A part of this polyimide solution was poured into 1 L of methanol to precipitate the polyimide. The polyimide separated by filtration was washed with methanol and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (hereinafter, also referred to as "resin C"). The IR spectrum of the obtained resin C was measured, 1704 cm ^-1 characteristic of imido group, absorption of 1770 cm ^-1 were observed. The glass transition temperature (Tg) of the resin C was 310 ° C., and the logarithmic viscosity was measured and found to be 0.87.

[Example 1]
[Preparation of base material]
In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.04 parts by mass of the following compound (z-25) (absorption maximum wavelength in dichloromethane, 933 nm), and compound (X) as compound (Z). The following compound (x-1) (absorption maximum wavelength 711 nm in dichloromethane) 0.06 parts by mass, the following compound (x-2) (absorption maximum wavelength 738 nm in dichloromethane) 0.07 parts by mass, and dichloromethane. Was added to prepare a solution having a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 8 hours to obtain a resin layer (1) having a thickness of 0.1 mm, a length of 210 mm and a width of 210 mm.

-Compound (z-25)

-Compound (x-1)

-Compound (x-2)

The following resin composition (1) is applied to one side of the obtained resin layer (1) with a bar coater so that the thickness of the obtained resin layer (2) is 3 μm, and heated in an oven at 70 ° C. for 2 minutes. The solvent was volatilized and removed. ^{Next, exposure (exposure amount 500 mJ / cm 2} , illuminance: 200 mW / cm ² ) is performed using a UV conveyor type exposure machine (manufactured by Eye Graphics Co., Ltd., eye ultraviolet curing device, model US2-X0405, 60 Hz). , The resin composition (1) was cured to form a resin layer (2) on the resin layer (1). Similarly, a resin layer (2) made of the resin composition (1) was formed on the other surface of the resin layer (1). As a result, a base material having the resin layer (2) containing no compound (Z) on both sides of the resin layer (1) containing the compound (Z) was obtained.

Resin composition (1): 60 parts by mass of tricyclodecanedimethanol acrylate, 40 parts by mass of dipentaerythritol hexaacrylate, 5 parts by mass of 1-hydroxycyclohexylphenyl ketone, and methyl ethyl ketone (solvent, solid content concentration in the obtained composition). (Used so as to be 30% by mass)

The spectral characteristics of the compound (z-25) in a dichloromethane solution and the Xa, Ta and Tb of the obtained base material were measured. The results are shown in Tables 10 and 11, respectively. Moreover, the spectral characteristics of the obtained base material are shown in FIG.

The requirements (A) to (D) in Table 10 indicate the requirements (A) to (D) in the column of <Compound (Z)>. In Table 10, in the transmission spectrum measured using a solution in which each compound is dissolved in dichloromethane (however, the transmission spectrum is a spectrum in which the transmittance at the absorption maximum wavelength is 10%), the wavelength is 950. The case of having a wavelength having a transmittance of 85% in the range of about 1150 nm was evaluated as ◯, and the case of not having the wavelength was evaluated as x.

<Heat resistance evaluation>
The base material obtained in the preparation of the base material was heated in an oven preheated to 155 ° C. for 7 hours, and the Tc and Td of the base material after this heating test were measured. The results are shown in Table 11.

<UV resistance evaluation>
A UV exposure machine (manufactured by Iwasaki Electric Co., Ltd., eye ultraviolet curing device US2-KO4501, illuminance: 180 mW / cm ² , irradiation amount: 560 mJ / cm ² ) was used as the base material obtained in the preparation of the base material. UV was irradiated, and Te and Tf of the base material after this UV irradiation were measured. The results are shown in Table 11.

[Manufacturing of optical filter]
A dielectric multilayer film (I) was formed on one side of the substrate obtained by producing the substrate, and a dielectric multilayer film (II) was further formed on the other surface of the substrate, and the thickness was about 0. A 110 mm optical filter was obtained.
The spectral transmittance measured from the vertical direction of the obtained optical filter was measured, and Tg and Th were determined. The results are shown in FIG. 2 and Table 11.

The dielectric multilayer film (I) is _{a laminated body in which silica (SiO 2} ) layers and titanium (TiO ₂ ) layers are alternately laminated at a vapor deposition temperature of 100 ° C. (28 layers in total). The dielectric multilayer film (II) is _{a laminated body in which silica (SiO 2} ) layers and titanium (TiO ₂ ) layers are alternately laminated at a vapor deposition temperature of 100 ° C. (24 layers in total).
In both the dielectric multilayer films (I) and (II), the silica layer and the titania layer are arranged in the order of the titania layer, the silica layer, the titania layer, ..., the silica layer, the titania layer, and the silica layer from the substrate side. The outermost layer of the optical filter was a silica layer.

Regarding the thickness and number of layers of each layer, the wavelength-dependent characteristics of the refractive index of the base material and the compounds (Z) and (X) used so that good transmittance in the visible region and reflection performance in the near infrared region can be achieved. Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center) according to the absorption characteristics of. When optimizing, in this embodiment, the input parameters (Target values) to the software are as shown in Table 8 below.

As a result of film configuration optimization, the dielectric multilayer film (I) is laminated with 28 layers in which silica layers having a physical film thickness of about 32 to 159 nm and titania layers having a physical film thickness of about 9 to 94 nm are alternately laminated. A multi-layer vapor deposition film having 24 layers, in which a dielectric multilayer film (II) is alternately laminated with a silica layer having a physical film thickness of about 39 to 193 nm and a titania layer having a physical film thickness of about 12 to 117 nm. And said. An example of the optimized film configuration is shown in Table 9 below.

