CN113292807A

CN113292807A - Resin composition, compound, base material, optical filter, solid-state imaging device, and optical sensor device

Info

Publication number: CN113292807A
Application number: CN202110188611.3A
Authority: CN
Inventors: 川部泰典; 长屋胜也; 内田洋介; 大崎仁视; 畠中创; 下河広幸; 面手真人; 大桥幸恵
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2020-02-21
Filing date: 2021-02-19
Publication date: 2021-08-24
Also published as: CN117757205A; JP2021134350A; TW202132473A; KR20210107545A

Abstract

The present invention provides a wavelength converter having a wavelength of about 700nm to 750nm or a wavelength of about 720nm to 900nmThere are provided a resin composition, a compound, a base material, an optical filter, a solid-state imaging device, and an optical sensor device, which have extremely high absorption, a large ratio of absorbance in the infrared region to absorbance in the visible region, and excellent light resistance (durability). A resin composition comprising: resin, and compound represented by the formula (I) [ Cn in the formula (I) ]⁺Is a monovalent cation represented by the formula (II), An^‑Is a monovalent anion]。Cn⁺An^‑ (I)

Description

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

Technical Field

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

Background

In solid-state imaging devices such as video cameras (camcorders), digital still cameras (digital still cameras), and mobile phones with camera functions, Charge Coupled Devices (CCDs) or Complementary Metal Oxide Semiconductor (CMOS) image sensors (image sensors) are used as solid-state imaging elements for color images. In these solid-state imaging devices, a silicon photodiode or the like having sensitivity to near infrared rays that cannot be perceived by the human eye is used as a light receiving portion. In addition, a silicon photodiode or the like is also used in the optical sensor device. For example, in many solid-state imaging devices, it is necessary to perform a sensitivity correction that causes natural colors to appear to the human eye and use an optical filter (e.g., a near-infrared cut filter) that selectively transmits or cuts light in a specific wavelength region.

As such a near infrared ray cut filter, filters manufactured by various methods have been used since now. For example, a near-infrared cut filter is known which uses a resin as a base material and contains a near-infrared absorbing dye in the resin (see, for example, patent document 1). However, the near-infrared cut filter described in patent document 1 may not have sufficient near-infrared absorption characteristics.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. 2008-303130

Disclosure of Invention

[ problems to be solved by the invention ]

As the near-infrared absorbing coloring matter, there have been conventionally used coloring matters such as polymethine-based, squarylium-based, porphyrin-based, dithiol metal complex-based, phthalocyanine-based, and diimmonium-based coloring matters, and among them, polymethine-based, squarylium-based coloring matters are frequently used in view of sufficient resistance to heat.

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

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

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

light resistance (durability) is not sufficient.

In addition, in the conventional near infrared ray cut filter, the reflected light from the filter may adversely affect an image such as a camera image as flare or ghost, and particularly, the adverse effect may be more significant when the reflection band of the near infrared ray cut filter overlaps a wavelength band that can be photoelectrically converted by the sensor.

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

[ means for solving problems ]

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

In the present invention, the description of "a to B" and the like indicating a numerical range is the same as "a or more and B or less", and a and B are included in the numerical range. In the present invention, the wavelengths Anm to Bnm represent the characteristic of 1nm wavelength resolution in the wavelength region of wavelength equal to or longer than Anm and wavelength Bnm or shorter.

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

Cn⁺An^- (I)

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

[ solution 1]

[ in the formula (II),

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

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

Y_A～Y_Eare each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group or-NR^gR^hRadical, amide radical, imide radical, cyano radical, silane radical, -Q¹、-N＝N-Q¹、-S-Q²、-SSQ²or-SO₂Q³，

Y_AAnd Y_C、Y_BAnd Y_D、Y_CAnd Y_ECan be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4 to 7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a 3 to 14 membered heteroaromatic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon group, alicyclic group and heteroaromatic group may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have ═ O,

Y_Awith R in the following formula (A-III)¹Or R⁵、Y_EAnd R in the following formula (B-III)⁵Or R¹May be bonded to each other to form a 4-to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom,

R^gand R^hEach independently is a hydrogen atom, -C (O) RⁱOr L shown below^a～L^hAny one of (1), Q¹Independently is L^a～L^hAny one of (1), Q²Independently a hydrogen atom or L^a～L^hAny one of (1), Q³Is hydroxy or L^a～L^hAny one of (1), RⁱIs L as follows^a～L^hAny one of (1) to (2)]

[ solution 2]

[ formula (A-I) to formula (A-III) -, which is the same as Y in the formula (II)_AThe bonded carbon is singly bonded,

wherein each of formulae (B-I) to (B-III) represents Y in the same manner as in the above formula (II)_EThe bonded carbon is double-bonded,

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

x is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or-NR⁸-，

R¹～R⁶Each independently is a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, -NR^gR^hradical-SRⁱRadical, -SO₂RⁱRadical, -OSO₂RⁱRadical, -C (O) RⁱOr L shown below^a～L^hAny one of the above-mentioned (A) and (B),

adjacent R¹～R⁶Can be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4 to 7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a 3 to 14 membered heteroaromatic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon group, alicyclic group and heteroaromatic group may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have ═ O,

R⁸independently a hydrogen atom, a halogen atom, -C (O) RⁱGroup (II) is as follows^a～L^hAny one of the above-mentioned (A) and (B),

R^gand R^hEach independently is a hydrogen atom, -C (O) RⁱOr L shown below^a～L^hAny one of the above-mentioned (A) and (B),

Rⁱindependently is L^a～L^hAny one of the above-mentioned (A) and (B),

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

(L^b): a C1-15 halogen-substituted alkyl group

(L^c): a C3-14 alicyclic hydrocarbon group which may have a substituent K

(L^d): a C6-14 aromatic hydrocarbon group which may have a substituent K

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

(L^f): -OR (R is a C1-12 hydrocarbon group which may have a substituent L)

(L^g): an acyl group having 1 to 9 carbon atoms and optionally having a substituent L

(L^h): c1-9 optionally having substituent LAlkoxycarbonyl group (a)

The substituent K is selected from the group L^a～L^bAt least one of said substituents L is selected from said group L^a～L^fAt least one of]。

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

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

[3]According to [1]Or [2]]The resin composition of, wherein R is¹～R⁶At least one of is said L^a、L^cOr L^d。

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

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

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

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

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

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

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

a substrate comprising a resin layer containing the compound (Z);

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

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

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

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

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

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

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

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

Cn⁺An^- (III)

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

[ solution 3]

[ in the formula (IV),

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

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

[ solution 4]

[ formula (A-I) to formula (A-III) -, which is the same as Y in the formula (II)_AThe carbon bound toThe row is linked with the single-row chain,

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

Rⁱindependently is L^a～L^hAny one of the above-mentioned (A) and (B),

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

(L^b): a C1-15 halogen-substituted alkyl group

(L^c): a C3-14 alicyclic hydrocarbon group which may have a substituent K

(L^d): a C6-14 aromatic hydrocarbon group which may have a substituent K

(L^e): can be used forA heterocyclic group having 3 to 14 carbon atoms and having a substituent K

(L^f): -OR (R is a C1-12 hydrocarbon group which may have a substituent L)

(L^h): alkoxycarbonyl group having 1 to 9 carbon atoms and optionally having substituent L

[ Effect of the invention ]

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

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

As described above, according to the present invention, since the optical filter having the above-described characteristics can be provided, the optical filter which can suppress the reflected light of light having a wavelength in the vicinity of 700nm to 750nm or in the vicinity of 720nm to 900nm and can provide a good image with less flare or ghost can be easily obtained. In addition, the incident angle dependency caused by the dielectric multilayer film can be suppressed when the optical filter is a filter having the dielectric multilayer film.

Drawings

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

Fig. 2 is a spectral transmittance spectrum of the base material obtained in example 28.

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

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

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

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

Detailed Description

Resin composition

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

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

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

< Compound (Z) >

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

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

Cn⁺An^- (I)

[ solution 5]

[ in the formula (II),

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

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

[ solution 6]

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

Rⁱindependently is L^a～L^hAny one of the above-mentioned (A) and (B),

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

(L^b): a warp of 1-15 carbon atomsHalogen substituted alkyl

(L^c): a C3-14 alicyclic hydrocarbon group which may have a substituent K

(L^d): a C6-14 aromatic hydrocarbon group which may have a substituent K

(L^f): -OR (R is a C1-12 hydrocarbon group which may have a substituent L)

The substituent K is selected from the group L^a～L^bAt least one of said substituents L is selected from said group L^a～L^fAt least one of]

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

Cn⁺An^- (III)

[ solution 7]

[ in the formula (IV),

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

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

[ solution 8]

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

Rⁱindependently is L^a～L^hAny one of the above-mentioned (A) and (B),

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

(L^b): a C1-15 halogen-substituted alkyl group

(L^c): a C3-14 alicyclic hydrocarbon group which may have a substituent K

(L^d): a C6-14 aromatic hydrocarbon group which may have a substituent K

(L^f): -OR (R is a C1-12 hydrocarbon group which may have a substituent L)

Further, the-NR⁸-is a group represented by the following formula (a), the-NR^gR^hThe group is a group represented by the following formula (b) — SRⁱThe group is a group represented by the following formula (c) — SO₂RⁱThe group is represented by the following formula (d) — OSO₂RⁱThe group is represented by the following formula (e), the-C (O) RⁱThe group is a group represented by the following formula (f).

Further, the-SSQ²is-S-S-Q²The group represented by the formula-SO₂Q³In the group represented by the following formula (d), R isⁱSubstituted by Q³And a substrate formed by the above process.

[ solution 9]

Further, Cn is the number of units A and B in the case where the unit A is the formula (A-I) and the unit B is the formula (B-I)⁺Represented by the following formula (II-1). That is, the single bond (-) of "-" in the formulae (A-I) to (A-III) corresponds to Y in the formula (II) or (IV)_AA single bond between the bonded carbon atom and the unit a, and a double bond (═ in the formulae (B-I) to (B-III) corresponds to Y in the formula (II) or (IV)_EThe double bond between the carbon atom to which it is bonded and the unit B.

[ solution 10]

Said Y is_BAnd Y_DMore preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, and Y_BAnd Y_DA 4-to 6-membered alicyclic hydrocarbon group bonded to each other (the alicyclic hydrocarbon group may have a substituent R selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a hydroxyl group, a halogen atom, and ═ O⁹)。

Further, in the case of Y_BAnd Y_DIn the case of a 4-to 6-membered alicyclic hydrocarbon group bonded to each other, the formula (II) or the formula (IV) is preferably represented by the following formulae (C-I) to (C-III), respectively.

[ solution 11]

[ solution 12]

[ solution 13]

As substituents R⁹Preferred are a hydrogen atom, a hydroxyl group, ═ O, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and cyclohexyl group, and more preferred are a hydrogen atom, a hydroxyl group, ═ O, methyl, ethyl, and tert-butyl groups.

Said Y is_A、Y_CAnd Y_EMore preferably a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a hydroxyl group, a phenylamino group (NHPh), a diphenylamino group, a methylphenylamino group, a dimethylamino group, a methyl group, a methoxy group, a phenyl group, a phenoxy group, a 4-methylphenoxy group, a methylthio group, a phenylthio group, or a-S- (4-tolyl) group (-S- (4-tolyl) group).

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

Said L^aCan also be: alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, butenyl, 1, 3-butadienyl, 2-methyl-1-propenyl, 2-pentenyl and hexenyl; ethynyl groupAlkynyl groups such as propynyl, butynyl, 2-methyl-1-propynyl and hexynyl.

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

As said L^cThe alicyclic hydrocarbon group of 3 to 14 carbon atoms which may have a substituent K in (b) preferably includes: cycloalkyl groups such as cyclopropyl, cyclopropylmethyl, methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, and cyclooctyl; polycyclic alicyclic groups such as norbornanyl and adamantyl.

As said L^dThe aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent K in (A) is preferably a phenyl group, a tolyl group, a xylyl group, a mesityl (trimethylphenyl) group, a cumenyl group, a bis (trifluoromethyl) phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthryl group, a phenanthryl group, a benzyl group (CH)₂Ph)。

As said L^eThe heterocyclic group having 3 to 14 carbon atoms and optionally having a substituent K in (1) is preferably furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, morpholine or pyridine.

