TW202132473A - Resin composition, compound, substrate, optical filter, solid photographing device and optical sensing device wherein the resin composition has a maximum absorption in a wavelength range of about 700 nm to about 750 nm or a wavelength range of about 720 nm to about 900 nm - Google Patents

Abstract

The present invention provides a resin composition having a maximum absorption in a wavelength range of about 700 nm to about 750 nm or a wavelength range of about 720 nm to about 900 nm, a large ratio of an absorbance in the infrared region to that in the visible light region, and an excellent light resistance (durability). A resin composition includes a resin and a compound represented by formula (I): Cn+ An-(I). In formula (I), Cn+ is a monovalent cation represented by formula (II) and An- is a monovalent anion. A is represented by formula (AI) to formula (A-III). B is represented by formula (BI) to formula (B-III). YA to YE are H, halogen atom, -OH, -COOH, -NO2, -NR g R h, amide group, amide group, -CN, silyl group, -Q 1, -N=NQ1, -SQ2, -SSQ2, -SO2Q3. YA and YC, YB and YD, YC and YE, YA and R1, R5 or YE in (A-III) and R1 or R5 in (B-III) can be bonded to form a ring. -* represents a single bond with the carbon bonded to YA in formula (II). =** represents a double bond with the carbon bonded to YE in formula (II). X is O, S, Se, Te or -NR 8-. R1 to R6 are H, halogen atom, sulfo group, -OH, -CN, -NO2, -COOH, phosphoric acid group, -NRgRh group, -SRi group, -SO2Ri group, -OSO2Ri group, -C(O)Ri group, or any one of La to Lh. R1 to R6 adjacent with each other may be bonded to form a ring.

Description

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

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

In solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions, a charge-coupled device (CCD) or complementary metal oxide semiconductor is used as a solid-state imaging element for color images (Complementary Metal Oxide Semiconductor, CMOS) image sensor (image sensor). Among these solid-state imaging devices, silicon photodiodes, etc., which are sensitive to near-infrared rays that the human eye cannot perceive, are used in the light receiving portion. In addition, in optical sensor devices, silicon photodiodes and the like are also used. For example, in solid-state imaging devices, it is often necessary to perform visual sensitivity corrections that present natural colors to the human eye, and use optical filters that selectively transmit or cut off light in a specific wavelength region (for example, near-infrared cut filters).器).

As such a near-infrared cut filter, filters manufactured by various methods have been used from the past. For example, there is known a near-infrared cut filter that uses a resin as a base material and contains a near-infrared absorbing dye in the resin (for example, refer to Patent Document 1). However, the near-infrared cut filter described in Patent Document 1 may not necessarily have sufficient near-infrared absorption characteristics. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-303130

[The problem to be solved by the invention] As the near-infrared absorbing pigments, pigments such as polymethine series, squaraine series, porphyrin series, dithiol metal complex series, phthalocyanine series, diiminium series, etc. have been used in the past. Among them, In terms of sufficient resistance to heat, dyes such as polymethine series and squaraine series are often used.

However, these pigments that have been used before have room for improvement in at least any of the following aspects: Since the maximum absorption wavelength is in the long wavelength region, it is required to have a compound with a maximum absorption near the wavelength of 700 nm to 750 nm or the wavelength of 720 nm to 900 nm; The aspect where the ratio of the absorbance in the infrared region to the absorbance in the visible light region is small; Areas where the light resistance (durability) is insufficient.

In addition, in the conventional near-infrared cut filter, the reflected light from the filter sometimes has an adverse effect on the camera image and other images as a flare or ghost, etc., especially in the near-infrared cut filter. When the reflection band overlaps with the wavelength band capable of photoelectric conversion by the sensor, the adverse effect may become more significant.

The present invention has been made in view of the above circumstances, and its object is to provide a light-resistance system that has a maximum absorption in the vicinity of a wavelength of 700 nm to 750 nm or a wavelength of 720 nm to 900 nm, and has a large ratio of absorbance in the infrared region to that in the visible light region. A resin composition with excellent performance (durability). [Technical means to solve the problem]

The inventors of the present invention conducted diligent studies to solve the above-mentioned problem, and as a result, found that the above-mentioned problem can be solved according to the following structural example, and completed the present invention. An example of the structure of the present invention is shown below. In addition, in the present invention, descriptions such as "A to B" that indicate a numerical range have the same meaning as "A or more and B or less", and A and B are included in the numerical range. In addition, in the present invention, the wavelengths A nm to B nm indicate the characteristics of the wavelength resolution at 1 nm in the wavelength region of the wavelength A nm or more and the wavelength B nm or less.

[1] A resin composition comprising: a resin, and the following formula (I), (Z) represented, Cn ⁺ An ^- (I) [In the formula (I), Cn ⁺ by the following formula (II) The represented monovalent cation, An ^- is a monovalent anion]

[式（II）中， 單元A為下述式（A-I）～式（A-III）的任一者， 單元B為下述式（B-I）～式（B-III）的任一者， Y_A ～Y_E 分別獨立地為氫原子、鹵素原子、羥基、羧基、硝基、-NR^g R^h 基、醯胺基、醯亞胺基、氰基、矽烷基、-Q¹ 、-N=N-Q¹ 、-S-Q² 、-SSQ² 、或-SO₂ Q³ ， Y_A 與Y_C 、Y_B 與Y_D 、Y_C 與Y_E 可相互鍵結而形成碳數6～14的芳香族烴基、可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基、或者包含至少一個氮原子、氧原子或硫原子的碳數3～14的雜芳香族基，這些芳香族烴基、脂環基及雜芳香族基可具有羥基、碳數1～9的脂肪族烴基或鹵素原子，另外，所述脂環基可具有=O， Y_A 與下述式（A-III）中的R¹ 或R⁵ 、Y_E 與下述式（B-III）中的R⁵ 或R¹ 可相互鍵結而形成可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基， R^g 及R^h 分別獨立地為氫原子、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者，Q¹ 獨立地為下述L^a ～L^h 的任一者，Q² 獨立地為氫原子或下述L^a ～L^h 的任一者，Q³ 為羥基或下述L^a ～L^h 的任一者，Rⁱ 為下述L^a ～L^h 的任一者][化1]

[In formula (II), unit A is any one of the following formula (AI) to formula (A-III), unit B is any one of the following formula (BI) to formula (B-III), Y _A to Y _E are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, a -NR ^g R ^h group, an amide group, an amide group, a cyano group, a silyl group, -Q ¹ , -N= NQ ¹ , -SQ ² , -SSQ ² , or -SO ₂ Q ³ , Y _A and Y _C , Y _B and Y _D , Y _C and Y _E can be bonded to each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms , A 4- to 7-member alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic The aliphatic hydrocarbon group, alicyclic group, and heteroaromatic group may have a hydroxyl group, an aliphatic hydrocarbon group with 1 to 9 carbon atoms, or a halogen atom, and the alicyclic group may have =0, Y _A and the following formula (A-III ) R ¹ or R ⁵ , Y _E ^{and R 5} or R ¹ in the following formula (B-III) may be bonded to each other to form 4 to 7 members which may contain at least one nitrogen atom, oxygen atom or sulfur atom membered alicyclic group, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, Q ¹ is independently represented by the following L ^a ~ L any one ^h, Q ² is independently a hydrogen atom or L ^a ~ L ^h following either one, Q ³ is hydroxy or L ^a ~ L ^h following either one, R ⁱ L ^a by the following Any one of ~L ^h]

[式（A-I）～式（A-III）中的-*表示與所述式（II）的Y_A 所鍵結的碳進行單鍵結， 式（B-I）～式（B-III）中的=**表示與所述式（II）的Y_E 所鍵結的碳進行雙鍵結， 式（A-I）～式（B-III）中， X獨立地為氧原子、硫原子、硒原子、碲原子或-NR⁸ -， R¹ ～R⁶ 分別獨立地為氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、-NR^g R^h 基、-SRⁱ 基、-SO₂ Rⁱ 基、-OSO₂ Rⁱ 基、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者， 鄰接的R¹ ～R⁶ 可相互鍵結而形成碳數6～14的芳香族烴基、可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基、或者包含至少一個氮原子、氧原子或硫原子的碳數3～14的雜芳香族基，這些芳香族烴基、脂環基及雜芳香族基可具有羥基、碳數1～9的脂肪族烴基或鹵素原子，另外，所述脂環基可具有=O， R⁸ 獨立地為氫原子、鹵素原子、-C(O)Rⁱ 基、下述L^a ～L^h 的任一者， R^g 及R^h 分別獨立地為氫原子、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者， Rⁱ 獨立地為下述L^a ～L^h 的任一者， （L^a ）：碳數1～15的脂肪族烴基 （L^b ）：碳數1～15的經鹵素取代的烷基 （L^c ）：可具有取代基K的碳數3～14的脂環式烴基 （L^d ）：可具有取代基K的碳數6～14的芳香族烴基 （L^e ）：可具有取代基K的碳數3～14的雜環基 ‏（L^f ）：-OR（R為可具有取代基L的碳數1～12的烴基） （L^g ）：可具有取代基L的碳數1～9的醯基 （L^h ）：可具有取代基L的碳數1～9的烷氧基羰基 所述取代基K為選自所述L^a ～L^b 中的至少一種，所述取代基L為選自所述L^a ～L^f 中的至少一種]。[化2]

[-* in formula (AI) to formula (A-III) represents _{a single bond with the carbon to which Y A} of the formula (II) is bonded, and in formula (BI) to formula (B-III) =** means that it _{is double-bonded with the carbon to which Y E} of the formula (II) is bonded. In formulas (AI) to (B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, Tellurium atom or -NR ⁸ -, R ¹ to R ⁶ are each independently 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, a -NR ^g R ^h group, and a -SR ⁱ group , -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group, -C (O) R ⁱ or the following group L ^a ~ L ^h is any one of, adjacent to R ¹ ~ R ⁶ may be bonded to each other to form a carbon Aromatic hydrocarbon group of 6 to 14, alicyclic group of 4 to 7 members which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or carbon 3 to 14 containing at least one nitrogen atom, oxygen atom or sulfur atom These aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbons or halogen atoms, and the alicyclic groups may have =0, R ⁸ is independently a hydrogen atom, a halogen atom, -C (O) R ⁱ groups, L ^a ~ L ^h following either one, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, R ⁱ is independently L ^a ~ L ^h following either one, (L ^a): an aliphatic hydrocarbon group having a carbon number of 1 to 15 (L ^b): carbon 1 to 15 halogen-substituted alkyl group (L ^c ): an alicyclic hydrocarbon group with 3 to 14 carbons that may have a substituent K (L ^d ): an aromatic 6 to 14 carbons that may have a substituent K Group hydrocarbon group (L ^e ): a heterocyclic group having 3 to 14 carbons which may have substituent K ‏(L ^f ): -OR (R is a hydrocarbon group having 1 to 12 carbons which may have substituent L) (L ^g ): an acyl group ^{having 1 to 9 carbons that may have a substituent L (L h} ): an alkoxycarbonyl group having 1 to 9 carbons that may have a substituent L The substituent K is selected from the group consisting of ^La to At least one of L ^b , and the substituent L is at least one selected from the group consisting of ^La to L ^f ].

[2] The resin composition according to [1], wherein the compound (Z) satisfies the following requirement (A), Prerequisite (A): Transmission spectrum measured using a solution prepared by dissolving the compound (Z) in dichloromethane (wherein, the transmission spectrum is a spectrum with a transmittance of 10% at an absorption maximum wavelength) Among them, the average transmittance at a wavelength of 430 nm to 580 nm is 93% or more.

[3] according to [1] or [2] The resin composition, wherein said at least one of R ¹ ~ R is the L ^a, L ^c or L ^{d 6} in.

[4] The resin composition according to any one of [1] to [3], wherein the compound (Z) satisfies the following requirement (B-1), Prerequisite (B-1): The absorption spectrum measured using a solution obtained by dissolving the compound (Z) in dichloromethane has a maximum value in the wavelength range of 720 nm 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): The absorption spectrum measured using a solution obtained by dissolving the compound (Z) in dichloromethane has a maximum value in the wavelength range of 700 nm to 750 nm.

[6] The resin composition according to any one of [1] to [5], wherein the resin is selected from the group consisting of cyclic (poly)olefin resins, aromatic polyether resins, and polyimide resins. Resins, polyester resins, polycarbonate resins, polyamide resins, polyarylate resins, polyether resins, polyether resins, polyparaphenylene resins, polyamide resins , Polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester curing resin, silsesquioxane UV curing type At least one resin from the group consisting of resin, acrylic ultraviolet curable resin, and vinyl ultraviolet curable resin.

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

[8] The substrate (i) according to [7], wherein the substrate (i) is the following substrate: A substrate comprising a resin layer containing the compound (Z); It includes two or more resin layers, and at least one of the two or more resin layers is a base material of a resin layer containing the compound (Z); or A base material including 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 in a solid-state imaging device. [11] The optical filter according to [9], which is used in an optical sensor device.

[12] A solid-state imaging device including the optical filter according to [9]. [13] An optical sensor device including the optical filter according to [9].

[14] A compound (Z), which is 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]

[式（IV）中， 單元A為下述式（A-I）～式（A-III）的任一者， 單元B為下述式（B-I）～式（B-III）的任一者， Y_A ～Y_E 分別獨立地為氫原子、鹵素原子、羥基、羧基、硝基、-NR^g R^h 基、醯胺基、醯亞胺基、氰基、矽烷基、-Q¹ 、-N=N-Q¹ 、-S-Q² 、-SSQ² 、或-SO₂ Q³ ， Y_A 與Y_C 、Y_B 與Y_D 、Y_C 與Y_E 可相互鍵結而形成碳數6～14的芳香族烴基、可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基、或者包含至少一個氮原子、氧原子或硫原子的碳數3～14的雜芳香族基，這些芳香族烴基、脂環基及雜芳香族基可具有羥基、碳數1～9的脂肪族烴基或鹵素原子，另外，所述脂環基可具有=O， Y_A 與下述式（A-III）中的R¹ 或R⁵ 、Y_E 與下述式（B-III）中的R⁵ 或R¹ 可相互鍵結而形成可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基， R^g 及R^h 分別獨立地為氫原子、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者，Q¹ 獨立地為下述L^a ～L^h 的任一者，Q² 獨立地為氫原子或下述L^a ～L^h 的任一者，Q³ 為羥基或下述L^a ～L^h 的任一者，Rⁱ 為下述L^a ～L^h 的任一者][化3]

[In formula (IV), unit A is any of the following formulas (AI) to (A-III), unit B is any of the following formulas (BI) to (B-III), Y _A to Y _E are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, a -NR ^g R ^h group, an amide group, an amide group, a cyano group, a silyl group, -Q ¹ , -N= NQ ¹ , -SQ ² , -SSQ ² , or -SO ₂ Q ³ , Y _A and Y _C , Y _B and Y _D , Y _C and Y _E can be bonded to each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms , A 4- to 7-member alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic The aliphatic hydrocarbon group, alicyclic group, and heteroaromatic group may have a hydroxyl group, an aliphatic hydrocarbon group with 1 to 9 carbon atoms, or a halogen atom, and the alicyclic group may have =0, Y _A and the following formula (A-III ) R ¹ or R ⁵ , Y _E ^{and R 5} or R ¹ in the following formula (B-III) may be bonded to each other to form 4 to 7 members which may contain at least one nitrogen atom, oxygen atom or sulfur atom membered alicyclic group, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, Q ¹ is independently represented by the following L ^a ~ L any one ^h, Q ² is independently a hydrogen atom or L ^a ~ L ^h following either one, Q ³ is hydroxy or L ^a ~ L ^h following either one, R ⁱ L ^a by the following Any one of ~L ^h]

[式（A-I）～式（A-III）中的-*表示與所述式（II）的Y_A 所鍵結的碳進行單鍵結， 式（B-I）～式（B-III）中的=**表示與所述式（II）的Y_E 所鍵結的碳進行雙鍵結， 式（A-I）～式（B-III）中， X獨立地為氧原子、硫原子、硒原子、碲原子或-NR⁸ -， R¹ ～R⁶ 分別獨立地為氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、-NR^g R^h 基、-SRⁱ 基、-SO₂ Rⁱ 基、-OSO₂ Rⁱ 基、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者， 鄰接的R¹ ～R⁶ 可相互鍵結而形成碳數6～14的芳香族烴基、可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基、或者包含至少一個氮原子、氧原子或硫原子的碳數3～14的雜芳香族基，這些芳香族烴基、脂環基及雜芳香族基可具有羥基、碳數1～9的脂肪族烴基或鹵素原子，另外，所述脂環基可具有=O， R⁸ 獨立地為氫原子、鹵素原子、-C(O)Rⁱ 基、下述L^a ～L^h 的任一者， R^g 及R^h 分別獨立地為氫原子、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者， Rⁱ 獨立地為下述L^a ～L^h 的任一者， （L^a ）：碳數1～15的脂肪族烴基 （L^b ）：碳數1～15的經鹵素取代的烷基 （L^c ）：可具有取代基K的碳數3～14的脂環式烴基 （L^d ）：可具有取代基K的碳數6～14的芳香族烴基 （L^e ）：可具有取代基K的碳數3～14的雜環基 ‏（L^f ）：-OR（R為可具有取代基L的碳數1～12的烴基） （L^g ）：可具有取代基L的碳數1～9的醯基 （L^h ）：可具有取代基L的碳數1～9的烷氧基羰基 所述取代基K為選自所述L^a ～L^b 中的至少一種，所述取代基L為選自所述L^a ～L^f 中的至少一種]。 [發明的效果][化4]

[-* in formula (AI) to formula (A-III) represents _{a single bond with the carbon to which Y A} of the formula (II) is bonded, and in formula (BI) to formula (B-III) =** means that it _{is double-bonded with the carbon to which Y E} of the formula (II) is bonded. In formulas (AI) to (B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, Tellurium atom or -NR ⁸ -, R ¹ to R ⁶ are each independently 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, a -NR ^g R ^h group, and a -SR ⁱ group , -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group, -C (O) R ⁱ or the following group L ^a ~ L ^h is any one of, adjacent to R ¹ ~ R ⁶ may be bonded to each other to form a carbon Aromatic hydrocarbon group of 6 to 14, alicyclic group of 4 to 7 members which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or carbon 3 to 14 containing at least one nitrogen atom, oxygen atom or sulfur atom These aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbons or halogen atoms, and the alicyclic groups may have =0, R ⁸ is independently a hydrogen atom, a halogen atom, -C (O) R ⁱ groups, L ^a ~ L ^h following either one, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, R ⁱ is independently L ^a ~ L ^h following either one, (L ^a): an aliphatic hydrocarbon group having a carbon number of 1 to 15 (L ^b): carbon 1 to 15 halogen-substituted alkyl group (L ^c ): an alicyclic hydrocarbon group with 3 to 14 carbons that may have a substituent K (L ^d ): an aromatic 6 to 14 carbons that may have a substituent K Group hydrocarbon group (L ^e ): a heterocyclic group having 3 to 14 carbons which may have substituent K ‏(L ^f ): -OR (R is a hydrocarbon group having 1 to 12 carbons which may have substituent L) (L ^g ): an acyl group ^{having 1 to 9 carbons that may have a substituent L (L h} ): an alkoxycarbonyl group having 1 to 9 carbons that may have a substituent L The substituent K is selected from the group consisting of ^La to At least one of L ^b , and the substituent L is at least one selected from the group consisting of ^La to L ^f ]. [Effects of the invention]

According to the present invention, it is possible to provide a device having a maximum absorption in the vicinity of a wavelength of 700 nm to 750 nm, or a wavelength of 720 nm to 900 nm, a large ratio of the absorbance in the infrared region to the absorbance in the visible light region, and sufficient resistance to heat or light. Resistant resin composition. Furthermore, according to the present invention, it is possible to provide an optical filter having these characteristics, in particular, sufficiently shielding light in the infrared region and capable of transmitting light in the visible light region at a high ratio. Therefore, according to the present invention, not only can the near infrared ray cut-off filter (near infrared ray cut-off filter, NIR-CF) be easily produced, but also the visible light-near infrared selective transmission filter (dual band pass filter) can be easily produced. (Dual bandpass filter, DBPF)) or near-infrared pass filter (infrared pass filter, IRPF) and other optical filters. Furthermore, in the present invention, having sufficient resistance to heat or light means that the optical characteristics do not change significantly before and after applying heat or irradiating light.