[Example 2]
In Example 1, 0.04 parts by mass of the following compound (z-130) (absorption maximum wavelength in dichloromethane) was used in place of 0.04 parts by mass of compound (z-25), and compound (x). -1) 0.06 parts by mass of the following compound (x-3) (absorption maximum wavelength 700 nm in dichloromethane) was used instead of 0.06 parts by mass, and 0.07 parts by mass of compound (x-2). The same as in Example 1 except that the following compound (x-4) (absorption maximum wavelength in dichloromethane, 732 nm) was used in an amount of 0.07 parts by mass, and resin B was used instead of resin A. To obtain a base material.
In the same manner as in Example 1, the spectral characteristics of the compound (z-130) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-130)

-Compound (x-3)

-Compound (x-4)

Subsequently, as in Example 1, a total of 28 dielectric multilayer films (I _{) in which silica (SiO 2} ) layers and titanium (TiO ₂ ) layers are alternately laminated on one side of the obtained base material. ), And a total of 24 layers of dielectric multilayer film (II) formed by alternately laminating _{silica (SiO 2} ) layers and titania (TiO ₂ ) layers on the other surface of the base material. , An optical filter having a thickness of about 0.110 mm was obtained.
The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the base material and the like, as in Example 1.
The spectral transmittance measured from the vertical direction of the obtained optical filter was measured, and Tg and Th were determined. The results are shown in Table 11.

[Example 3]
In Example 1, 0.05 parts by mass of the following compound (z-184) (absorption maximum wavelength in dichloromethane, 1065 nm) was used instead of 0.04 parts by mass of the compound (z-25), and the compound (x). -2) Based on the same method as in Example 1 except that 0.07 parts by mass of compound (x-4) was used instead of 0.07 parts by mass and resin C was used instead of resin A. I got the material.
In the same manner as in Example 1, the spectral characteristics of compound (z-184) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-184)

[Example 4]
In Example 1, 0.05 parts by mass of the following compound (z-191) (absorption maximum wavelength in dichloromethane, 861 nm) was used instead of 0.04 parts by mass of the compound (z-25), and the compound (x). -1) Example 1 except that 0.06 parts by mass of compound (x-3) was used instead of 0.06 parts by mass and Acriviewer manufactured by Nippon Catalyst Co., Ltd. was used instead of resin A. A substrate was obtained in the same manner as above.
In the same manner as in Example 1, the spectral characteristics of compound (z-191) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-191)

[Example 5]
In Example 1, 0.05 parts by mass of the following compound (z-211) (absorption maximum wavelength in dichloromethane, 976 nm) was used instead of 0.04 parts by mass of the compound (z-25). A base material was obtained in the same manner as in Example 1 except that Pure Ace manufactured by Teijin Limited was used instead.
In the same manner as in Example 1, the spectral characteristics of compound (z-211) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-211)

[Example 6]
A substrate was obtained in the same manner as in Example 1 except that compound (x-1) and compound (x-2) were not used in Example 1.
Xa, Ta to Tf of the obtained base material were determined in the same manner as in Example 1. The results are shown in Table 11.

[Example 7]
A substrate was obtained in the same manner as in Example 2 except that compound (x-3) and compound (x-4) were not used in Example 2.
Xa, Ta to Tf of the obtained base material were determined in the same manner as in Example 2. The results are shown in Table 11.

[Example 8]
A substrate was obtained in the same manner as in Example 3 except that compound (x-1) and compound (x-4) were not used in Example 3.
Xa, Ta to Tf of the obtained base material were determined in the same manner as in Example 3. The results are shown in Table 11.

[Example 9]
In Example 4, 0.06 parts by mass of the following compound (z-273) (absorption maximum wavelength in dichloromethane) was used instead of 0.05 parts by mass of compound (z-191). A substrate was obtained in the same manner as in Example 4.
In the same manner as in Example 4, the spectral characteristics of compound (z-273) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-273)

[Example 10]
In Example 5, the following compound (z-277) (absorption maximum wavelength in dichloromethane, 892 nm) was used in place of 0.05 parts by mass, except that 0.05 parts by mass was used. A substrate was obtained in the same manner as in Example 5.
In the same manner as in Example 5, the spectral characteristics of compound (z-277) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-277)

[Example 11]
In Example 1, 0.04 parts by mass of the following compound (z-298) (absorption maximum wavelength in dichloromethane, 1016 nm) was used instead of 0.04 parts by mass of compound (z-25). A substrate was obtained in the same manner as in Example 1.
In the same manner as in Example 1, the spectral characteristics of compound (z-298) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-298)

[Example 12]
In Example 2, 0.04 parts by mass of the following compound (z-311) (absorption maximum wavelength in dichloromethane) was used instead of 0.04 parts by mass of the compound (z-130). A substrate was obtained in the same manner as in Example 2.
In the same manner as in Example 2, the spectral characteristics of compound (z-311) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-311)

[Example 13]
In Example 3, 0.04 parts by mass of the following compound (z-332) (absorption maximum wavelength in dichloromethane, 932 nm) was used instead of 0.05 parts by mass of compound (z-184). A substrate was obtained in the same manner as in Example 3.
In the same manner as in Example 3, the spectral characteristics of compound (z-332) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-332)

[Example 14]
In Example 1, 0.04 parts by mass of the following compound (z-359) (absorption maximum wavelength in dichloromethane) was used instead of 0.04 parts by mass of compound (z-25). A substrate was obtained in the same manner as in Example 1.
In the same manner as in Example 1, the spectral characteristics of compound (z-359) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-359)

[Example 15]
In Example 1, 0.04 parts by mass of the following compound (z-360) (absorption maximum wavelength in dichloromethane, 943 nm) was used instead of 0.04 parts by mass of the compound (z-25), and the compound (x). -1) A substrate was obtained in the same manner as in Example 1 except that 0.06 parts by mass of compound (x-3) was used instead of 0.06 parts by mass.
In the same manner as in Example 1, the spectral characteristics of compound (z-360) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-360)

[Example 15-1]
In Example 1, 0.04 parts by mass of the following compound (z-362) (absorption maximum wavelength in dichloromethane, 893 nm) was used instead of 0.04 parts by mass of the compound (z-25). A base material was obtained in the same manner as in Example 1 except that Pure Ace manufactured by Teijin Limited was used instead.
In the same manner as in Example 1, the spectral characteristics of compound (z-362) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-362)

