JP2023153056A - Composition, optical member, solid-state imaging device, optical sensor device and compound - Google Patents

Abstract

To provide a composition which is excellent in near-infrared light shielding property and UV resistance, in an obtained optical member.SOLUTION: There are provided a composition which contains a resin (i) or a polymerizable compound (ii), and a compound (Z) represented by formula (I): Cn+An-, wherein the compound (Z) has a maximum absorption wavelength λmax in a wavelength range of 400-1,300 nm in dichloromethane of wavelength 1,100 nm<λmax<1,200 nm; and an optical member, a solid-state imaging device, an optical sensor device and a compound including the same. In the formula (I), Cn+ represents a monovalent cation represented by the following formula (II), and An- represents a counter anion. The details of a substituent in formula (II) are described in the specifications.SELECTED DRAWING: None

Description

The present invention relates to compositions, optical members, solid-state imaging devices, optical sensor devices, and compounds.

Solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions use solid-state imaging devices such as CCD and CMOS image sensors. A silicon photodiode is used that is sensitive to near-infrared radiation, which cannot be detected. For these solid-state image sensors, it is necessary to perform visibility correction to make colors look natural to the human eye, and optical filters (for example, near-infrared rays) that selectively transmit or cut light in a specific wavelength range are required. A cut filter) is often used.

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

Structurally defined infrared dyes that are soluble in methylene chloride and have an infrared absorption maximum above 1100 nm have been disclosed (see, for example, US Pat.

International Patent No. 2019/151344 International Publication No. 2014/057018

https://www. Chukan. co. jp/JelvxL/sys/wp-content/uploads/2019/08/NIR_1100-1. pdf

Cut filters used in solid-state image sensors and the like can be broadly divided into primary color filters and complementary color filters. Primary color filters are used for color reproducibility, and complementary color filters are used for sensitivity.
In recent years, the level of image quality required for camera images has become extremely high even in mobile devices and the like.

Conventionally, polymethine dyes, squarylium dyes, diimonium dyes, and the like are known as dyes used in such cut filters. Diimonium dyes can absorb in a wide range, especially in the wavelength region of 1100 nm or later, but their low UV resistance makes it difficult to apply them to cut filters. Heptamethine dyes with a benzo[c,d]indolenine skeleton have good UV resistance, but it was difficult to shift the maximum absorption wavelength to 1100 nm or more while maintaining good visible light transmittance and UV resistance. .

The problem to be solved by one embodiment of the present invention is to provide a composition that has excellent near-infrared light shielding properties and UV resistance in the obtained optical filter.

As a result of intensive studies to solve the above problems, the present inventors have found that by applying a specific compound (Z), the resulting optical member has excellent near-infrared light shielding properties and UV resistance. They discovered this and completed the present invention.
Examples of aspects of the problem to be solved by the present invention are shown below.

<1> Contains a resin (i) or a polymerizable compound (ii) and a compound (Z) represented by the following formula (I), wherein the compound (Z) has a wavelength of 400 nm to 1300 nm in dichloromethane. A composition whose maximum absorption wavelength λmax in a wavelength range is 1100 nm<λmax<1200 nm.
Cn ⁺ An ^- formula (I)
[In formula (I), Cn ⁺ represents a monovalent cation represented by the following formula (II), and An ^- represents a counter anion. ]