As said L^fthe-OR in (A) is preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, methoxymethyl, methoxyethyl, pentyloxy, hexyloxy, octyloxy, phenoxy (OPh), 4-methylphenoxy, cyclohexyloxy.

As said L^gThe acyl group having 1 to 9 carbon atoms which may have a substituent L in (A) is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group or a trifluoromethylcarbonyl group.

As said L^hThe alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L in (A) is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group。

The X is preferably an oxygen atom, a sulfur atom, -NR⁸Particularly preferred is an oxygen atom.

In the formula (II) or the formula (IV), the unit a and the unit B on the left and right may be the same or different, and when the units are the same, the synthesis is easy, and therefore, the unit a and the unit B are preferable.

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

The R is¹～R⁶Each independently preferably represents a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a 1, 1-dimethylbutyl group, a cyclopropyl group, a cyclopropylmethyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,4, 6-trimethylphenyl group, a 3, 5-bis (trifluoromethyl) phenyl group, a hydroxyl group, an amino group, or a dimethylamino group (NMe)₂) Diethylamino (NEt)₂) Dibutylamino (N (N-Bu)₂) Cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoroformylamino group, pentafluoroacetylamino group, t-butyrylamino group, cyclohexanylamino group, N-butylsulfonyl group, benzyl group, diphenylmethyl group, trifluoromethyl group, difluoromethyl group, methoxy group, and more preferably hydrogen atom, chlorine atom, fluorine atom, bromine atom, methyl group, ethyl group, N-propyl group, isopropyl group, N-butyl group, sec-butyl group, t-butyl group, cyclohexyl group, phenyl group, amino group, benzyl group, diphenylmethyl group, trifluoromethyl group, difluoromethyl group, methoxy group.

The above-mentioned R is preferably a compound having high near infrared ray cut-off performance and high visible light transmission performance at an absorption maximum near a wavelength of 700nm to 750nm or a wavelength of 720nm to 900nm, excellent optical characteristics, sufficient resistance to heat or light, and the like, in terms of easily obtaining the compound¹～R⁶At least one of is said L^a、L^cOr L^d. Further, in the case where the unit A is the formula (A-III) and the unit B is the formula (B-III), "R¹～R⁶At least one of is L^a、L^cOr L^d"isMeans "R¹、R²、R⁴、R⁵At least one of is L^a、L^cOr L^d”。

As said R⁸Preferably, the hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, benzyl group, n-pentyl group, n-hexyl group, and tert-butyl group are used, and more preferably, the hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and benzyl group are used.

As said An^-The monovalent anion is not particularly limited, and preferably includes: chloride ion, bromide ion, iodide ion, PF₄ ^-The perchlorate anion, the tris-trifluoromethanesulfonylmethylate anion, the tetrafluoroborate anion, the hexafluorophosphate anion, the bis (trifluoromethanesulfonyl) imide anion, the trifluoromethanesulfonate anion, the tetrakis (pentafluorophenyl) borate anion, the tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate anion and the like are more preferable, the bis (trifluoromethanesulfonyl) imide anion, the trifluoromethanesulfonate anion, the tris-trifluoromethanesulfonylmethate anion, the tetrakis (pentafluorophenyl) borate anion, the tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate anion are more preferable, and the bis (trifluoromethanesulfonyl) imide anion, the tris-trifluoromethanesulfonylmethate anion, the tetrakis (trifluoromethyl) phenyl) borate anion and the like are still more preferable, and the bis (trifluoromethanesulfonyl) imide anion, the tris-trifluoromethanesulfonylmethate anion, the hexafluorophosphate anion and the like are still more preferable, and the compound (Z) having more excellent heat resistance can be easily obtained, Tetrakis (pentafluorophenyl) borate, tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, and tetrakis (pentafluorophenyl) borate are particularly preferable.

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

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

[ Table 1]

[ Table 2]

Compound (I)

A，B

X

Y_A，Y_E

Y_B，Y_D

Y_C

R¹

R²

R³

R⁴

R⁵

R⁶

An

(z-51)

(A-I)，(B-I)

O

H

tert-Bu

H

PF₄

(z-52)

(A-I)，(B-I)

O

H

tert-Bu

H

Cl

(z-53)

(A-I)，(B-I)

O

H

tert-Bu

H

Br

(z-54)

(A-I)，(B-I)

O

H

tert-Bu

H

I

(z-55)

(A-I)，(B-I)

O

H

Cl

H

tert-Bu

H

F

H

B(C₆F₅)₄

(z-56)

(A-I)，(B-I)

O

H

Cl

H

tert-Bu

H

Cl

H

B(C₆F₅)₄

(z-57)

(A-I)，(B-I)

O

H

Cl

H

tert-Bu

H

Br

H

B(C₆F₅)₄

(z-58)

(A-I)，(B-I)

O

H

Cl

H

tert-Bu

H

Me

H

B(C₆F₅)₄

(z-59)

(A-I)，(B-I)

O

H

tert-Bu

H

B(C₆F₅)₄

(z-60)

(A-I)，(B-I)

O

H

Cl

H

tert-Bu

H

OCH₃

H

B(C₆F₅)₄

(z-61)

(A-I)，(B-I)

O

H

Cl

H

tert-Bu

H

NHCOCF₃

H

B(C₆F₅)₄

(z-62)

(A-I)，(B-I)

O

H

i-Pr

H

F

H

B(C₆F₅)₄

(z-63)

(A-I)，(B-I)

O

H

i-Pr

H

Cl

H

B(C₆F₅)₄

(z-64)

(A-I)，(B-I)

O

H

i-Pr

H

Br

H

B(C₆F₅)₄

(z-65)

(A-I)，(B-I)

O

H

i-Pr

H

Me

H

B(C₆F₅)₄

(z-66)

(A-I)，(B-I)

O

H

i-Pr

H

i-Pr

H

B(C₆F₅)₄

(z-67)

(A-I)，(B-I)

O

H

i-Pr

H

OCH₃

H

B(C₆F₅)₄

(z-68)

(A-I)，(B-I)

O

H

i-Pr

H

CF₃

H

B(C₆F₅)₄

(z-69)

(A-I)，(B-I)

O

H

Ph

H

F

H

B(C₆F₅)₄

(z-70)

(A-I)，(B-I)

O

H

Ph

H

Cl

H

B(C₆F₅)₄

(z-71)

(A-I)，(B-I)

O

H

Ph

H

Br

H

B(C₆F₅)₄

(z-72)

(A-I)，(B-I)

O

H

Ph

H

Me

H

B(C₆F₅)₄

(z-73)

(A-I)，(B-I)

O

H

Ph

H

i-Pr

H

B(C₆F₅)₄

(z-74)

(A-I)，(B-I)

O

H

Ph

H

OCH₃

H

B(C₆F₅)₄

(z-75)

(A-I)，(B-I)

O

H

Ph

H

NHCOCF₃

H

B(C₆F₅)₄

(z-76)

(A-II)，(B-II)

N

H

tert-Bu

H

B(C₆F₅)₄

(z-77)

(A-II)，(B-II)

S

H

tert-Bu

H

B(C₆F₅)₄

(z-78)

(A-II)，(B-II)

O

CH₃

H

tert-Bu

H

B(C₆F₅)₄

(z-79)

(A-II)，(B-II)

O

H

F

H

tert-Bu

H

B(C₆F₅)₄

(z-80)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

B(C₆F₅)₄

(z-81)

(A-II)，(B-II)

O

H

Br

H

tert-Bu

H

B(C₆F₅)₄

(z-82)

(A-II)，(B-II)

O

H

CH₃

H

tert-Bu

H

B(C₆F₅)₄

(z-83)

(A-II)，(B-II)

O

H

OCH₃

H

tert-Bu

H

B(C₆F₅)₄

(z-84)

(A-II)，(B-II)

O

H

OPh

H

tert-Bu

H

B(C₆F₅)₄

(z-85)

(A-II)，(B-II)

O

H

N(CH₃)₂

H

tert-Bu

H

B(C₆F₅)₄

(z-86)

(A-II)，(B-II)

O

H

NHPh

H

tert-Bu

H

B(C₆F₅)₄

(z-87)

(A-II)，(B-II)

O

H

NPh₂

H

tert-Bu

H

B(C₆F₅)₄

(z-88)

(A-II)，(B-II)

O

H

SCH₃

H

tert-Bu

H

B(C₆F₅)₄

(z-89)

(A-II)，(B-II)

O

H

SPh

H

tert-Bu

H

B(C₆F₅)₄

(z-90)

(A-II)，(B-II)

O

H

Ph

H

B(C₆F₅)₄

(z-91)

(A-II)，(B-II)

O

H

i-Pr

H

B(C₆F₅)₄

(z-92)

(A-II)，(B-II)

O

H

Cyclopropyl group

H

B(C₆F₅)₄

(z-93)

(A-II)，(B-II)

O

H

Cyclopropyl methyl group

H

B(C₆F₅)₄

(z-94)

(A-II)，(B-II)

O

H

Cyclohexyl radical

H

B(C₆F₅)₄

(z-95)

(A-II)，(B-II)

O

H

Adamantyl radical

H

B(C₆F₅)₄

(z-96)

(A-II)，(B-II)

O

H

2,4, 6-trimethylphenyl

H

B(C₆F₅)₄

(z-97)

(A-II)，(B-II)

O

H

3, 5-bis (trifluoromethyl) phenyl

H

B(C₆F₅)₄

(z-98)

(A-II)，(B-II)

O

H

tert-Bu

Cl

H

B(C₆F₅)₄

(z-99)

(A-II)，(B-II)

O

H

tert-Bu

Br

H

B(C₆F₅)₄

(z-100)

(A-II)，(B-II)

O

H

tert-Bu

Ph

H

B(C₆F₅)₄

[ Table 3]

Compound (I)

A，B

X

Y_A，Y_E

Y_B，Y_D

Y_C

R¹

R²

R³

R⁴

R⁵

R⁶

An

(z-101)

(A-II)，(B-II)

O

H

tert-Bu

Me

H

B(C₆F₅)₄

(z-102)

(A-II)，(B-II)

O

H

tert-Bu

i-Pr

H

B(C₆F₅)₄

(z-103)

(A-II)，(B-II)

O

H

tert-Bu

NHCOCF₃

H

B(C₆F₅)₄

(z-104)

(A-II)，(B-II)

O

H

tert-Bu

H

F

H

B(C₆F₅)₄

(z-105)

(A-II)，(B-II)

O

H

tert-Bu

H

Cl

H

B(C₆F₅)₄

(z-106)

(A-II)，(B-II)

O

H

tert-Bu

H

Br

H

B(C₆F₅)₄

(z-107)

(A-II)，(B-II)

O

H

tert-Bu

H

Me

H

B(C₆F₅)₄

(z-108)

(A-II)，(B-II)

O

H

tert-Bu

H

i-Pr

H

B(C₆F₅)₄

(z-109)

(A-II)，(B-II)

O

H

tert-Bu

H

OCH₃

H

B(C₆F₅)₄

(z-110)

(A-II)，(B-II)

O

H

tert-Bu

H

CF₃

H

B(C₆F₅)₄

(z-111)

(A-II)，(B-II)

O

H

tert-Bu

H

F

H

B(C₆F₅)₄

(z-112)

(A-II)，(B-II)

O

H

tert-Bu

H

Cl

H

B(C₆F₅)₄

(z-113)

(A-II)，(B-II)

O

H

tert-Bu

H

Br

H

B(C₆F₅)₄

(z-114)

(A-II)，(B-II)

O

H

tert-Bu

H

Me

H

B(C₆F₅)₄

(z-115)

(A-II)，(B-II)

O

H

tert-Bu

H

i-Pr

H

B(C₆F₅)₄

(z-116)

(A-II)，(B-II)

O

H

tert-Bu

H

OCH₃

H

B(C₆F₅)₄

(z-117)

(A-II)，(B-II)

O

H

tert-Bu

H

NHCOCF₃

H

B(C₆F₅)₄

(z-118)

(A-II)，(B-II)

O

H

tert-Bu

H

F

B(C₆F₅)₄

(z-119)

(A-II)，(B-II)

O

H

tert-Bu

H

Cl

B(C₆F₅)₄

(z-120)

(A-II)，(B-II)