[Example 15-2]
In Example 1, 0.04 parts by mass of the following compound (z-363) (absorption maximum wavelength in dichloromethane) was used instead of 0.04 parts by mass of compound (z-25). A substrate was obtained in the same manner as in Example 1.
In the same manner as in Example 1, the spectral characteristics of compound (z-363) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-363)

[Example 15-3]
In Example 1, 0.04 parts by mass of the following compound (z-364) (absorption maximum wavelength in dichloromethane, 941 nm) was used instead of 0.04 parts by mass of the compound (z-25). A substrate was obtained in the same manner as in Example 1 except that resin B was used instead.
In the same manner as in Example 1, the spectral characteristics of compound (z-364) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-364)

[Example 15-4]
In Example 1, 0.04 parts by mass of the following compound (z-365) (absorption maximum wavelength in dichloromethane) was used instead of 0.04 parts by mass of the compound (z-25). A substrate was obtained in the same manner as in Example 1 except that resin C was used instead.
In the same manner as in Example 1, the spectral characteristics of compound (z-365) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-365)

[Example 15-5]
Except for the fact that in Example 1, 0.04 parts by mass of the following compound (z-366) (absorption maximum wavelength in dichloromethane) was used instead of 0.04 parts by mass of the compound (z-25). A substrate was obtained in the same manner as in Example 1.
In the same manner as in Example 1, the spectral characteristics of compound (z-366) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-366)

[Example 15-6]
Except for the fact that in Example 1, 0.04 parts by mass of the following compound (z-376) (absorption maximum wavelength in dichloromethane, 942 nm) was used instead of 0.04 parts by mass of the compound (z-25). A substrate was obtained in the same manner as in Example 1.
In the same manner as in Example 1, the spectral characteristics of compound (z-376) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-376)

[Example 15-7]
Except for the fact that in Example 1, 0.04 parts by mass of the following compound (z-368) (absorption maximum wavelength in dichloromethane) was used instead of 0.04 parts by mass of compound (z-25). A substrate was obtained in the same manner as in Example 1.
In the same manner as in Example 1, the spectral characteristics of compound (z-368) in dichloromethane were measured, and Xa, Ta to Tf of the obtained substrate were measured. The results are shown in Tables 10 and 11, respectively.

-Compound (z-368)

[Example 16]
In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.56 parts by mass of the compound (x-1), 0.68 parts by mass of the compound (x-2), and dichloromethane as the compound (X). In addition, a solution having a resin concentration of 20% by mass was prepared and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (E16-1).
Similarly, 100 parts by mass of resin A, 0.42 parts by mass of the following compound (z-128) (maximum absorption wavelength in dichloromethane: 942 nm), and dichloromethane are added as compound (Z), and the resin concentration is 20 parts by mass. % Was prepared and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (E16-2).

-Compound (z-128)

The following resin composition (2) is applied to both sides of a transparent glass support "OA-10G" (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd., which is cut to a size of 200 mm × 200 mm, and the thickness after drying is about. After applying with spin coating so as to be 1 μm, the solvent is volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes to form a glass support and a coating resin layer (1) and a coating resin layer (2) described later. An adhesive layer that functions as an adhesive layer was formed.

Next, using a spin coater, a resin solution (E16-1) was applied to one side of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, and the temperature was 80 ° C. on a hot plate. The solvent was volatilized and removed by heating for 5 minutes to form a coating resin layer (2). Further, using a spin coater, a resin solution (E16-2) was applied to the other surface of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, and 80 on a hot plate. The solvent was volatilized and removed by heating at ° C. for 5 minutes to form the coating resin layer (1). As a result, a base material having a thickness of 222 μm was obtained by laminating a resin layer containing the compound (Z) on one surface of the glass support and laminating a resin layer containing no compound (Z) on the other surface.
In the same manner as in Example 1, the spectral characteristics of the compound (z-128) in dichloromethane were measured, and Xa, Ta to Tf of the obtained base material were determined. The results are shown in Tables 10 and 12.

Resin composition (2): Isocyanuric acid ethylene oxide-modified triacrylate (trade name: Aronix M-315, manufactured by Toa Synthetic Co., Ltd.) 30 parts by mass, 1,9-nonanediol diacrylate 20 parts by mass, methacrylic acid 20 parts by mass Parts, 30 parts by mass of glycidyl methacrylate, 5 parts by mass of 3-glycidoxypropyltrimethoxysilane, 5 parts by mass of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by BASF Japan Co., Ltd.) and Sun Aid SI-110 main agent ( A composition obtained by mixing 1 part by mass of Sanshin Kagaku Kogyo Co., Ltd., dissolving it in propylene glycol monomethyl ether acetate so that the solid content concentration becomes 50% by mass, and then filtering it with a millipore filter having a pore size of 0.2 μm.

Subsequently, as in Example 1, a total of 28 dielectric multilayer films (I _{) in which silica (SiO 2} ) layers and titanium (TiO ₂ ) layers are alternately laminated on one side of the obtained base material. ), And a total of 24 layers of dielectric multilayer film (II) formed by alternately laminating _{silica (SiO 2} ) layers and titania (TiO ₂ ) layers on the other surface of the base material. , An optical filter having a thickness of about 0.226 mm was obtained.
The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the base material and the like, as in Example 1.
The spectral transmittance measured from the vertical direction of the obtained optical filter was measured, and Tg and Th were determined. The results are shown in Table 12.

[Example 17]
In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.68 parts by mass of the compound (x-2), 0.55 parts by mass of the compound (x-3), and dichloromethane as the compound (X). In addition, a solution having a resin concentration of 20% by mass was prepared and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (E17-1).
Similarly, 100 parts by mass of resin A, 0.45 parts by mass of the following compound (z-199) (maximum absorption wavelength in dichloromethane: 884 nm), and dichloromethane are added as compound (Z), and the resin concentration is 20 parts by mass. % Was prepared and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (E17-2).