As described above, according to the present invention, it is possible to provide an optical filter having the above-mentioned characteristics. Therefore, it is possible to easily obtain reflected light that can suppress light having a wavelength around 700 nm to 750 nm, or a wavelength around 720 nm to 900 nm, and An optical filter that can provide a good image with less flare or ghosting. In addition, it is possible to suppress the incident angle dependence of the dielectric multilayer film when the optical filter is a filter having a dielectric multilayer film.

"Resin composition" The resin composition of the present invention (hereinafter also referred to as "this composition") is not particularly limited as long as it contains a resin and the compound (Z). Examples of the form of such a resin composition include: a resin film (resin layer, resin substrate) containing the compound (Z); A resin film (resin layer) of the compound (Z); a liquid composition containing a resin, a compound (Z), and a solvent. This composition may contain two or more kinds of resins, and may contain two or more kinds of compounds (Z).

<Compound (Z)> The compound (Z) is a compound represented by the following formula (I). The compound (Z) has high near-infrared cut-off performance and high visible light transmission performance at a wavelength near 700 nm to 750 nm, or a wavelength near 720 nm to 900 nm, and has excellent optical properties. It is resistant to heat or light. Have sufficient patience. Cn ⁺ An ^- (I) [in the formula (I), Cn ⁺ is a monovalent cation represented by the following formula (II), An ^- is a monovalent anion]

[式（II）中， 單元A為下述式（A-I）～式（A-III）的任一者， 單元B為下述式（B-I）～式（B-III）的任一者， Y_A ～Y_E 分別獨立地為氫原子、鹵素原子、羥基、羧基、硝基、-NR^g R^h 基、醯胺基、醯亞胺基、氰基、矽烷基、-Q¹ 、-N=N-Q¹ 、-S-Q² 、-SSQ² 、或-SO₂ Q³ ， Y_A 與Y_C 、Y_B 與Y_D 、Y_C 與Y_E 可相互鍵結而形成碳數6～14的芳香族烴基、可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基、或者包含至少一個氮原子、氧原子或硫原子的碳數3～14的雜芳香族基，這些芳香族烴基、脂環基及雜芳香族基可具有羥基、碳數1～9的脂肪族烴基或鹵素原子，另外，所述脂環基可具有=O， Y_A 與下述式（A-III）中的R¹ 或R⁵ 、Y_E 與下述式（B-III）中的R⁵ 或R¹ 可相互鍵結而形成可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基， R^g 及R^h 分別獨立地為氫原子、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者，Q¹ 獨立地為下述L^a ～L^h 的任一者，Q² 獨立地為氫原子或下述L^a ～L^h 的任一者，Q³ 為羥基或下述L^a ～L^h 的任一者，Rⁱ 為下述L^a ～L^h 的任一者][化5]

[In formula (II), unit A is any one of the following formula (AI) to formula (A-III), unit B is any one of the following formula (BI) to formula (B-III), Y _A to Y _E are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, a -NR ^g R ^h group, an amide group, an amide group, a cyano group, a silyl group, -Q ¹ , -N= NQ ¹ , -SQ ² , -SSQ ² , or -SO ₂ Q ³ , Y _A and Y _C , Y _B and Y _D , Y _C and Y _E can be bonded to each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms , A 4- to 7-member alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic The aliphatic hydrocarbon group, alicyclic group, and heteroaromatic group may have a hydroxyl group, an aliphatic hydrocarbon group with 1 to 9 carbon atoms, or a halogen atom, and the alicyclic group may have =0, Y _A and the following formula (A-III ) R ¹ or R ⁵ , Y _E ^{and R 5} or R ¹ in the following formula (B-III) may be bonded to each other to form 4 to 7 members which may contain at least one nitrogen atom, oxygen atom or sulfur atom membered alicyclic group, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, Q ¹ is independently represented by the following L ^a ~ L any one ^h, Q ² is independently a hydrogen atom or L ^a ~ L ^h following either one, Q ³ is hydroxy or L ^a ~ L ^h following either one, R ⁱ L ^a by the following Any one of ~L ^h]

[式（A-I）～式（A-III）中的-*表示與所述式（II）的Y_A 所鍵結的碳進行單鍵結， 式（B-I）～式（B-III）中的=**表示與所述式（II）的Y_E 所鍵結的碳進行雙鍵結， 式（A-I）～式（B-III）中， X獨立地為氧原子、硫原子、硒原子、碲原子或-NR⁸ -， R¹ ～R⁶ 分別獨立地為氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、-NR^g R^h 基、-SRⁱ 基、-SO₂ Rⁱ 基、-OSO₂ Rⁱ 基、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者， 鄰接的R¹ ～R⁶ 可相互鍵結而形成碳數6～14的芳香族烴基、可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基、或者包含至少一個氮原子、氧原子或硫原子的碳數3～14的雜芳香族基，這些芳香族烴基、脂環基及雜芳香族基可具有羥基、碳數1～9的脂肪族烴基或鹵素原子，另外，所述脂環基可具有=O， R⁸ 獨立地為氫原子、鹵素原子、-C(O)Rⁱ 基、下述L^a ～L^h 的任一者， R^g 及R^h 分別獨立地為氫原子、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者， Rⁱ 獨立地為下述L^a ～L^h 的任一者， （L^a ）：碳數1～15的脂肪族烴基 （L^b ）：碳數1～15的經鹵素取代的烷基 （L^c ）：可具有取代基K的碳數3～14的脂環式烴基 （L^d ）：可具有取代基K的碳數6～14的芳香族烴基 （L^e ）：可具有取代基K的碳數3～14的雜環基 ‏（L^f ）：-OR（R為可具有取代基L的碳數1～12的烴基） （L^g ）：可具有取代基L的碳數1～9的醯基 （L^h ）：可具有取代基L的碳數1～9的烷氧基羰基 所述取代基K為選自所述L^a ～L^b 中的至少一種，所述取代基L為選自所述L^a ～L^f 中的至少一種][化6]

[-* in formula (AI) to formula (A-III) represents _{a single bond with the carbon to which Y A} of the formula (II) is bonded, and in formula (BI) to formula (B-III) _{=** means that the carbon to which Y E} of the formula (II) is bonded is double-bonded. In formulas (AI) to (B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, Tellurium atom or -NR ⁸ -, R ¹ to R ⁶ are each independently 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, a -NR ^g R ^h group, and a -SR ⁱ group , -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group, -C (O) R ⁱ or the following group L ^a ~ L ^h is any one of, adjacent to R ¹ ~ R ⁶ may be bonded to each other to form a carbon Aromatic hydrocarbon group of 6 to 14, alicyclic group of 4 to 7 members which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or carbon 3 to 14 containing at least one nitrogen atom, oxygen atom or sulfur atom These aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbons or halogen atoms, and the alicyclic groups may have =0, R ⁸ is independently a hydrogen atom, a halogen atom, -C (O) R ⁱ groups, L ^a ~ L ^h following either one, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, R ⁱ is independently L ^a ~ L ^h following either one, (L ^a): an aliphatic hydrocarbon group having a carbon number of 1 to 15 (L ^b): carbon 1 to 15 halogen-substituted alkyl group (L ^c ): an alicyclic hydrocarbon group with 3 to 14 carbons that may have a substituent K (L ^d ): an aromatic 6 to 14 carbons that may have a substituent K Group hydrocarbon group (L ^e ): a heterocyclic group having 3 to 14 carbons which may have substituent K ‏(L ^f ): -OR (R is a hydrocarbon group having 1 to 12 carbons which may have substituent L) (L ^g ): an acyl group ^{having 1 to 9 carbons that may have a substituent L (L h} ): an alkoxycarbonyl group having 1 to 9 carbons that may have a substituent L. The substituent K is selected from the group consisting of ^La to At least one of L ^b , and the substituent L is at least one selected from the group consisting of ^La to L ^f ]

In addition, the compound (Z) of the present invention is a compound 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]

[式（IV）中， 單元A為下述式（A-I）～式（A-III）的任一者， 單元B為下述式（B-I）～式（B-III）的任一者， Y_A ～Y_E 分別獨立地為氫原子、鹵素原子、羥基、羧基、硝基、-NR^g R^h 基、醯胺基、醯亞胺基、氰基、矽烷基、-Q¹ 、-N=N-Q¹ 、-S-Q² 、-SSQ² 、或-SO₂ Q³ ， Y_A 與Y_C 、Y_B 與Y_D 、Y_C 與Y_E 可相互鍵結而形成碳數6～14的芳香族烴基、可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基、或者包含至少一個氮原子、氧原子或硫原子的碳數3～14的雜芳香族基，這些芳香族烴基、脂環基及雜芳香族基可具有羥基、碳數1～9的脂肪族烴基或鹵素原子，另外，所述脂環基可具有=O， Y_A 與下述式（A-III）中的R¹ 或R⁵ 、Y_E 與下述式（B-III）中的R⁵ 或R¹ 可相互鍵結而形成可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基， R^g 及R^h 分別獨立地為氫原子、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者，Q¹ 獨立地為下述L^a ～L^h 的任一者，Q² 獨立地為氫原子或下述L^a ～L^h 的任一者，Q³ 為羥基或下述L^a ～L^h 的任一者，Rⁱ 為下述L^a ～L^h 的任一者][化7]

[In formula (IV), unit A is any of the following formulas (AI) to (A-III), unit B is any of the following formulas (BI) to (B-III), Y _A to Y _E are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, a -NR ^g R ^h group, an amide group, an amide group, a cyano group, a silyl group, -Q ¹ , -N= NQ ¹ , -SQ ² , -SSQ ² , or -SO ₂ Q ³ , Y _A and Y _C , Y _B and Y _D , Y _C and Y _E can be bonded to each other to form an aromatic hydrocarbon group with 6 to 14 carbon atoms , A 4- to 7-member alicyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom, or a heteroaromatic group with 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, these aromatic The aliphatic hydrocarbon group, alicyclic group, and heteroaromatic group may have a hydroxyl group, an aliphatic hydrocarbon group with 1 to 9 carbon atoms, or a halogen atom, and the alicyclic group may have =0, Y _A and the following formula (A-III ) R ¹ or R ⁵ , Y _E ^{and R 5} or R ¹ in the following formula (B-III) may be bonded to each other to form 4 to 7 members which may contain at least one nitrogen atom, oxygen atom or sulfur atom membered alicyclic group, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, Q ¹ is independently represented by the following L ^a ~ L any one ^h, Q ² is independently a hydrogen atom or L ^a ~ L ^h following either one, Q ³ is hydroxy or L ^a ~ L ^h following either one, R ⁱ L ^a by the following Any one of ~L ^h]

[式（A-I）～式（A-III）中的-*表示與所述式（II）的Y_A 所鍵結的碳進行單鍵結， 式（B-I）～式（B-III）中的=**表示與所述式（II）的Y_E 所鍵結的碳進行雙鍵結， 式（A-I）～式（B-III）中， X獨立地為氧原子、硫原子、硒原子、碲原子或-NR⁸ -， R¹ ～R⁶ 分別獨立地為氫原子、鹵素原子、磺基、羥基、氰基、硝基、羧基、磷酸基、-NR^g R^h 基、-SRⁱ 基、-SO₂ Rⁱ 基、-OSO₂ Rⁱ 基、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者， 鄰接的R¹ ～R⁶ 可相互鍵結而形成碳數6～14的芳香族烴基、可包含至少一個氮原子、氧原子或硫原子的4員～7員的脂環基、或者包含至少一個氮原子、氧原子或硫原子的碳數3～14的雜芳香族基，這些芳香族烴基、脂環基及雜芳香族基可具有羥基、碳數1～9的脂肪族烴基或鹵素原子，另外，所述脂環基可具有=O， R⁸ 獨立地為氫原子、鹵素原子、-C(O)Rⁱ 基、下述L^a ～L^h 的任一者， R^g 及R^h 分別獨立地為氫原子、-C(O)Rⁱ 基或下述L^a ～L^h 的任一者， Rⁱ 獨立地為下述L^a ～L^h 的任一者， （L^a ）：碳數1～15的脂肪族烴基 （L^b ）：碳數1～15的經鹵素取代的烷基 （L^c ）：可具有取代基K的碳數3～14的脂環式烴基 （L^d ）：可具有取代基K的碳數6～14的芳香族烴基 （L^e ）：可具有取代基K的碳數3～14的雜環基 ‏（L^f ）：-OR（R為可具有取代基L的碳數1～12的烴基） （L^g ）：可具有取代基L的碳數1～9的醯基 （L^h ）：可具有取代基L的碳數1～9的烷氧基羰基 所述取代基K為選自所述L^a ～L^b 中的至少一種，所述取代基L為選自所述L^a ～L^f 中的至少一種][化8]

[-* in formula (AI) to formula (A-III) represents _{a single bond with the carbon to which Y A} of the formula (II) is bonded, and in formula (BI) to formula (B-III) _{=** means that the carbon to which Y E} of the formula (II) is bonded is double-bonded. In formulas (AI) to (B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, Tellurium atom or -NR ⁸ -, R ¹ to R ⁶ are each independently 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, a -NR ^g R ^h group, and a -SR ⁱ group , -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group, -C (O) R ⁱ or the following group L ^a ~ L ^h is any one of, adjacent to R ¹ ~ R ⁶ may be bonded to each other to form a carbon Aromatic hydrocarbon group of 6 to 14, alicyclic group of 4 to 7 members which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or carbon 3 to 14 containing at least one nitrogen atom, oxygen atom or sulfur atom These aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbons or halogen atoms, and the alicyclic groups may have =0, R ⁸ is independently a hydrogen atom, a halogen atom, -C (O) R ⁱ groups, L ^a ~ L ^h following either one, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, R ⁱ is independently L ^a ~ L ^h following either one, (L ^a): an aliphatic hydrocarbon group having a carbon number of 1 to 15 (L ^b): carbon 1 to 15 halogen-substituted alkyl group (L ^c ): an alicyclic hydrocarbon group with 3 to 14 carbons that may have a substituent K (L ^d ): an aromatic 6 to 14 carbons that may have a substituent K Group hydrocarbon group (L ^e ): a heterocyclic group having 3 to 14 carbons which may have substituent K ‏(L ^f ): -OR (R is a hydrocarbon group having 1 to 12 carbons which may have substituent L) (L ^g ): an acyl group ^{having 1 to 9 carbons that may have a substituent L (L h} ): an alkoxycarbonyl group having 1 to 9 carbons that may have a substituent L. The substituent K is selected from the group consisting of ^La to At least one of L ^b , and the substituent L is at least one selected from the group consisting of ^La to L ^f ]

Furthermore, the -NR ⁸ -is a group represented by the following formula (a), the -NR ^g R ^h group is a group represented by the following formula (b), and the -SR ⁱ group is the following The group represented by the formula (c), the -SO ₂ R ⁱ group is a group represented by the following formula (d), the -OSO ₂ R ⁱ group is a group represented by the following formula (e), The -C(O)R ⁱ group is a group represented by the following formula (f). In addition, the -SSQ ² is a group represented by ^{-SSQ 2} _{, and the -SO 2} Q ³ is a group obtained by substituting ^{R i with Q 3} in the group represented by the following formula (d).

[化9]

In addition, when the unit A is the formula (AI) and the unit B is the formula (BI), Cn ^{+ is} represented by the following formula (II-1). That is, the single bond (-) of "*-" in the formulas (AI) to (A-III) corresponds to the carbon atom _{to which Y A in the formula (II) or formula (IV) is bonded} The single bond with unit A, the double bond (=) of "**=" in the formula (BI) ~ formula (B-III) is equivalent to the formula (II) or formula (IV) The double bond between the carbon atom bonded by Y _{E and the unit B.}

[化10]

The Y _B and Y _D are each independently more preferably a 4-membered to 6-membered alicyclic hydrocarbon group formed by a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, and a Y _B and Y _{D bonded to each other.} ^{(The alicyclic hydrocarbon group may have a substituent R 9} selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a hydroxyl group, a halogen atom, and =0).

Furthermore, in the case of _{a 4-membered to 6-membered alicyclic hydrocarbon group formed by bonding Y B} and Y _{D to} each other, the formula (II) or the formula (IV) may be each preferably represented by the following formula (CI) ~ Formula (C-III) said.

[化11]

[化12]

[化13]

As the substituent R ⁹ , a hydrogen atom, a hydroxyl group, =O, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, and a cyclohexyl group are preferable, and a hydrogen atom is more preferable , Hydroxy, =0, methyl, ethyl, tert-butyl.

The Y _A , Y _C and Y _E are each independently a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a hydroxyl group, a phenylamino group (NHPh), a diphenylamino group, and a methylphenylamino group. , Dimethylamino, methyl, methoxy, phenyl, phenoxy, 4-methylphenoxy, methylthio, phenylthio, -S-(4-tolyl) group (-S -(4-tolyl) base).

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

The ^La may also be: vinyl, 1-propenyl, 2-propenyl, butenyl, 1,3-butadienyl, 2-methyl-1-propenyl, 2-pentenyl, Alkenyl such as hexenyl; alkynyl such as ethynyl, propynyl, butynyl, 2-methyl-1-propynyl, and hexynyl.

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

As the ^{alicyclic hydrocarbon group having 3 to 14 carbon atoms in the L c} that may have the substituent K, preferably, cyclopropyl, cyclopropylmethyl, methylcyclopropyl, cyclobutyl, and cyclopropyl Cycloalkyl groups such as pentyl, cyclohexyl, methylcyclohexyl, cycloheptyl and cyclooctyl; polycyclic alicyclic groups such as norbornyl and adamantyl.

The aromatic hydrocarbon group having 6 to 14 carbons and which may have a substituent K in the L ^d is preferably a phenyl group, a tolyl group, a xylyl group, a mesityl group (trimethylphenyl group), and a cumenyl group , Bis (trifluoromethyl) phenyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl, benzyl (CH ₂ Ph).

Examples of the L ^e may have a substituent group K carbon atoms heterocyclic group having 3 to 14, preferably furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene , Morpholine, pyridine.

The -OR in the L ^f is preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, methoxymethyl, methoxyethyl, pentoxy, hexyl Oxy, octyloxy, phenoxy (OPh), 4-methylphenoxy, cyclohexyloxy.

The acyl group having 1 to 9 carbons and which may have the substituent L in the L ^g is preferably an acetyl group, a propyl group, a butyryl group, an isobutyryl group, a benzyl group, and a 4-propylbenzyl group , Trifluoromethylcarbonyl.

The alkoxycarbonyl group having 1 to 9 carbon atoms in the L ^h that may have the substituent L is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, and a butoxy group. Carbonyl, 2-trifluoromethylethoxycarbonyl, 2-phenylethoxycarbonyl.

The X is preferably an oxygen atom, a sulfur atom, or -NR ⁸ -, and particularly preferably an oxygen atom.