O

H

tert-Bu

H

Br

B(C₆F₅)₄

(z-121)

(A-II)，(B-II)

O

H

tert-Bu

H

N(SO₂CF₃)₂

(z-122)

(A-II)，(B-II)

O

H

tert-Bu

H

C(SO₂CF₃)₃

(z-123)

(A-II)，(B-II)

O

H

tert-Bu

H

BF₄

(z-124)

(A-II)，(B-II)

O

H

tert-Bu

H

ClO₄

(z-125)

(A-II)，(B-II)

O

H

tert-Bu

H

PF₄

(z-126)

(A-II)，(B-II)

O

H

tert-Bu

H

Cl

(z-127)

(A-II)，(B-II)

O

H

tert-Bu

H

Br

(z-128)

(A-II)，(B-II)

O

H

tert-Bu

H

I

(z-129)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

F

H

B(C₆F₅)₄

(z-130)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

Cl

H

B(C₆F₅)₄

(z-131)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

Br

H

B(C₆F₅)₄

(z-132)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

Me

H

B(C₆F₅)₄

(z-133)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

i-Pr

H

B(C₆F₅)₄

(z-134)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

OCH₃

H

B(C₆F₅)₄

(z-135)

(A-II)，(B-II)

O

H

Cl

H

tert-Bu

H

NHCOCF₃

H

B(C₆F₅)₄

(z-136)

(A-II)，(B-II)

O

H

i-Pr

H

F

H

B(C₆F₅)₄

(z-137)

(A-II)，(B-II)

O

H

i-Pr

H

Cl

H

B(C₆F₅)₄

(z-138)

(A-II)，(B-II)

O

H

i-Pr

H

Br

H

B(C₆F₅)₄

(z-139)

(A-II)，(B-II)

O

H

i-Pr

H

Me

H

B(C₆F₅)₄

(z-140)

(A-II)，(B-II)

O

H

i-Pr

H

i-Pr

H

B(C₆F₅)₄

(z-141)

(A-II)，(B-II)

O

H

i-Pr

H

OCH₃

H

B(C₆F₅)₄

(z-142)

(A-II)，(B-II)

O

H

i-Pr

H

CF₃

H

B(C₆F₅)₄

(z-143)

(A-II)，(B-II)

O

H

Ph

H

F

H

B(C₆F₅)₄

(z-144)

(A-II)，(B-II)

O

H

Ph

H

Cl

H

B(C₆F₅)₄

(z-145)

(A-II)，(B-II)

O

H

Ph

H

Br

H

B(C₆F₅)₄

(z-146)

(A-II)，(B-II)

O

H

Ph

H

Me

H

B(C₆F₅)₄

(z-147)

(A-II)，(B-II)

O

H

Ph

H

i-Pr

H

B(C₆F₅)₄

(z-148)

(A-II)，(B-II)

O

H

Ph

H

OCH₃

H

B(C₆F₅)₄

(z-149)

(A-II)，(B-II)

O

H

Ph

H

NHCOCF₃

H

B(C₆F₅)₄

(z-150)

(A-I)，(B-I)

O

H

tert-Bu

H

NMe₂

H

B(C₆F₅)₄

[ Table 4]

Further, R in Table 4³And R⁴The "C-1, C-2" in the column means R in said formula (A-I) and said formula (B-I)³And R⁴The aromatic hydrocarbon group having 6 carbon atoms bonded to each other means that the units A and B correspond to the structures represented by the following formulas C-1 and C-2.

In addition, Y in Table 4_A、Y_E、R¹And R⁵"D-1" in the column means Y_AAnd R in the formula (A-III)¹、Y_EAnd R in the formula (B-III)⁵Specifically, the 6-membered alicyclic group formed by bonding together means that the cation of the compound (z-163) is represented by the following formula D-1.

[ solution 14]

[ solution 15]

The compound (Z) is preferably a compound soluble in an organic solvent, and particularly preferably a compound soluble in methylene chloride.

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

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

Requirement (a): in the transmission spectrum measured using a solution obtained by dissolving the compound (Z) in methylene chloride (wherein the transmission spectrum is a spectrum having a transmittance of 10% at an absorption maximum wavelength; hereinafter, the transmission spectrum is also referred to as "the transmission spectrum of the compound (Z)), the average value of the transmittances at wavelengths of 430nm to 580nm is preferably 93% or more, and more preferably 95% or more. The average value of the transmittance is preferably high, and therefore the upper limit thereof is not particularly limited and may be 100%.

When the compound (Z) satisfies the requirement (a), it is possible to sufficiently cut off light having a wavelength in the near infrared region to be cut off and further suppress a decrease in visible light transmittance.

In the present invention, the average transmittance at the wavelengths Anm to Bnm is a value calculated by measuring the transmittance at each wavelength of 1nm in units of Anm to Bnm and dividing the total value of the transmittances by the number of measured transmittances (wavelength range, B-a + 1).

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

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

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

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

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

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

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

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

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

The resin sheet has a thickness in the range of 90 to 110 [ mu ] m, the content of the compound (Z) in the resin sheet is such an amount that the absorbance Ai at the maximum absorption wavelength [ lambda ] a of the resin sheet falls within the range of 0.5 to 1.5, and the resin is Akon (ARTON) manufactured by JSR (Strand) and contains 0.3 parts by mass of Irganox 1010 (BASF Japan) (Strand) per 100 parts by mass of the resin in the resin sheet.

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

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

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

Requirement (D): in the spectral absorption spectrum measured using a solution obtained by dissolving the compound (Z) in methylene chloride, when the absorbance at the longest wavelength among the maximum absorption wavelengths is represented by ∈ a, and the maximum value of the absorbance at a wavelength of 430nm to 580nm is represented by ∈ bmax, ∈ a/∈ bmax is preferably 20 or more, more preferably 25 or more, and still more preferably 27 or more. Since ε a/ε bmax is preferably large, the upper limit is not particularly limited, and is, for example, 10000 or less.

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

The content of the compound (Z) in the present composition is preferably 0.02 to 2.0 parts by mass, more preferably 0.02 to 1.5 parts by mass, and particularly preferably 0.03 to 1.5 parts by mass, based on 100 parts by mass of the resin.

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

< resin >

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

The resin used in the present composition may be a single resin or two or more resins.

The resin is not particularly limited as long as the effects of the present invention are not impaired, and for example, a resin having a glass transition temperature (Tg) of preferably 110 to 380 ℃, more preferably 110 to 370 ℃, and particularly preferably 120 to 360 ℃ is exemplified in terms of being excellent in thermal stability, moldability with respect to the shape of a film (plate), and the like, and being capable of easily obtaining a film in which a dielectric multilayer film can be formed by high-temperature vapor deposition at a vapor deposition temperature of about 100 ℃ or higher. Further, when the Tg of the resin is 140 ℃ or higher, a film in which a dielectric multilayer film can be formed by vapor deposition at a higher temperature is particularly preferable.

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

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

The resin has a polystyrene-equivalent weight average molecular weight (Mw) of usually 15,000 to 350,000, preferably 30,000 to 250,000, and a number average molecular weight (Mn) of usually 10,000 to 150,000, preferably 20,000 to 100,000, as measured by a Gel Permeation Chromatography (GPC) method.

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

Specific examples of these resins include those described in International publication No. 2019/168090.

< other ingredients >

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

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

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

[ Compound (X) ]

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

Examples of the compound (X) include: squarylium compounds, phthalocyanine compounds, polymethine compounds, naphthalocyanine compounds, ketanium compounds, octaporphyrin (octaphyrin) compounds, diimmonium compounds, perylene compounds, and metal dithiolate compounds.

The compound (X) is preferably a squarylium compound, more preferably one or more squarylium compounds and another compound (X'), and particularly preferably a phthalocyanine compound and a polymethine compound.

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

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

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

[ ultraviolet absorbers ]

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

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

[ antioxidant ]

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

< additive >

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

These additives may be used singly or in combination of two or more.

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

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

Basic Material (i)

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

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

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

When the substrate (i) is a multilayer, examples of the substrate (i) include: a base material comprising two or more resin layers, at least one of the two or more resin layers being the resin layer; or a substrate comprising the resin layer and a glass support, and suitable examples thereof include: a substrate (A) comprising a laminate obtained by laminating the resin layer on a support such as a glass support or a resin support as a base; the substrate (B) comprises a laminate in which a resin layer such as an overcoat layer containing a curable resin or the like is laminated on the resin layer.

The substrate (i) is particularly preferably the substrate (B) in terms of manufacturing cost, ease of adjustment of optical characteristics, an effect of removing scratches of the resin layer, improvement of scratch resistance of the substrate (i), and the like.

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

The glass support is preferably a transparent glass support or an absorbing glass support. Among these, the use of an absorbing glass support is preferable because it can sufficiently cut off light having a wavelength in the near infrared region.

The thickness of the substrate (i) is not particularly limited, and is suitably selected depending on the intended use, 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 optical filter using the base material (i) can be made thin and light in weight, and can be suitably used in various applications such as solid-state imaging devices. In particular, when the single-layer base material (i) is used for a lens unit such as a camera module, the lens unit is preferably low in back and light in weight.

[ method for producing base Material (i) ]

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

When the substrate (i) is the substrate (a), the present composition is melt-molded or cast on the support, and preferably applied by a method such as spin coating, slit coating, or ink jet, and then the solvent is dried and removed, and further irradiated with light or heated as necessary, thereby producing a substrate having the present resin layer formed on the support.

Melt forming

Specific examples of the melt molding include: a method of melt-molding pellets obtained by melt-kneading the present composition; a method of melt-molding the present composition; a method of melt-molding pellets obtained by removing a solvent from a liquid composition of the present invention containing a solvent. Examples of the melt molding method include: injection molding, melt extrusion molding, blow molding, or the like.

Tape casting

As the casting, there can be mentioned: a method of removing a solvent by casting a liquid composition containing a solvent on a suitable support; a method in which the present composition curable by a light-curable resin and/or a thermosetting resin is cast on an appropriate support to remove the solvent, and then cured by an appropriate method such as ultraviolet irradiation or heating.

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

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

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

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

The amount of the residual solvent in the resin layers such as the resin layer, the resin support and the overcoat layer is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3% by mass or less, more preferably 1% by mass or less, and 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 which is hardly deformed or hardly changed in properties and can easily exhibit a desired function can be obtained.

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

Optical filter

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

In order to further exhibit the effects and the like of the present invention, specific examples of such a filter include: near infrared cut filter (NIR-CF), visible-near infrared selective transmission filter (DBPF), near infrared transmission filter (IRPF). The filter can be used as a filter for an Alternative Light Source (ALS) used in scientific search or the like. These filters may have a conventional structure except for the substrate (i).

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

Characteristic (a): in the region of a wavelength of 430nm to 580nm, the average value of the transmittance measured from the perpendicular direction of the optical filter is preferably 75% or more, and more preferably 80% or more. The average value of the transmittance is preferably high, and therefore the upper limit thereof is not particularly limited and may be 100%.

When the present filter satisfies the above-mentioned characteristic (a), it can cut off light having a wavelength in the near infrared region to be cut off sufficiently and also suppress a decrease in visible light transmittance, and thus it can be used more suitably as NIR-CF or DBPF.

In the case where the substrate (i) contains a compound satisfying the requirement (B-1) and the present filter is NIR-CF or DBPF, a filter satisfying the following characteristic (B-1) is preferable.

Characteristic (b-1): in the region of 700nm to 800nm in wavelength, the average reflectance of unpolarized light incident from an angle of 5 ° in the vertical direction of at least one surface of the polarizing optical filter is preferably 25% or less, and more preferably 15% or less. The average reflectance is preferably low, and therefore the lower limit thereof is not particularly limited and may be 0%.

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

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

Characteristic (b-2): in the region of 650nm to 800nm, the average reflectance of unpolarized light incident from an angle of 5 ° in the vertical direction of at least one surface of the polarizing optical filter is preferably 25% or less, and more preferably 15% or less. The average reflectance is preferably low, and therefore the lower limit thereof is not particularly limited and may be 0%.

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

In the present invention, the average reflectance at the wavelengths Anm to Bnm is a value calculated by measuring the reflectance at each wavelength in units of 1nm of from Anm to Bnm and dividing the total value of the reflectances by the number of measured reflectances (wavelength range, B-a + 1).