-Compound (z-199)

A resin solution (E17-1) is applied to one side of a resin support (Zeonoa film ZF-16, manufactured by Nippon Zeon Corporation, 100 μm thickness) so that the thickness after drying is 10 μm, and the thickness is 8 at 80 ° C. After drying for hours, it was further dried in vacuum at 150 ° C. for 8 hours to form the coating resin layer (2). Further, a resin solution (E17-2) was applied to the other surface of the resin support so as to have a thickness of 10 μm after drying, dried at 80 ° C. for 8 hours, and then further in vacuum at 150 ° C. It was dried for 8 hours to form a coating resin layer (1). As a result, a substrate having a thickness of 120 μm having a resin layer containing the compound (Z) on one surface of the resin support and a resin layer not containing the compound (Z) on the other surface was obtained.
In the same manner as in Example 1, the spectral characteristics of compound (z-199) in dichloromethane were measured, and Xa, Ta to Tf of the obtained base material were determined. The results are shown in Tables 10 and 12.

Subsequently, as in Example 1, a total of 28 dielectric multilayer films (I _{) in which silica (SiO 2} ) layers and titanium (TiO ₂ ) layers are alternately laminated on one side of the obtained base material. ), And a total of 24 layers of dielectric multilayer film (II) formed by alternately laminating _{silica (SiO 2} ) layers and titania (TiO ₂ ) layers on the other surface of the base material. , An optical filter having a thickness of about 0.124 mm was obtained.
The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the base material and the like, as in Example 1.
The spectral transmittance measured from the vertical direction of the obtained optical filter was measured, and Tg and Th were determined. The results are shown in Table 12.

[Example 18]
To the container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.52 parts by mass of the following compound (z-153) (absorption maximum wavelength in dichloromethane: 1054 nm), and dichloromethane as the compound (Z) were added. A solution having a resin concentration of 20% by mass was prepared and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (E18).

-Compound (z-153)

The resin composition (2) is applied to one side of an absorbent glass support "BS-6" (thickness 200 μm) manufactured by Matsunami Glass Ind. Co., Ltd., which is cut to a size of 200 mm × 200 mm, and the film thickness after drying is increased. After applying with spin coating to a thickness of about 1 μm, the solvent is volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes to function as an adhesive layer between the absorbent glass support and the coating resin layer (1) described later. An adhesive layer was formed.

Next, the resin solution (E18) is applied onto the adhesive layer using a spin coater so that the film thickness after drying is 10 μm, and the solvent is volatilized by heating on a hot plate at 80 ° C. for 5 minutes. It was removed to form a coating resin layer (1). As a result, a base material having a thickness of 211 μm was obtained by laminating a resin layer containing the compound (Z) on one side of the absorbent glass support.
In the same manner as in Example 1, the spectral characteristics of compound (z-153) in dichloromethane were measured, and Xa, Ta to Tf of the obtained base material were determined. The results are shown in Tables 10 and 12.

Subsequently, as in Example 1, a total of 28 dielectric multilayer films (I _{) in which silica (SiO 2} ) layers and titanium (TiO ₂ ) layers are alternately laminated on one side of the obtained base material. ), And a total of 24 layers of dielectric multilayer film (II) formed by alternately laminating _{silica (SiO 2} ) layers and titania (TiO ₂ ) layers on the other surface of the base material. , An optical filter having a thickness of about 0.215 mm was obtained.
The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the base material and the like, as in Example 1.
The spectral transmittance measured from the vertical direction of the obtained optical filter was measured, and Tg and Th were determined. The results are shown in Table 12.

[Example 19]
In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.57 parts by mass of the compound (x-3), 0.68 parts by mass of the compound (x-4), and dichloromethane as the compound (X). In addition, a solution having a resin concentration of 20% by mass was prepared and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (E19-1).
Similarly, 100 parts by mass of the resin A, 0.52 parts by mass of the compound (z-211) as the compound (Z), and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass and having a pore size of 5 μm. Filtration was carried out with a millipore filter to obtain a resin solution (E19-2).

The resin composition (2) is applied to both sides of a transparent glass support "OA-10G" (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd., which is cut to a size of 200 mm × 200 mm, and the thickness after drying is about. After applying with spin coating so as to be 1 μm, the solvent is volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes, and the glass support and the coating resin layer (1) and the coating resin layer (2) described later will be described later. ) And an adhesive layer that functions as an adhesive layer was formed.

Next, using a spin coater, a resin solution (E19-1) was applied to one side of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, and the temperature was 80 ° C. on a hot plate. The solvent was volatilized and removed by heating for 5 minutes to form a coating resin layer (2). Further, using a spin coater, a resin solution (E19-2) was applied to the other surface of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, and 80 on a hot plate. The solvent was volatilized and removed by heating at ° C. for 5 minutes to form the coating resin layer (1). As a result, a base material having a thickness of 222 μm was obtained by laminating a resin layer containing the compound (Z) on one surface of the glass support and laminating a resin layer containing no compound (Z) on the other surface.
Xa, Ta to Tf of the obtained base material were determined in the same manner as in Example 1. The results are shown in Table 12.

[Example 20]
In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.57 parts by mass of the compound (x-3), 0.68 parts by mass of the compound (x-4), and dichloromethane as the compound (X). In addition, a solution having a resin concentration of 20% by mass was prepared and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (E20-1).
Similarly, 100 parts by mass of resin A, 0.42 parts by mass of the following compound (z-72) (maximum absorption wavelength in dichloromethane: 937 nm), and dichloromethane are added as compound (Z), and the resin concentration is 20 parts by mass. % Was prepared and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (E20-2).