In the formula (II) or the formula (IV), the left and right units A and B may be the same or different. If they are the same, they are easy to synthesize and are therefore preferred. Furthermore, here, the same combination of unit A and unit B is formula (AI) and formula (BI), formula (A-II) and formula (B-II), formula (A-III) and formula (B- III).

The R ¹ to R ⁶ are each independently preferably a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, 1,1-Dimethylbutyl, cyclopropyl, cyclopropylmethyl, cyclohexyl, adamantyl, phenyl, 2,4,6-trimethylphenyl, 3,5-bis(trifluoro Methyl) phenyl, hydroxyl, amino, dimethylamino (NMe ₂ ), diethylamino (NEt ₂ ), dibutylamino (N(n-Bu) ₂ ), cyano, nitro Group, acetamido, propylamino, N-methylacetamido, trifluoromethanamido, pentafluoroacetamido, tert-butyamido, cyclohexanamido Group, n-butylsulfonyl group, benzyl group, diphenylmethyl group, trifluoromethyl group, difluoromethyl group, methoxy group, more preferably hydrogen atom, chlorine atom, fluorine atom, bromine atom, methyl group, Ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclohexyl, phenyl, amino, benzyl, diphenylmethyl, trifluoromethyl, difluoromethyl , Methoxy.

It is easy to obtain high near-infrared cut-off performance and high visible light transmission performance at a wavelength near 700 nm to 750 nm, or a wavelength near 720 nm to 900 nm, with excellent optical properties, and resistance to heat or light. For aspects sufficient resistance compound, preferably the R ¹ ~ R of said at least one of L ^a, L ^c or L ^{d 6} in. Further, in the case where A is a unit of the formula (A-III), B is the unit of the formula (B-III) a, "R ¹ ~ R at least one of L ^{a 6,} L ^c or L ^{d "means" R 1, R 2, R} 4, at least one of L ^a, L ^c or L ^d "R ⁵ a.

The R ⁸ is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, benzyl, n-pentyl, n-hexyl, tert-butyl, more preferably a hydrogen atom, methyl Group, ethyl, n-propyl, isopropyl, n-butyl, benzyl.

Examples of the An ^-, if it is a monovalent anion, is not particularly limited, preferably include: chloride, bromide, iodide, PF ₄ ^-, perchloric acid anion, tris - trifluoromethane sulfonic acyl A Base anion, tetrafluoroborate anion, hexafluorophosphate anion, bis(trifluoromethanesulfonyl) imine anion, trifluoromethanesulfonate anion, tetra(pentafluorophenyl) borate anion, tetra( 3,5-bis(trifluoromethyl)phenyl)borate anion, etc., more preferably bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonate anion, tris-trifluoromethanesulfonate Methylate anion, tetrakis(pentafluorophenyl) borate anion, tetrakis(3,5-bis(trifluoromethyl)phenyl) borate anion, it is easy to obtain a compound with more excellent heat resistance (Z ) And the like, bis(trifluoromethanesulfonyl) imide anion, tris-trifluoromethanesulfonyl methide anion, tetrakis(pentafluorophenyl) borate anion, tetrakis(3 , 5-bis(trifluoromethyl)phenyl)borate anion, particularly preferably tetra(pentafluorophenyl)borate anion.

As specific examples of the compound represented by formula (I) or formula (III), for example, compounds (z-1) to (z-173) described in the following Tables 1 to 4 can be cited. Specifically, these compounds (Z) can be synthesized, for example, by the method described in the following Examples.

[Table 1] Compound A, B X Y _A , Y _E Y _B , Y _D Y _C R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ An (Z-1) (AI), (BI) O H H Cl H tert-Bu H H i-Pr H B(C ₆ F ₅ ) ₄ (Z-2) (AI), (BI) N H H H H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-3) (AI), (BI) S H H H H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-4) (AI), (BI) O CH ₃ H H H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-5) (AI), (BI) O H H F H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-6) (AI), (BI) O H H Cl H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-7) (AI), (BI) O H H Br H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-8) (AI), (BI) O H H CH ₃ H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-9) (AI), (BI) O H H OCH ₃ H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-10) (AI), (BI) O H H OPh H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-11) (AI), (BI) O H H N(CH ₃ ) ₂ H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-12) (AI), (BI) O H H NHPh H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-13) (AI), (BI) O H H NPh ₂ H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-14) (AI), (BI) O H H SCH ₃ H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-15) (AI), (BI) O H H SPh H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-16) (AI), (BI) O H H H H Ph H H H H B(C ₆ F ₅ ) ₄ (Z-17) (AI), (BI) O H H H H i-Pr H H H H B(C ₆ F ₅ ) ₄ (Z-18) (AI), (BI) O H H H H Cyclopropyl H H H H B(C ₆ F ₅ ) ₄ (Z-19) (AI), (BI) O H H H H Cyclopropylmethyl H H H H B(C ₆ F ₅ ) ₄ (Z-20) (AI), (BI) O H H H H Cyclohexyl H H H H B(C ₆ F ₅ ) ₄ (Z-21) (AI), (BI) O H H H H Adamantyl H H H H B(C ₆ F ₅ ) ₄ (Z-22) (AI), (BI) O H H H H 2,4,6-trimethylphenyl H H H H B(C ₆ F ₅ ) ₄ (Z-23) (AI), (BI) O H H H H 3,5-bis(trifluoromethyl)phenyl H H H H B(C ₆ F ₅ ) ₄ (Z-24) (AI), (BI) O H H H H tert-Bu Cl H H H B(C ₆ F ₅ ) ₄ (Z-25) (AI), (BI) O H H H H tert-Bu Br H H H B(C ₆ F ₅ ) ₄ (Z-26) (AI), (BI) O H H H H tert-Bu Ph H H H B(C ₆ F ₅ ) ₄ (Z-27) (AI), (BI) O H H H H tert-Bu Me H H H B(C ₆ F ₅ ) ₄ (Z-28) (AI), (BI) O H H H H tert-Bu i-Pr H H H B(C ₆ F ₅ ) ₄ (Z-29) (AI), (BI) O H H H H tert-Bu NHCOCF ₃ H H H B(C ₆ F ₅ ) ₄ (Z-30) (AI), (BI) O H H H H tert-Bu H F H H B(C ₆ F ₅ ) ₄ (Z-31) (AI), (BI) O H H H H tert-Bu H Cl H H B(C ₆ F ₅ ) ₄ (Z-32) (AI), (BI) O H H H H tert-Bu H Br H H B(C ₆ F ₅ ) ₄ (Z-33) (AI), (BI) O H H H H tert-Bu H Me H H B(C ₆ F ₅ ) ₄ (Z-34) (AI), (BI) O H H H H tert-Bu H i-Pr H H B(C ₆ F ₅ ) ₄ (Z-35) (AI), (BI) O H H H H tert-Bu H OCH ₃ H H B(C ₆ F ₅ ) ₄ (Z-36) (AI), (BI) O H H H H tert-Bu H CF ₃ H H B(C ₆ F ₅ ) ₄ (Z-37) (AI), (BI) O H H H H tert-Bu H H F H B(C ₆ F ₅ ) ₄ (Z-38) (AI), (BI) O H H H H tert-Bu H H Cl H B(C ₆ F ₅ ) ₄ (Z-39) (AI), (BI) O H H H H tert-Bu H H Br H B(C ₆ F ₅ ) ₄ (Z-40) (AI), (BI) O H H H H tert-Bu H H Me H B(C ₆ F ₅ ) ₄ (Z-41) (AI), (BI) O H H H H tert-Bu H H i-Pr H B(C ₆ F ₅ ) ₄ (Z-42) (AI), (BI) O H H H H tert-Bu H H OCH ₃ H B(C ₆ F ₅ ) ₄ (Z-43) (AI), (BI) O H H H H tert-Bu H H NHCOCF ₃ H B(C ₆ F ₅ ) ₄ (Z-44) (AI), (BI) O H H H H tert-Bu H H H F B(C ₆ F ₅ ) ₄ (Z-45) (AI), (BI) O H H H H tert-Bu H H H Cl B(C ₆ F ₅ ) ₄ (Z-46) (AI), (BI) O H H H H tert-Bu H H H Br B(C ₆ F ₅ ) ₄ (Z-47) (AI), (BI) O H H H H tert-Bu H H H H N(SO ₂ CF ₃ ) ₂ (Z-48) (AI), (BI) O H H H H tert-Bu H H H H C(SO ₂ CF ₃ ) ₃ (Z-49) (AI), (BI) O H H H H tert-Bu H H H H BF ₄ (Z-50) (AI), (BI) O H H H H tert-Bu H H H H ClO ₄

[Table 2] Compound A, B X Y _A , Y _E Y _B , Y _D Y _C R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ An (Z-51) (AI), (BI) O H H H H tert-Bu H H H H PF ₄ (Z-52) (AI), (BI) O H H H H tert-Bu H H H H Cl (Z-53) (AI), (BI) O H H H H tert-Bu H H H H Br (Z-54) (AI), (BI) O H H H H tert-Bu H H H H I (Z-55) (AI), (BI) O H H Cl H tert-Bu H H F H B(C ₆ F ₅ ) ₄ (Z-56) (AI), (BI) O H H Cl H tert-Bu H H Cl H B(C ₆ F ₅ ) ₄ (Z-57) (AI), (BI) O H H Cl H tert-Bu H H Br H B(C ₆ F ₅ ) ₄ (Z-58) (AI), (BI) O H H Cl H tert-Bu H H Me H B(C ₆ F ₅ ) ₄ (Z-59) (AI), (BI) O H H H H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-60) (AI), (BI) O H H Cl H tert-Bu H H OCH ₃ H B(C ₆ F ₅ ) ₄ (Z-61) (AI), (BI) O H H Cl H tert-Bu H H NHCOCF ₃ H B(C ₆ F ₅ ) ₄ (Z-62) (AI), (BI) O H H H H i-Pr H F H H B(C ₆ F ₅ ) ₄ (Z-63) (AI), (BI) O H H H H i-Pr H Cl H H B(C ₆ F ₅ ) ₄ (Z-64) (AI), (BI) O H H H H i-Pr H Br H H B(C ₆ F ₅ ) ₄ (Z-65) (AI), (BI) O H H H H i-Pr H Me H H B(C ₆ F ₅ ) ₄ (Z-66) (AI), (BI) O H H H H i-Pr H i-Pr H H B(C ₆ F ₅ ) ₄ (Z-67) (AI), (BI) O H H H H i-Pr H OCH ₃ H H B(C ₆ F ₅ ) ₄ (Z-68) (AI), (BI) O H H H H i-Pr H CF ₃ H H B(C ₆ F ₅ ) ₄ (Z-69) (AI), (BI) O H H H H Ph H H F H B(C ₆ F ₅ ) ₄ (Z-70) (AI), (BI) O H H H H Ph H H Cl H B(C ₆ F ₅ ) ₄ (Z-71) (AI), (BI) O H H H H Ph H H Br H B(C ₆ F ₅ ) ₄ (Z-72) (AI), (BI) O H H H H Ph H H Me H B(C ₆ F ₅ ) ₄ (Z-73) (AI), (BI) O H H H H Ph H H i-Pr H B(C ₆ F ₅ ) ₄ (Z-74) (AI), (BI) O H H H H Ph H H OCH ₃ H B(C ₆ F ₅ ) ₄ (Z-75) (AI), (BI) O H H H H Ph H H NHCOCF ₃ H B(C ₆ F ₅ ) ₄ (Z-76) (A-II), (B-II) N H H H H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-77) (A-II), (B-II) S H H H H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-78) (A-II), (B-II) O CH ₃ H H H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-79) (A-II), (B-II) O H H F H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-80) (A-II), (B-II) O H H Cl H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-81) (A-II), (B-II) O H H Br H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-82) (A-II), (B-II) O H H CH ₃ H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-83) (A-II), (B-II) O H H OCH ₃ H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-84) (A-II), (B-II) O H H OPh H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-85) (A-II), (B-II) O H H N(CH ₃ ) ₂ H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-86) (A-II), (B-II) O H H NHPh H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-87) (A-II), (B-II) O H H NPh ₂ H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-88) (A-II), (B-II) O H H SCH ₃ H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-89) (A-II), (B-II) O H H SPh H tert-Bu H H H H B(C ₆ F ₅ ) ₄ (Z-90) (A-II), (B-II) O H H H H Ph H H H H B(C ₆ F ₅ ) ₄ (Z-91) (A-II), (B-II) O H H H H i-Pr H H H H B(C ₆ F ₅ ) ₄ (Z-92) (A-II), (B-II) O H H H H Cyclopropyl H H H H B(C ₆ F ₅ ) ₄ (Z-93) (A-II), (B-II) O H H H H Cyclopropylmethyl H H H H B(C ₆ F ₅ ) ₄ (Z-94) (A-II), (B-II) O H H H H Cyclohexyl H H H H B(C ₆ F ₅ ) ₄ (Z-95) (A-II), (B-II) O H H H H Adamantyl H H H H B(C ₆ F ₅ ) ₄ (Z-96) (A-II), (B-II) O H H H H 2,4,6-trimethylphenyl H H H H B(C ₆ F ₅ ) ₄ (Z-97) (A-II), (B-II) O H H H H 3,5-bis(trifluoromethyl)phenyl H H H H B(C ₆ F ₅ ) ₄ (Z-98) (A-II), (B-II) O H H H H tert-Bu Cl H H H B(C ₆ F ₅ ) ₄ (Z-99) (A-II), (B-II) O H H H H tert-Bu Br H H H B(C ₆ F ₅ ) ₄ (Z-100) (A-II), (B-II) O H H H H tert-Bu Ph H H H B(C ₆ F ₅ ) ₄

[table 3] Compound A, B X Y _A , Y _E Y _B , Y _D Y _C R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ An (Z-101) (A-II), (B-II) O H H H H tert-Bu Me H H H B(C ₆ F ₅ ) ₄ (Z-102) (A-II), (B-II) O H H H H tert-Bu i-Pr H H H B(C ₆ F ₅ ) ₄ (Z-103) (A-II), (B-II) O H H H H tert-Bu NHCOCF ₃ H H H B(C ₆ F ₅ ) ₄ (Z-104) (A-II), (B-II) O H H H H tert-Bu H F H H B(C ₆ F ₅ ) ₄ (Z-105) (A-II), (B-II) O H H H H tert-Bu H Cl H H B(C ₆ F ₅ ) ₄ (Z-106) (A-II), (B-II) O H H H H tert-Bu H Br H H B(C ₆ F ₅ ) ₄ (Z-107) (A-II), (B-II) O H H H H tert-Bu H Me H H B(C ₆ F ₅ ) ₄ (Z-108) (A-II), (B-II) O H H H H tert-Bu H i-Pr H H B(C ₆ F ₅ ) ₄ (Z-109) (A-II), (B-II) O H H H H tert-Bu H OCH ₃ H H B(C ₆ F ₅ ) ₄ (Z-110) (A-II), (B-II) O H H H H tert-Bu H CF ₃ H H B(C ₆ F ₅ ) ₄ (Z-111) (A-II), (B-II) O H H H H tert-Bu H H F H B(C ₆ F ₅ ) ₄ (Z-112) (A-II), (B-II) O H H H H tert-Bu H H Cl H B(C ₆ F ₅ ) ₄ (Z-113) (A-II), (B-II) O H H H H tert-Bu H H Br H B(C ₆ F ₅ ) ₄ (Z-114) (A-II), (B-II) O H H H H tert-Bu H H Me H B(C ₆ F ₅ ) ₄ (Z-115) (A-II), (B-II) O H H H H tert-Bu H H i-Pr H B(C ₆ F ₅ ) ₄ (Z-116) (A-II), (B-II) O H H H H tert-Bu H H OCH ₃ H B(C ₆ F ₅ ) ₄ (Z-117) (A-II), (B-II) O H H H H tert-Bu H H NHCOCF ₃ H B(C ₆ F ₅ ) ₄ (Z-118) (A-II), (B-II) O H H H H tert-Bu H H H F B(C ₆ F ₅ ) ₄ (Z-119) (A-II), (B-II) O H H H H tert-Bu H H H Cl B(C ₆ F ₅ ) ₄ (Z-120) (A-II), (B-II) O H H H H tert-Bu H H H Br B(C ₆ F ₅ ) ₄ (Z-121) (A-II), (B-II) O H H H H tert-Bu H H H H N(SO ₂ CF ₃ ) ₂ (Z-122) (A-II), (B-II) O H H H H tert-Bu H H H H C(SO ₂ CF ₃ ) ₃ (Z-123) (A-II), (B-II) O H H H H tert-Bu H H H H BF ₄ (Z-124) (A-II), (B-II) O H H H H tert-Bu H H H H ClO ₄ (Z-125) (A-II), (B-II) O H H H H tert-Bu H H H H PF ₄ (Z-126) (A-II), (B-II) O H H H H tert-Bu H H H H Cl (Z-127) (A-II), (B-II) O H H H H tert-Bu H H H H Br (Z-128) (A-II), (B-II) O H H H H tert-Bu H H H H I (Z-129) (A-II), (B-II) O H H Cl H tert-Bu H H F H B(C ₆ F ₅ ) ₄ (Z-130) (A-II), (B-II) O H H Cl H tert-Bu H H Cl H B(C ₆ F ₅ ) ₄ (Z-131) (A-II), (B-II) O H H Cl H tert-Bu H H Br H B(C ₆ F ₅ ) ₄ (Z-132) (A-II), (B-II) O H H Cl H tert-Bu H H Me H B(C ₆ F ₅ ) ₄ (Z-133) (A-II), (B-II) O H H Cl H tert-Bu H H i-Pr H B(C ₆ F ₅ ) ₄ (Z-134) (A-II), (B-II) O H H Cl H tert-Bu H H OCH ₃ H B(C ₆ F ₅ ) ₄ (Z-135) (A-II), (B-II) O H H Cl H tert-Bu H H NHCOCF ₃ H B(C ₆ F ₅ ) ₄ (Z-136) (A-II), (B-II) O H H H H i-Pr H F H H B(C ₆ F ₅ ) ₄ (Z-137) (A-II), (B-II) O H H H H i-Pr H Cl H H B(C ₆ F ₅ ) ₄ (Z-138) (A-II), (B-II) O H H H H i-Pr H Br H H B(C ₆ F ₅ ) ₄ (Z-139) (A-II), (B-II) O H H H H i-Pr H Me H H B(C ₆ F ₅ ) ₄ (Z-140) (A-II), (B-II) O H H H H i-Pr H i-Pr H H B(C ₆ F ₅ ) ₄ (Z-141) (A-II), (B-II) O H H H H i-Pr H OCH ₃ H H B(C ₆ F ₅ ) ₄ (Z-142) (A-II), (B-II) O H H H H i-Pr H CF ₃ H H B(C ₆ F ₅ ) ₄ (Z-143) (A-II), (B-II) O H H H H Ph H H F H B(C ₆ F ₅ ) ₄ (Z-144) (A-II), (B-II) O H H H H Ph H H Cl H B(C ₆ F ₅ ) ₄ (Z-145) (A-II), (B-II) O H H H H Ph H H Br H B(C ₆ F ₅ ) ₄ (Z-146) (A-II), (B-II) O H H H H Ph H H Me H B(C ₆ F ₅ ) ₄ (Z-147) (A-II), (B-II) O H H H H Ph H H i-Pr H B(C ₆ F ₅ ) ₄ (Z-148) (A-II), (B-II) O H H H H Ph H H OCH ₃ H B(C ₆ F ₅ ) ₄ (Z-149) (A-II), (B-II) O H H H H Ph H H NHCOCF ₃ H B(C ₆ F ₅ ) ₄ (Z-150) (AI), (BI) O H H H H tert-Bu H NMe ₂ H H B(C ₆ F ₅ ) ₄