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

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

By satisfying the above characteristics (a), characteristics (b-1) and characteristics (b-2), the present filter can reduce the intensity of reflected light in the near infrared light, particularly in the wavelength region of 650nm to 800nm, while maintaining the transmittance of visible light well, and therefore, in recent years, in an imaging device such as a digital still camera, which has been advanced to have high performance, it is possible to minimize the decrease in sensitivity in the visible light region and to eliminate image defects caused by the reflected light.

The thickness of the present filter may be appropriately selected depending on the intended use, and is preferably thin in accordance with the recent trend toward thinner and lighter solid-state imaging devices and the like.

Since the filter includes the base material (i), the filter can be made thin.

The thickness of the 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, and is preferably 20 μm, for example.

＜NIR-CF＞

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

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

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

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

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

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

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

＜DBPF＞

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

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

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

＜IRPF＞

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

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

Additionally, IRPFs may also use visible light absorbers to cut off visible light.

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

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

In addition, in the IRPF, the transmittance of near infrared rays to be transmitted is preferably high, and specifically, the IRPF has a light transmission band Ya in which the maximum transmittance (T) measured from the perpendicular direction of the filter is present in a region having a wavelength of 750nm or more_IR) Preferably 45% or more, and more preferably 50% or more.

< dielectric multilayer film >

The filter comprises the base material (i) and a dielectric multilayer film. The dielectric multilayer film may be a laminate in which high refractive index material layers and low refractive index material layers are alternately laminated.

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

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

The material constituting the low refractive index material layer may have a refractive index of 1.6 or less, and a material having a refractive index of usually 1.2 to 1.6 may be selected. Examples of such materials include: silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride and sodium aluminum 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 obtained by laminating these material layers can be formed. For example, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately stacked can be directly formed on the base material (i) by a Chemical Vapor Deposition (CVD) method, a sputtering method, a vacuum Deposition method, an ion-assisted Deposition method, an ion plating method, or the like.

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

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

In the present filter, by appropriately selecting the types of materials constituting the high refractive index material layer and the low refractive index material layer, the thicknesses of the respective layers of the high refractive index material layer and the low refractive index material layer, the order of lamination, and the number of lamination in combination with the absorption characteristics of the compound (Z), etc., it is possible to ensure sufficient transmittance in a wavelength region to be transmitted (for example, visible region), and also to reduce the reflectance when light (for example, near infrared light) enters from an oblique direction while having sufficient light cutoff characteristics in a wavelength region to be cut off (for example, near infrared region).

In order to optimize the condition of the dielectric multilayer Film, parameters may be set so as to achieve both the antireflection effect in a wavelength region to be transmitted (for example, visible region) and the light-blocking effect in a wavelength region to be blocked (for example, near infrared region) by using, for example, optical Film design software (for example, manufactured by Thin Film Center, inc.). In the case of the software, for example, there may be mentioned: in forming the dielectric multilayer film of NIR-CF, a parameter setting method is used, such as setting the Target transmittance at a wavelength of 400nm to 700nm to 100%, setting the Target Tolerance (Target Tolerance) to 1, setting the Target transmittance at a wavelength of 705nm to 950nm to 0%, and setting the Target Tolerance to 0.5.

These parameters may also be used to change the value of the target tolerance by dividing the wavelength range more finely in conjunction with various characteristics of the substrate (i) and the like.

< other functional membranes >

For the purpose of improving the surface hardness of the substrate (i) or the dielectric multilayer film, improving chemical resistance, antistatic property, removing damage, and the like, the filter may be provided with a functional film such as an antireflection film, a hard coat film, or an antistatic film as appropriate between the substrate (i) and the dielectric multilayer film, on the surface of the substrate (i) opposite to the surface provided with the dielectric multilayer film, or on the surface of the dielectric multilayer film opposite to the surface provided with the substrate (i), within a range not impairing the effects of the present invention.

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

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

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

Examples of the coating agent include Ultraviolet (UV)/Electron Beam (EB) curable resins and thermosetting resins, and specifically include: vinyl compounds, urethane-based, urethane acrylate-based, epoxy-based, and epoxy acrylate-based resins, and the like. One coating agent may be used alone, or two or more coating agents may be used.

The curable composition containing these coating agents includes: and curable compositions of vinyl, urethane acrylate, epoxy, and epoxy acrylate.

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

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

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

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.

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

[ use of optical Filter ]

The present filter is excellent in, for example, the ability to cut off light having a wavelength in a region to be cut off and the ability to transmit light having a wavelength to be transmitted. Therefore, the present invention is useful for correcting the visibility of a solid-state imaging device such as a CCD or CMOS image sensor as a camera module. In particular, the present invention is useful in digital still cameras, cameras for smartphones, cameras for mobile phones, digital video cameras, cameras for wearable devices, Personal Computer (PC) cameras, monitoring cameras, cameras for automobiles, infrared cameras, televisions, car navigation systems, portable information terminals, video game machines, portable game machines, fingerprint authentication systems, digital music players, various sensing systems, infrared communication, and the like. Further, the present invention is also useful as a heat ray cut filter or the like mounted on a glass plate or the like of an automobile, a building or the like.

Solid-state imaging device

The solid-state imaging device of the present invention includes the present filter. Here, the solid-state imaging device is a device including a solid-state imaging element such as a CCD or CMOS image sensor, and specifically, can be used in applications such as a digital still camera, a camera for a smartphone, a camera for a mobile phone, a camera for a wearable device, and a digital video camera.

Optical sensor device

The optical sensor device of the present invention is not particularly limited as long as it includes the filter, and may have a conventional configuration.

For example, a device having a light-receiving element and the filter can be mentioned, and specifically, a device having a light-receiving element (semiconductor substrate), a protective film, the filter and other filters can be mentioned.

[ examples ]

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

[ Synthesis examples ]

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

For the compound (Z), for example, Japanese patent laid-open Nos. 2009-108267, 5-59291, 2014-95007, 2011-52218, 2007/114398, 2003-246940, and "heterocyclic compound chemistry: cyanine Dyes and Related Compounds (Chemistry of Heterocyclic Compounds: The Cyanine Dyes and Related Compounds) (Vol.18 (Wiley, 1964)), (Near-Infrared Dyes for High Technology Applications) (Style.P.G. (Springer, 1997).

The compound (X) can be synthesized, for example, by referring to the methods described in Japanese patent No. 3366697, Japanese patent No. 2846091, Japanese patent No. 2864475, Japanese patent No. 3703869, Japanese patent application laid-open No. Sho 60-228448, Japanese patent application laid-open No. Hei 1-146846, Japanese patent application laid-open No. Hei 1-228960, Japanese patent No. 4081149, Japanese patent application laid-open No. Sho 63-124054, phthalocyanine-chemical and functional- (IPC, 1997), Japanese patent application laid-open No. 2007-1699315, Japanese patent application laid-open No. 2009-open No. 108267, Japanese patent application laid-open No. 2010-241873, Japanese patent No. 3699464, and Japanese patent No. 4740631.

[ intermediate Synthesis example 1]

[ solution 16]

In a 200mL eggplant type flask equipped with a stirrer, 21.8g of ethyl pivalate was added to 18.33 g of compound a synthesized by the method described in Bioorganic and Medicinal Chemistry (2013, vol.21, #11, p.2826-2831), 5 minutes later, 4.0g of sodium hydride (60% dispersed in Paraffin Liquid) was added, and the mixture was stirred at 80 ℃ for 3 hours. Thereafter, the mixture was cooled to room temperature, and 100mL of a 1N aqueous hydrochloric acid solution was added for neutralization, and then the solution was transferred to a separatory funnel, and 150mL of ethyl acetate was used to extract an organic phase. Then, magnesium sulfate 15g was added to the extracted organic phase and stirred for 15 minutes, and then the magnesium sulfate was removed by filtration through a filter, and the filtrate was put into a 300mL eggplant type flask, and the solvent was distilled off by using an evaporator, whereby compound a-2 was obtained.

A stirrer was placed in an eggplant type flask containing the compound a-2, and 20mL of concentrated hydrochloric acid was added thereto and stirred at 40 ℃. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 200mL of a 1N aqueous sodium hydroxide solution was added for neutralization. Then, the mixture was transferred to a separatory funnel, 150mL of ethyl acetate was added and the organic phase was extracted, and thereafter, 15g of magnesium sulfate was added and stirred for 15 minutes. Then, magnesium sulfate was removed by filtration through a filter, and then the filtrate was placed in a 300mL round bottom flask, and the solvent was distilled off using an evaporator. Thereafter, the compound remaining in the flask was separated and purified by silica gel chromatography, whereby 5.0g of the objective compound a-3 was obtained. Furthermore, compounds were identified by liquid chromatography-mass spectrometry (LC-MS) and¹h-nuclear magnetic resonance (¹H-nuclear magnetic resonance，¹H-NMR) analysis.

[ intermediate Synthesis example 2]

[ solution 17]

In a 200mL round bottom flask equipped with a stirrer, 30mL of diethyl ether and 33g of compound a were placed, and the flask was cooled in an ice bath with stirring. After cooling in an ice bath for 5 minutes, 13.5mL of a 1mol/L solution of methyl magnesium iodide in diethyl ether was added over 10 minutes, followed by heating to 35 ℃ and stirring for 2 hours. Then, the reaction solution was cooled in an ice bath, 30mL of a 20% perchloric acid aqueous solution was added, the precipitated solid was separated by filtration, washed with 20mL of water, and dried under reduced pressure at 50 ℃ to obtain 2.5g of a compoundObject a-4. Furthermore, the identification of the compounds is by use of¹H-NMR analysis was carried out.

[ Synthesis example of Compound (z-1) ]

[ solution 18]

In a 100mL round bottom flask equipped with a stirrer, were placed compound a-41.5 g, N- [2-chloro-3- (phenylamino) -2-propenylidene ] -aniline monohydrochloride (N- [2-chloro-3- (phenylamino) -2-propenylidine ] -benzamine monohydrochloride)0.6g, acetonitrile 25mL, anhydrous acetic acid 7.5mL, and pyridine 0.6mL, and the mixture was refluxed for 5 hours. Then, the mixture was cooled to room temperature, and the solvent was distilled off by an evaporator, followed by addition of 5mL of acetic acid and cooling and standing at 5 ℃ for 2 days. Thereafter, the deposited solid was filtered under reduced pressure, and washed with 5mL of acetic acid and 10mL of hexane to obtain 0.17g of compound a-5.

In a 100mL round bottom flask equipped with a stirrer, compound a-50.1 g, lithium tetrakis-pentafluorophenyl borate 0.2g, methylene chloride 20mL, and water 10mL were added, and the mixture was stirred at room temperature for 1 hour. Then, the mixture was transferred to a separatory funnel, the aqueous phase was removed, and then the organic phase was washed with 20mL of water 2 times, and 1g of sodium sulfate was added thereto and stirred for 15 minutes. Thereafter, sodium sulfate was removed by filtration through a filter, and the filtrate was placed in a 300mL eggplant type flask, and the solvent was distilled off using an evaporator and dried under reduced pressure at 50 ℃. Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 3]

[ solution 19]

In a 300mL round bottom flask equipped with a stirrer, 5g of flavone (compound a-6) and 50mL of Tetrahydrofuran (THF) were added, and the mixture was cooled in an ice bath. After cooling in ice bath for 5 minutes24.7mL of a 1mol/L solution of magnesium methyl iodide in diethyl ether was added over 10 minutes, followed by heating to 35 ℃ and stirring for 2 hours. Subsequently, the reaction solution was cooled in an ice bath, 50mL of a 20% perchloric acid aqueous solution was added, and the precipitated solid was separated by filtration, washed with 50mL of water, and dried under reduced pressure at 50 ℃ to obtain 4.5g of compound a-7. Furthermore, the identification of the compounds is by use of¹H-NMR analysis was carried out.

[ Synthesis example of Compound (z-16) ]

[ solution 20]

In a 100mL round bottom flask equipped with a stirrer, compound a-70.7 g, malonaldehyde bisanilide hydrochloride 0.26g, acetonitrile 10mL, anhydrous acetic acid 5mL, and pyridine 0.2mL were added, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure and washed with 10mL of diethyl ether, whereby 0.6g of compound a-8 was obtained.