-Compound (z-72)

A resin solution (E20-1) is applied to one side of a resin support (Zeonoa film ZF-16, manufactured by Nippon Zeon Corporation, 100 μm thickness) so that the thickness after drying is 10 μm, and the thickness is 8 at 80 ° C. After drying for hours, it was further dried in vacuum at 150 ° C. for 8 hours to obtain a coated resin layer (2). Further, a resin solution (E20-2) was applied to the other surface of the resin support so that the thickness after drying was 10 μm, dried at 80 ° C. for 8 hours, and then further in vacuum at 150 ° C. Was dried for 8 hours to form a coating resin layer (1). As a result, a substrate having a thickness of 120 μm having a resin layer containing the compound (Z) on one surface of the resin support and a resin layer not containing the compound (Z) on the other surface was obtained.
In the same manner as in Example 1, the spectral characteristics of compound (z-72) in dichloromethane were measured, and Xa, Ta to Tf of the obtained base material were determined. The results are shown in Tables 10 and 12.

[Example 21]
In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.56 parts by mass of the compound (x-1), 0.68 parts by mass of the compound (x-2), and dichloromethane as the compound (X). In addition, a solution having a resin concentration of 20% by mass was prepared and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (E21-1).
Similarly, 100 parts by mass of the resin A, 0.45 parts by mass of the compound (z-311) as the compound (Z), and dichloromethane were added to prepare a solution having a resin concentration of 20% by mass and having a pore size of 5 μm. Filtration was carried out with a millipore filter to obtain a resin solution (E21-2).

The resin composition (2) is applied to both sides of a transparent glass support "OA-10G" (thickness 200 μm) manufactured by Nippon Electric Glass Co., Ltd., which is cut to a size of 200 mm × 200 mm, and the thickness after drying is about. After applying with spin coating so as to be 1 μm, the solvent is volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes to form a glass support and a coating resin layer (1) and a coating resin layer (2) described later. An adhesive layer that functions as an adhesive layer was formed.

Next, using a spin coater, a resin solution (E21-1) was applied to one side of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, and the temperature was 80 ° C. on a hot plate. The solvent was volatilized and removed by heating for 5 minutes to form a coating resin layer (2). Further, using a spin coater, a resin solution (E21-2) was applied to the other surface of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, and 80 on a hot plate. The solvent was volatilized and removed by heating at ° C. for 5 minutes to form the coating resin layer (1). As a result, a base material having a thickness of 222 μm was obtained by laminating a resin layer containing the compound (Z) on one surface of the glass support and laminating a resin layer containing no compound (Z) on the other surface.
Xa, Ta to Tf of the base material obtained in the same manner as in Example 1 were determined. The results are shown in Tables 10 and 12.

[Comparative Example 1]
A substrate was obtained in the same manner as in Example 1 except that compound (Z) was not used in Example 1.
Xa and Ta to Tf were determined in the same manner as in Example 1 except that this base material was used. The results are shown in Table 11.

[Comparative Example 2]
In Example 2, 0.06 parts by mass of compound (x-1), 0.07 parts by mass of compound (x-4), and compound (x-5) were used as compound (X) without using compound (Z). A substrate was obtained in the same manner as in Example 2 except that 0.06 parts by mass (absorption maximum wavelength in dichloromethane, 1095 nm) was used.
In the same manner as in Example 2, the spectral characteristics of the compound (x-5) in dichloromethane were measured, and Xa, Ta to Tf of the obtained base material were determined. The results are shown in Tables 10 and 11, respectively. Further, the spectral characteristics of the obtained base material are shown in FIG.

-Compound (x-5)

Subsequently, as in Example 1, a total of 28 dielectric multilayer films (I _{) in which silica (SiO 2} ) layers and titanium (TiO ₂ ) layers are alternately laminated on one side of the obtained base material. ), And a total of 24 layers of dielectric multilayer film (II) formed by alternately laminating _{silica (SiO 2} ) layers and titania (TiO ₂ ) layers on the other surface of the base material. , An optical filter having a thickness of about 0.110 mm was obtained.
The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the base material and the like, as in Example 1.
The spectral transmittance measured from the vertical direction of the obtained optical filter was measured, and Tg and Th were determined. The results are shown in Table 11. Further, the spectral characteristics of the obtained optical filter are shown in FIG.

[Comparative Example 3]
In Example 3, 0.07 parts by mass of compound (x-2), 0.06 parts by mass of compound (x-3), and compound (x-6) were used as compound (X) without using compound (Z). A substrate was obtained in the same manner as in Example 3 except that 0.05 parts by mass (absorption maximum wavelength in dichloromethane, 835 nm) was used.
In the same manner as in Example 3, the spectral characteristics of the compound (x-6) in dichloromethane were measured, and Xa, Ta to Tf of the obtained base material were determined. The results are shown in Tables 10 and 11, respectively.

-Compound (x-6)

[Comparative Example 4]
In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.29 parts by mass of the compound (x-1), 0.32 parts by mass of the compound (x-4), and the compound (x) as the compound (X). -5) A solution having a resin concentration of 20% by mass was prepared by adding 0.30 parts by mass and dichloromethane, and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (H4-1).

Next, a resin solution (H4-1) was applied to one side of the adhesive layer using a spin coater so that the film thickness after drying was 10 μm, and heated on a hot plate at 80 ° C. for 5 minutes. The solvent was volatilized and removed to form the coating resin layer (1). Further, using a spin coater, a resin solution (H4-1) was applied to the other surface of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, and 80 on a hot plate. The solvent was volatilized and removed by heating at ° C. for 5 minutes to form the coating resin layer (2). As a result, a substrate having a thickness of 222 μm was obtained by laminating a resin layer containing no compound (Z) on both sides of the glass support.
Xa, Ta to Tf of the obtained base material were determined in the same manner as in Example 1. The results are shown in Table 12.

[Comparative Example 5]
In a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.27 parts by mass of the compound (x-3), 0.31 parts by mass of the compound (x-4), and dichloromethane as the compound (X). In addition, a solution having a resin concentration of 20% by mass was prepared and filtered through a millipore filter having a pore size of 5 μm to obtain a resin solution (H5-1).