[Table 4] Compound A, B X Y _A , Y _E Y _B , Y _D Y _C R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ An (Z-151) (AI), (BI) O H H H H tert-Bu H NEt ₂ H H B(C ₆ F ₅ ) ₄ (Z-152) (AI), (BI) O H H H H tert-Bu H N(n-Bu) ₂ H H B(C ₆ F ₅ ) ₄ (Z-153) (AI), (BI) O H H Cl H tert-Bu H NEt ₂ H H B(C ₆ F ₅ ) ₄ (Z-154) (AI), (BI) O H H H H tert-Bu H NEt ₂ H H N(SO ₂ CF ₃ ) ₂ (Z-155) (AI), (BI) O H H Me H tert-Bu H NEt ₂ H H B(C ₆ F ₅ ) ₄ (Z-156) (AI), (BI) O H H H H tert-Bu Ph H Me H B(C ₆ F ₅ ) ₄ (Z-157) (AI), (BI) O H H H H tert-Bu C-1, C-2 H H B(C ₆ F ₅ ) ₄ (Z-158) (AI), (BI) O H H H H 1,1-Dimethylbutyl C-1, C-2 H H B(C ₆ F ₅ ) ₄ (Z-159) (AI), (BI) O H H H H Cyclopropylmethyl C-1, C-2 H H B(C ₆ F ₅ ) ₄ (Z-160) (AI), (BI) O H H Br H tert-Bu Ph H Me H B(C ₆ F ₅ ) ₄ (Z-161) (AI), (BI) O H H Cl H 1,1-Dimethylbutyl C-1, C-2 H H B(C ₆ F ₅ ) ₄ (Z-162) (AI), (BI) O H H Cl H Cyclopropylmethyl C-1, C-2 H H B(C ₆ F ₅ ) ₄ (Z-163) (A-III), (B-III) O D-1 H H D-1 Adamantyl - Adamantyl D-1 - B(C ₆ F ₅ ) ₄ (Z-164) (A-III), (B-III) O H H H H tert-Bu - tert-Bu H - B(C ₆ F ₅ ) ₄ (Z-165) (A-III), (B-III) O H H H H Methylcyclopropyl - Methylcyclopropyl H - B(C ₆ F ₅ ) ₄ (Z-166) (A-III), (B-III) O H H H H Methylcyclohexyl - Methylcyclohexyl H - B(C ₆ F ₅ ) ₄ (Z-167) (A-III), (B-III) O H H H H Adamantyl - Adamantyl H - B(C ₆ F ₅ ) ₄ (Z-168) (A-III), (B-III) O H H Cl H tert-Bu - tert-Bu H - B(C ₆ F ₅ ) ₄ (Z-169) (A-III), (B-III) O H H Cl H Adamantyl - Adamantyl H - B(C ₆ F ₅ ) ₄ (Z-170) (A-III), (B-III) O H H OCH ₃ H Adamantyl - Adamantyl H - B(C ₆ F ₅ ) ₄ (Z-171) (A-III), (B-III) O H H H H Adamantyl - Adamantyl CH ₃ - B(C ₆ F ₅ ) ₄ (Z-172) (A-III), (B-III) O CH ₃ H H H Adamantyl - Adamantyl H - B(C ₆ F ₅ ) ₄ (Z-173) (A-III), (B-III) O H H CH ₃ H Adamantyl - Adamantyl H - B(C ₆ F ₅ ) ₄

In Table ^3, R 4 and R ⁴ column of "C-1, C-2 " means that the formula (AI) and the formula (BI) in R ³ and R ⁴ bonded to each other The formation of an aromatic hydrocarbon group having a carbon number of 6 specifically means that the part corresponding to the unit A and the unit B is a structure represented by the following formula C-1 and formula C-2. In addition, "D-1" in the columns _{of Y A} , Y _E , R ¹ and R ^{5 in} _{Table 4 means Y A} ^{and R 1} , Y _{E in} the formula (A-III) and the formula ( In B-III), R ^{5 is} bonded to each other to form a 6-membered alicyclic group. Specifically, it means that the cation of the compound (z-163) is represented by the following formula D-1.

[化14]

[化15]

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

The compound (Z) is preferably a compound that satisfies the following requirement (A). Prerequisite (A): The transmission spectrum measured using a solution prepared by dissolving the compound (Z) in dichloromethane (wherein, the transmission spectrum is a spectrum with a transmittance of 10% at a maximum absorption wavelength; the following is also In the transmission spectrum referred to as the "transmission spectrum of the compound (Z)"), the average value of the transmittance at a wavelength of 430 nm to 580 nm is preferably 93% or more, and more preferably 95% or more. The average value of the transmittance is preferably high, so the upper limit is not particularly limited, and may be 100%. If the compound (Z) satisfies the above-mentioned requirement (A), it can sufficiently cut off the light of the wavelength of the near-infrared region to be cut off, while further suppressing the decrease in the visible light transmittance.

Furthermore, in the present invention, the average transmittance at wavelengths A nm to B nm is determined by measuring the transmittance at each wavelength in the unit of 1 nm from A nm to B nm and dividing by the total value of the transmittance. A value calculated with the number of measured transmittances (wavelength range, B-A+1).

The compound (Z) is preferably a compound that satisfies the following requirement (B-1) or requirement (B-2). Prerequisite (B-1): In the absorption spectrum measured using a solution prepared by dissolving the compound (Z) in dichloromethane, the wavelength is preferably in the range of 720 nm to 900 nm, and more preferably the wavelength is 740 nm It is particularly preferable that the maximum value is in the range of 740 nm to 860 nm in the wavelength range of -880 nm. If the maximum absorption wavelength of the compound (Z) is in the above range, it is possible to easily obtain optics that can suppress the reflected light of light having a wavelength of around 720 nm to 900 nm, and can provide good images with little flare or ghosting. filter. As a suitable example of the compound (Z) satisfying the requirement (B-1), the unit A is any one of the formula (AI) to the formula (A-II), and the unit B is a compound of any one of the aforementioned formulas (BI) to (B-II).

Prerequisite (B-2): In the absorption spectrum measured using a solution prepared by dissolving the compound (Z) in dichloromethane, the wavelength is preferably in the range of 700 nm to 750 nm, more preferably 705 nm It is particularly preferable that the maximum value is in the range of 710 nm to 745 nm in wavelength in the range of -748 nm. If the maximum absorption wavelength of the compound (Z) is in the above range, it is possible to easily obtain optics that can suppress the reflected light of light having a wavelength around 700 nm to 750 nm, and can provide good images with less flare or ghosting. filter. Suitable examples of the compound (Z) satisfying the requirement (B-2) include: the unit A is the formula (A-III), and the unit B is the formula (B-III) )compound of.

The compound (Z) is preferably a compound that satisfies the following requirement (C). Prerequisite (C): Absorbance Ai at the maximum absorption wavelength λa in the wavelength range of 700 nm to 1000 nm of the resin plate containing the resin and the compound (Z), after irradiating the resin plate with a fluorescent lamp for 30 days The retention rate D (=Af×100/Ai) of the absorbance Af at λa is preferably 95% or more, and more preferably 97% or more. The retention rate D is preferably high, so the upper limit thereof is not particularly limited, and may be 100%. Furthermore, the thickness of the resin plate is in the range of 90 μm to 110 μm, and the content of the compound (Z) relative to the resin is such that the absorbance Ai at the maximum absorption wavelength λa of the resin plate enters the range of 0.5 to 1.5 In that amount, the resin is ARTON manufactured by JSR (Stock), and contains 0.3 parts by mass of Irganox 1010 (BASF Japan) with respect to 100 parts by mass of the resin in the resin plate. ) (Stock) Manufacturing).

The compound (Z) having the retention rate D in the above-mentioned range can be said to have excellent light resistance (durability). By using such a compound (Z), an optical filter exhibiting desired optical characteristics for a long period of time can be easily obtained. Specifically, the retention rate D can be measured by the method described in the following Examples.

The compound (Z) more preferably satisfies the following requirement (D). Prerequisite (D): In the spectroscopic absorption spectrum measured using a solution prepared by dissolving the compound (Z) in dichloromethane, the absorbance at the longest wavelength among the maximum absorption wavelengths is set to εa and the wavelength is 430 nm When the maximum value of the absorbance at -580 nm is εbmax, εa/εbmax is preferably 20 or more, more preferably 25 or more, and still more preferably 27 or more. εa/εbmax is preferably large, so the upper limit is not particularly limited, and is, for example, 10,000 or less. If the compound (Z) satisfies the above-mentioned 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. In an optical filter with a dielectric multilayer film, The incident angle dependence caused by the multilayer film can be suppressed.

The content of the compound (Z) in the composition relative to 100 parts by mass of the resin is preferably 0.02 parts by mass to 2.0 parts by mass, more preferably 0.02 parts by mass to 1.5 parts by mass, and particularly preferably 0.03 parts by mass to 1.5 parts by mass. If the content of the compound (Z) is in the above range, it is possible to easily obtain near-infrared rays that can efficiently cut off the wavelengths in the vicinity of 700 nm to 750 nm, or the wavelengths in the vicinity of 720 nm to 900 nm, and more visible light transmittance. Excellent composition.

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

The resin is not particularly limited as long as it does not impair the effects of the present invention. For example, it is excellent in thermal stability and moldability to the shape of a film (plate), and can be easily obtained by heating at 100°C or higher. In terms of forming a film of a dielectric multilayer film by high-temperature vapor deposition at a vapor deposition temperature of a certain degree, the glass transition temperature (Tg) is preferably 110°C to 380°C, more preferably 110°C to 370°C, and particularly preferred It is a resin with a temperature of 120°C to 360°C. In addition, if the Tg of the resin is 140° C. or higher, a film that can be vapor-deposited to form a dielectric multilayer film at a higher temperature can be obtained, which is particularly preferred.

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

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

Examples of the resin include: cyclic (poly)olefin resin, aromatic polyether resin, polyimide resin, polyester resin, polycarbonate resin, polyamide (aromatic poly) Amide) resins, polyarylate resins, polyether resins, polyether sulfide resins, polyparaphenylene resins, polyamide imide resins, polyethylene naphthalate (PEN) ) Resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curable resins, silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins Resin, vinyl-based UV-curable resin. As specific examples of these resins, the resins described in International Publication No. 2019/168090 and the like can be cited.

＜Other ingredients＞ To the extent that the effects of the present invention are not impaired, the composition may further contain compounds (X) other than compound (Z) [absorbers other than ultraviolet absorbers], antioxidants, ultraviolet absorbers, fluorescent matting agents, and Other components such as metal complex compounds.

These other components may be used individually by 1 type, respectively, and may use 2 or more types. These other components may be mixed with resin etc. when preparing this composition, and may be added when synthesizing resin. In addition, the addition amount may be appropriately selected according to the desired characteristics and the like, and it is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass relative to 100 parts by mass of the resin.

[Compound (X)] The present composition may contain one or two or more kinds of compounds (X) other than the compound (Z) [absorbers other than ultraviolet absorbers]. Examples of the compound (X) include squaraine-based compounds, phthalocyanine-based compounds, polymethine-based compounds, naphthalocyanine-based compounds, croconium-based compounds, and octaphyrin. Based compounds, diimonium based compounds, perylene based compounds, metal dithiolate based compounds.

The compound (X) preferably contains a squaraine-based compound, and more preferably contains one or more squaraine-based compounds and another compound (X'), as the other compound (X'), Particularly preferred are phthalocyanine-based compounds and polymethine-based compounds.

The squaraine-based compound has a sharp absorption peak, has excellent visible light transmittance and a high molar absorption coefficient, but sometimes generates fluorescence that causes scattered light when light is absorbed. In this case, by using a squarylium compound in combination with the compound (X′), scattered light can be suppressed. In this way, if the scattered light is suppressed, when the optical filter obtained from the present composition is used in a photographing device or the like, the obtained camera image quality becomes better.

The maximum absorption wavelength of the compound (X) is preferably 650 nm to 1100 nm, more preferably 650 nm to 950 nm, still more preferably 680 nm to 850 nm, and particularly preferably 690 nm to 740 nm. By using the compound (X) having an absorption maximum wavelength in the above-mentioned range, an optical filter with more excellent visual sensitivity correction can be easily obtained.

[Ultraviolet absorber] Examples of the ultraviolet absorber include azomethine-based compounds, indole-based compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, triazine-based compounds, anthracene-based compounds, and Japanese Patent Laid-Open The compound described in the 2019-014707 Bulletin.

Particularly preferred are azomethine-based compounds, indole-based compounds, benzotriazole-based compounds, and cyanoacrylate-based compounds. By containing these compounds, it is possible to easily obtain an optical filter that is also less dependent on the angle of incidence in the near-ultraviolet wavelength region. When the optical filter is used in a photographing device or the like, the obtained camera image quality becomes Better.

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

＜Additives＞ The present composition may further contain additives such as organic solvents, mold release agents, surfactants, antistatic agents, adhesion aids, light diffusion materials, and the like, within the range that does not impair the effects of the present invention. These additives may be used individually by 1 type, respectively, and may use 2 or more types.

In particular, when the present composition is made into a liquid composition, it is preferable to use an organic solvent. As an example of the said organic solvent, the solvent which can dissolve resin is preferable, Specifically, esters, ketones, aromatic hydrocarbons, and halogen-containing compounds are mentioned. In addition, when the resin layer is manufactured by the flow casting described later, the resin layer can be easily manufactured by using a leveling agent or a defoaming agent.

"Substrate (i)" The substrate (i) of the present invention is a substrate formed of the present composition and containing the compound (Z). The substrate (i) may be a single layer or a multilayer, as long as it has a resin layer (hereinafter also referred to as "the present resin layer") formed of the present composition and containing the compound (Z). The base material (i) may have two or more current resin layers. In this case, the two or more current resin layers 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-made substrate) is the base material (i). In the case where the base material (i) is a multilayer, as the base material (i), examples include: two or more resin layers, and at least one of the two or more resin layers is the base of the resin layer. Or a substrate containing this resin layer and a glass support. Suitable examples include: the substrate (A), which includes laminating the resin layer on a support such as a glass support or a resin support as a base The base material (B) includes a laminate in which a resin layer such as an overcoat layer containing a curable resin or the like is laminated on the resin layer. The base material (i) is particularly preferably a base material in terms of manufacturing cost, ease of adjustment of optical characteristics, and the effect of eliminating damage to the resin layer, or improving the damage resistance of the base material (i).材 (B).

In addition, the resin layer, such as an overcoat layer in the said resin-made support body or a base material (B), means the resin layer which does not contain a compound (Z). The resin layer not containing the compound (Z) is not particularly limited as long as it contains a resin. Examples of the resin include the same resins as those described in the column of the present composition. In addition, 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 absorption glass support. Among these, if an absorption glass support is used, light of a wavelength in the near-infrared region can be sufficiently cut off, which is preferable.

The thickness of the substrate (i) can be appropriately selected according to the intended use and is not particularly limited, but is preferably 10 μm to 250 μm, more preferably 15 μm to 230 μm, and particularly preferably 20 μm to 150 μm. If the thickness of the substrate (i) is in the above range, the optical filter using the substrate (i) can be thinned and lightened, and can be suitably used for various applications such as solid-state imaging devices. In particular, when the single-layer substrate (i) is used in a lens unit such as a camera module, the lens unit can be reduced in profile and weight, which is preferable.

[Method of manufacturing base material (i)] The resin layer, such as the present resin layer, the resin support body, and the overcoat layer, can be formed by, for example, melt molding or flow casting. Furthermore, if necessary, after the molding, an antireflective agent or a hard coating layer may be applied. Coating agents such as paint and/or antistatic agent.

In the case where the substrate (i) is the substrate (A), for example, the present composition is melt-molded or cast-molded on the support, and it is preferable to use spin coating, slit coating, or spraying. After the solvent is applied by ink or the like, the solvent is dried and removed, and light irradiation or heating is further carried out as necessary to produce a substrate with the resin layer formed on the support.

·Melt forming Specific examples of the melt forming include: a method of melt-forming pellets obtained by melt-kneading the present composition; a method of melt-forming the present composition; and a method of melt-forming the present composition; A method in which the pellets obtained by removing the solvent are melt-molded and the like. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding, and the like.

·Casting Examples of the casting molding include: a method of casting a liquid composition containing a solvent on an appropriate support to remove the solvent; and including a photocurable resin and/or a thermosetting resin as the resin After the curable composition is cast on an appropriate support to remove the solvent, it is cured by an appropriate method such as ultraviolet radiation 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 the support after casting, and in addition, When the substrate (i) is the substrate (A), the substrate (i) can be obtained by not peeling off the coating film after casting.

As said suitable support, for example, a glass plate, a steel strip, a steel cylinder, and a support made of resin (for example, a polyester film, a cyclic olefin resin film) are mentioned.

Furthermore, the resin layer can also be formed on the optical component by a method such as: coating the liquid composition on an optical component such as glass plate, quartz or plastic and drying the solvent; or coating A method in which the curable composition described above is applied, and then hardened and dried.

In the case of forming resins such as the resin support and the overcoat layer by melt molding or casting, the desired composition containing the resin (including no compound (Z)) may be used instead of the resin. The present composition in the column of melt molding or cast molding may be used.

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

"Optical Filter" The optical filter of the present invention (hereinafter also referred to as "this filter") has the above-mentioned base material (i) and a dielectric multilayer film. In terms of further exerting the effects of the present invention, specific examples of this filter include: a near infrared cut filter (NIR-CF), a visible-near infrared selective transmission filter (DBPF), and a near infrared cut filter (NIR-CF). Infrared transmission filter (IRPF). In addition, this filter can also be used as a filter for alternative light sources (ALS: Alternative Light Sources) used in scientific research, etc. These filters should just have a conventionally well-known structure in addition to the said base material (i).

When this filter is NIR-CF or DBPF, it is preferably a filter that satisfies the following characteristic (a). Characteristics (a): In the wavelength region of 430 nm to 580 nm, the average transmittance when measured from the vertical 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, so the upper limit is not particularly limited, and may be 100%. If this filter satisfies the above-mentioned characteristic (a), it can sufficiently cut off the light of the wavelength of the near infrared region to be cut off, while further suppressing the decrease in the visible light transmittance, so it can be more suitably used as NIR-CF or DBPF.

When the base material (i) contains a compound that satisfies the requirement (B-1) and the filter is NIR-CF or DBPF, it is preferable to satisfy the following characteristics (b-1) Filter. Characteristic (b-1): In the wavelength range of 700 nm to 800 nm, the average reflectance of unpolarized light incident from an angle of 5° from the vertical direction of at least one surface of the optical filter is preferably 25% or less, more preferably Less than 15%. The average reflectance is preferably low, so the lower limit is not particularly limited, and may be 0%. By using this filter that satisfies the above-mentioned characteristic (b-1), the intensity of reflected light in the wavelength region of 700 nm to 800 nm can be reduced, so that image defects caused by the reflected light can be eliminated.

When the base material (i) contains a compound that satisfies the requirement (B-2) and the filter is NIR-CF or DBPF, it is preferable to satisfy the following characteristics (b-2) Filter. Characteristic (b-2): In the wavelength region of 650 nm to 800 nm, the average reflectance of unpolarized light incident from the vertical direction of at least one surface of the optical filter at an angle of 5° is preferably 25% or less, and more preferably Less than 15%. The average reflectance is preferably low, so the lower limit is not particularly limited, and may be 0%. By using this filter that satisfies the above-mentioned characteristic (b-2), the intensity of reflected light in the wavelength region of 650 nm to 800 nm can be reduced, so that image defects caused by the reflected light can be eliminated.