In a 100mL round bottom flask equipped with a stirrer, compound a-80.1 g, lithium tetrakis-pentafluorophenyl borate 0.2g, methylene chloride 20mL, and water 10mL were added, and the mixture was stirred at room temperature for 3 hours. Then, the mixture was transferred to a separatory funnel, the aqueous phase was removed, the organic phase was washed with 20mL of water 2 times, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, the residue was dissolved in 0.5mL of acetone, 10mL of methanol was added and ice-bath cooling was performed, and the precipitated solid was recovered by suction filtration and dried under reduced pressure at 50 ℃ to obtain 0.07g of compound (z-16). Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 4]

[ solution 21]

In a 200mL eggplant type flask equipped with a stirrer, compounds a to 94 g and 21.8g of ethyl pivalate were added and stirred, and after 5 minutes, 3.2g of sodium hydride (60% dispersed in a paraffin liquid) was added and then stirred at 80 ℃ for 3 hours. Thereafter, the mixture was cooled to room temperature, and after 30mL of a 1N aqueous hydrochloric acid solution was added for neutralization, the organic phase was extracted with 150mL of ethyl acetate. Then, after 15g of magnesium sulfate was added to the organic phase and stirred for 15 minutes, the magnesium sulfate was removed by filtration through a filter, the filtrate was placed in a 300mL eggplant type flask, and the solvent was distilled off by using an evaporator, whereby compound a-10 was obtained.

A stirrer was placed in an eggplant type flask containing the compound a-10, and 20mL of concentrated hydrochloric acid was added thereto and stirred at 40 ℃. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 240mL of a 1N aqueous solution of sodium hydroxide was added for neutralization. Then, the solution was transferred to a separatory funnel, 200mL of ethyl acetate was added and the organic phase was extracted, and thereafter, 15g of magnesium sulfate was added and stirred for 15 minutes. Thereafter, magnesium sulfate was removed by filtration through a filter, and the filtrate was placed in a 300mL round bottom flask, and the solvent was distilled off using an evaporator. Thereafter, the compound remaining in the flask was separated and purified by silica gel chromatography, whereby 2.0g of the objective compound a-11 was obtained. Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 5]

[ solution 22]

In a 200mL round bottom flask equipped with a stirrer, compound a-112.7 g and 50mL of diethyl ether were added, and the mixture was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 24.7mL of a 1mol/L solution of methyl magnesium iodide in diethyl ether was added over 10 minutes, followed by heating to 35 ℃ and stirring for 2 hours. Then, the reaction solution was cooled in an ice bath, 50mL of a 20% perchloric acid aqueous solution was added, and the precipitated solid was separated by filtration, washed with 50mL of water, and dried under reduced pressure at 50 ℃ to obtain 0.7g of compound a-12. Furthermore, identification of the CompoundsIs to utilize¹H-NMR analysis was carried out.

[ Synthesis example of Compound (z-59) ]

[ solution 23]

In a 100mL round bottom flask equipped with a stirrer, compound a-120.5 g, malonaldehyde bisanilide hydrochloride 0.22g, acetonitrile 7.5mL, anhydrous acetic acid 2.5mL, and pyridine 0.2mL were added, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10mL of acetic acid and 10mL of acetonitrile, and dried under reduced pressure at 50 ℃.

In a 100mL round bottom flask equipped with a stirrer, compound a-130.3 g, lithium tetrakis-pentafluorophenyl borate 0.8g, dichloromethane 50mL, and water 20mL were added, and the mixture was stirred at room temperature for 3 hours. Then, the mixture was transferred to a separatory funnel, the aqueous phase was removed, the organic phase was washed with 20mL of water 2 times, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, the residue was dissolved in 20mL of acetone, 100mL of water was added, and 13g of the solvent was distilled off by an evaporator, followed by cooling in an ice bath. Thereafter, the precipitated solid was recovered by suction filtration, washed with 50mL of methanol, and dried under reduced pressure at 50 ℃ to obtain 0.5g of the compound (z-59). Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 6]

[ solution 24]

In a 200mL eggplant type flask equipped with a stirrer, 144.5 g of the compound a and 21.8g of ethyl isobutyrate were charged and stirred, and after 5 minutes, 3.2g of sodium hydride (60% dispersed in a paraffin liquid) was added and then stirred at 80 ℃ for 3 hours. Thereafter, the mixture was cooled to room temperature, and after 30mL of a 1N aqueous hydrochloric acid solution was added for neutralization, the organic phase was extracted with 150mL of ethyl acetate. Then, magnesium sulfate 15g was added to the organic phase and stirred for 15 minutes, and then the magnesium sulfate was removed by filtration through a filter, and the filtrate was put into a 300mL eggplant type flask, and the solvent was distilled off by using an evaporator, whereby compound a-15 was obtained.

A stirrer was placed in an eggplant type flask containing the compound a-15, and 20mL of concentrated hydrochloric acid was added thereto and stirred at 40 ℃. After stirring for 1 hour, the reaction solution was cooled in an ice bath and neutralized by adding 240mL of a 1N aqueous solution of sodium hydroxide. Thereafter, the solution was transferred to a separatory funnel, 200mL of ethyl acetate was added and the organic phase was extracted, and thereafter, 15g of magnesium sulfate was added and stirred for 15 minutes. Then, magnesium sulfate was removed by filtration through a filter, and the filtrate was placed in a 300mL round bottom flask, and the solvent was distilled off using an evaporator. Thereafter, the compound remaining in the flask was separated and purified by silica gel chromatography, whereby 0.4g of the objective compound a-16 was obtained. Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 7]

[ solution 25]

In a 100mL round bottom flask equipped with a stirrer, compound a-160.4 g and 10mL of diethyl ether were added, and the mixture was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 5.0mL of a 1mol/L solution of methyl magnesium iodide in diethyl ether was added over 10 minutes, followed by heating to 35 ℃ and stirring for 2 hours. Then, the reaction solution was cooled in an ice bath, 10mL of a 20% perchloric acid aqueous solution was added, 20mL of dichloromethane was added, and the mixture was transferred to a separatory funnel, and the organic phase was recovered. The solvent was distilled off from the organic phase using an evaporator, and the solid residue was stirred, 20mL of diethyl ether was added, and the mixture was stirred for 20 minutes. Then, the solid content was collected by suction filtration and dried under reduced pressure at 50 ℃ to obtain 0.5g of compound a-17. Furthermore, the identification of the compounds is by use of¹H-NMR analysis was carried out.

[ Synthesis example of Compound (z-62) ]

[ solution 26]

In a 100mL round bottom flask equipped with a stirrer, compound a-170.4 g, malonaldehyde bisanilide hydrochloride 0.16g, acetonitrile 7.5mL, anhydrous acetic acid 2.5mL, and pyridine 0.2mL were added, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10mL of diethyl ether, and dried under reduced pressure at 50 ℃ to obtain 0.35g of compound a-18.

In a 100mL round bottom flask equipped with a stirrer, compound a-180.3 g, lithium tetrakis-pentafluorophenyl borate 0.8g, dichloromethane 50mL, and water 20mL were added, and the mixture was stirred at room temperature for 3 hours. Thereafter, the mixture was transferred to a separatory funnel, the aqueous phase was removed, the organic phase was washed with 20mL of water 2 times, the solvent was distilled off from the organic phase using an evaporator, and the solid was dried under reduced pressure at 50 ℃ to obtain 0.4g of compound (z-62). Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 8]

[ solution 27]

In a 200mL eggplant type flask equipped with a stirrer, 28.7g of compound a-1915 g and methyl 4, 4-dimethyl-3-oxopentanoate were added and the mixture was stirred at 180 ℃ for 24 hours. Thereafter, the mixture was cooled to room temperature, 250mL of hexane and 200mL of 1N aqueous hydrochloric acid solution were added, and the mixture was transferred to a separatory funnel to remove the aqueous phase. Then, after a solvent was distilled off from the organic phase by using an evaporator, the compound remaining in the flask was separated and purified by silica gel chromatography, whereby 7g of the objective compound a-20 was obtained. Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 9]

[ solution 28]

In a 100mL round bottom flask equipped with a stirrer, 20mL of diethyl ether and compound a-203.5 g were added, and the mixture was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 14.0mL of a 1mol/L solution of methyl magnesium iodide in diethyl ether was added over 10 minutes, followed by heating to 35 ℃ and stirring for 2 hours. Then, after naturally cooling to room temperature, the obtained reaction solution was added over 5 minutes to a beaker containing 100mL of water and a stirrer. Thereafter, 20g of a 40% aqueous solution of fluoroboric acid was added over 10 minutes, and after stirring for 30 minutes, the mixture was transferred to a separatory funnel. Then, 30mL of dichloromethane was added to conduct liquid separation, thereby removing the aqueous phase, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, the residue was dissolved in 30mL of dichloromethane, 50mL of diisopropyl ether was added, 40g of the solvent was removed by an evaporator, the mixture was cooled in an ice bath, and the precipitated solid was collected by suction filtration and dried under reduced pressure at 50 ℃ to obtain 2.3g of compound a-21. Furthermore, the identification of the compounds is by use of¹H-NMR analysis was carried out.

[ Synthesis example of Compound (z-151) ]

[ solution 29]

In a 100mL round bottom flask equipped with a stirrer, compound a-210.5 g, malonaldehyde bisanilide hydrochloride 0.18g, and pyridine 15mL were added, and the mixture was refluxed for 2 hours. Thereafter, the mixture was cooled to room temperature, and then the solvent was distilled off by an evaporator and the mixture was separated by column chromatography, whereby 0.2g of compound a-22 was obtained.

In a 100mL round bottom flask equipped with a stirrer, compound a-220.2 g, lithium tetrakis-pentafluorophenyl borate 0.8g, dichloromethane 50mL, and water 20mL were added and the mixture was placed in the flaskStirred at room temperature for 3 hours. Thereafter, the mixture was transferred to a separatory funnel, the aqueous phase was removed, the organic phase was washed with 20mL of water 2 times, the solvent was distilled off from the organic phase using an evaporator, and the mixture was separated by column chromatography, whereby 0.2g of compound (z-151) was obtained. Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 10]

[ solution 30]

In a 200mL eggplant type flask equipped with a stirrer, 0.3g of sodium hydride (60% dispersed in a paraffin liquid) was added after 5 minutes while stirring the mixture of compounds a to 231.9 g and ethyl pivalate was added, and then the mixture was stirred at 80 ℃ for 3 hours. Thereafter, the mixture was cooled to room temperature, and after 30mL of a 1N aqueous hydrochloric acid solution was added for neutralization, the organic phase was extracted with 150mL of ethyl acetate. Then, magnesium sulfate 5g was added to the organic phase, and the mixture was stirred for 15 minutes, after which the magnesium sulfate was removed by filtration through a filter, the filtrate was placed in a 300mL eggplant type flask, and the solvent was distilled off by using an evaporator, whereby compound a-241.3 g was obtained.

A stirrer was placed in an eggplant type flask containing 241.3 g of the compound a, and 20mL of concentrated hydrochloric acid was added thereto and stirred at 40 ℃. After stirring for 1 hour, the reaction solution was cooled in an ice bath and neutralized by adding 240mL of a 1N aqueous solution of sodium hydroxide. Then, the solution was transferred to a separatory funnel, 200mL of ethyl acetate was added and the organic phase was extracted, and thereafter, 5g of magnesium sulfate was added and stirred for 15 minutes. Thereafter, magnesium sulfate was removed by filtration through a filter, and the filtrate was placed in a 300mL round bottom flask, and the solvent was distilled off using an evaporator. Thereafter, the compound remaining in the flask was separated and purified by silica gel chromatography, whereby 1.1g of compound a-25 was obtained. Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 11]

[ solution 31]

In a 200mL round bottom flask equipped with a stirrer, compound a-251.5 g and 50mL of diethyl ether were added, and the mixture was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 1mol/L of 1.5mL of a methyl magnesium iodide diethyl ether solution was added over 10 minutes, followed by heating to 35 ℃ and stirring for 2 hours. Then, the reaction solution was cooled in an ice bath, 50mL of a 20% perchloric acid aqueous solution was added, and the precipitated solid was separated by filtration, washed with 50mL of water, and dried under reduced pressure at 50 ℃ to obtain 3.0g of compound a-26. Furthermore, the identification of the compounds is by use of¹H-NMR analysis was carried out.