A resin solution (H5-1) is applied to one side of a resin support (Zeonoa film ZF-16, manufactured by Nippon Zeon Corporation, 100 μm thickness) so that the thickness after drying is 10 μm, and the thickness is 8 at 80 ° C. After drying for hours, it was further dried in vacuum at 150 ° C. for 8 hours to form the coating resin layer (1). Further, a resin solution (H5-1) was applied to the other surface of the resin support so as to have a thickness of 10 μm after drying, dried at 80 ° C. for 8 hours, and then further in vacuum at 150 ° C. It was dried for 8 hours to form a coating resin layer (2). As a result, a substrate having a thickness of 120 μm having a resin layer containing no compound (Z) on both sides of the transparent resin substrate was obtained.
Xa, Ta to Tf of the obtained base material were determined in the same manner as in Example 1. The results are shown in Table 12.

Claims

With resin
A resin composition represented by the following formula (I) and containing a compound (Z) having a maximum absorption wavelength in the wavelength range of 850 to 1100 nm.
Cn + An - (I)
[In formula (I), Cn + is a monovalent cation represented by the following formula (II), and An - is a monovalent anion. ]

[In Formula (II), the Y A and Y D are each independently, a carbon atom, a sulfur atom, an oxygen atom, a group having at least one selected from a nitrogen atom and a phosphorus atom, a hydrogen atom or a halogen atom,
Z A to Z C and Y B to Y C are independently groups having at least one selected from a carbon atom, a sulfur atom, an oxygen atom, a nitrogen atom, a phosphorus atom and a silicon atom, a hydrogen atom or a halogen atom, or a halogen atom. , Z A to Z C may be joined to each other to form a ring, or Y B and Y C may be joined to each other to form a ring.
Unit A and unit B are independent groups having a heteroaromatic ring.
Some groups in unit A may be bonded to Y A to form a cyclic hydrocarbon group having 5 or 6 carbon atoms, and some groups in unit B may be bonded to Y D. It may form a cyclic hydrocarbon group having 5 or 6 carbon atoms.
Z B is a halogen atom or a group represented by any of the following formulas (A-1) to (A-2), and Y B and Y C are formed by being bonded to each other. When the 5-membered alicyclic hydrocarbon group is a 5-membered alicyclic hydrocarbon group and all the substituents other than Z B in the 5-membered alicyclic hydrocarbon group are hydrogen atoms, the unit A is represented by the following formula (A-3). It is not a group represented, and unit B is not a group represented by the following formula (A-4).
Z B is a chlorine atom and is a 6-membered alicyclic hydrocarbon group formed by mutual bonding of Y B and Y C, and the 6-membered alicyclic hydrocarbon group. When all the substituents other than Z B are hydrogen atoms, the unit A is not a group represented by the following formula (A-5), and the unit B is a group represented by the following formula (A-6). not,
Z B is a group represented by the following formula (A-7), and is a 5-membered alicyclic hydrocarbon group formed by bonding Y B and Y C to each other, and When all the substituents other than Z B in the 5-membered alicyclic hydrocarbon group are hydrogen atoms, the unit A is not a group represented by the following formula (A-8), and the unit B is represented by the following formula. It is not a group represented by (A-9). ]

[In formulas (A-3) to (A-4), Y a1 is an independently substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, and − * in the formula (A-3) is the above. It indicates that a single bond and carbon Y a binds the formula (II), wherein = ** is the (a-4) in the carbon and to the double bond Y D of the formula (II) are bound Is shown. ]

Wherein (A-5) ~ (A -6), Y a2 is a n- butyl group, the formula (A-5) in the - * is a carbon Y A of the formula (II) are bound It indicates that a single bond is formed, and = ** in the formula (A-6) indicates that the Y D of the formula (II) is double bonded to the carbon to which it is bonded. ]

[In formula (A-7), Rx and Ry are independently hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group. , Butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, cyclooctyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group, methoxy group, ethoxy group, propoxy group, fluoro group, chloro group, bromo Group, iodo group, cyano group or nitro group. ]

[In formulas (A-8) to (A-9), Y a3 is an alkyl group having a linear or branched carbon number of 1 to 5 independently, and-* in the formula (A-8) is , Indicates that Y A of the formula (II) is single-bonded to the carbon to which it is bonded, and = ** in the formula (A-9) is a double bond to the carbon to which Y D of the formula (II) is bonded. Indicates to do. ]
The unit A is a group represented by any of the following formulas (AI) to (A-III).
The unit B is a group represented by any of the following formulas (BI) to (B-III).
Y A and Y D are independently hydrogen atoms, halogen atoms, or hydrocarbon groups having 1 to 8 carbon atoms.
Z A to Z C and Y B to Y C are independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, -NR g R h group, amide group, imide group, cyano group, silyl group, -Q 1 , -N = N-Q 1 , -S-Q 2 , -SSQ 2 , or -SO 2 Q 3 ,
A 5- to 6-membered fat that may contain at least one aromatic hydrocarbon group, nitrogen atom, oxygen atom or sulfur atom having 6 to 14 carbon atoms, in which two adjacent two of Z A to Z C are bonded to each other. It may form a ring group or a complex aromatic group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, and these alicyclic groups, aromatic hydrocarbon groups and complex. The aromatic group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.
A 5- to 6-membered alicyclic group in which Y B and Y C are bonded to each other and may contain at least one aromatic hydrocarbon group having 6 to 14 carbon atoms, a nitrogen atom, an oxygen atom or a sulfur atom, or It may form a heteroaromatic group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, and these alicyclic groups, aromatic hydrocarbon groups and heteroaromatic groups may form. It may have an aliphatic hydrocarbon group or a halogen atom having 1 to 9 carbon atoms.
R g and R h are each independently a hydrogen atom, an −C (O) R i group or any of the following L b to L f , and Q 1 is any of the following L b to L g. Q 2 is a hydrogen atom or any of the following L b to L f , Q 3 is either a hydroxyl group or the following L b to L f , and R i is any of the following L b to L f. is there,
The resin composition according to claim 1.