Furthermore, in the present invention, the average reflectance of wavelengths A nm to B nm is determined by measuring the reflectance at each wavelength in units of 1 nm from A nm to B nm and dividing by the total value of the reflectance. A value calculated by the number of measured reflectance (wavelength range, B-A+1). It is infinitely difficult to measure the reflectance of unpolarized light incident from the vertical direction. Therefore, in the present invention, the reflection characteristics of unpolarized light incident from an angle of 5° from the vertical direction are measured.

"Unpolarized light" refers to light that does not have a deviation in the polarization direction, and refers to a collection of waves in which electric fields are substantially uniformly distributed in all directions. "Average transmittance of unpolarized light" can use the average value of "Average transmittance of S-polarized light" and "Average transmittance of P-polarized light". The "average reflectance of unpolarized light" can use the average value of "average reflectance of S-polarized light" and "average reflectance of P-polarized light".

This filter satisfies the above characteristics (a) and characteristics (b-1) or characteristics (b-2), and while maintaining the transmittance of visible light, it is possible to reduce near-infrared light, especially the wavelength of 650 nm to 800 The intensity of reflected light in the wavelength region of nm, therefore, in recent years, in photographing devices such as digital still cameras that have advanced in performance, the reduction in sensitivity in the visible light region can be suppressed to a minimum, and the reflection caused by the reflected light can be eliminated. The image is bad.

The thickness of the present filter may be appropriately selected according to the intended use, and it is also preferable that the thickness of the present filter is thin in accordance with the trend of thinning and weight reduction of solid-state imaging devices and the like in recent years. Since the present filter includes the substrate (i), it can be made thinner.

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

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

When NIR-CF is used in a solid-state imaging device or the like, the transmittance in the near-infrared wavelength region is preferably low. In particular, the light receiving sensitivity of the solid-state imaging element is relatively high in the region with a known wavelength of 800 nm to 1200 nm. By reducing the transmittance of the wavelength region, the camera image and the visual sensitivity of the human eye can be effectively corrected. Achieve excellent color reproducibility. In addition, by reducing the transmittance in the wavelength range of 850 nm to 1200 nm, it is possible to effectively prevent the near-infrared light used in the security authentication function from reaching the image sensor.

Regarding NIR-CF, in the wavelength region of 850 nm to 1200 nm, the average transmittance when measured from the vertical direction of the filter is preferably 5% or less, more preferably 4% or less, and still more preferably 3% or less, Particularly preferably, it is 2% or less. If the average transmittance at a wavelength of 850 nm to 1200 nm is in the above range, near infrared rays can be sufficiently cut off, and excellent color reproducibility can be achieved, which is preferable.

When NIR-CF is used in a solid-state imaging device or the like, the visible light transmittance is preferably high. Specifically, in the wavelength region of 430 nm to 580 nm, the average transmittance when measured from the vertical direction of the filter is preferably 75% or more, more preferably 80% or more, and even more preferably 83% or more, especially Preferably it is 85% or more. If the average transmittance at a wavelength of 430 nm to 580 nm is in the above range, excellent photographic sensitivity can be achieved.

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

DBPF is also the same as NIR-CF. When used in solid-state imaging devices, the visible light transmittance is preferably high. For the same reason as described above, the average transmittance at a wavelength of 430 nm to 580 nm is preferably It is in the same range as the 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 of a wavelength to be cut (part of visible light and/or near-infrared rays). In addition, IRPF can also use visible light absorbers to cut off visible light.

IRPF can be suitably used in optical systems such as infrared surveillance cameras, in-vehicle infrared cameras, infrared communications, various sensor systems, infrared alarms, night vision devices, etc. When used in these applications, it is preferably transparent The transmittance of light of wavelengths other than near-infrared rays is low. In particular, in the wavelength region of 380 nm to 700 nm, the average transmittance when measured from the vertical direction of the filter is preferably 10% or less, and more preferably 5% or less.

In addition, with regard to IRPF, the transmittance of near-infrared rays to be transmitted is preferably high. Specifically, there is a light transmission band Ya in the wavelength range of 750 nm or more. The maximum transmittance (T _IR ) in the direction measurement is preferably 45% or more, and more preferably 50% or more.

＜Dielectric multilayer film＞ This filter has the above-mentioned base material (i) and a dielectric multilayer film. As said dielectric multilayer film, the laminated body etc. which laminated|stacked alternately the high-refractive-index material layer and the low-refractive-index material layer, etc. are mentioned. The dielectric multilayer film may be provided on one side of the substrate (i), or may be provided on both sides. When installed on one side, the manufacturing cost and ease of manufacture are excellent. When installed on both sides, an optical filter that has high strength and is hard to warp or twist can be obtained. When the filter is used in a solid-state imaging device or the like, the warpage or distortion of the filter is preferably small, and therefore, it is preferable to provide a dielectric multilayer film on both sides of the substrate (i).

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

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

The method of laminating the high refractive index material layer and the low refractive index material is not particularly limited as long as a dielectric multilayer film formed by laminating these materials can be formed. For example, chemical vapor deposition (Chemical Vapor Deposition, CVD) method, sputtering method, vacuum evaporation method, ion assisted evaporation method or ion plating method can be used to directly form a high refractive index on the substrate (i) A dielectric multilayer film formed by alternately laminating material layers and low-refractive index material layers.

Generally, if the wavelength of the light to be blocked (for example: near infrared) is set to λ (nm), the thickness of each layer of the high refractive index material layer and the low refractive index material layer is preferably 0.1 λ to 0.5 λ thickness. As the value of λ (nm), in the case of NIR-CF, it is, for example, 700 nm to 1400 nm, and preferably 750 nm to 1300 nm. If the thickness of each layer of the high refractive index material layer and the low refractive index material layer is within the above range, the product (n×d) of the refractive index (n) and the film thickness (d), that is, the optical film thickness becomes the same as λ/ 4 is approximately the same value, and depending on the relationship between the optical characteristics of reflection and refraction, there is a tendency that blocking-transmission of a specific wavelength can be easily controlled.

Regarding the total number of layers of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film, for example, in the case of NIR-CF, the total optical filter is preferably 16 to 70, and more preferably 20 Layer ~ 60 layers. If the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, or the total number of layers are within the above range, a sufficient manufacturing margin can be ensured, and the warpage or dielectric of the optical filter can be reduced. Cracks in the multilayer film.

In this filter, combining the absorption characteristics of the compound (Z), etc., the types of materials that constitute the high refractive index material layer and the low refractive index material layer, and the layers of the high refractive index material layer and the low refractive index material layer are appropriately selected. The thickness, the order of the layers, and the number of layers can ensure sufficient transmittance in the wavelength region to be transmitted (e.g., visible region), and sufficient light in the wavelength region to be cut off (e.g., near-infrared region) Cut-off characteristics, and can reduce the reflectivity of light (for example: near infrared) incident from an oblique direction.

Here, in order to optimize the conditions of the dielectric multilayer film, for example, optical film design software (for example, Essential Macleod, manufactured by Thin Film Center) can be used to take into account the wavelength to be transmitted. The parameters can be set in the way of the anti-reflection effect of the area (for example: the visible area) and the light cut-off effect of the wavelength area to be cut off (for example: the near-infrared area). In the case of the software, for example, when the dielectric multilayer film of NIR-CF is formed, the target transmittance at a wavelength of 400 nm to 700 nm is set to 100%, and the value of the target tolerance (Target Tolerance) is set to 1. And set the target transmittance of wavelength 705 nm ~ 950 nm to 0%, and set the target tolerance value to 0.5 and other parameter setting methods. These parameters can also be combined with the various characteristics of the substrate (i) to divide the wavelength range more finely to change the value of the target tolerance.

＜Other functional films＞ For the purpose of improving the surface hardness of the substrate (i) or the dielectric multilayer film, improving chemical resistance, antistatic, and eliminating damage, the filter can be used on the substrate ( i) Between the dielectric multilayer film, the surface of the substrate (i) opposite to the surface on which the dielectric multilayer film is provided, or the dielectric multilayer film on the opposite side of the surface on which the substrate (i) is provided On the surface, a functional film such as an anti-reflection film, a hard coat film, or an antistatic film is appropriately provided.

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

The method of laminating the functional film is not particularly limited, and examples include coating agents such as antireflection agents, hard coat agents, and/or antistatic agents on the substrate (i) or the dielectric multilayer film in the same manner as described above. Methods of melt forming or casting.

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

Examples of the coating agent include ultraviolet (Ultraviolet, UV)/electron beam (EB) curable resins or thermosetting resins. Specifically, examples include vinyl compounds or urethanes. Ester resins, urethane acrylate resins, acrylate resins, epoxy resins, and epoxy acrylate resins. One type of coating agent may be used alone, or two or more types may be used. Examples of the curable composition containing these coating agents include vinyl type, urethane type, urethane acrylate type, acrylate type, epoxy type, and epoxy acrylate type. Curable composition, etc.

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

In the curable composition, when the total amount of the curable composition is 100% by mass, the blending ratio of the polymerization initiator is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 5% by mass. If the blending ratio of the polymerization initiator is in the above range, a curable composition having excellent curing characteristics and handling properties can be easily obtained, and an anti-reflective film, hard coat film, or hard coat film having the desired hardness can be easily obtained. Functional film such as antistatic film.

Furthermore, an organic solvent may be added to the curable composition as a solvent, and as the organic solvent, a known solvent may be used. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetic acid Ethyl, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other esters; ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc. Ethers; aromatic hydrocarbons such as benzene, toluene, and xylene; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. One kind of these solvents may be used alone, or two or more kinds may be used.

The thickness of the functional film is preferably 0.1 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 0.7 μm 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 substrate (i), the functional film or the dielectric multilayer The surface of the film is subjected to surface treatment such as corona treatment or plasma treatment.

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

"Solid State Photographic Installation" The solid-state imaging device of the present invention includes the filter. Here, the solid-state imaging device is a device including a solid-state imaging element such as a CCD or CMOS image sensor. Specifically, it can be used for digital still cameras, smartphone cameras, mobile phone cameras, wearable device cameras, and digital cameras. Cameras and other uses.

"Optical Sensor Device" The optical sensor device of the present invention is not particularly limited as long as it includes the filter, as long as it has a previously known structure. For example, a device having a light-receiving element and this filter can be cited, and specifically, a device having a light-receiving element (semiconductor substrate), a protective film, this filter, other filters, and the like can be cited. [Example]

Hereinafter, the present invention will be explained more specifically based on examples, but the present invention is not limited to these examples at all.

[Synthesis example] The compound (Z) and compound (X) used in the following examples are synthesized based on commonly known synthesis methods. For the compound (Z), for example, Japanese Patent Laid-Open No. 2009-108267, Japanese Patent Laid-Open No. 5-59291, Japanese Patent Laid-Open No. 2014-95007, Japanese Patent Laid-Open No. 2011-52218, International Publication No. 2007/114398, Japanese Patent Laid-Open No. 2003-246940, "Chemistry of Heterocyclic Compounds: The Cyanine Dyes and Related Compounds" (Volume 18 (Wiley (Wiley) ), 1964)), "Near-Infrared Dyes for High Technology Applications (Near-Infrared Dyes for High Technology Applications)" (Springer (Springer), 1997). The compound (X) can refer to, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, and Japanese Patent Laid-Open Hei. 1-146846, Japanese Patent Laid-Open No. 1-228960, Japanese Patent No. 4081149, Japanese Patent Laid-Open No. 63-124054, "Phthalocyanine-Chemistry and Function -" (IPC, 1997), It is synthesized by the methods described in Japanese Patent Laid-Open No. 2007-169315, Japanese Patent Laid-Open No. 2009-108267, Japanese Patent Laid-Open No. 2010-241873, Japanese Patent No. 3699464, and Japanese Patent No. 4740631.

[Intermediate Synthesis Example 1] [化16]

In a 200 mL eggplant-shaped flask with a stirrer, the method described in "Bioorganic and Medicinal Chemistry" (2013, vol. 21, # 11, p. 2826-2831) Synthetic compound a-1 8.33 g, add 21.8 g of ethyl pivalate, 5 minutes later, add 4.0 g of sodium hydride (60% dispersion in Paraffin Liquid), and stir at 80°C for 3 Hour. After that, it was cooled to room temperature, 100 mL of 1 N hydrochloric acid aqueous solution was added to neutralize, the liquid was transferred to a separatory funnel, and the organic phase was extracted with 150 mL of ethyl acetate. Then, 15 g of magnesium sulfate was added to the extracted organic phase and stirred for 15 minutes. After that, the magnesium sulfate was removed by filtration through a filter. The filtrate was put into a 300 mL eggplant-shaped flask, and the solvent was distilled off using an evaporator. This obtains compound a-2.

Put a stir bar in the eggplant-shaped flask containing compound a-2, add 20 mL of concentrated hydrochloric acid, and stir at 40°C. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 200 mL of 1 N sodium hydroxide aqueous solution was added for neutralization. Then, the liquid was transferred to a separatory funnel, 150 mL of ethyl acetate was added and the organic phase was extracted, after which 15 g of magnesium sulfate was added and stirred for 15 minutes. Then, the magnesium sulfate was removed by filtration through a filter, and then the filtrate was put into a 300 mL eggplant-shaped flask, and the solvent was distilled off using an evaporator. Thereafter, the compound remaining in the flask was separated and purified by silica gel chromatography to obtain 5.0 g of the target compound a-3. Further, the compound was identified using liquid chromatography - mass spectrometry (liquid chromatography-mass spectroscopy, LC -MS) and ¹ H- nuclear magnetic resonance ^{(1 H-nuclear magnetic resonance,} 1 H-NMR) performed.

[Intermediate Synthesis Example 2] [化17]

In a 200 mL eggplant-shaped flask with a stir bar, 3 g of compound a-3 and 30 mL of diethyl ether were placed, and the mixture was cooled in an ice bath while stirring. After cooling in an ice bath for 5 minutes, 13.5 mL of 1 mol/L methylmagnesium iodide diethyl ether solution was added over 10 minutes, then heated to 35°C and stirred for 2 hours. Then, the reaction solution was cooled in an ice bath, 30 mL of 20% perchloric acid aqueous solution was added, the precipitated solid was separated by filtration, washed with 20 mL of water, and dried under reduced pressure at 50°C to obtain 2.5 g of compound a-4. In addition, the identification of the compound was performed by ¹ H-NMR analysis.

[Synthesis example of compound (z-1)] [化18]

Put 1.5 g of compound a-4 and N-[2-chloro-3-(phenylamino)-2-propenylene]-aniline monohydrochloride in a 100 mL eggplant-shaped flask with a stir bar (N-[2-chloro-3-(phenylamino)-2-propenylidene]-benzenamine monohydrochloride) 0.6 g, acetonitrile 25 mL, anhydrous acetic acid 7.5 mL, and pyridine 0.6 mL, heated to reflux for 5 hours. Then, it was cooled to room temperature, and the solvent was distilled off with an evaporator, after that, 5 mL of acetic acid was added, and it was allowed to cool and stand still at 5°C for 2 days. After that, the precipitated solid was filtered under reduced pressure and washed with 5 mL of acetic acid and 10 mL of hexane to obtain 0.17 g of compound a-5.

Put 0.1 g of compound a-5, 0.2 g of lithium tetra-pentafluorophenyl borate, 20 mL of dichloromethane, and 10 mL of water into a 100 mL eggplant-shaped flask with a stir bar, and stir at room temperature 1 hour. Then, the liquid was transferred to a separatory funnel, and after the aqueous phase was removed, the organic phase was washed twice with 20 mL of water, and 1 g of sodium sulfate was added and stirred for 15 minutes. After that, sodium sulfate was removed by filtration through a filter, the filtrate was put into a 300 mL eggplant-shaped flask, the solvent was distilled off using an evaporator, and dried under reduced pressure at 50°C to obtain 0.05 g of compound (z- 1). In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

[Intermediate Synthesis Example 3] [Chemical 19]

In a 300 mL eggplant-shaped flask with a stir bar, add 5 g of flavonoids (compound a-6) and 50 mL of tetrahydrofuran (THF), and cool in an ice bath. After cooling in an ice bath for 5 minutes, 24.7 mL of 1 mol/L methylmagnesium iodide diethyl ether solution was added over 10 minutes, then heated to 35°C and stirred for 2 hours. Then, the reaction solution was cooled in an ice bath, 50 mL of 20% perchloric acid aqueous solution was added, the precipitated solid was separated by filtration, washed with 50 mL of water, and dried under reduced pressure at 50°C to obtain 4.5 g of compound a-7. In addition, the identification of the compound was performed by ¹ H-NMR analysis.

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

In a 100 mL eggplant-shaped flask with a stir bar, add 0.7 g of compound a-7, 0.26 g of malondialdehyde dianiline hydrochloride, 10 mL of acetonitrile, 5 mL of anhydrous acetic acid, and 0.2 mL of pyridine. Heat to reflux for 2 hours. After that, it was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, and washed with 10 mL of diethyl ether, thereby obtaining 0.6 g of compound a-8.

In a 100 mL eggplant-shaped flask with a stir bar, add 0.1 g of compound a-8, 0.2 g of lithium tetra-pentafluorophenyl borate, 20 mL of dichloromethane, and 10 mL of water, and stir at room temperature 3 hours. Then, the liquid was transferred to a separatory funnel, and after removing the water phase, the organic phase was washed twice with 20 mL of water, and the solvent was distilled off from the organic phase using an evaporator. After that, the residue was dissolved in 0.5 mL of acetone, 10 mL of methanol was added and cooled in an ice bath, the precipitated solid was recovered by suction filtration, and dried under reduced pressure at 50°C to obtain 0.07 g of the compound (Z-16). In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

[Intermediate Synthesis Example 4] [化21]

In a 200 mL eggplant-shaped flask with a stir bar, add 4 g of compound a-9 and 21.8 g of ethyl pivalate and stir. After 5 minutes, add sodium hydride (60%, dispersed in paraffin liquid). ) 3.2 g, after which it was stirred at 80°C for 3 hours. After that, it was cooled to room temperature, 30 mL of 1 N hydrochloric acid aqueous solution was added to neutralize, and the organic phase was extracted with 150 mL of ethyl acetate. Then, 15 g of magnesium sulfate was added to the organic phase and stirred for 15 minutes. After that, the magnesium sulfate was removed by filtration through a filter, the filtrate was put into a 300 mL eggplant-shaped flask, and the solvent was distilled off using an evaporator. Compound a-10.

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

[Intermediate Synthesis Example 5] [化22]

In a 200 mL eggplant-shaped flask with a stir bar, 2.7 g of compound a-11 and 50 mL of diethyl ether were added, and the mixture was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 24.7 mL of 1 mol/L methylmagnesium iodide diethyl ether solution was added over 10 minutes, then heated to 35°C and stirred for 2 hours. Then, the reaction solution was cooled in an ice bath, 50 mL of 20% perchloric acid aqueous solution was added, the precipitated solid was separated by filtration, washed with 50 mL of water, and dried under reduced pressure at 50°C to obtain 0.7 g of compound a-12. In addition, the identification of the compound was performed by ¹ H-NMR analysis.

[Synthesis Example of Compound (z-59)] [Chemical Form 23]

In a 100 mL eggplant-shaped flask with a stir bar, add 0.5 g of compound a-12, 0.22 g of malondialdehyde dianiline hydrochloride, 7.5 mL of acetonitrile, 2.5 mL of anhydrous acetic acid, and 0.2 mL of pyridine. Heat to reflux for 2 hours. After that, it was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10 mL of acetic acid and 10 mL of acetonitrile, and dried under reduced pressure at 50°C to obtain 0.35 g of compound a-13 .