[ Synthesis example of Compound (z-157) ]

[ solution 32]

In a 100mL round bottom flask equipped with a stirrer, compound a-267.0 g, malonaldehyde bisanilide hydrochloride 2.5g, acetonitrile 50mL, anhydrous acetic acid 10mL, and pyridine 10mL were added, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10mL of acetic acid and 10mL of acetonitrile, and dried under reduced pressure at 50 ℃.

In a 100mL round bottom flask equipped with a stirrer, compound a-270.6 g, lithium tetrakis-pentafluorophenyl borate 1.2g, dichloromethane 50mL, and water 50mL were added, and the mixture was stirred at room temperature for 3 hours. Then, the mixture was transferred to a separatory funnel, the aqueous phase was removed, the organic phase was washed with 20mL of water 2 times, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, the residue was dissolved in 20mL of acetone, 100mL of water was added, and 10g of the solvent was distilled off by an evaporator, followed by cooling in an ice bath. Thereafter, the precipitated solid was collected by suction filtration, washed with 50mL of methanol, and dried at 50 ℃ under reduced pressure to obtain a solid1.0g of Compound (z-157). Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 12]

[ solution 33]

In a 200mL round bottom flask equipped with a stirrer, 22g of 1-adamantanecarbonyl chloride (compound a-28) and 5.2g of methylcyclohexane were charged, and the mixture was heated to 90 ℃ and stirred for 10 minutes while 10g of trifluoromethanesulfonic acid was added dropwise. Then, after cooling to 0 ℃, 150mL of hexane, 50mL of diethyl ether and 50mL of water were added thereto, followed by stirring, and the precipitated solid was separated by filtration and dried under reduced pressure at 50 ℃, whereby 4.2g of compound a-35 was obtained. Furthermore, the identification of the compounds is by use of¹H-NMR analysis was carried out.

[ Synthesis example of Compound (z-163 ]

[ chemical 34]

In a 100mL round bottom flask equipped with a stirrer, compound a-350.5 g, malonaldehyde bisanilide hydrochloride 0.1g, acetonitrile 4mL, anhydrous acetic acid 1mL, and pyridine 1mL were added, and the mixture was stirred at 90 ℃ for 10 minutes. After cooling to 0 ℃, the precipitated solid was separated by filtration, washed with 2mL of acetonitrile, and dried under reduced pressure at 50 ℃ to obtain 0.3g of compound a-36. Furthermore, the identification of the compounds is by use of¹H-NMR analysis was carried out.

In a 100mL round bottom flask equipped with a stirrer, compound a-360.3 g, lithium tetrakis-pentafluorophenyl borate 0.4g, methylene chloride 20mL, and water 20mL were added, and the mixture was stirred at room temperature for 4 hours. Then, the mixture was transferred to a separatory funnel, the aqueous phase was removed, the organic phase was washed with 20mL of water 2 times, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, makeThe residue was dissolved in methylene chloride, methanol was added thereto, and the precipitated solid was recovered by suction filtration and dried under reduced pressure at 50 ℃ to obtain 0.4g of a compound (z-163). Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 13]

[ solution 35]

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

Thereafter, 60mL of concentrated hydrochloric acid was added without purifying compound a-38, and the mixture was stirred at 40 ℃. After 1 hour, the reaction solution was cooled in an ice bath, and neutralized by adding a 1N aqueous solution of sodium hydroxide. After the mixture was washed with ethyl acetate-water, sodium sulfate was added thereto and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography, whereby compound a-39(15.4g) was obtained. The compounds were identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 14]

[ solution 36]

Compound a-39(15.4g), phenylboronic acid (11.7g), tetrakis (triphenylphosphine) palladium (1.0g), and potassium carbonate (60.0g) were dissolved in a mixed solution of 50mL of toluene and 50mL of water, and the mixture was heated at 110 ℃ for 12 hours with vigorous stirring. After the mixture was left to cool to room temperature, the mixture was washed with toluene-water, and the organic layer was dried over sodium sulfate, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography, whereby compound a-40(12.4g) was obtained.

Compound a-40(12.4g) and 90mL of tetrahydrofuran were cooled in an ice bath with stirring. After cooling in an ice bath for 5 minutes, a solution of magnesium methyliodide in diethyl ether (1mol/L, 50mL) was added dropwise, heated to 35 ℃ and stirred for 2 hours. Then, the reaction solution was cooled in an ice bath, 90mL of a 20% perchloric acid aqueous solution was added, and the precipitated solid was separated by filtration, washed with 60mL of water, and dried under reduced pressure at 50 ℃ to obtain compound a-41(10.4 g). Identification of the Compound by¹H-NMR analysis was carried out.

[ Synthesis example of Compound (z-156) ]

[ solution 37]

In a 100mL round bottom flask equipped with a stirrer, compound a-417.0 g, malonaldehyde bisanilide hydrochloride 2.5g, acetonitrile 50mL, anhydrous acetic acid 10mL, and pyridine 10mL were added, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10mL of acetic acid and 10mL of acetonitrile, and dried under reduced pressure at 50 ℃.

In a 100mL round bottom flask equipped with a stirrer, compound a-420.6 g, lithium tetrakis-pentafluorophenyl borate 1.2g, dichloromethane 50mL, and water 50mL were added, and the mixture was stirred at room temperature for 3 hours. Then, the mixture was transferred to a separatory funnel, the aqueous phase was removed, the organic phase was washed with 20mL of water 2 times, and the solvent was distilled off from the organic phase using an evaporator. Thereafter, the residue was dissolved in 20mL of acetone, 100mL of water was added, and 10g of the solvent was distilled off by an evaporator, followed by cooling in an ice bath. Thereafter, the precipitated solid was collected by suction filtration, washed with 50mL of methanol, and dried under reduced pressure at 50 ℃ to obtain 1.0g of compound (z-156). Furthermore, the device is provided withThe compounds are identified by LC-MS and¹H-NMR analysis was carried out.

[ intermediate Synthesis example 15]

[ solution 38]

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

[ Synthesis example of Compound (z-161) ]

[ solution 39]

Compound a-45 was obtained in the same manner as in intermediate Synthesis example 10, except that ethyl pivalate was changed to Compound a-44.

Changing compound a-23 to compound a-45 and changing malonaldehyde bisanilide hydrochloride to N- [2-chloro-3- (phenylamino) -2-propenylene]Compound (z-161) was obtained in the same manner as in intermediate Synthesis example 11 and Compound (z-157) except that aniline monohydrochloride was used. Furthermore, compounds were identified by LC-MS and¹H-NMR analysis was carried out.

< Condition (A) >

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

< Condition (B) >

The requirement (B) was measured by using an absorption spectrum measured by using a spectrophotometer (V-7200) manufactured by japan spectroscopy (japan). The results are shown in table 5.

< Condition (C) >

Into a vessel, 100 parts by mass of the resin a obtained in resin synthesis example 1, 0.3 parts by mass of Irganox 1010 (manufactured by BASF Japan) and the compound (Z) or the compound (X) used in the following test, and methylene chloride were charged to prepare a solution having a resin concentration of 20% by mass.

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

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

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

< Condition (D) >

In an absorption spectrum measured using a spectrophotometer (V-7200) manufactured by japan spectroscopy (thigh) using a solution obtained by dissolving a compound (Z) or a compound (X) used in the following test in methylene chloride, the absorbance at the longest wavelength among the maximum absorption wavelengths is represented by ∈ a, and the maximum value of the absorbance at a wavelength of 430nm to 580nm is represented by ∈ bmax, and ∈ a/∈ -bmax is calculated. The results are shown in table 5.

< molecular weight >

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

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

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

The resin synthesized in resin synthesis example 3 described later was measured not for molecular weight by the above-described method but for logarithmic viscosity by the following method (c).

(c) A part of the polyimide solution was put into anhydrous methanol to precipitate polyimide, and the resultant was separated from the unreacted monomer by filtration, and then dried under vacuum at 80 ℃ for 12 hours. 0.1g of the obtained polyimide was dissolved in 20mL of N-methyl-2-pyrrolidone (diluted polyimide solution), and the logarithmic viscosity (. mu.) at 30 ℃ was determined from the following formula using Cannon-Fenske viscometer.

μ＝{ln(ts/t0)}/C

t 0: flowing-down time of solvent (N-methyl-2-pyrrolidone)

ts: flow down time of thin polyimide solution

C：0.5g/dL

< glass transition temperature (Tg) >

The glass transition temperature of the resin was measured using a differential scanning calorimeter (DSC6200) manufactured by Hitachi High-Tech Science (stock), and the glass transition temperature was measured at a temperature increase rate: the measurement was carried out at 20 ℃ per minute under a nitrogen stream.

[ resin Synthesis example 1]

The following 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ] is introduced^2,5.1^7,10]100 parts by mass of dodec-3-ene (hereinafter also referred to as "DNM"), 18 parts by mass of 1-hexene (molecular weight modifier) and 300 parts by mass of toluene (solvent for ring-opening polymerization) were charged in a reaction vessel purged with nitrogen, and the solution was heated to 80 ℃. Then, 0.2 part by mass of a toluene solution of triethylaluminum (0.6 mol/liter) and 0.9 part by mass of a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol/liter) were added to the solution in the reaction vessel as a polymerization catalyst, and the solution was heated and stirred at 80 ℃ for 3 hours to perform a ring-opening polymerization reaction, thereby obtaining a ring-opening polymer solution. The polymerization conversion in the polymerization reaction was 97%.

[ solution 40]

1,000 parts by mass of the obtained ring-opened polymer solution was charged into an autoclave, and 0.12 part by mass of RuHCl (CO) [ P (C)₆H₅)₃]₃At a hydrogen pressure of 100kg/cm²And the reaction temperature was 165 ℃ and the mixture was stirred with heating for 3 hours to effect hydrogenation. After the obtained reaction solution (hydrogenated polymer solution) was cooled, the pressure of hydrogen gas was released. The obtained reaction solution was poured into a large amount of methanol, and a coagulated product was separated and recovered, followed by drying 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 ℃.

[ resin Synthesis example 2]

Into a 3L four-necked flask were charged 35.12g (0.253mol) of 2, 6-difluorobenzonitrile, 87.60g (0.250mol) of 9, 9-bis (4-hydroxyphenyl) fluorene, 41.46g (0.300mol) of potassium carbonate, 443g of N, N-dimethylacetamide and 111g of toluene. Then, a thermometer, a stirrer, a three-way cock with a nitrogen inlet, a Dean-Stark tube, and a cooling tube were placed in the four-necked flask. Then, after the flask was purged with nitrogen, the obtained solution was reacted at 140 ℃ for 3 hours, and the produced water was removed from the dean-stark tube as needed. When no water was produced, the temperature was gradually increased to 160 ℃ and the reaction was carried out at the temperature for 6 hours. Thereafter, the reaction mixture was cooled to room temperature (25 ℃), the formed salt was removed with filter paper, the filtrate was put into methanol to reprecipitate, and the filtrate (residue) was separated by filtration separation. The obtained filtrate was vacuum-dried at 60 ℃ overnight, whereby a white powder (hereinafter also referred to as "resin B") was obtained (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 ℃.

[ resin Synthesis example 3]

In a 500mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a side-capped dropping funnel, a dean-Stark tube and a cooling tube, 1, 4-bis (methylene blue) was placed under a nitrogen stream27.66g (0.08 mol) of (4-amino-. alpha.,. alpha. -dimethylbenzyl) benzene and 7.38g (0.02 mol) of 4,4' -bis (4-aminophenoxy) biphenyl were dissolved in 68.65g of γ -butyrolactone and 17.16g of N, N-dimethylacetamide. The obtained solution was cooled to 5 ℃ using an ice water bath, and 22.62g (0.1 mol) of 1,2,4, 5-cyclohexanetetracarboxylic dianhydride and 0.50g (0.005 mol) of triethylamine as an imidization catalyst were added together while maintaining the same temperature. After the addition, the temperature was raised to 180 ℃ and the mixture was refluxed for 6 hours while distilling off the distillate as needed. After the reaction was completed, the mixture was air-cooled until the internal temperature became 100 ℃, and then 143.6g of N, N-dimethylacetamide was added to dilute the mixture, and the mixture was cooled while stirring, whereby 264.16g of a polyimide solution having a solid content of 20 mass% was obtained. A portion of the polyimide solution was poured into 1L of methanol and polyimide was precipitated. The polyimide separated by filtration was washed with methanol and then dried in a vacuum dryer at 100 ℃ for 24 hours, whereby a white powder (hereinafter also referred to as "resin C") was obtained. The obtained resin C was measured for its Infrared (IR) spectrum, and as a result, 1704cm of an Infrared (IR) spectrum unique to the imide group was observed^-1、1770cm^-1Absorption of (2). The glass transition temperature (Tg) of resin C was 310 ℃ and the logarithmic viscosity was measured to be 0.87.