[Formula (A-I) ~ (A -III) in the - * indicates that the single bonds and carbon to which Y A is attached of the formula (II),
= ** in formulas (BI) to (B-III) indicate that Y D of the formula (II) is double bonded to the carbon to which it is bonded.
In formulas (AI)-(B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -N (R 8 )-.
R 1 to R 6 are independently hydrogen atom, halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR g R h group, -SR i group, -SO 2 R. It is either an i group, an -OSO 2 R i group, an -C (O) R i group, or the following L b to L i.
Adjacent two of R 1 to R 6 may be bonded to each other to form a cyclic hydrocarbon group having 5 or 6 carbon atoms.
R 1 or R 4 in the formula (A-III), the formula in combination with Y A in (II) may form a cyclic hydrocarbon group having 5 or 6 carbon atoms,
R 1 or R 4 in the formula (B-III) may be bonded to Y D in the formula (II) to form a cyclic hydrocarbon group having 5 or 6 carbon atoms.
R 8 is a hydrogen atom, a halogen atom, an −C (O) R i group, or any of the following L b to Li i.
R g and R h are independently either a hydrogen atom, an −C (O) R i group, or L b to L f below.
R i is one of the following L b to L f ,
(L b ): aliphatic hydrocarbon group having 1 to 15 carbon atoms (L c ): halogen-substituted alkyl group (L d ): alicyclic hydrocarbon group (L e ): aromatic hydrocarbon group (L f ) : Heterocyclic group (L g ): -OR (R is a hydrocarbon group)
(L h ): Acyl group which may have a substituent L ( Li ): An alkoxycarbonyl group which may have a substituent L The substituent L is at least one selected from the above L b to L f. Is. ]
The resin composition according to claim 1 or 2, wherein the compound (Z) satisfies the following requirement (A).
Requirement (A): In a transmission spectrum measured using a solution of the compound (Z) in dichloromethane (however, the transmission spectrum is a spectrum in which the transmittance at the absorption maximum wavelength is 10%). The average value of the light transmittance at a wavelength of 430 to 580 nm is 70% or more.
The resin composition according to any one of claims 1 to 3, wherein the compound (Z) satisfies the following requirements (C) and (D).
Requirement (C): In a transmission spectrum measured using a solution of the compound (Z) in dichloromethane (however, the transmission spectrum is a spectrum in which the transmittance at the absorption maximum wavelength is 10%). Having a wavelength in the wavelength range of 950 to 1150 nm and having a transmittance of 85% Requirement (D): A transmission spectrum measured using a solution of the compound (Z) in dichloromethane (however, the transmission spectrum is It is a spectrum in which the transmittance at the absorption maximum wavelength is 10%.) At a wavelength longer than the absorption maximum wavelength, the wavelength on the shortest wavelength side (Wa) at which the transmittance is 20% and the transmittance are 70%. The absolute value of the difference from the wavelength (Wb) on the shortest wavelength side is 10 to 60 nm.
The resin is a cyclic (poly) olefin resin, an aromatic polyether resin, a polyimide resin, a polyester resin, a polycarbonate resin, a polyamide resin, a polyarylate resin, a polysulfone resin, or a polyether sulfone resin. , Polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester curable resin, silsesquioxane ultraviolet The resin composition according to any one of claims 1 to 4, which is at least one resin selected from the group consisting of a curable resin, an acrylic ultraviolet curable resin, and a vinyl ultraviolet curable resin.
An optical filter having a base material (i) containing a resin layer containing a compound (Z) formed from the resin composition according to any one of claims 1 to 5 and a dielectric multilayer film.
The base material (i) is
A substrate composed of a resin layer containing the compound (Z),
A base material containing two or more resin layers, wherein at least one of the two or more resin layers is a resin layer containing the compound (Z), or a base material.
The optical filter according to claim 6, which is a base material containing a glass support and a resin layer containing the compound (Z).
The optical filter according to claim 6 or 7, wherein the optical filter is a near-infrared ray cut filter satisfying the following characteristics (a) and (b).
Characteristic (a): The average value of the transmittance measured from the vertical direction of the optical filter is 75% or more in the wavelength region of 430 to 580 nm. Characteristic (b): The vertical direction of the optical filter in the wavelength region of 850 to 1200 nm. The average value of transmittance measured from 5% or less
The optical filter according to claim 6 or 7, wherein the optical filter is a visible light-near infrared selective transmission filter satisfying the following characteristics (c) and (d).
Characteristic (c): The average value of the transmittance measured from the vertical direction of the optical filter is 75% or more in the region of wavelength 430 to 580 nm. Characteristic (d): Light ray blocking band Za and light rays in the region of wavelength 650 nm or more. It has a transmission band Zb and a light blocking band Zc, and the center wavelength of each band is Za <Zb <Zc.
The minimum transmittances of Za and Zc measured from the vertical direction of the optical filter are 15% or less, respectively.
The maximum transmittance measured from the vertical direction of the optical filter in Zb is 55% or more.
The optical filter according to claim 6 or 7, wherein the optical filter is a near-infrared ray transmitting filter satisfying the following characteristics (e) and (f).
Characteristic (e): The average value of the transmittance measured from the vertical direction of the optical filter is 10% or less in the region of wavelength 380 to 700 nm. Characteristic (f): The light transmission band Ya is provided in the region of wavelength 750 nm or more. However, in the light transmittance band Ya, the maximum transmittance ( TIR ) measured from the vertical direction of the optical filter is 45% or more.
The optical filter according to any one of claims 6 to 10, which is for a solid-state image sensor.
The optical filter according to any one of claims 6 to 10, which is for an optical sensor device.
A solid-state image sensor provided with the optical filter according to any one of claims 6 to 10.
An optical sensor device including the optical filter according to any one of claims 6 to 10.
A compound (Z) represented by the following formula (I) and having a maximum absorption wavelength in the wavelength range of 850 to 1100 nm.
Cn + An - (I)
[In formula (I), Cn + is a monovalent cation represented by the following formula (II), and An - is a monovalent anion. ]