In a 100 mL eggplant-shaped flask with a stir bar, add 0.3 g of compound a-13, 0.8 g of lithium tetra-pentafluorophenyl borate, 50 mL of dichloromethane, and 20 mL of water, and stir at room temperature 3 hours. Then, the liquid was transferred to a separatory funnel, and after removing the water phase, the organic phase was washed twice with 20 mL of water, and the solvent was distilled off from the organic phase using an evaporator. After that, the residue was dissolved in 20 mL of acetone, 100 mL of water was added, and 13 g of the solvent was distilled off using an evaporator. After that, it was cooled in an ice bath. Thereafter, the precipitated solid was recovered by suction filtration, washed with 50 mL of methanol, and the solid was dried under reduced pressure at 50° C. to obtain 0.5 g of compound (z-59). In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

[Intermediate Synthesis Example 6] [化24]

In a 200 mL eggplant-shaped flask with a stir bar, add 4.5 g of compound a-14 and 21.8 g of ethyl isobutyrate and stir. After 5 minutes, add sodium hydride (60%, dispersed in paraffin liquid). ) 3.2 g, after which it was stirred at 80°C for 3 hours. After that, it was cooled to room temperature, 30 mL of 1 N hydrochloric acid aqueous solution was added to neutralize, and the organic phase was extracted with 150 mL of ethyl acetate. Then, 15 g of magnesium sulfate was added to the organic phase and stirred for 15 minutes. After that, the magnesium sulfate was removed by filtration through a filter. The filtrate was placed in a 300 mL eggplant-shaped flask, and the solvent was distilled off using an evaporator to obtain a compound a-15.

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

[Intermediate Synthesis Example 7] [化25]

In a 100 mL eggplant-shaped flask with a stir bar, 0.4 g of compound a-16 and 10 mL of diethyl ether were added and cooled in an ice bath. After cooling in an ice bath for 5 minutes, add 5.0 mL of 1 mol/L methylmagnesium iodide diethyl ether solution over 10 minutes, then heat to 35°C and stir for 2 hours. Then, the reaction solution was cooled in an ice bath, 10 mL of 20% perchloric acid aqueous solution was added, 20 mL of dichloromethane was added, and the liquid was transferred to a separatory funnel to recover the organic phase. The solvent was distilled off from the organic phase using an evaporator, the solid residue was stirred, 20 mL of diethyl ether was added, and the mixture was stirred for 20 minutes. Then, the solid content was filtered by suction filtration, and dried under reduced pressure at 50°C, thereby obtaining 0.5 g of compound a-17. In addition, the identification of the compound was performed by ¹ H-NMR analysis.

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

In a 100 mL eggplant-shaped flask with a stir bar, add 0.4 g of compound a-17, 0.16 g of malondialdehyde dianiline hydrochloride, 7.5 mL of acetonitrile, 2.5 mL of anhydrous acetic acid, and 0.2 mL of pyridine. Heat to reflux for 2 hours. After that, it was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10 mL of diethyl ether, and dried under reduced pressure at 50° C. to obtain 0.35 g of compound a-18.

In a 100 mL eggplant-shaped flask with a stir bar, add 0.3 g of compound a-18, 0.8 g of lithium tetra-pentafluorophenyl borate, 50 mL of dichloromethane, and 20 mL of water, and stir at room temperature 3 hours. After that, transfer the liquid to a separatory funnel, remove the water phase, wash the organic phase twice with 20 mL of water, use an evaporator to distill off the solvent from the organic phase, and dry the solid under reduced pressure at 50°C. Thus, 0.4 g of compound (z-62) was obtained. In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

[Intermediate Synthesis Example 8] [化27]

In a 200 mL eggplant-shaped flask with a stir bar, 15 g of compound a-19 and 28.7 g of methyl 4,4-dimethyl-3-oxopentanoate were added, and the mixture was stirred at 180°C for 24 hours. After that, it was cooled to room temperature, 250 mL of hexane and 200 mL of 1 N hydrochloric acid aqueous solution were added, and the liquid was transferred to a separatory funnel to remove the water phase. Then, after the solvent was distilled off from the organic phase using an evaporator, the compound remaining in the flask was separated and purified by silica gel chromatography, thereby obtaining 7 g of the target compound a-20. In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

[Intermediate Synthesis Example 9] [化28]

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

[Synthesis Example of Compound (z-151)] [Chemical Formula 29]

In a 100 mL eggplant-shaped flask with a stir bar, 0.5 g of compound a-21, 0.18 g of malondialdehyde dianiline hydrochloride, and 15 mL of pyridine were added, and the mixture was heated to reflux for 2 hours. Then, after cooling to room temperature, the solvent was distilled off by an evaporator, and the column chromatography was used for separation to obtain 0.2 g of compound a-22.

In a 100 mL eggplant-shaped flask with a stir bar, add 0.2 g of compound a-22, 0.8 g of lithium tetra-pentafluorophenyl borate, 50 mL of dichloromethane, and 20 mL of water, and stir at room temperature 3 hours. After that, the liquid was transferred to a separatory funnel, the aqueous phase was removed, the organic phase was washed twice with 20 mL of water, the solvent was distilled off from the organic phase using an evaporator, and the column chromatography was used to separate the obtained 0.2 g compound (z-151). In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

[Intermediate Synthesis Example 10] [化30]

Put 1.9 g of compound a-23 and 2.0 g of ethyl pivalate into a 200 mL eggplant-shaped flask with a stir bar and stir. After 5 minutes, add sodium hydride (60%, dispersed in paraffin liquid). ) 0.3 g, after which it was stirred at 80°C for 3 hours. After that, it was cooled to room temperature, 30 mL of 1 N hydrochloric acid aqueous solution was added to neutralize, and the organic phase was extracted with 150 mL of ethyl acetate. Then, 5 g of magnesium sulfate was added to the organic phase and stirred for 15 minutes. After that, the magnesium sulfate was removed by filtration through a filter, the filtrate was put into a 300 mL eggplant-shaped flask, and the solvent was distilled off using an evaporator. Compound a-24 1.3 g.

Put a stir bar in an eggplant-shaped flask containing 1.3 g of compound a-24, add 20 mL of concentrated hydrochloric acid, and stir at 40°C. After stirring for 1 hour, the reaction solution was cooled in an ice bath, and 240 mL of 1 N sodium hydroxide aqueous solution was added for neutralization. Subsequently, the liquid was transferred to a separatory funnel, 200 mL of ethyl acetate was added and the organic phase was extracted, after which 5 g of magnesium sulfate was added and stirred for 15 minutes. After that, magnesium sulfate was removed by filtration through a filter, the filtrate was put into a 300 mL eggplant-shaped flask, and the solvent was distilled off using an evaporator. Thereafter, the compound remaining in the flask was separated and purified by silica gel chromatography to obtain 1.1 g of compound a-25. In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

[Intermediate Synthesis Example 11] [化31]

In a 200 mL eggplant-shaped flask with a stir bar, 1.5 g of compound a-25 and 50 mL of diethyl ether were added, and the mixture was cooled in an ice bath. After cooling in an ice bath for 5 minutes, 1.5 mL of 1 mol/L methylmagnesium iodide diethyl ether solution was added over 10 minutes, and then heated to 35°C and stirred for 2 hours. Then, the reaction solution was cooled in an ice bath, 50 mL of 20% perchloric acid aqueous solution was added, the precipitated solid was separated by filtration, washed with 50 mL of water, and dried under reduced pressure at 50°C to obtain 3.0 g of compound a-26. In addition, the identification of the compound was performed by ¹ H-NMR analysis.

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

In a 100 mL eggplant-shaped flask with a stir bar, add compound a-26 7.0 g, malondialdehyde dianiline hydrochloride 2.5 g, acetonitrile 50 mL, anhydrous acetic acid 10 mL, and pyridine 10 mL, Heat to reflux for 2 hours. After that, it was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10 mL of acetic acid and 10 mL of acetonitrile, and dried under reduced pressure at 50°C to obtain 5.1 g of compound a-27 .

In a 100 mL eggplant-shaped flask with a stir bar, add 0.6 g of compound a-27, 1.2 g of lithium tetra-pentafluorophenyl borate, 50 mL of dichloromethane, and 50 mL of water, and stir at room temperature 3 hours. Then, the liquid was transferred to a separatory funnel, and after removing the water phase, the organic phase was washed twice with 20 mL of water, and the solvent was distilled off from the organic phase using an evaporator. After that, the residue was dissolved in 20 mL of acetone, 100 mL of water was added, and the solvent was distilled to an amount of 10 g using an evaporator, and then cooled in an ice bath. Thereafter, the precipitated solid was recovered by suction filtration, washed with 50 mL of methanol, and then dried under reduced pressure at 50° C. to obtain 1.0 g of compound (z-157). In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

[Intermediate Synthesis Example 12] [Chemical 33]

Put 22 g of 1-adamantane carbonyl chloride (compound a-28) and 5.2 g of methylene cyclohexane in a 200 mL eggplant-shaped flask with a stir bar. After heating to 90°C, drip Add 10 g of trifluoromethanesulfonic acid and stir for 10 minutes. Then, after cooling to 0°C, 150 mL of hexane, 50 mL of diethyl ether, and 50 mL of water were added and stirred. The precipitated solid was filtered and separated by filtration, and dried under reduced pressure at 50°C. Thus, 4.2 g of compound a-35 was obtained. In addition, the identification of the compound was performed by ¹ H-NMR analysis.

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

Put 0.5 g of compound a-35, 0.1 g of malondialdehyde dianiline hydrochloride, 4 mL of acetonitrile, 1 mL of anhydrous acetic acid, and 1 mL of pyridine into a 100 mL eggplant-shaped flask with a stir bar. Stir at 90°C for 10 minutes. After cooling to 0°C, the precipitated solid was separated by filtration by filtration, washed with 2 mL of acetonitrile, and dried under reduced pressure at 50°C to obtain 0.3 g of compound a-36. In addition, the identification of the compound was performed by ¹ H-NMR analysis.

In a 100 mL eggplant-shaped flask with a stir bar, add 0.3 g of compound a-36, 0.4 g of lithium tetra-pentafluorophenyl borate, 20 mL of dichloromethane, and 20 mL of water, and stir at room temperature 4 hours. Then, the liquid was transferred to a separatory funnel, and after removing the water phase, the organic phase was washed twice with 20 mL of water, and the solvent was distilled off from the organic phase using an evaporator. After that, the residue was dissolved in dichloromethane, methanol was added, and the precipitated solid was recovered by suction filtration, and dried under reduced pressure at 50° C. to obtain 0.4 g of compound (z-163). In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

[Intermediate Synthesis Example 13] [化35]

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

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

[Intermediate Synthesis Example 14] [化36]

Dissolve compound a-39 (15.4 g), phenylboronic acid (11.7 g), tetrakis(triphenylphosphine) palladium (1.0 g), and potassium carbonate (60.0 g) in a mixed solution of 50 mL toluene and 50 mL water In the process, heating was carried out at 110°C for 12 hours while vigorously stirring. After leaving to cool to room temperature, liquid separation and washing were performed with toluene-water, sodium sulfate was added to the organic layer and dried, and the solvent was distilled off using an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain compound a-40 (12.4 g).

While stirring compound a-40 (12.4 g) and 90 mL of tetrahydrofuran, cooling was performed in an ice bath. After cooling in an ice bath for 5 minutes, add methylmagnesium iodide diethyl ether solution (1 mol/L, 50 mL) dropwise, heat to 35°C, and stir for 2 hours. Then, the reaction solution was cooled in an ice bath, 90 mL of 20% perchloric acid aqueous solution was added, the precipitated solid was separated by filtration, washed with 60 mL of water, and dried under reduced pressure at 50°C to obtain Compound a-41 (10.4 g). The identification of the compound was performed by ¹ H-NMR analysis.

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

In a 100 mL eggplant-shaped flask with a stir bar, add compound a-41 7.0 g, malondialdehyde dianiline hydrochloride 2.5 g, acetonitrile 50 mL, anhydrous acetic acid 10 mL, and pyridine 10 mL, Heat to reflux for 2 hours. After that, it was cooled to room temperature, and the precipitated solid was recovered by filtration under reduced pressure, washed with 10 mL of acetic acid and 10 mL of acetonitrile, and dried under reduced pressure at 50°C to obtain 5.0 g of compound a-42 .

In a 100 mL eggplant-shaped flask with a stir bar, add 0.6 g of compound a-42, 1.2 g of lithium tetra-pentafluorophenyl borate, 50 mL of dichloromethane, and 50 mL of water, and stir at room temperature 3 hours. Then, the liquid was transferred to a separatory funnel, and after removing the water phase, the organic phase was washed twice with 20 mL of water, and the solvent was distilled off from the organic phase using an evaporator. After that, the residue was dissolved in 20 mL of acetone, 100 mL of water was added, and the solvent was distilled to an amount of 10 g using an evaporator, and then cooled in an ice bath. Thereafter, the precipitated solid was recovered by suction filtration, washed with 50 mL of methanol, and then dried under reduced pressure at 50° C. to obtain 1.0 g of compound (z-156). In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

[Intermediate Synthesis Example 15] [Chemical 38]

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

[Synthesis Example of Compound (z-161)] [Chemical 39]

Except that ethyl pivalate was changed to compound a-44, the same method as that of Intermediate Synthesis Example 10 was used to obtain compound a-45.

Change compound a-23 to compound a-45, and change malondialdehyde dianiline hydrochloride to N-[2-chloro-3-(phenylamino)-2-propenylene]-aniline Except for the monohydrochloride compound, the compound (z-161) was obtained by the same method as the synthesis example of the intermediate synthesis example 11 and the compound (z-157). In addition, the identification of the compound was performed by LC-MS and ¹ H-NMR analysis.

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

＜Required condition (B)＞ Absorption measured by using a solution prepared by dissolving compound (Z) or compound (X) in dichloromethane and using a spectrophotometer (V-7200) manufactured by JASCO Corporation Spectroscopy, the necessary condition (B) is measured. The results are shown in Table 5.

＜Required condition (C)＞ In the container, 100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 0.3 parts by mass of Irganox 1010 (manufactured by BASF Japan (Stock)), and those used in the following test were added Compound (Z) or compound (X), and dichloromethane were used to prepare a solution with a resin concentration of 20% by mass. In addition, when the following compound (z-1), compound (x-3), and compound (z-163) are used, the amount used is 0.05 parts by mass, and the following compound (z-16 In the case of ), the usage amount is set to 0.06 parts by mass, and the following compound (z-59), compound (z-62), compound (z-156), compound (z-157), compound (z -158), compound (z-159), compound (z-160), compound (z-161), compound (z-162), the usage amount is set to 0.04 parts by mass, and the following compounds are used In the case of (z-151), the usage amount is set to 0.08 parts by mass, and when the following compound (x-4) is used, the usage amount is set to 0.03 parts by mass. The use amount of each of these compounds is an amount adjusted so that the absorbance at the absorption maximum wavelength of the obtained solution is about 1 based on the molar absorption coefficient of each compound.

The obtained solution was cast on a smooth glass plate, and after drying at 20°C for 8 hours, it was peeled from the glass plate. Furthermore, the peeled coating film was dried under reduced pressure at 100° C. for 8 hours to obtain a resin layer for light resistance evaluation with a thickness of 0.1 mm, a length of 210 mm, 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 JASCO Corporation, and the absorbance Ai at the maximum absorption wavelength λa in the range of 700 nm to 1000 nm was measured. After that, a fluorescent lamp (manufactured by TWINBIRD Industrial Co., Ltd., arm type Touch the inverter fluorescent lamp LK-H766B, total beam: 1334 lm), and irradiate the fluorescent lamp for 30 days. The absorbance Af under the λa of the resin layer for light resistance evaluation 30 days after the fluorescent lamp was irradiated was measured, and the absorbance retention D (=Af×100/Ai) was calculated. The results are shown in Table 5.

＜Required condition (D)＞ Absorption measured using a solution prepared by dissolving compound (Z) or compound (X) in dichloromethane used in the following test and using a spectrophotometer (V-7200) manufactured by JASCO Corporation In the spectrum, the absorbance at the longest wavelength among the maximum absorption wavelengths is εa, and the maximum absorbance at the wavelengths of 430 nm to 580 nm is εbmax, and εa/εbmax is calculated. The results are shown in Table 5.

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

<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, etc. (A) Use a gel permeation chromatography (GPC) device (150C type) manufactured by Waters, column: H-type column manufactured by Tosoh (stock), and developing solvent: o-dichlorobenzene ), to measure the weight average molecular weight (Mw) and number average molecular weight (Mn) converted from standard polystyrene. (B) Using a GPC device (HLC-8220 type, column: TSKgel α-M, developing solvent: THF) manufactured by Tosoh Co., Ltd., to measure the weight average molecular weight (Mw) in terms of standard polystyrene and Number average molecular weight (Mn).

In addition, about the resin synthesized in the resin synthesis example 3 mentioned later, the molecular weight measurement by the said method was not performed, but the logarithmic viscosity measurement by the following method (c) was performed. (C) A part of the polyimide solution was poured into anhydrous methanol to precipitate the polyimine, and filtered to separate the unreacted monomer, and then vacuum dried at 80°C for 12 hours. Dissolve 0.1 g of the obtained polyimine in 20 mL of N-methyl-2-pyrrolidone (dilute polyimide solution), use a Cannon-Fenske viscometer, and determine The equation finds the logarithmic viscosity (μ) at 30°C. μ={ln(ts/t0)}/C t0: the flow time of the solvent (N-methyl-2-pyrrolidone) ts: the flow time of the thin polyimide solution C: 0.5 g/dL

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

[Resin Synthesis Example 1] The following formula (a) 8- methyl-8-methoxy represented carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] twelve-3-ene (hereinafter Also called "DNM") 100 parts by mass, 18 parts by mass of 1-hexene (molecular weight modifier), and 300 parts by mass of toluene (solvent for ring-opening polymerization) were charged into a nitrogen-substituted reaction vessel, and the The solution was heated to 80°C. Then, to the solution in the reaction vessel, 0.2 parts by mass of a toluene solution (0.6 mol/liter) of triethylaluminum as a polymerization catalyst and a toluene solution of tungsten hexachloride modified with methanol (concentration of 0.025 mol/liter) were added. ) 0.9 parts by mass, and heating and stirring the solution at 80° C. for 3 hours, thereby proceeding a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in the polymerization reaction was 97%.

[化40]

1,000 parts by mass of the obtained ring-opening polymer solution was charged into an autoclave, and 0.12 parts by mass of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] was added to the ring-opening polymer solution. _3. Under the conditions of a hydrogen pressure of 100 kg/cm ² and a reaction temperature of 165° C., heat and stir for 3 hours to carry out the hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was depressurized. The obtained reaction solution was poured into a large amount of methanol, and the coagulum was separated and recovered, and dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The number average molecular weight (Mn) of the obtained resin A was 32,000, the weight average molecular weight (Mw) was 137,000, and the glass transition temperature (Tg) was 165°C.