[In formula (II), R ¹ to R ⁶ , Y _B , Y _C , and Z _A to Z _C each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a phosphoric acid group, Silyl group, R _i , -OR _i , -C(=O)R _i , -OC(=O)R _i , -CO ₂ R _i , -NR _g R _h , -SQ ₂ , -SO ₂ Q ₃ , or -OSO ₂ R _i ,
The above R ⁴ and R ⁵ may be combined to form a fused ring containing an oxygen atom fused to a benzene ring, and R ⁷ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms. , one or more carbon atoms in the hydrocarbon group may be substituted with an oxygen atom, nitrogen atom, or sulfur atom, and Y _B , Y _C , and Z _A to Z _C represent two adjacent groups. may combine with each other to form a 5-membered ring structure, 6-membered ring structure, or 7-membered ring structure, and when Y _B , Y _C , and Z _A to Z _C form a ring, directly bond to the ring. The hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms, the ring members of the ring structure include carbon atoms, and the ring members are selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms. The ring structure may further include one type, and the ring structure may be any of a fused ring structure, a bridged ring structure, and a spiro ring structure.
The above Y _A and Y _D each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 8 carbon atoms, and the above Y _A forms a ring structure with the above R ¹ or the above Y _B. Y _D may form a ring structure with R ¹ or Y _C , and R _g and R _h each independently represent a hydrogen atom, R _i , or -C(=O)R represents _i ,
Q ₂ represents a hydrogen atom or R _i ,
Q ₃ represents a hydroxyl group or R _i ,
R _i is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O-, -NR- and -S-. It is a group represented by a bond, has a total number of carbon atoms of 1 to 20, and may have a substituent, and R represents a hydrogen atom or a monovalent organic group. ]
<2> An optical member having a base material (i) formed from the composition according to <1> and including a layer containing a compound (Z).
<3> The optical member according to <2>, wherein the base material (i) is any one of the following base materials (i-1) to (i-3).
(i-1) A base material comprising a resin support not containing the compound (Z) and a resin layer containing the compound (Z) (i-2) A glass support and the compound (Z) (i-3) A base material that is a resin support containing the compound (Z).
<4> The optical member according to <3>, wherein the transmittance of the base material (i) satisfies the following (α) to (ε).
(α): In the wavelength range of 350 to 450 nm, there exists a wavelength where the transmittance is less than 50% to more than 50% (β): In the wavelength range of 430 to 570 nm (visible region), the average value of transmittance is 70% or more (γ ): In the wavelength range of 600 to 700 nm, there exists a wavelength where the transmittance is from more than 50% to less than 50% (δ): In the wavelength range of 700 to 800 nm, the average value of transmittance is 1% or less (ε): Wavelength of 800 to 1100 nm <5> An optical member having a dielectric multilayer film on at least one surface of the optical member according to any one of <2> to <4>, wherein the maximum value of transmittance is 40% or less.
<6> The optical member according to <5>, which satisfies the following characteristics (a) and (b).
Characteristic (a): In the wavelength range of 430 to 570 nm, the average value of transmittance when measured from the vertical direction of the optical member is 70% or more. Characteristic (b): In the wavelength range of 850 to 1200 nm, the average value of transmittance is 70% or more in the vertical direction of the optical member. <7> A solid-state imaging device comprising the optical member according to any one of <2> to <6>, wherein the average value of transmittance is 5% or less when measured from <7>.
<8> An optical sensor device comprising the optical member according to any one of <2> to <6>.
<9> A compound (Z) represented by the following formula (I).
Cn ⁺ An ^- formula (I)
[In formula (I), Cn ⁺ represents a monovalent cation represented by the following formula (II), and An ^- represents a counter anion. ]

[In formula (II), R ¹ to R ⁶ , Y _B , Y _C , and Z _A to Z _C each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a phosphoric acid group, Silyl group, R _i , -OR _i , -C(=O)R _i , -OC(=O)R _i , -CO ₂ R _i , -NR _g R _h , -SQ ₂ , -SO ₂ Q ₃ , or -OSO ₂ R _i ,
The above R ⁴ and R ⁵ may be combined to form a fused ring containing an oxygen atom fused to a benzene ring, and R ⁷ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms. , one or more carbon atoms in the hydrocarbon group may be substituted with an oxygen atom, nitrogen atom, or sulfur atom, and Y _B , Y _C , and Z _A to Z _C represent two adjacent groups. may combine with each other to form a 5-membered ring structure, 6-membered ring structure, or 7-membered ring structure, and when Y _B , Y _C , and Z _A to Z _C form a ring, directly bond to the ring. The hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms, the ring members of the ring structure include carbon atoms, and the ring members are selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms. The ring structure may further include one type, and the ring structure may be any of a fused ring structure, a bridged ring structure, and a spiro ring structure.
The above Y _A and Y _D each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 8 carbon atoms, and the above Y _A forms a ring structure with the above R ¹ or the above Y _B. Y _D may form a ring structure with R ¹ or Y _C ,
The R _g and R _h each independently represent a hydrogen atom, R _i , or -C(=O)R _i ,
Q ₂ represents a hydrogen atom or R _i ,
Q ₃ represents a hydroxyl group or R _i ,
R _i is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O-, -NR- and -S-. It is a group represented by a bond, has a total number of carbon atoms of 1 to 20, and may have a substituent, and R represents a hydrogen atom or a monovalent organic group. ]

According to one embodiment of the present invention, a composition is provided that has excellent near-infrared light shielding properties and UV resistance in the obtained optical member. Further, according to an embodiment of the present invention, an optical member having excellent near-infrared light shielding properties and UV resistance, and a solid-state imaging device and an optical sensor device including the same are provided.

The content of the present invention will be explained in detail below. Although the content of the constituent elements described below may be explained based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
In this specification, "~" indicating a numerical range is used to include the numerical values written before and after it as the lower limit and upper limit.
Further, in this specification, unless otherwise specified, each component in the composition may be contained alone or in combination of two or more.
As used herein, when a plurality of each component is present in the composition, the amount of each component in the composition means the total amount of the corresponding substance present in the composition, unless otherwise specified.
In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.
Further, in this specification, the solid content concentration (TSC) is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
The present invention will be explained in detail below.

[Composition]
The composition according to the present invention contains a resin (i) or a polymerizable compound (ii) and a compound (Z) represented by the following formula (I).

<Resin (i)>
There is no particular restriction on the resin (i), and examples thereof include thermoplastic resins, photo-curable resins, and thermosetting resins.

<<Thermoplastic resin>>
The thermoplastic resin is appropriately selected depending on the purpose, and includes, for example, polyolefin resin, polyether resin, polyimide resin, polycarbonate resin, polyester resin, polyamide (aramid) resin, polyarylate resin, and polysulfone. Examples include polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, fluorinated aromatic polymer resins, and (modified) acrylic resins.