[ example 1]

[ production of base Material ]

Into a vessel, 100 parts by mass of the resin A obtained in resin Synthesis example 1, 0.20 part by mass of the following compound (Z-1) (absorption maximum wavelength in methylene chloride is 787nm) as the compound (Z), 0.038 part by mass of the following compound (X-1) (absorption maximum wavelength in methylene chloride is 711nm) as the compound (X), 0.075 part by mass of the following compound (X-2) (absorption maximum wavelength in methylene chloride is 738nm), and methylene chloride were charged 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 ℃ for 8 hours, and then peeled from the glass plate. The peeled coating film was dried under reduced pressure at 100 ℃ for 8 hours to obtain a resin layer (1) having a thickness of 0.1mm, a length of 210mm and a width of 210 mm.

Compound (z-1)

[ solution 41]

Compound (x-1)

[ solution 42]

Compound (x-2)

[ solution 43]

The following resin composition (1) was applied to one surface of the obtained resin layer (1) by a bar coater so that the thickness of the obtained resin layer (2) was 3 μm, and the resin layer was heated in an oven at 70 ℃ for 2 minutes to volatilize and remove the solvent. Next, exposure (exposure amount 500 mJ/cm) was carried out using a UV conveyor type exposure machine (manufactured by Eygraphics, Egyo ultraviolet hardening apparatus, model No. US2-X0405, 60Hz)²Illuminance: 200mW/cm²) The resin composition (1) is cured to form a resin layer (2) on the resin layer (1). In the same manner, the resin layer (2) containing the resin composition (1) is also formed on the other surface of the resin layer (1). Thus, a substrate having resin layers (2) not containing the compound (Z) on both sides of the resin layer (1) containing the compound (Z) was obtained.

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

(light resistance)

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

The residual dye ratio after exposure to a fluorescent lamp for 500 hours was 95% or more, and the residual dye ratio was "o" and "x" when the residual dye ratio was less than 95%. The results are shown in Table 8.

[ production of optical Filter ]

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

The dielectric multilayer film (I) is prepared by depositing silicon dioxide (SiO) at a deposition temperature of 100 deg.C₂) Layer with titanium dioxide (TiO)₂) A laminate (26 layers in total) in which the layers are alternately laminated. The dielectric multilayer film (II) is formed by depositing silicon dioxide (SiO) at a deposition temperature of 100 deg.C₂) Layer with titanium dioxide (TiO)₂) A laminate (22 layers in total) in which the layers are alternately laminated.

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

The thickness and number of layers of each layer are optimized by using optical Film design software (core mclaud, Thin Film Center, manufactured by Thin Film Center) so that favorable transmittance in the visible region and reflection performance in the near infrared region can be achieved, depending on the wavelength dependence of the refractive index of the substrate, or the absorption characteristics of the compound (Z) and the compound (X) used. In the optimization, in the present embodiment, the input parameters (Target values) to the software are set as shown in table 6 below.

[ Table 6]

As a result of optimizing the film structure, the dielectric multilayer film (I) was formed as a multilayer deposited film having a number of 26 layers in which a silicon dioxide layer having a physical thickness of about 37 to 168nm and a titanium dioxide layer having a physical thickness of about 11 to 104nm were alternately stacked, and the dielectric multilayer film (II) was formed as a multilayer deposited film having a number of 22 layers in which a silicon dioxide layer having a physical thickness of about 40 to 191nm and a titanium dioxide layer having a physical thickness of about 10 to 110nm were alternately stacked. An example of the optimized film structure is shown in table 7 below.

[ Table 7]

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

[ example 2]

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

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

Compound (z-16)

[ solution 44]

Then, Silica (SiO) was formed on one surface of the obtained substrate in the same manner as in example 1₂) Layer with titanium dioxide (TiO)₂) A dielectric multilayer film (I) of 26 layers in total, wherein the layers are alternately laminated, and further, silicon dioxide (SiO) is formed on the other surface of the substrate₂) Layer with titanium dioxide (TiO)₂) A total of 22 dielectric multilayer films (II) in which the layers were alternately laminated were used to obtain an optical filter having a thickness of about 0.110 mm.

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

The average value T and the average value R of the obtained optical filter were obtained in the same manner as in example 1. The results are shown in Table 8.

[ example 3]

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

Compound (z-59)

[ solution 45]

Then, Silica (SiO) was formed on one surface of the obtained substrate in the same manner as in example 1₂) Layer with titanium dioxide (TiO)₂) A dielectric multilayer film (I) of 26 layers in total, wherein the layers are alternately laminated, and further, silicon dioxide (SiO) is formed on the other surface of the substrate₂) Layer with titanium dioxide (TiO)₂) Total of 2 layers alternately laminated2 layers of dielectric multilayer film (II), an optical filter with a thickness of about 0.110mm was obtained.

[ example 4]

A substrate was obtained in the same manner as in example 1 except that in example 1, 0.2 part by mass of the following compound (z-62) (absorption maximum wavelength in methylene chloride is 757nm) was used in place of 0.2 part by mass of the compound (z-1), and subchunk (acryviewa) produced by japan catalyst (stock) was used in place of the resin a.

Compound (z-62)

[ solution 46]

[ example 5]

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

Compound (z-151)

[ solution 47]

[ example 6]

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

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

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

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

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

Thus, a substrate having a thickness of 222 μm was obtained in which a resin layer containing the compound (Z) was laminated on one surface of the glass support and a resin layer containing no compound (Z) was laminated on the other surface.

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

Resin composition (2): an ethylene oxide isocyanurate-modified triacrylate (trade name: Aronix M-315, manufactured by Toyo Synthesis Co., Ltd.) in an amount of 30 parts by mass, 1, 9-nonanediol diacrylate in an amount of 20 parts by mass, methacrylic acid in an amount of 20 parts by mass, glycidyl methacrylate in an amount of 30 parts by mass, 3-glycidoxypropyltrimethoxysilane in an amount of 5 parts by mass, 1-hydroxycyclohexyl benzophenone (trade name: Yanjia good (IRGACURE)184, manufactured by BASF Japan) in an amount of 5 parts by mass, and Sanxin-aid SI-110 as a main agent (manufactured by Sanxin chemical industry Co., Ltd.) were mixed together, and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 50 mass%, and then filtered through a microporous filter having a pore size of 0.2 μm.

Then, referring to example 1, on the surface of the coating resin layer (2), silicon dioxide (SiO) was formed₂) Layer with titanium dioxide (TiO)₂) A dielectric multilayer film (I) of 26 layers in total, which is formed by alternately laminating layers, and silicon dioxide (SiO) is formed on the surface of the coating resin layer (1)₂) Layer with titanium dioxide (TiO)₂) A total of 22 dielectric multilayer films (II) in which the layers were alternately laminated were used to obtain an optical filter having a thickness of about 0.226 mm.

The average value T and the average value R of the obtained optical filter were obtained in the same manner as in example 1. The results are shown in Table 9.

[ example 7]

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

Compound (x-3)

[ solution 48]

Then, Silica (SiO) was formed on one surface of the obtained substrate in the same manner as in example 1₂) Layer with titanium dioxide (TiO)₂) A dielectric multilayer film (I) of 26 layers in total, wherein the layers are alternately laminated, and further, silicon dioxide (SiO) is formed on the other surface of the substrate₂) Layer with titanium dioxide (TiO)₂) A dielectric multilayer film (II) of 22 layers in total, which was obtained by alternately laminating layersAn optical filter having a thickness of about 0.110 mm.

[ example 8]

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

Compound (x-5)

[ solution 49]

[ example 9]

A substrate was obtained in the same manner as in example 1 except that 0.16 part by mass of compound (z-16) (having an absorption maximum wavelength of 825nm in methylene chloride) and 0.12 part by mass of compound (z-59) (having an absorption maximum wavelength of 770nm in methylene chloride) were used in example 1 in place of 0.2 part by mass of compound (z-1).

[ example 10]

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

Compound (y-1)

[ solution 50]

Then, Silica (SiO) was formed on one surface of the obtained substrate in the same manner as in example 1₂) Layer with titanium dioxide (TiO)₂) A total of 26 layers of electricity formed by alternately laminating layersA dielectric multilayer film (I), and further silicon dioxide (SiO) is formed on the other surface of the substrate₂) Layer with titanium dioxide (TiO)₂) A total of 22 dielectric multilayer films (II) in which the layers were alternately laminated were used to obtain an optical filter having a thickness of about 0.110 mm.

[ example 11]

A base material was obtained in the same manner as in example 6 except that in example 6, a near-infrared-absorbing glass substrate "BS-11" (thickness: 0.2mm) manufactured by Sonbo Nitri industry (Strand) was used in place of the transparent glass support "OA-10G" (thickness: 200 μm) manufactured by Nippon Denshoku (Strand) glass.

Then, Silica (SiO) was formed on the surface of the coating resin layer (2) in the same manner as in example 6₂) Layer with titanium dioxide (TiO)₂) A dielectric multilayer film (I) of 26 layers in total, which is formed by alternately laminating layers, and silicon dioxide (SiO) is formed on the surface of the coating resin layer (1)₂) Layer with titanium dioxide (TiO)₂) A total of 22 dielectric multilayer films (II) in which the layers were alternately laminated were used to obtain an optical filter having a thickness of about 0.226 mm.

[ example 12]

A substrate was obtained in the same manner as in example 1 except that 0.1 part by mass of the following compound (z-156) (having an absorption maximum wavelength of 785nm in methylene chloride) was used in place of 0.2 part by mass of the compound (z-1) in example 1.

Compound (z-156)

[ solution 51]

[ example 13]

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

Compound (z-157)

[ solution 52]

[ example 14]

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

Compound (z-158)

[ Hua 53]

[ example 15]

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

Compound (z-159)

[ solution 54]

[ example 16]

A substrate was obtained in the same manner as in example 12 except that 0.1 part by mass of the following compound (z-160) (having an absorption maximum wavelength of 791nm in methylene chloride) was used in example 12 in place of 0.1 part by mass of the compound (z-156).

Compound (z-160)

[ solution 55]

[ example 17]

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

Compound (z-161)

[ solution 56]

[ example 18]

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

Compound (z-162)

[ solution 57]

[ example 19]

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

Compound (z-163)

[ solution 58]

Comparative example 1

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

Comparative example 2

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

Compound (x-3)

[ chemical 59]

Then, Silica (SiO) was formed on one surface of the obtained substrate in the same manner as in example 1₂) Layer with titanium dioxide (TiO)₂) A dielectric multilayer film (I) of 26 layers in total, wherein the layers are alternately laminated, and further, silicon dioxide (SiO) is formed on the other surface of the substrate₂) Layer with titanium dioxide (TiO)₂)22 dielectric multilayer film (I) layers alternately stackedI) An optical filter with a thickness of about 0.110mm was obtained.

Comparative example 3

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

Compound (x-4)

[ solution 60]

[ Table 9]

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

[ Synthesis example of Compound (z-164) ]

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

Compound (m-1)

[ solution 61]

The compound (m-1) (1 equivalent) obtained above and malonaldehyde bisanilide hydrochloride (0.5 equivalent) were charged in an eggplant-shaped flask, and acetonitrile and anhydrous acetic acid were added thereto and stirred. Then, pyridine (1 equivalent) was added dropwise and stirred at room temperature for 2 hours. Thereafter, acetonitrile, anhydrous acetic acid, and pyridine were removed by an evaporator, and a liquid separation operation was performed using methyl chloride/water. The organic phase was recovered, and 1.5 equivalents of LiFABA (lithium ═ tetrakis (pentafluorophenyl) borohydride) and water were added thereto, followed by vigorous stirring for 3 hours. Thereafter, the organic phase was recovered, and methyl chloride was removed by an evaporator to obtain a compound (z-164).