[Resin Synthesis Example 2] In a 3 L four-necked flask, add 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis(4-hydroxyphenyl) fluorene, and 41.46 g of potassium carbonate ( 0.300 mol), 443 g of N,N-dimethylacetamide and 111 g of toluene. Then, in the four-necked flask, a thermometer, a stirrer, a three-way stopcock with a nitrogen inlet pipe, a Dean-Stark pipe and a cooling pipe were installed. Then, after the inside of the flask was replaced with nitrogen, the obtained solution was reacted at 140°C for 3 hours, and the generated water was removed from the Dean-Stark tube at any time. When the generation of water was not confirmed, the temperature was slowly raised to 160°C, and the reaction was carried out at the temperature in the state for 6 hours. After that, it was cooled to room temperature (25° C.), the generated salt was removed with filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was separated by filtration. The obtained filtrate was vacuum dried at 60° C. overnight, thereby obtaining a white powder (hereinafter also referred to as “resin B”) (yield 95%). The number average molecular weight (Mn) of the obtained resin B was 75,000, the weight average molecular weight (Mw) was 188,000, and the glass transition temperature (Tg) was 285°C.

[Resin Synthesis Example 3] In a 500 mL five-necked flask including a thermometer, a stirrer, a nitrogen introduction tube, a dropping funnel with a side tube, a Dean-Stark tube, and a cooling tube, put it in a nitrogen flow 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene 27.66 g (0.08 mol) and 4,4'-bis(4-aminophenoxy)biphenyl 7.38 g ( 0.02 mol), and dissolved in 68.65 g of γ-butyrolactone and 17.16 g of N,N-dimethylacetamide. Use an ice-water bath to cool the obtained solution to 5°C, while keeping the same temperature, add 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and as an alcohol Triethylamine as an imidization catalyst 0.50 g (0.005 mol). After the addition, the temperature was raised to 180°C, and the distillate was distilled off at any time, while refluxing for 6 hours. After the completion of the reaction, air cooling was performed until the internal temperature reached 100°C, and 143.6 g of N,N-dimethylacetamide was added to dilute, and the mixture was cooled while stirring to obtain a polymer having a solid content concentration of 20% by mass. Amide solution 264.16 g. A part of the polyimide solution was poured into 1 L of methanol and the polyimide was precipitated. After washing the filtered polyimide with methanol, it was dried in a vacuum dryer at 100° C. for 24 hours to obtain a white powder (hereinafter also referred to as "resin C"). The infrared (IR) spectrum of the obtained resin C was measured, and as a result, the absorption of ^{1704 cm -1} and 1770 cm ^{-1 peculiar to the imino group was observed.} The glass transition temperature (Tg) of the resin C was 310°C, and the logarithmic viscosity was measured to be 0.87.

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

·Compound (z-1) [化41]

·Compound (x-1) [化42]

·Compound (x-2) [化43]

Using a bar coater, the following resin composition (1) was applied to one side of the obtained resin layer (1) so that the thickness of the obtained resin layer (2) was 3 μm, and then placed in an oven. The solvent was evaporated and removed by heating at 70°C for 2 minutes. Next, use a UV conveyor type exposure machine (manufactured by Eyegraphics (stock), Eye UV curing device, model US2-X0405, 60 Hz) for exposure (exposure amount 500 mJ/cm ² , Illumination: 200 mW/cm ² ) to harden the resin composition (1) to form the 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). In this way, a substrate having a resin layer (2) not containing the compound (Z) on both sides of the resin layer (1) containing the compound (Z) is obtained.

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

(Lightfastness) The obtained substrate was exposed to an indoor fluorescent lamp for 500 hours, and the light resistance of the near-infrared absorbing dye contained in the resin was evaluated. Light resistance is based on the absorbance of the fluorescent lamp before and after exposure based on the wavelength with the highest absorption intensity of the substrate (hereinafter referred to as "λa"; in the case where the substrate has multiple absorption maxima, λa is the wavelength with the highest absorption intensity) before and after exposure of the fluorescent lamp The residual rate (%) of the pigment was calculated and evaluated by changing it. The case where the residual rate of the pigment after exposure to a fluorescent lamp was 95% or more was set to "○", and the case where it was less than 95% was set to "×". The results are shown in Table 8.

〔Fabrication of Optical Filter〕 A dielectric multilayer film (I) is formed on one side of the substrate obtained in the production of the substrate, and then a dielectric multilayer film (II) is formed on the other side of the substrate to obtain an optical filter with a thickness of about 0.110 mm .

The dielectric multilayer film (I) is a laminate (26 layers in total) in which silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO ₂ ) layers are alternately laminated at a vapor deposition temperature of 100°C. The dielectric multilayer film (II) is a laminate (22 layers in total) in which silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO ₂ ) layers are alternately laminated at a vapor deposition temperature of 100°C. In either of the dielectric multilayer film (I) and the dielectric multilayer film (II), a titanium dioxide layer, a silicon dioxide layer, a titanium dioxide layer,... a silicon dioxide layer, a titanium dioxide layer, and a titanium dioxide layer A silicon dioxide layer and a titanium dioxide layer are alternately stacked in the order of the silicon layer, and the outermost layer of the optical filter is set as the silicon dioxide layer.

Regarding the thickness and the number of layers of each layer, in order to achieve good transmittance in the visible region and reflection performance in the near-infrared region, depending on the wavelength-dependent characteristics of the refractive index of the substrate, or the compound (Z) and compound used ( The absorption characteristics of X) are optimized using optical film design software (Essential Macleod, manufactured by Thin Film Center). When performing optimization, in this embodiment, the input parameters (Target values) for the software are set as shown in Table 6 below.

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

The result of the optimization of the film structure is that the dielectric multilayer film (I) is made by alternately stacking a silicon dioxide layer with a physical film thickness of about 37 nm to 168 nm and a titanium dioxide layer with a physical film thickness of about 11 nm to 104 nm. The 26-layer multi-layer vapor-deposited film, the dielectric multilayer film (II) is made by alternately stacking a silicon dioxide layer with a physical film thickness of about 40 nm to 191 nm and a titanium dioxide layer with a physical film thickness of about 10 nm to 110 nm. It is a multi-layer vapor-deposited film with 22 layers. An example of the optimized membrane structure is shown in Table 7 below.

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

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

[Example 2] In Example 1, 0.08 parts by mass of the following compound (z-16) (maximum absorption wavelength in dichloromethane is 825 nm) was used instead of 0.2 parts by mass of the compound (z-1), and resin B was used instead Except resin A, it carried out similarly to Example 1, and obtained the base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-16) [化44]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 3] In Example 1, 0.14 parts by mass of the following compound (z-59) (maximum absorption wavelength in dichloromethane at 770 nm) was used instead of 0.2 parts by mass of the compound (z-1), and resin C was used instead Except resin A, it carried out similarly to Example 1, and obtained the base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-59) [化45]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 4] In Example 1, 0.2 parts by mass of the following compound (z-62) (maximum absorption wavelength in dichloromethane is 757 nm) was used instead of 0.2 parts by mass of the compound (z-1), and a Japanese catalyst (stock ) Except that the manufactured acryviewa was used instead of resin A, the same procedure as in Example 1 was carried out to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-62) [化46]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 5] In Example 1, 0.08 parts by mass of compound (z-151) (maximum absorption wavelength in dichloromethane is 824 nm) was used instead of 0.2 parts by mass of compound (z-1). Otherwise, the same as in Example 1. The same procedure was carried out to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-151) [Chemical 47]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 6] In a container, 100 parts by mass of resin A obtained in Resin Synthesis Example 1, 0.38 parts by mass of compound (x-1) as compound (X), 0.75 parts by mass of compound (x-2), and dichloromethane are added, A solution with a resin concentration of 20% by mass was prepared and filtered with a microporous filter with a pore diameter of 5 μm to obtain a resin solution (E6-1). In the same way, 100 parts by mass of resin A, 2 parts by mass of the compound (z-1) as compound (Z), and dichloromethane were added to prepare a solution with a resin concentration of 20% by mass, and a pore size of 5 μm was used. Filter with a microporous filter to obtain a resin solution (E6-2).

Using a spin coater, the following resin composition (2) was applied to a transparent film made by Nippon Electric Glass Co., Ltd. cut into a size of 200 mm×200 mm so that the film thickness after drying was about 1 μm Both sides of the glass support "OA-10G" (thickness 200 μm) are heated on a hot plate at 80°C for 2 minutes to volatilize and remove the solvent, forming a glass support and the coating resin layer (1) and the coating resin layer described later. The adhesive layer that is coated with the resin layer (2) functions as an adhesive layer.

Next, using a spin coater, the resin solution (E6-1) was applied to one side of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, on the hot plate The solvent was volatilized and removed by heating at 80° C. for 5 minutes to form a coating resin layer (2). Furthermore, using a spin coater, the resin solution (E6-2) was applied to the other surface of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, on the hot plate The solvent was volatilized and removed by heating at 80° C. for 5 minutes to form a coating resin layer (1). In this way, a substrate with a thickness of 222 μm in which a resin layer containing the compound (Z) is laminated on one side of the glass support and a resin layer containing no compound (Z) is laminated on the other side. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 9.

Resin composition (2): Isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.) 30 parts by mass, 1,9- 20 parts by mass of nonanediol diacrylate, 20 parts by mass of methacrylic acid, 30 parts by mass of glycidyl methacrylate, 5 parts by mass of 3-glycidoxypropyltrimethoxysilane, 1-hydroxycyclohexyl diphenyl Methyl ketone (trade name: IRGACURE 184, manufactured by BASF Japan (stock)) 5 parts by mass and san-aid SI-110 main agent (Sanshin Chemical Industry Co., Ltd.) Manufacturing) 1 part by mass is mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 50% by mass, and then filtered through a microporous filter with a pore size of 0.2 μm

Then, referring to Example 1, on the surface of the coated resin layer (2), a total of 26 dielectric multilayer films (I) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers were formed,} Furthermore, on the surface of the coated resin layer (1), a total of 22 layers of dielectric multilayer film (II) formed by alternately laminating silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of approximately 0.226 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 9.

[Example 7] In Example 1, 0.01 parts by mass of the following compound (x-3) (maximum absorption wavelength in dichloromethane: 931 nm) was additionally used, except that the same procedure as in Example 1 was carried out to obtain a substrate . With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (x-3) [化48]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 8] In Example 1, 0.03 parts by mass of the following compound (x-5) (maximum absorption wavelength in dichloromethane is 1095 nm) was additionally used, except that the same procedure as in Example 1 was carried out to obtain a substrate . With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (x-5) [化49]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 9] In Example 1, 0.16 parts by mass of compound (z-16) (maximum absorption wavelength in dichloromethane is 825 nm) and compound (z-59) (maximum absorption wavelength in dichloromethane is 770 nm ) Except for 0.12 part by mass instead of 0.2 part by mass of the compound (z-1), the same procedure as in Example 1 was carried out to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 10] In Example 1, 0.17 parts by mass of the following compound (y-1) (maximum absorption wavelength in dichloromethane: 394 nm) was additionally used, and except for that, the same procedure as in Example 1 was carried out to obtain a substrate . With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (y-1) [化50]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 11] In Example 6, the near-infrared absorbing glass substrate "BS-11" (thickness 0.2 mm) manufactured by Matsuba Glass Co., Ltd. was used instead of the transparent glass support "OA-10G" manufactured by Nippon Electric Glass Co., Ltd. ( Thickness 200 μm), except for this, the same procedure as in Example 6 was carried out to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 9.

Then, in the same manner as in Example (2) in the surface of the coating resin layer 6 is formed silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the surface of the coated resin layer (1), a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers is formed to obtain a thickness of about} 0.226 mm optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 9.

[Example 12] In Example 1, 0.1 parts by mass of the following compound (z-156) (the maximum absorption wavelength in dichloromethane is 785 nm) was used instead of 0.2 parts by mass of the compound (z-1). Example 1 was carried out in the same manner to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-156) [Chemical 51]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 13] In Example 12, 0.1 parts by mass of the following compound (z-157) (maximum absorption wavelength in dichloromethane is 788 nm) was used instead of 0.1 part by mass of the compound (z-156). Example 12 was carried out in the same manner to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-157) [化52]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 14] In Example 12, 0.1 parts by mass of the following compound (z-158) (the maximum absorption wavelength in dichloromethane is 790 nm) was used instead of 0.1 parts by mass of the compound (z-156). Example 12 was carried out in the same manner to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-158) [Chemical 53]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 15] In Example 12, 0.1 parts by mass of the following compound (z-159) (the maximum absorption wavelength in dichloromethane is 800 nm) was used instead of 0.1 parts by mass of the compound (z-156). Example 12 was carried out in the same manner to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-159) [Chemical 54]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 16] In Example 12, 0.1 parts by mass of the following compound (z-160) (the maximum absorption wavelength in dichloromethane is 791 nm) was used instead of 0.1 parts by mass of the compound (z-156). Example 12 was carried out in the same manner to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-160) [化55]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 17] In Example 12, 0.1 parts by mass of the following compound (z-161) (the maximum absorption wavelength in dichloromethane is 800 nm) was used instead of 0.1 parts by mass of the compound (z-156). Example 12 was carried out in the same manner to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-161) [化56]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 18] In Example 12, 0.1 parts by mass of the following compound (z-162) (maximum absorption wavelength in dichloromethane is 810 nm) was used instead of 0.1 part by mass of the compound (z-156). Example 12 was carried out in the same manner to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-162) [Chemical 57]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Example 19] In Example 12, 0.1 parts by mass of the following compound (z-163) (maximum absorption wavelength in dichloromethane is 760 nm) was used instead of 0.1 part by mass of the compound (z-156). Example 12 was carried out in the same manner to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (z-163) [化58]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Comparative Example 1] In Example 1, except for not using the compound (Z), the same procedure as in Example 1 was carried out to obtain a substrate. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Comparative Example 2] In Example 1, instead of using the compound (Z), as the compound (X), 0.038 parts by mass of the compound (x-1), 0.075 parts by mass of the compound (x-2), and the compound (x-3) were used ( Except that the maximum absorption wavelength in dichloromethane was 931 nm) 0.2 parts by mass, the same procedure as in Example 1 was carried out to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (x-3) [化59]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

[Comparative Example 3] In Example 1, instead of using compound (Z), as compound (X), 0.038 parts by mass of compound (x-1), 0.075 parts by mass of compound (x-2), and compound (x-4) (in Except that the maximum absorption wavelength in dichloromethane is 760 nm) 0.08 parts by mass, the same procedure as in Example 1 was carried out to obtain a base material. With respect to the obtained substrate, the light resistance was evaluated in the same manner as in Example 1. The results are shown in Table 8.

·Compound (x-4) [化60]

Then, in the same manner as in Example 1, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (I 26 layer ), and on the other side of the substrate, a total of 22 layers of dielectric multilayer film (II) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.110 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 1, after considering the wavelength dependence of the refractive index of the substrate, etc., the same design parameters as in Example 1 were used. Regarding the obtained optical filter, in the same manner as in Example 1, the average value T and the average value R were determined. The results are shown in Table 8.

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

[Table 9] Example 6 Example 11 Substrate Support OA-10G BS-11 Resin layer (1) Resin Resin A Resin A (Z-1) 2 2 (Z-16) - - (Z-59) - - (Z-62) - - (X-177) - - Resin layer (2) Resin Resin A Resin A (X-1) 0.38 0.38 (X-2) 0.75 0.75 (X-3) - - (X-4) - - (X-5) - - Light fastness ○ ○ Optical filter Dielectric multilayer film (I) 26 26 Dielectric multilayer film (II) twenty two twenty two Optical properties R (%) 8.6 9.0 T (%) 90.3 86.6

The optical filters obtained in Examples 1 to 19 can reduce the intensity of reflected light in near-infrared light, especially in the wavelength region of 700 nm to 800 nm, while maintaining the transmittance of visible light. In recent years, in photographing devices such as digital still cameras that have advanced in performance, it is useful to minimize the reduction in sensitivity in the visible light region and eliminate image defects caused by the reflected light.

[Synthesis example of compound (z-164)] In an eggplant-shaped flask, acetyl chloride (2 equal amounts) and tert-butyl alcohol (1 equal amount) were charged and stirred while being heated in an oil bath adjusted to 85°C. To this, trifluoromethanesulfonic acid (1 equivalent) was added dropwise over 5 minutes, and after the dropwise addition was completed, the set temperature of the oil bath was set to 100° C., and the mixture was stirred for 30 minutes. After cooling to room temperature, diethyl ether and water were added, and the precipitated solid was collected by filtration to obtain the following compound (m-1).

·Compound (m-1) [化61]

In an eggplant-shaped flask, the obtained compound (m-1) (1 equivalent) and malondialdehyde dianiline hydrochloride (0.5 equivalent) were charged, and acetonitrile and anhydrous acetic acid were added to it. Stir. Then, pyridine (1 equivalent) was added dropwise and stirred at room temperature for 2 hours. After that, acetonitrile, anhydrous acetic acid, and pyridine were removed using an evaporator, and liquid separation was performed using methyl chloride/water. The organic phase was recovered, and 1.5 equal amounts of LiFABA (lithium = tetrakis (pentafluorophenyl) borohydride) and water were added thereto, and stirred vigorously for 3 hours. After that, the organic phase was recovered, and the chlorinated methane was removed by an evaporator to obtain the compound (z-164).

·Compound (z-164): The maximum absorption wavelength in dichloromethane is 715 nm [Chem. 62]

[Synthesis example of compound (z-165)] In the synthesis example of the compound (z-164), except that acetyl chloride was changed to 1-methylcyclopropane carboxylic acid chloride, the compound (z-165) was obtained by the same method as in the synthesis example. ·Compound (z-165): The maximum absorption wavelength in dichloromethane is 727 nm

[化63]

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

·Compound (z-166): The maximum absorption wavelength in dichloromethane is 719 nm [Chemical 64]

[Synthesis example of compound (z-167)] In the synthesis example of the compound (z-164), except that acetyl chloride was changed to 1-adamantane carboxylic acid chloride, the compound (z-167) was obtained by the same method as in the synthesis example.

·Compound (z-167): The maximum absorption wavelength in dichloromethane is 721 nm [Chem. 65]

[Synthesis example of compound (z-168)] In the synthesis example of compound (z-164), the malondialdehyde dianiline hydrochloride was changed to the following compound (m-2), except that the compound ( z-168).

·Compound (m-2) [化66]

·Compound (z-168): The maximum absorption wavelength in dichloromethane is 720 nm [Chemical 67]

[Synthesis example of compound (z-169)] In the synthesis example of the compound (z-167), except that malondialdehyde dianiline hydrochloride was changed to the compound (m-2), the compound ( z-169).

·Compound (z-169): the maximum absorption wavelength in dichloromethane is 726 nm [Chemical 68]

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

·Compound (m-3) [化69]

·Compound (z-170): The maximum absorption wavelength in dichloromethane is 739 nm [Chemical 70]

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

·Compound (m-4) [化71]

·Compound (z-171): The maximum absorption wavelength in dichloromethane is 734 nm [Chemical 72]

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

·Compound (m-5) [化73]

· Compound (z-172): The maximum absorption wavelength in dichloromethane is 738 nm [Chemical 74]

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

·Compound (m-6) [化75]

·Compound (z-173): The maximum absorption wavelength in dichloromethane is 724 nm [Chemical 76]

[Example 20 to Example 32 and Comparative Example 4 to Comparative Example 7] 〔Production of base material〕 It carried out similarly to Example 1, and specifically, the base material was produced as follows. The resin, the compound (Z), the compound (X), the compound (Y), and dichloromethane were added at the ratio described in Table 12 to prepare a solution with a resin concentration of 20% by mass. The obtained solution was cast on a smooth glass plate, and after drying at 20°C for 8 hours, it was peeled from the glass plate. Furthermore, the peeled coating film was dried under reduced pressure at 100° C. for 8 hours to obtain a resin layer (1) having a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm. In addition, the numerical value described in the column of compound (Z), compound (X), and compound (Y) in Table 12 shows the content (mass part) of each compound with respect to 100 mass parts of resins.