<<Photo or thermosetting resin>>
Examples of photo- or thermosetting resins (hereinafter also simply referred to as "curable resins") include epoxy resins, allyl ester-based curable resins, silsesquioxane-based photo-curable resins, and acrylic photo-curable resins. Examples include curable resins such as resins and vinyl photocurable resins.
Further, the curable resin may be a resin that is cured by the action of heat or light.
Preferable examples of the curable resin include epoxy resins, silsesquioxane photocurable resins, and acrylic photocurable resins.

When used for applications such as optical filters, the resin (i) is preferably a transparent resin, and the transparent resin is not particularly limited as long as it does not impair the effects of the present invention. It is sufficient that the material has heat resistance to ensure moldability and withstand processing such as vapor deposition as necessary, and has a glass transition temperature (Tg) of preferably 110 to 380°C, more preferably 110°C. -370°C, more preferably 120-360°C. Further, it is more preferable that the glass transition temperature of the resin is 140° C. or higher, since a film that can be molded and processed at high temperatures can be obtained.

The transparent resin has a total light transmittance (JIS K7105) of preferably 75 to 95%, more preferably 78 to 95 when a resin plate with a thickness of 0.1 mm is formed from the resin. %, particularly preferably 80 to 95%. If a resin having a total light transmittance within this range is used, the resulting substrate will exhibit good transparency as an optical film.

The weight average molecular weight (Mw) of the transparent resin in terms of polystyrene, measured by gel permeation chromatography (GPC) method, is usually 15,000 to 350,000, preferably 30,000 to 250,000, and the number The average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.
The above Tg, Mw and Mn can be measured by a known method, for example, specifically, by the method described in the Examples.

Specific examples of transparent resins include cyclic (poly)olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, Polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate (PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin , epoxy resins, allyl ester curable resins, silsesquioxane UV curable resins, acrylic UV curable resins, and vinyl UV curable resins. More specifically, the resins described in [0077] to [0091] of International Publication No. 2016/158461 may be mentioned, and these may be synthesized by a generally known method.

<Polymerizable compound (ii)>
The polymerizable compound (ii) refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include ethylenically unsaturated groups, oxiranyl groups, oxetanyl groups, and N-alkoxymethylamino groups. Examples of the ethylenically unsaturated group include a (meth)acryloyl group and a vinyl group, and among these, a (meth)acryloyl group is preferred.
As the polymerizable compound (ii), compounds having two or more (meth)acryloyl groups and compounds having two or more N-alkoxymethylamino groups are preferable, and compounds having two or more (meth)acryloyl groups are preferable. Compounds are more preferred.
The polymerizable compound (ii) may be used alone or in combination of two or more.

<Compound (Z)>
The compound (Z) represented by the following formula (I) has a maximum absorption wavelength λmax of 1100 nm<λmax<1200 nm in the wavelength range of 400 nm to 1300 nm in dichloromethane.

Cn ⁺ An ^- formula (I)
[In formula (I), Cn ⁺ represents a monovalent cation represented by the following formula (II), and An ^- represents a counter anion. ]

[In formula (II), R ¹ to R ⁶ , Y _B , Y _C , and Z _A to Z _C each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a phosphoric acid group, Silyl group, R _i , -OR _i , -C(=O)R _i , -OC(=O)R _i , -CO ₂ R _i , -NR _g R _h , -SQ ₂ , -SO ₂ Q ₃ , or -OSO ₂ R _i ,
The above R ⁴ and R ⁵ may be combined to form a fused ring containing an oxygen atom fused to a benzene ring, and R ⁷ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms. , one or more carbon atoms in the hydrocarbon group may be substituted with an oxygen atom, nitrogen atom, or sulfur atom, and Y _B , Y _C , and Z _A to Z _C represent two adjacent groups. may combine with each other to form a 5-membered ring structure, 6-membered ring structure, or 7-membered ring structure, and when Y _B , Y _C , and Z _A to Z _C form a ring, directly bond to the ring. The hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms, the ring members of the ring structure include carbon atoms, and the ring members are selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms. The ring structure may further include one type, and the ring structure may be any of a fused ring structure, a bridged ring structure, and a spiro ring structure.
The above Y _A and Y _D each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 8 carbon atoms, and the above Y _A forms a ring structure with the above R ¹ or the above Y _B. Y _D may form a ring structure with R ¹ or Y _C , and R _g and R _h each independently represent a hydrogen atom, R _i , or -C(=O) R _i , Q ₂ represents a hydrogen atom or R _i , Q ₃ represents a hydroxyl group or R _i ,
R _i is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O-, -NR- and -S-. It is a group represented by a bond, has a total number of carbon atoms of 1 to 20, and may have a substituent, and R represents a hydrogen atom or a monovalent organic group. ]

<<Halogen atom>>
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Among these, the halogen atom is preferably a fluorine atom, a chlorine atom, or a bromine atom.