Compound (z-164): absorption maximum wavelength in methylene chloride of 715nm

[ solution 62]

[ Synthesis example of Compound (z-165) ]

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

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

[ solution 63]

[ Synthesis example of Compound (z-166) ]

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

Compound (z-166): absorption maximum wavelength in dichloromethane is 719nm

[ solution 64]

[ Synthesis example of Compound (z-167) ]

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

Compound (z-167): absorption maximum wavelength in dichloromethane is 721nm

[ solution 65]

[ Synthesis example of Compound (z-168) ]

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

Compound (m-2)

[ solution 66]

Compound (z-168): absorption maximum wavelength in dichloromethane of 720nm

[ solution 67]

[ Synthesis example of Compound (z-169) ]

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

Compound (z-169): absorption maximum wavelength in dichloromethane of 726nm

[ solution 68]

[ Synthesis example of Compound (z-170) ]

Compound (z-170) was obtained in the same manner as in the above synthesis example, except that compound (m-3) was used instead of compound (m-2) in the synthesis example of compound (z-169).

Compound (m-3)

[ solution 69]

Compound (z-170): absorption maximum wavelength in dichloromethane of 739nm

[ solution 70]

[ Synthesis example of Compound (z-171 ]

Compound (z-171) was obtained in the same manner as in the above synthesis example, except that compound (m-1) was changed to compound (m-4) described below in the synthesis example of compound (z-167).

Compound (m-4)

[ solution 71]

Compound (z-171): absorption maximum wavelength in dichloromethane of 734nm

[ chemical formula 72]

[ Synthesis example of Compound (z-172) ]

Compound (z-172) was obtained in the same manner as in the above synthesis example, except that compound (m-5) was used instead of compound (m-1) in the synthesis example of compound (z-167).

Compound (m-5)

[ solution 73]

Compound (z-172): absorption maximum wavelength in dichloromethane of 738nm

[ chemical formula 74]

[ Synthesis example of Compound (z-173) ]

Compound (z-173) was obtained by the same method as in the above synthesis example, except that compound (m-6) was used instead of compound (m-2) in the synthesis example of compound (z-169).

Compound (m-6)

[ solution 75]

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

[ 76]

Examples 20 to 32 and comparative examples 4 to 7

[ production of base Material ]

In the same manner as in example 1, specifically, a substrate was produced as follows.

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

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

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

[ solution 77]

The following resin composition (1) was applied to one surface of the obtained resin layer (1) by a bar coater so that the thickness of the obtained resin layer (2) was 3 μm, and the resin layer was heated in an oven at 70 ℃ for 2 minutes to volatilize and remove the solvent. Next, exposure (exposure amount 500 mJ/cm) was carried out using a UV conveyor type exposure machine (manufactured by Eygraphics, Egyo ultraviolet hardening apparatus, model No. US2-X0405, 60Hz)²Illuminance: 200mW/cm²) The resin composition (1) is cured to form a resin layer (2) on the resin layer (1). In the same manner, the resin layer (2) containing the resin composition (1) is also formed on the other surface of the resin layer (1).

< spectral transmittance >

The transmittance of the obtained substrate in the near infrared region having a wavelength of 650nm to 800nm and the visible light transmittance at a wavelength of 430nm to 580nm were measured using a spectrophotometer (V-7200) manufactured by Nippon spectral (Kagaku) corporation. The transmittance is measured using the spectrophotometer under the condition that light is incident perpendicularly to the surface of the substrate. The parameters measured by using this apparatus are as follows. The results are shown in Table 12.

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

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

In addition, as for Te and Tf, an UV exposure apparatus (manufactured by Kawasaki electric gas (Strand), Eye, apparatus for ultraviolet curing US2-KO4501, illuminance: 180mW/cm was used²The irradiation amount: 560mJ/cm²) The obtained substrate was irradiated with UV, and the transmittance of the substrate after the UV irradiation was measured (UV resistance evaluation).

Xa: the wavelength of light having a lowest transmittance measured from the direction perpendicular to the substrate at a wavelength of 650 to 800nm

Ta: a minimum transmittance measured from the perpendicular direction of the substrate at a wavelength of 650nm to 800nm

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

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

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

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

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

[ production of optical Filter ]

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

The dielectric multilayer film (III) is formed by depositing silicon dioxide (SiO) at a deposition temperature of 100 DEG C₂) Layer with titanium dioxide (TiO)₂) A laminate (28 layers in total) in which the layers are alternately laminated. The dielectric multilayer film (IV) is formed by depositing silicon dioxide (SiO) at a deposition temperature of 100 deg.C₂) Layer with titanium dioxide (TiO)₂) With layers alternately stackedLaminate (24 layers in total).

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

The thickness and number of layers of each layer are optimized by using optical Film design software (core mclaud, Thin Film Center, manufactured by Thin Film Center) so that favorable transmittance in the visible region and reflection performance in the near infrared region can be achieved, depending on the wavelength dependence of the refractive index of the substrate, or the absorption characteristics of the compound (Z) and the compound (X) used. In the optimization, in the present embodiment, input parameters (target values) to the software are set as shown in table 10 below.

[ Table 10]

As a result of optimizing the film structure, the dielectric multilayer film (III) was formed as a multilayer deposited film having a stacking number of 28 in which a silicon dioxide layer having a physical thickness of about 32 to 159nm and a titanium dioxide layer having a physical thickness of about 9 to 94nm were alternately stacked, and the dielectric multilayer film (IV) was formed as a multilayer deposited film having a stacking number of 24 in which a silicon dioxide layer having a physical thickness of about 39 to 193nm and a titanium dioxide layer having a physical thickness of about 12 to 117nm were alternately stacked. An example of the optimized film structure is shown in table 11 below.

[ Table 11]

< spectral transmittance >

The transmittance of the obtained optical filter in the near infrared region having a wavelength of 650nm to 800nm and the visible light transmittance at a wavelength of 430nm to 580nm were measured using a spectrophotometer (V-7200) manufactured by Nippon spectral (Kagaku). The transmittance is a transmittance measured by using the spectrophotometer under the condition that light is incident perpendicularly with respect to the optical filter. The parameters measured by using this apparatus are as follows. The results are shown in Table 12.

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

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

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

Example 33 to example 43 and comparative example 8

In the same manner as in example 6, specifically, a substrate was produced as follows.

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

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

In example 39, a near-infrared-absorbing glass substrate "BS-11" (thickness: 200 μm) manufactured by Sonbo Nitri industry (strand) and cut into a size of 200mm X200 mm was used in place of "OA-10G".

Next, the resin solution (E-1) was applied to one surface of the glass support having the adhesive layer formed thereon using a spin coater so that the dried film thickness was 10 μm, and the coated resin layer (2) was formed by heating the glass support on a hot plate at 80 ℃ for 5 minutes to evaporate and remove the solvent.

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

The numerical values given for compounds z-164 to z-173 in table 13 represent the content (parts by mass) of each compound per 100 parts by mass of the resin in the resin layer (1), and the numerical values given for compounds x-1, x-2, and y-1 in table 13 represent the content (parts by mass) of each compound per 100 parts by mass of the resin in the resin layer (2).

The measurement was carried out in the same manner as in example 20 to measure Xa, Ta to Tf of the substrate. The results are shown in Table 13.

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

Then, Silica (SiO) was formed on one surface of the obtained substrate in the same manner as in example 20₂) Layer with titanium dioxide (TiO)₂) A dielectric multilayer film (III) of 28 layers in total, wherein the layers are alternately laminated, and further, silicon dioxide (SiO) is formed on the other surface of the substrate₂) Layer with titanium dioxide (TiO)₂) A total of 24 dielectric multilayer films (IV) were alternately laminated to obtain an optical filter having a thickness of about 0.226 mm.

The dielectric multilayer film was designed in the same manner as in example 20, taking into account the wavelength dependence of the refractive index of the substrate, and the like, and then using the same design parameters as in example 20.

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

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

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

Claims

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

Cn⁺An^- (I)

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

in the formula (II), the compound is shown in the specification,

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

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

Y_AAnd Y_C、Y_BAnd Y_DAnd Y_CAnd Y_ECan be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4 to 7 membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a 3 to 14 membered heteroaromatic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic hydrocarbon group, alicyclic group and heteroaromatic group may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have ═ O,

Y_Awith R in the following formula (A-III)¹Or R⁵And Y_EAnd R in the following formula (B-III)⁵Or R¹May be bonded to each other to form a 4-to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom,

R^gand R^hEach independently is a hydrogen atom, -C (O) RⁱOr L shown below^a～L^hAny one of (1), Q¹Independently is L^a～L^hAny one of (1), Q²Independently a hydrogen atom or L^a～L^hAny one of (1), Q³Is hydroxy or L^a～L^hAny one of (1), RⁱIs L as follows^a～L^hAny of (a);

wherein in formulae (A-I) to (A-III) represents a group represented by formula (II) and Y_AThe bonded carbon is singly bonded,

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

R⁸independently a hydrogen atom, a halogen atom, -C (O) RⁱOr L shown below^a～L^hAny one of the above-mentioned (A) and (B),

Rⁱindependently is L^a～L^hAny one of (1) to (2)，

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

L^b: a C1-15 halogen-substituted alkyl group

L^c: a C3-14 alicyclic hydrocarbon group which may have a substituent K

L^d: a C6-14 aromatic hydrocarbon group which may have a substituent K

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

L^f: -OR, R is a C1-12 hydrocarbon group which may have a substituent L

L^g: an acyl group having 1 to 9 carbon atoms and optionally having a substituent L

L^h: alkoxycarbonyl group having 1 to 9 carbon atoms and optionally having substituent L

The substituent K is selected from the group L^a～L^bAt least one of said substituents L is selected from said group L^a～L^fAt least one of (1).

2. The resin composition according to claim 1, wherein the compound Z satisfies the following requirement A,

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

3. The resin composition according to claim 1 or 2, wherein R is¹～R⁶At least one of is said L^a、L^cOr L^d。

4. The resin composition according to claim 1 or 2, wherein the compound Z satisfies the following requirement B-1,

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

5. The resin composition according to claim 1 or 2, wherein the compound Z satisfies the following requirement B-2,

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

6. The resin composition according to claim 1 or 2, wherein the resin is at least one resin selected from the group consisting of a cyclic (poly) olefin-based resin, an aromatic polyether-based resin, a polyimide-based resin, a polyester-based resin, a polycarbonate-based resin, a polyamide-based resin, a polyarylate-based resin, a polysulfone-based resin, a polyethersulfone-based resin, a polyphenylene-based resin, a polyamideimide-based resin, a polyethylene naphthalate-based resin, a fluorinated aromatic polymer-based resin, (modified) acrylic-based resin, an epoxy-based resin, an allyl-based curing resin, a silsesquioxane-based ultraviolet curing resin, an acrylic-based ultraviolet curing resin, and a vinyl-based ultraviolet curing resin.

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

8. The substrate i according to claim 7, wherein the substrate i is a substrate comprising:

a substrate comprising a resin layer containing the compound Z;

a substrate comprising two or more resin layers, at least one of the two or more resin layers being a resin layer containing the compound Z; or

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

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

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

11. The optical filter of claim 9, for use in an optical sensor device.

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

13. An optical sensor device comprising the optical filter of claim 9.

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

Cn⁺An^-(III)

in the formula (III), Cn⁺Is a monovalent cation represented by the following formula (IV), An^-Is a monovalent anion;

in the formula (IV), the compound is shown in the specification,

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

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

Y_AAnd Y_C、Y_BAnd Y_DAnd Y_CAnd Y_ECan be bonded to each other to form an aromatic hydrocarbon group having 6 to 14 carbon atoms, a 4-to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atomOr a heteroaromatic group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, wherein the aromatic hydrocarbon group, alicyclic group or heteroaromatic group may have a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom, and the alicyclic group may have ═ O,

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

Rⁱindependently is L^a～L^hAny one of the above-mentioned (A) and (B),

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

L^b: a C1-15 halogen-substituted alkyl group

L^c: a C3-14 alicyclic hydrocarbon group which may have a substituent K

L^d: a C6-14 aromatic hydrocarbon group which may have a substituent K

L^f: -OR, R is a C1-12 hydrocarbon group which may have a substituent L