In addition, the compound (x-6) in Table 12 is a compound represented by the following formula (the absorption maximum wavelength in dichloromethane is 717 nm). [化77]

Using a bar coater, the following resin composition (1) was applied to one side of the obtained resin layer (1) so that the thickness of the obtained resin layer (2) was 3 μm, and then placed in an oven. The solvent was evaporated and removed by heating at 70°C for 2 minutes. Next, use a UV conveyor type exposure machine (manufactured by Eyegraphics (stock), Eye UV curing device, model US2-X0405, 60 Hz) for exposure (exposure amount 500 mJ/cm ² , Illumination: 200 mW/cm ² ) to harden the resin composition (1) to form the 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).

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

<Spectral transmittance> The obtained base material has a near-infrared transmittance with a wavelength of 650 nm to 800 nm and a visible light transmittance with a wavelength of 430 nm to 580 nm using a spectrophotometer manufactured by JASCO Corporation ( V-7200) to determine. The transmittance is measured using the spectrophotometer under the condition that light is incident perpendicularly to the surface of the substrate. The parameters measured using this device are as follows. The results are shown in Table 12. The spectral transmittance spectra of the substrates obtained in Example 20 and Example 28 are shown in FIGS. 1 to 2, respectively. In addition, regarding the following Tc and Td, the obtained substrate was heated in an oven preheated to 155° C. for 7 hours, and the transmittance of the substrate after the heating test (evaluation of heat resistance) was measured. In addition, for Te and Tf, a UV exposure machine (manufactured by Iwasaki Electric Co., Ltd., Eye UV curing device US2-KO4501, illuminance: 180 mW/cm ² , irradiation: 560 mJ/cm ² ) The obtained substrate was irradiated with UV, and the transmittance of the substrate after the UV irradiation was measured (UV resistance evaluation).

Xa: The wavelength of light with the lowest transmittance measured from the vertical direction of the substrate in the wavelength of 650 nm to 800 nm Ta: The lowest transmittance measured from the vertical direction of the substrate in the wavelength of 650 nm to 800 nm Tb: The average transmittance of light with a wavelength of 430 nm to 580 nm measured from the vertical direction of the substrate Tc: The lowest transmittance of light with a wavelength of 650 nm to 800 nm after the heating test, measured from the vertical direction of the substrate Td: The average transmittance of light with a wavelength of 430 nm to 580 nm after the heating test, measured from the vertical direction of the substrate Te: The lowest transmittance of light with a wavelength of 650 nm to 800 nm after UV irradiation, measured from the vertical direction of the substrate Tf: The average transmittance of light with a wavelength of 430 nm to 580 nm after UV irradiation, measured from the vertical direction of the substrate

〔Fabrication of Optical Filter〕 A dielectric multilayer film (III) is formed on one side of the substrate obtained in the production of the substrate, and then a dielectric multilayer film (IV) is formed on the other side of the substrate to obtain an optical filter with a thickness of about 0.110 mm .

The dielectric multilayer film (III) is a laminate (28 layers in total) in which silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO ₂ ) layers are alternately laminated at a vapor deposition temperature of 100°C. The dielectric multilayer film (IV) is a laminate (24 layers in total) in which silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO ₂ ) layers are alternately laminated at a vapor deposition temperature of 100°C. In either of the dielectric multilayer film (III) and the dielectric multilayer film (IV), there are a titanium dioxide layer, a silicon dioxide layer, a titanium dioxide layer,... a silicon dioxide layer, a titanium dioxide layer, and a titanium dioxide layer from the substrate side. A silicon dioxide layer and a titanium dioxide layer are alternately stacked in the order of the silicon layer, and the outermost layer of the optical filter is set as the silicon dioxide layer.

Regarding the thickness and number of each layer, in order to achieve good transmittance in the visible region and reflection performance in the near-infrared region, it depends on the wavelength-dependent characteristics of the refractive index of the substrate, or the compound (Z) and compound used ( The absorption characteristics of X) are optimized using optical film design software (Essential Macleod, manufactured by Thin Film Center). When performing optimization, in this embodiment, the input parameters (target values) for the software are set as shown in Table 10 below.

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

The result of the optimization of the film structure is that the dielectric multilayer film (III) is made by alternately stacking a silicon dioxide layer with a physical film thickness of about 32 nm to 159 nm and a titanium dioxide layer with a physical film thickness of about 9 nm to 94 nm. The 28-layer multilayer vapor-deposited film, the dielectric multilayer film (IV) is made by alternately stacking a silicon dioxide layer with a physical film thickness of about 39 nm to 193 nm and a titanium dioxide layer with a physical film thickness of about 12 nm to 117 nm. A multi-layer vapor-deposited film with 24 layers is formed. An example of the optimized membrane structure is shown in Table 11 below.

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

＜Spectral transmittance＞ The obtained optical filter has a near-infrared transmittance with a wavelength of 650 nm to 800 nm and a visible light transmittance with a wavelength of 430 nm to 580 nm using a spectrophotometer (V-7200) manufactured by JASCO Corporation. To determine. The transmittance is the transmittance measured using the spectrophotometer under the condition that light is incident perpendicularly to the optical filter. The parameters measured using this device are as follows. The results are shown in Table 12. The spectral transmittance spectra of the optical filters obtained in Example 20 and Example 28 are shown in FIGS. 3 to 4, respectively.

Tg: The average transmittance of light with a wavelength of 650 nm to 800 nm measured from the vertical direction of the optical filter Th: The average transmittance of light with a wavelength of 430 nm to 580 nm measured from the vertical direction of the optical filter

[Example 33 to Example 43 and Comparative Example 8] It carried out similarly to Example 6, and specifically, the base material was produced as follows. Add resin A, compound (X), compound (Y), and dichloromethane in the proportions listed in Table 13, to prepare a solution with a resin concentration of 20% by mass, and filter with a 5 μm pore filter , To obtain a resin solution (E-1). Resin A, compound (Z), and dichloromethane were added in the proportions described in Table 13 to prepare a solution with a resin concentration of 20% by mass, and filtered with a microporous filter with a pore size of 5 μm to obtain a resin solution ( E-2).

Using a spin coater, the following resin composition (2) was applied to a transparent film made by Nippon Electric Glass Co., Ltd. cut into a size of 200 mm×200 mm so that the film thickness after drying was about 1 μm Both sides of the glass support "OA-10G" (thickness 200 μm) are heated on a hot plate at 80°C for 2 minutes to volatilize and remove the solvent, forming a glass support and the coating resin layer (1) and the coating resin layer described later. The adhesive layer that is coated with the resin layer (2) functions as an adhesive layer. In addition, only Example 39 uses the near-infrared absorbing glass substrate "BS-11" (thickness 200 μm) manufactured by Matsuba Glass Industry Co., Ltd., cut into a size of 200 mm × 200 mm, instead of "OA-10G" .

Next, using a spin coater, the resin solution (E-1) was applied to one side of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, on the hot plate The solvent was volatilized and removed by heating at 80° C. for 5 minutes to form a coating resin layer (2). Furthermore, using a spin coater, the resin solution (E-2) was applied to the other surface of the glass support on which the adhesive layer was formed so that the film thickness after drying was 10 μm, on the hot plate The solvent was volatilized and removed by heating at 80° C. for 5 minutes to form a coating resin layer (1). In this way, a substrate with a thickness of 222 μm in which a resin layer containing the compound (Z) is laminated on one side of the glass support and a resin layer containing no compound (Z) is laminated on the other side. In addition, the numerical values described in compound z-164 to compound z-173 in Table 13 represent the content (parts by mass) of each compound relative to 100 parts by mass of the resin in the resin layer (1), and the compound x in Table 13 -1. The numerical values described in compound x-2 and compound y-1 indicate the content (parts by mass) of each compound with respect to 100 parts by mass of the resin in the resin layer (2). In the same manner as in Example 20, Xa and Ta to Tf of the substrate were measured. The results are shown in Table 13. The spectral transmittance spectrum of the substrate obtained in Example 36 is shown in FIG. 5.

Resin composition (2): Isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix (Aronix) M-315, manufactured by Toagosei Co., Ltd.) 30 parts by mass, 1,9- 20 parts by mass of nonanediol diacrylate, 20 parts by mass of methacrylic acid, 30 parts by mass of glycidyl methacrylate, 5 parts by mass of 3-glycidoxypropyltrimethoxysilane, 1-hydroxycyclohexyl diphenyl Methyl ketone (trade name: IRGACURE 184, manufactured by BASF Japan (stock)) 5 parts by mass and san-aid SI-110 main agent (Sanshin Chemical Industry Co., Ltd.) Manufacturing) 1 part by mass is mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 50% by mass, and then filtered through a microporous filter with a pore size of 0.2 μm

Then, in the same manner as in Example 20, obtained on one side of the substrate to form silicon dioxide (SiO ₂₎ layer of titanium dioxide (TiO ₂₎ layers are alternately laminated from the total dielectric multilayer film (III 28 layer ), and on the other side of the substrate, a total of 24 layers of dielectric multilayer film (IV) formed by alternately stacking silicon _{dioxide (SiO 2} ) layers and titanium dioxide (TiO _{2) layers was formed to obtain a thickness of about 0.226 mm} Optical filter. Regarding the design of the dielectric multilayer film, as in Example 20, the same design parameters as in Example 20 were used after taking into consideration the wavelength dependence of the refractive index of the base material and the like. In the same manner as in Example 20, the Tg and Th of the optical filter were measured. The results are shown in Table 13. The spectral transmittance spectrum of the optical filter obtained in Example 36 is shown in FIG. 6.

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

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

The optical filters obtained in Examples 20 to 43 can maintain the transmittance of visible light while reducing the intensity of reflected light in near-infrared light, especially in the wavelength region of 700 nm to 750 nm. In recent years, in photographing devices such as digital still cameras that have advanced in performance, it is useful to minimize the reduction in sensitivity in the visible light region and eliminate image defects caused by the reflected light.

without

FIG. 1 is the spectral transmittance spectrum of the substrate obtained in Example 20. 2 is the spectral transmittance spectrum of the substrate obtained in Example 28. 3 is the spectral transmittance spectrum of the optical filter obtained in Example 20. 4 is the spectral transmittance spectrum of the optical filter obtained in Example 28. FIG. 5 is the spectral transmittance spectrum of the substrate obtained in Example 36. FIG. FIG. 6 is the spectral transmittance spectrum of the optical filter obtained in Example 36. FIG.

Claims (14)

A resin composition comprising: a resin, and a compound (Z) represented by the following formula ^{(I), Cn + An -} (I) [In the formula (I), Cn ⁺ by the following formula (II) represented by Monovalent cation, An ^- is a monovalent anion]

[In formula (II), unit A is any of the following formulas (AI) to (A-III), unit B is any of the following formulas (BI) to (B-III), Y _A to Y _E are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, a -NR ^g R ^h group, an amide group, an amide group, a cyano group, a silyl group, -Q ¹ , -N= NQ ¹ , -SQ ² , -SSQ ² , or -SO ₂ Q ³ , Y _A and Y _C , Y _B and Y _D , and Y _C and Y _E can be bonded to each other to form an aromatic with 6 to 14 carbon atoms Hydrocarbyl groups, 4-membered to 7-membered alicyclic groups which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a C3-14 heteroaromatic group containing at least one nitrogen atom, oxygen atom or sulfur atom, these The 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 =0, Y _A and the following formula (A- III) R ¹ or R ⁵ , and Y _E ^{and R 5} or R ¹ in the following formula (B-III) may be bonded to each other to form four members that may contain at least one nitrogen atom, oxygen atom or sulfur atom to 7-membered alicyclic group, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, Q ¹ is independently represented by the following L ^a ~ L ^h is any one, Q ² is independently a hydrogen atom or L ^a ~ L ^h following either one, Q ³ is hydroxy or L ^a ~ L ^h following either one, R ⁱ is the following Any one of L ^a ～L ^h]

[-* in formula (AI) to formula (A-III) represents _{a single bond with the carbon to which Y A} of the formula (II) is bonded, and in formula (BI) to formula (B-III) =** means that it _{is double-bonded with the carbon to which Y E} of the formula (II) is bonded. In formulas (AI) to (B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, Tellurium atom or -NR ⁸ -, R ¹ to R ⁶ are each independently 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, a -NR ^g R ^h group, and a -SR ⁱ group , -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group, -C (O) R ⁱ or the following group L ^a ~ L ^h is any one of, adjacent to R ¹ ~ R ⁶ may be bonded to each other to form a carbon Aromatic hydrocarbon group of 6 to 14, alicyclic group of 4 to 7 members which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or carbon 3 to 14 containing at least one nitrogen atom, oxygen atom or sulfur atom These aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbons or halogen atoms, and the alicyclic groups may have =0, R ⁸ is independently a hydrogen atom, a halogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, R ⁱ is independently L ^a ~ L ^h following either one, (L ^a): an aliphatic hydrocarbon group having a carbon number of 1 to 15 (L ^b): carbon 1 to 15 halogen-substituted alkyl group (L ^c ): an alicyclic hydrocarbon group with 3 to 14 carbons that may have a substituent K (L ^d ): an aromatic 6 to 14 carbons that may have a substituent K Group hydrocarbon group (L ^e ): a heterocyclic group having 3 to 14 carbons which may have substituent K ‏(L ^f ): -OR (R is a hydrocarbon group having 1 to 12 carbons which may have substituent L) (L ^g ): an acyl group ^{having 1 to 9 carbons that may have a substituent L (L h} ): an alkoxycarbonyl group having 1 to 9 carbons that may have a substituent L The substituent K is selected from the group consisting of ^La to At least one of L ^b , and the substituent L is at least one selected from the group consisting of ^La to L ^f ]. The resin composition according to claim 1, wherein the compound (Z) satisfies the following requirement (A), Prerequisite (A): Transmission spectrum measured using a solution prepared by dissolving the compound (Z) in dichloromethane (wherein, the transmission spectrum is a spectrum with a transmittance of 10% at an absorption maximum wavelength) Among them, the average transmittance at a wavelength of 430 nm to 580 nm is 93% or more. The requested item or request a resin composition according to item 2, wherein said at least one of R ¹ ~ R ⁶ is the L ^a, L ^c or L ^d. The resin composition according to claim 1 or 2, wherein the compound (Z) satisfies the following requirement (B-1), Prerequisite (B-1): The absorption spectrum measured using a solution obtained by dissolving the compound (Z) in dichloromethane has a maximum value in the wavelength range of 720 nm to 900 nm. The resin composition according to claim 1 or 2, wherein the compound (Z) satisfies the following requirement (B-2), Requirement (B-2): The absorption spectrum measured using a solution obtained by dissolving the compound (Z) in dichloromethane has a maximum value in the wavelength range of 700 nm to 750 nm. The resin composition according to claim 1 or claim 2, wherein the resin is selected from the group consisting of cyclic (poly)olefin resins, aromatic polyether resins, polyimide resins, polyester resins, Polycarbonate-based resin, polyamide-based resin, polyarylate-based resin, polyether-based resin, polyether-based resin, polyparaphenylene-based resin, polyamide-imide-based resin, polyethylene naphthalate Ester resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester curable resins, silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins At least one resin in the group consisting of resin and vinyl-based ultraviolet curable resin. A base material (i) formed of the resin composition according to any one of claims 1 to 6 and containing a compound (Z). The substrate (i) according to claim 7, wherein the substrate (i) is the following substrate: A substrate comprising a resin layer containing the compound (Z); It includes two or more resin layers, and at least one of the two or more resin layers is a base material of a resin layer containing the compound (Z); or A base material including a glass support and a resin layer containing the compound (Z). An optical filter having the base material (i) according to claim 7 or claim 8, and a dielectric multilayer film. The optical filter according to claim 9, which is used in a solid-state imaging device. The optical filter according to claim 9, which is used in an optical sensor device. A solid-state photography device includes the optical filter according to claim 9. An optical sensor device comprising the optical filter according to claim 9. Compound (Z), which is 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 Valence anion]

[In formula (IV), unit A is any of the following formulas (AI) to (A-III), unit B is any of the following formulas (BI) to (B-III), Y _A to Y _E are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, a -NR ^g R ^h group, an amide group, an amide group, a cyano group, a silyl group, -Q ¹ , -N= NQ ¹ , -SQ ² , -SSQ ² , or -SO ₂ Q ³ , Y _A and Y _C , Y _B and Y _D , and Y _C and Y _E can be bonded to each other to form an aromatic with 6 to 14 carbon atoms Hydrocarbyl groups, 4-membered to 7-membered alicyclic groups which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or a C3-14 heteroaromatic group containing at least one nitrogen atom, oxygen atom or sulfur atom, these The 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 =0, Y _A and the following formula (A- III) R ¹ or R ⁵ , and Y _E ^{and R 5} or R ¹ in the following formula (B-III) may be bonded to each other to form four members that may contain at least one nitrogen atom, oxygen atom or sulfur atom to 7-membered alicyclic group, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, Q ¹ is independently represented by the following L ^a ~ L ^h is any one, Q ² is independently a hydrogen atom or L ^a ~ L ^h following either one, Q ³ is hydroxy or L ^a ~ L ^h following either one, R ⁱ is the following Any one of L ^a ～L ^h]

[-* in formula (AI) to formula (A-III) represents _{a single bond with the carbon to which Y A} of the formula (II) is bonded, and in formula (BI) to formula (B-III) =** means that it _{is double-bonded with the carbon to which Y E} of the formula (II) is bonded. In formulas (AI) to (B-III), X is independently an oxygen atom, a sulfur atom, a selenium atom, Tellurium atom or -NR ⁸ -, R ¹ to R ⁶ are each independently 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, a -NR ^g R ^h group, and a -SR ⁱ group , -SO ₂ R ⁱ group, -OSO ₂ R ⁱ group, -C (O) R ⁱ or the following group L ^a ~ L ^h is any one of, adjacent to R ¹ ~ R ⁶ may be bonded to each other to form a carbon Aromatic hydrocarbon group of 6 to 14, alicyclic group of 4 to 7 members which may contain at least one nitrogen atom, oxygen atom or sulfur atom, or carbon 3 to 14 containing at least one nitrogen atom, oxygen atom or sulfur atom These aromatic hydrocarbon groups, alicyclic groups and heteroaromatic groups may have hydroxyl groups, aliphatic hydrocarbon groups with 1 to 9 carbons or halogen atoms, and the alicyclic groups may have =0, R ⁸ is independently a hydrogen atom, a halogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, R ^g and R ^h are each independently a hydrogen atom, -C (O) R ⁱ groups or L ^a ~ L ^h following either one, R ⁱ is independently L ^a ~ L ^h following either one, (L ^a): an aliphatic hydrocarbon group having a carbon number of 1 to 15 (L ^b): carbon 1 to 15 halogen-substituted alkyl group (L ^c ): an alicyclic hydrocarbon group with 3 to 14 carbons that may have a substituent K (L ^d ): an aromatic 6 to 14 carbons that may have a substituent K Group hydrocarbon group (L ^e ): a heterocyclic group having 3 to 14 carbons which may have substituent K ‏(L ^f ): -OR (R is a hydrocarbon group having 1 to 12 carbons which may have substituent L) (L ^g ): an acyl group ^{having 1 to 9 carbons that may have a substituent L (L h} ): an alkoxycarbonyl group having 1 to 9 carbons that may have a substituent L The substituent K is selected from the group consisting of ^La to At least one of L ^b , and the substituent L is at least one selected from the group consisting of ^La to L ^f ].

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