<<R _i >>
The hydrocarbon group having 1 to 20 carbon atoms in R _i is not particularly limited, and may be a saturated or unsaturated hydrocarbon group, or a linear, branched or cyclic hydrocarbon group. It's okay.
Examples of the above hydrocarbon group having 1 to 20 carbon atoms include an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred examples include groups.

The substituent is preferably a halogen-substituted alkyl group, and in the halogen-substituted alkyl group, some or all of the hydrogen atoms contained in the alkyl group are halogen atoms such as fluorine, chlorine, bromine, and iodine atoms. Examples include groups substituted with .
The above halogen-substituted alkyl group is preferably a halogen-substituted alkyl group having 1 to 12 carbon atoms, more preferably a halogen-substituted alkyl group having 1 to 10 carbon atoms, and a halogen-substituted alkyl group having 1 to 5 carbon atoms. More preferably, it is a group.
Examples of the halogen-substituted alkyl group having 1 to 5 carbon atoms include trichloromethyl group, trifluoromethyl group, 1,1-dichloroethyl group, pentachloroethyl group, pentafluoroethyl group, heptachloropropyl group, heptafluoropropyl group. Examples include groups.
Among these, the halogen-substituted alkyl group having 1 to 5 carbon atoms is preferably a fluorine-substituted alkyl group having 1 to 5 carbon atoms, and particularly preferably a pentafluoroethyl group or a trifluoromethyl group.

The alicyclic hydrocarbon group having 3 to 20 carbon atoms may be a saturated or unsaturated alicyclic hydrocarbon group, and may be monocyclic or polycyclic. The polycycle may be a bridged polycycle or a spirocycle.
The number of ring members of the alicyclic hydrocarbon group is not particularly limited, but is preferably from 3 to 14, more preferably from 3 to 8, and even more preferably from 3 to 6.
The alicyclic hydrocarbon group having 3 to 20 carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 14 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. Preferably, an alicyclic hydrocarbon group having 3 to 10 carbon atoms is more preferable.

Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclohexyl group, t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, -cyclohexenyl group, norbornane group, adamantyl group, etc.

The aromatic hydrocarbon group having 6 to 20 carbon atoms may be monocyclic or polycyclic. The aromatic hydrocarbon group having 6 to 20 carbon atoms is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenylene group.

The substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms in R _i is preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms. is an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group (Pent ), hexyl group (Hex), 1,1-dimethylbutyl group, octyl group (Oct), nonyl group, decyl group, dodecyl group, more preferably methyl group, ethyl group, n-propyl group, isopropyl group , n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, 1,1-dimethylbutyl group, and octyl group.
The unsaturated hydrocarbon group having 1 to 20 carbon atoms in R _i is, for example, a vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, Alkenyl groups such as 2-pentenyl group and hexenyl group; alkynyl groups such as ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group and hexynyl group.

<<A group represented by a bond between a hydrocarbon group and at least one structure selected from the group consisting of -O-, -NR-, and -S-, and has a total number of carbon atoms of 1 to 20. A group which may have a substituent>>
Examples of the group represented by a bond between a hydrocarbon group and -O- include a polyoxyalkylene group.
A polyoxyalkylene group is a group represented by a repeating unit of an alkylene group and -O-, and the alkylene groups may be the same or different.
The alkylene group in the polyoxyalkylene group preferably has 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, and the alkylene group is preferably an ethylene group or a propylene group.
When the polyoxyalkylene group includes alkylene groups having different carbon numbers, the polyoxyalkylene group may be a random bond or a block bond.
The terminal of the polyoxyalkylene group is not particularly limited, and may be a hydrogen atom or an alkyl group.
Examples of the group represented by a bond between a hydrocarbon group and -O- include a methoxypolyethylene glycol group, a methoxypolypropylene glycol group, and a polyethylene glycol group.

As a group represented by a bond between a hydrocarbon group and -NR- (R represents a hydrogen atom or a monovalent organic group), a group represented by a bond between a hydrocarbon group and -NR- (R is (representing a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms), more specifically, a monoalkylamino group, a dialkylamino group, a monoalkylaminoalkylene group, a dialkylaminoalkylene group, a monoalkylaminoarylene group , dialkylaminoarylene group, monoarylamino group, monoarylmonoalkylamino group, diarylamino group, monoarylaminoalkylene group, monoarylmonoalkylaminoalkylene group, diarylaminoalkylene group, diarylamino group, monoarylaminoarylene group , a monoarylmonoalkylaminoarylene group, a diarylaminoarylene group, and the like.

Examples of the group represented by a bond between a hydrocarbon group and -S- include an alkylthioalkylene group, an alkyl(polythio)alkylene group, and an alkylthio group.

<<-OR _i >>
R _i in -OR _i has the same meaning as R _i above, and is preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 10 aliphatic hydrocarbon groups or alicyclic hydrocarbon groups having 3 to 12 carbon atoms, more preferably substituted or unsubstituted hydrocarbon groups having 1 to 6 carbon atoms or alicyclic groups having 3 to 12 carbon atoms. The formula is a hydrocarbon group.
The substituent is preferably a halogen-substituted alkyl group, more preferably a fluorine-substituted alkyl group.
-OR _i is preferably a methoxy group (OMe), an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group (OBu), a methoxymethyl group, a methoxyethyl group, a pentyloxy group, a hexyloxy group, an octyloxy group , phenoxy group, 4-methylphenoxy group, cyclopentyloxy group, and cyclohexyloxy group.