[In formula (II), unit A is a group represented by any of the following formulas (AI) to (A-III).
Unit B is a group represented by any of the following formulas (BI) to (B-III).
Y A and Y D are independently hydrogen atoms, halogen atoms or hydrocarbon groups having 1 to 8 carbon atoms.
Z A to Z C and Y B to Y C are independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, -NR g R h group, amide group, imide group, cyano group, silyl group,- Q 1 , -N = N-Q 1 , -S-Q 2 , -SSQ 2 , or -SO 2 Q 3 ,
A 5- to 6-membered fat that may contain at least one aromatic hydrocarbon group, nitrogen atom, oxygen atom or sulfur atom having 6 to 14 carbon atoms, in which two adjacent two of Z A to Z C are bonded to each other. It may form a ring group or a complex aromatic group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, and these alicyclic groups, aromatic hydrocarbon groups and complex. The aromatic group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.
A 5- to 6-membered alicyclic group in which Y B and Y C are bonded to each other and may contain at least one aromatic hydrocarbon group having 6 to 14 carbon atoms, a nitrogen atom, an oxygen atom or a sulfur atom, or It may form a heteroaromatic group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, and these alicyclic groups, aromatic hydrocarbon groups and heteroaromatic groups may form. It may have an aliphatic hydrocarbon group or a halogen atom having 1 to 9 carbon atoms.
R g and R h are each independently a hydrogen atom, an −C (O) R i group or any of the following L b to L f , and Q 1 is any of the following L b to L g. Q 2 is a hydrogen atom or any of the following L b to L f , Q 3 is either a hydroxyl group or the following L b to L f , and R i is any of the following L b to L f. Yes,
Z B is a halogen atom or a group represented by any of the following formulas (A-1) to (A-2), and Y B and Y C are formed by being bonded to each other. When the 5-membered alicyclic hydrocarbon group is a 5-membered alicyclic hydrocarbon group and all the substituents other than Z B in the 5-membered alicyclic hydrocarbon group are hydrogen atoms, the unit A is represented by the following formula (A-3). It is not a group represented, and unit B is not a group represented by the following formula (A-4).
Z B is a chlorine atom and is a 6-membered alicyclic hydrocarbon group formed by mutual bonding of Y B and Y C, and the 6-membered alicyclic hydrocarbon group. When all the substituents other than Z B are hydrogen atoms, the unit A is not a group represented by the following formula (A-5), and the unit B is a group represented by the following formula (A-6). not,
Z B is a group represented by the following formula (A-7), and is a 5-membered alicyclic hydrocarbon group formed by bonding Y B and Y C to each other, and When all the substituents other than Z B in the 5-membered alicyclic hydrocarbon group are hydrogen atoms, the unit A is not a group represented by the following formula (A-8), and the unit B is represented by the following formula. It is not a group represented by (A-9). ]

[Formula (A-I) ~ (A -III) in the - * indicates that the single bonds and carbon to which Y A is attached of the formula (II),
= ** in formulas (BI) to (B-III) indicate that Y D of the formula (II) is double bonded to the carbon to which it is bonded.
In formulas (AI)-(B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -N (R 8 )-.
R 1 to R 6 are independently hydrogen atom, halogen atom, sulfo group, hydroxyl group, cyano group, nitro group, carboxy group, phosphate group, -NR g R h group, -SR i group, -SO 2 R. It is either an i group, an -OSO 2 R i group, an -C (O) R i group, or the following L b to L i.
Adjacent two of R 1 to R 6 may be bonded to each other to form a cyclic hydrocarbon group having 5 or 6 carbon atoms.
R 1 or R 4 in the formula (A-III), the formula in combination with Y A in (II) may form a cyclic hydrocarbon group having 5 or 6 carbon atoms,
R 1 or R 4 in the formula (B-III) may be bonded to Y D in the formula (II) to form a cyclic hydrocarbon group having 5 or 6 carbon atoms.
R 8 is a hydrogen atom, a halogen atom, an −C (O) R i group, or any of the following L b to Li i.
R g and R h are independently either a hydrogen atom, an −C (O) R i group, or L b to L f below.
R i is one of the following L b to L f ,
(L b ): aliphatic hydrocarbon group having 1 to 15 carbon atoms (L c ): halogen-substituted alkyl group (L d ): alicyclic hydrocarbon group (L e ): aromatic hydrocarbon group (L f ) : Heterocyclic group (L g ): -OR (R is a hydrocarbon group)
(L h ): Acyl group which may have a substituent L ( Li ): An alkoxycarbonyl group which may have a substituent L The substituent L is at least one selected from the above L b to L f. Is. ]

[In formulas (A-3) to (A-4), Y a1 is an independently substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, and − * in the formula (A-3) is the above. It indicates that a single bond and carbon Y a binds the formula (II), wherein = ** is the (a-4) in the carbon and to the double bond Y D of the formula (II) are bound Is shown. ]

Wherein (A-5) ~ (A -6), Y a2 is a n- butyl group, the formula (A-5) in the - * is a carbon Y A of the formula (II) are bound It indicates that a single bond is formed, and = ** in the formula (A-6) indicates that the Y D of the formula (II) is double bonded to the carbon to which it is bonded. ]

[In formula (A-7), Rx and Ry are independently hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group. , Butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, cyclooctyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group, methoxy group, ethoxy group, propoxy group, fluoro group, chloro group, bromo Group, iodo group, cyano group or nitro group. ]

[In formulas (A-8) to (A-9), Y a3 is an alkyl group having a linear or branched carbon number of 1 to 5 independently, and-* in the formula (A-8) is , Indicates that Y A of the formula (II) is single-bonded to the carbon to which it is bonded, and = ** in the formula (A-9) is a double bond to the carbon to which Y D of the formula (II) is bonded. Indicates to do. ]