<<-C(=O)R _i >>
R _i in -C(=O)R _i has the same meaning as R _i above, and is preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group. An aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably substituted or unsubstituted carbon atoms. A hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
-C(=O)R _i is preferably, for example, a substituted or unsubstituted acyl group having 1 to 20 carbon atoms. The substituent is preferably a halogen-substituted alkyl group, more preferably a fluorine-substituted alkyl group. Among these, preferred are acyl groups having 1 to 9 carbon atoms, and more preferred are acetyl group, propionyl group, butyryl group, isobutyryl group, benzoyl group, 4-propylbenzoyl group, and trifluoromethylcarbonyl group.

<<-CO ₂ R _i >>
-CO ₂ R _i has the same meaning as R _i above, and is preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. A hydrocarbon group, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms. -CO ₂ R _i includes, for example, a substituted or unsubstituted alkoxycarbonyl group having 1 to 20 carbon atoms. Among these, preferred are alkoxycarbonyl groups having 1 to 9 carbon atoms, and more preferred are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, and 2-trifluoromethylethoxy. Carbonyl group, 2-phenylethoxycarbonyl group.

<<-NR _g R _h >>
In -NR _g R _h , R _g and R _h each independently represent a hydrogen atom, R _i , or -C(=O)R _i .
R _i and -C(=O)R _i have the same meanings as the above R _i and -C(=O)R _i , and preferred embodiments are also the same. Among these, a hydrogen atom or R _i is preferred, and a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferred.

<<-SQ ₂ >>
-SQ ₂ represents a hydrogen atom or R _i . -R _i in SQ ₂ has the same meaning as R _i above, and preferred embodiments are also the same. Among these, a hydrogen atom or R _i is preferred, and a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferred.

<<-SO ₂ Q ₃ >>
In -SO ₂ Q ₃ , Q ₃ represents a hydroxyl group or R _i . R _i in -SO ₂ Q ₃ has the same meaning as R _i above, and preferred embodiments are also the same. Among these, a hydrogen atom or R _i is preferred, and a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferred.

<<-OSO ₂ R _i >>
In -OSO ₂ R _i , R _i has the same meaning as R _i above, and preferred embodiments are also the same.

<<Z _A and Z _C >>
The Z _A and Z _C are each independently more preferably a hydrogen atom.

＜＜Z _B ＞＞
Z _B is preferably a hydrogen atom, a chlorine atom, a dimethylamino group, a diethylamino group, a dibutylamino group, a diphenylamino group (-NPh ₂ ), a methylphenylamino group, a methyl group, a phenyl group, a phenylthio group (PhS-) , 4-methylphenoxy group (O-(4-tolyl)), -S-(4-tolyl) group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-furyl group, 3-furyl group , 2-thienyl group, or 3-thienyl group, more preferably dimethylamino group, diethylamino group, dibutylamino group, diphenylamino group (-NPh ₂ ), methylphenylamino group, methyl group, phenyl group, or , phenylthio group (PhS-).

<<R ¹ to R ³ and R ⁶ >>
R ¹ to R ³ and R ⁶ are each independently preferably a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or R _i , more preferably a hydrogen atom or a halogen atom, and even more preferably hydrogen It is an atom.

<<R ⁴ and R ⁵ >>
R ⁴ and R ⁵ are each independently preferably a hydrogen atom, a halogen atom, R _i or -OR _i , or R ⁴ and R ⁵ are bonded and formed by condensation to a benzene ring. A fused ring containing an oxygen atom, more preferably R _i , -OR _i , or a fused ring containing an oxygen atom formed by bonding R ⁴ and R ⁵ to a benzene ring. .
R _i in R ⁴ and R ⁵ is, for example, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, etc. are preferably mentioned.
-OR _i in R ⁴ and R ⁵ has the same meaning as -OR _i above, and preferred embodiments are also the same.
The number of ring members of the fused ring containing an oxygen atom formed by bonding R ⁴ and R ⁵ to a benzene ring is preferably 4 to 7, more preferably 5 or 6.
The fused ring containing an oxygen atom formed by bonding R ⁴ and R ⁵ to a benzene ring may have a substituent, for example, a substituent having 1 to 10 carbon atoms. Examples include hydrocarbon groups, halogen atoms, halogenated alkyl groups, and the like.

<<R ⁷ >>
R ⁷ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms, even if one or more carbon atoms in the hydrocarbon group are substituted with an oxygen atom, nitrogen atom, or sulfur atom. good.
The substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms may be a saturated or unsaturated hydrocarbon group, or may be a linear, branched or cyclic hydrocarbon group.
Examples of substituted or unsubstituted hydrocarbon groups having 1 to 25 carbon atoms include aliphatic hydrocarbon groups having 1 to 25 carbon atoms, alicyclic hydrocarbon groups having 3 to 25 carbon atoms, and alicyclic hydrocarbon groups having 6 to 25 carbon atoms. Preferred examples include aromatic hydrocarbon groups.
The substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms is preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or , an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms. 6 to 12 aromatic hydrocarbon groups.
The substituent is preferably a halogen-substituted alkyl group, more preferably a fluorine-substituted alkyl group.
The hydrocarbon group in which one or more carbon atoms are substituted with an oxygen atom, nitrogen atom, or sulfur atom is preferably a group in which one or more carbon atoms in the hydrocarbon group are substituted with an oxygen atom.
The group in which one or more carbon atoms in the hydrocarbon group are substituted with oxygen atoms has the same meaning as the group represented by the bond between the hydrocarbon group and -O- in R _i above, and preferred embodiments are also The same is true.

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

Although Y _A may form a ring structure with R ¹ or Y _B , it is preferable not to form a ring structure.
Y _D may form a ring structure with R ¹ or Y _C , but preferably does not form a ring structure.

<<Y _B and Y _C >>
Y _B and Y _C are each independently preferably a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, a -NR _g R _h group, an amide group (-NR _g R _h ), an imide group, or a cyano group. group, silyl group, R _i , -N=N-Q ₁ , -SQ ₂ , -SO ₂ Q ₃ , or a 5-membered ring structure, 6-membered, formed by mutual bonding of Y _B and Y _C A ring structure or a 7-membered ring structure (the ring member may include one selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom), and more preferably a hydrogen atom, a halogen atom, a hydroxyl group, Carboxy group, nitro group, -NR _g R _h group, amide group (-NR _g R _h ), imido group, cyano group, silyl group, R _i , -N=N-Q ₁ , -SQ ₂ , -SO ₂ Q ₃ or an aromatic hydrocarbon group having 6 to 14 carbon atoms formed by mutual bonding of Y _B and Y _C ; may contain at least one nitrogen atom, oxygen atom or sulfur atom as a ring member A 5- to 6-membered alicyclic hydrocarbon group; or a 5- to 7-membered heteroaromatic group, more preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, 5- or 6-membered alicyclic hydrocarbon group formed by mutual bonding of Y _B and Y _C , particularly preferred. is a 5- or 6-membered alicyclic hydrocarbon group formed by bonding a hydrogen atom, a methyl group, a tert-butyl group, Y _B and Y _C to each other.

When Y _B and Y _C are 5- or 6-membered alicyclic hydrocarbon groups formed by bonding with each other, formula (II) is preferably represented by the following formula (C-1) or ( C-2).

In formulas (C-1) and (C-2), Z _A to Z _C , Y _A , Y _D , and R ¹ to R ⁷ are Z _A to Z _C , Y in formula (II) above; It has the same meaning as _A , Y _D , and R ¹ to R ⁷ , and its preferred embodiments are also the same.

＜＜An ^- ＞＞
An ^- is not particularly limited as long as it is a monovalent anion, but preferably chloride ion, bromide ion, iodine ion, perchlorate anion, tristrifluoromethanesulfonylmethide anion, tetrafluoroborate anion, hexafluoroline More preferred examples include acid anions, bis(trifluoromethanesulfonyl)imide anions, trifluoromethanesulfonic acid anions, tetrakis(pentafluorophenyl)borate anions, and tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anions. is bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonate anion, tristrifluoromethanesulfonylmethide anion, tetrakis(pentafluorophenyl)borate anion, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion More preferably, bis(trifluoromethanesulfonyl)imide anion, tristrifluoromethanesulfonylmethide anion, tetrakis( These include pentafluorophenyl)borate anion and tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion, particularly preferably tetrakis(pentafluorophenyl)borate anion.

Unlike squarylium compounds, polymethine compounds, diimonium compounds, etc. that have been used conventionally, the compound (Z) used in the present invention is an ionic compound containing a specific cation. By using such an ionic compound, an optical filter with unprecedented UV resistance can be obtained.

The maximum absorption wavelength λmax of compound (Z) is 1100 nm<λmax<1200 nm, preferably 1100 nm<λmax<1155 nm, in the wavelength range of 400 nm to 1300 nm in dichloromethane.
When the maximum absorption wavelength λmax of the compound (Z) is within such a range, unnecessary near-infrared rays that cause various ghosts can be efficiently cut.

Compound (Z) can be synthesized by a generally known method, for example, with reference to the synthesis method described in Japanese Patent No. 5941844.

<Composition>
The content of compound (Z) in the composition is preferably 0.01 to 2.0 parts by mass, more preferably 0 parts by mass, based on 100 parts by mass of resin (i) or polymerizable compound (ii). 0.02 to 1.75 parts by weight, particularly preferably 0.03 to 1.5 parts by weight.
When the content of the compound (Z) is within the above range, when used for optical applications such as optical filters, it will have excellent UV resistance, with both good near-infrared absorption characteristics and high visible light transmittance. Optical filters can be obtained.

In addition to the resin, the composition may also contain a known solvent described below and components other than the compound (Z), which are appropriately selected depending on the purpose. Furthermore, the method for preparing the composition is not particularly limited as long as it can be mixed uniformly.

[Optical member]
The optical member according to the present invention has a base material (i) formed from a composition and including a layer containing a compound (Z).
The base material (i) may be a single layer or a multilayer.

The base material (i) is preferably an optical member that is any one of the following base materials (i-1) to (i-3).
(i-1) A base material comprising a resin support not containing the compound (Z) and a resin layer containing the compound (Z) (i-2) A glass support and a resin support containing the compound (Z) (i-3) Base material that is a resin support containing the compound (Z) The descriptions of (i-1) to (i-3) are as follows: ” and/or one or more resin layers containing the compound (Z).

<<(i-1)>>
The base material (i-1) is, for example, formed from a composition containing the compound (Z) and a resin or a polymerizable compound on a resin substrate formed from a resin composition that does not contain the compound (Z). Examples include a base material on which a resin layer is laminated.

<<(i-2)>>
As the base material (i-2), for example, a resin layer formed from a composition containing the compound (Z) and a resin such as a curable resin is laminated on a glass support that does not contain the compound (Z). Examples include base materials.
The glass support is preferably a glass support that does not contain a near-infrared absorber from the viewpoint of the strength of the base material and the ability to reduce the thickness of the base material.On the other hand, from the viewpoint of reducing the near-infrared transmittance, a glass support containing CuO-containing phosphoric acid Glass supports containing near-infrared absorbers selected from the group consisting of salt glasses and CuO-containing fluorophosphate glasses are preferred.

<<(i-3)>>
The base material (i-3) is, for example, a base material made of a resin layer formed from a composition containing the compound (Z) and a resin (hereinafter also referred to as "resin substrate (i-3)"). etc.

As a method for forming a resin layer made of the above composition on a support, the above composition may be applied onto the support by a known coating method. Examples of the coating method include a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), a bar coating method, and the like.

Examples of the supports used for the substrates (i-1) and (i-2) include glass plates, steel belts, steel drums, and the transparent resin supports described above (for example, polyester films, cyclic olefin resins). film).

When using a glass support, a glass support that does not contain a near-infrared absorber is preferable from the viewpoint of the strength of the substrate and the ability to reduce the thickness of the substrate, and a CuO-containing phosphate glass is preferable from the viewpoint of reducing near-infrared transmittance. A glass support containing a near-infrared absorber selected from the group consisting of CuO-containing fluorophosphate glass and CuO-containing fluorophosphate glass is particularly preferred.

In the optical member, it is preferable that the transmittance of the base material (i) satisfies the following (α) to (ε). Note that the transmittance of the base material (i) in (α) to (ε) above means the transmittance measured from the vertical direction of the base material (i).
(α): Preferably, there is a wavelength in which the transmittance is less than 50% to more than 50% in the wavelength range of 350 to 450 nm, more preferably in the wavelength range of 375 to 435 nm, and still more preferably less than 50% in the wavelength range of 400 to 420 nm. There is a wavelength that exceeds 50% of the wavelength.

(β): In the wavelength range of 430 to 570 nm (visible region), the average value of transmittance is preferably 70% or more, more preferably 72.5% or more, and still more preferably 75% or more. Since the higher the average value of the transmittance, the higher the average value, the upper limit is not particularly limited and may be 100%.

(γ): It is preferable that there is a wavelength in which the transmittance is from more than 50% to less than 50% in the wavelength range of 600 to 700 nm, more preferably in the range of 615 to less than 690 nm, even more preferably in the range of 620 to 680 nm, the transmittance is 50%. There are wavelengths that range from more than 50% to less than 50%.
In the wavelength range of 600 to 700 nm, if there is a wavelength where the transmittance is from more than 50% to less than 50%, a filter that has both broad and steep near-infrared absorption and high transmittance can be obtained, and unnecessary near-infrared rays can be selected. In addition to being able to cut efficiently, when a dielectric multilayer film is formed on the substrate (i), it is possible to reduce the incidence angle dependence of optical properties near the visible wavelength to near-infrared wavelength region. can.

(δ): At a wavelength of 700 to 800 nm, the average value of transmittance is preferably 1% or less, more preferably 0.75% or less, and still more preferably 0.5% or less.

(ε): At a wavelength of 800 to 1100 nm, the maximum value of transmittance is preferably 40% or less, more preferably 35% or less, and still more preferably 30% or less.

The shortest wavelength (IR ₅₀ ) at which the transmittance measured from the vertical direction of the substrate (i) in the wavelength range of 600 nm to 700 nm is from more than 50% to 50% or less may be any of the following. The wavelength is preferably from 610 to less than 700 nm, more preferably from 620 to 690 nm, particularly preferably from 630 to 685 nm.

If the (IR ₅₀ ) of the base material (i) is within the above range, a filter can be obtained that has both broad and steep near-infrared absorption and high transmittance, and selectively and efficiently cuts unnecessary near-infrared rays. In addition, when a dielectric multilayer film is formed on the substrate (i), it is possible to reduce the incidence angle dependence of optical properties near the visible wavelength to near-infrared wavelength region, and eliminate ghosting and color shading. It is possible to obtain a good camera image with reduced .

The thickness of the base material (i) can be appropriately selected depending on the desired use, and is not particularly limited. The thickness of the base material (i-1) of the layer, and the total thickness in the case of laminated base materials (i-2) and (i-3), is preferably 20 to 230 μm, more preferably 35 to 220 μm, particularly preferably 50 to It is 210 μm.

When the thickness of the base material (i) is within the above range, the optical filter using the base material (i) can be made thinner and lighter, and can be suitably used in various applications such as solid-state imaging devices. can. In particular, when the base material (i) made of the transparent resin substrate (i-1) is used for a lens unit such as a camera module, it is preferable because the lens unit can be made lower in height and lighter in weight. .

<Other dyes (X)>
The base material (i) may further contain other dyes (X) that do not correspond to the compound (Z).

Other dyes (X) include, for example, polymethine compounds other than compound (Z), squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, octaphylline compounds, and diimonium compounds. , pyrrolopyrrole compounds, boron dipyrromethene (BODIPY) compounds, perylene compounds, and metal dithiolate compounds. These contents are not particularly limited. The dye (X) may be included in the resin layer or substrate containing the compound (Z), or may be provided separately as another resin layer, or may be included in the resin substrate used as a support. It may be

<Other ingredients>
The base material (i) may further contain additives such as ultraviolet absorbers and antioxidants within a range that does not impair the effects of the present invention. These other components may be used alone or in combination of two or more.

Examples of the ultraviolet absorber include azomethine-based compounds, indole-based compounds, benzotriazole-based compounds, triazine-based compounds, anthracene-based compounds, cyanoacrylate-based compounds, and compounds described in JP 2019-014707A, etc. . Among these, azomethine compounds, indole compounds, benzotriazole compounds, and cyanoacrylate compounds are particularly preferred from the viewpoint of absorption wavelength and compound stability.

By containing an ultraviolet absorber, it is possible to easily obtain an optical filter with less dependence on the angle of incidence even in the near-ultraviolet wavelength region, and when this optical filter is used in an imaging device, etc., the obtained camera image quality is better. becomes.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, and tetrakis. Examples include [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane and tris(2,4-di-t-butylphenyl)phosphite.

In addition, commercially available products include, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-60, ADEKA STAB AO-80, ADEKA STAB PE-8, ADEKA STAB PE- 36, Adeka Stab HP-10, Adeka Stab 2112, Adeka Stab 1178, Adeka Stab 1500, Adeka Stab C, Adeka Stab 135A, Adeka Stab 3010, Adeka Stab TPP, Adeka Stab AO-4125, Adeka Stab AO-503, Johoku Kagaku Co., Ltd. JP-360, JP-351 , JP-3CP, JP-308E, JP-310, JP-312L, JP-333E, JP-308, JPM-311, JPM-313, JPH-1200, JP-318E, JP-650, JC-356, BASF Tinuvin (registered trademark) 360, Tinuvin (registered trademark) 111FDL, Tinuvin (registered trademark) 123, Tinuvin (registered trademark) 144, Tinuvin (registered trademark) 152, Tinuvin (registered trademark) 249, Tinuvin (registered trademark) 292, Tinuvin (registered trademark) 770DF, Tinuvin (registered trademark) 5100, Irganox (registered trademark) 1010, Irganox (registered trademark) 1035, Irganox (registered trademark) 1076, Irganox (registered trademark) 1135, Irganox (registered trademark) 1720, etc. Can be mentioned.

Note that these additives may be mixed together with the transparent resin etc. when producing the base material (i), or may be added when synthesizing the resin. Further, it may be contained in a resin layer that does not contain the compound (Z). The amount added is appropriately selected depending on the desired properties, but is usually 0.01 to 5.0 parts by mass, preferably 0.01 to 5.0 parts by mass, per 100 parts by mass of the transparent resin (total in the case of multilayer). It is 0.05 to 2.0 parts by mass.

<Method for manufacturing base material (i)>
When the base material (i) is a base material containing the resin substrate (i-3), the resin substrate (i) can be formed, for example, by melt molding or cast molding, and further includes the necessary Accordingly, by coating with a coating agent such as an antireflection agent, a hard coating agent, and/or an antistatic agent after molding, a base material on which an overcoat layer is laminated can be manufactured.

When the base material (i) is a base material in which a resin layer such as an overcoat layer made of a curable resin containing the compound (Z) is laminated on a glass support or a base resin support. For example, by melt molding or cast molding a resin solution containing the compound (Z) on a glass support or a base resin support, preferably by a method such as spin coating, slit coating, or inkjet coating. By subsequently removing the solvent by drying and further performing light irradiation or heating as necessary, a base material in which a resin layer is formed on a glass support or a resin support serving as a base can be manufactured.

<<Melting molding>>
Specifically, the melt-molding method includes a method of melt-molding a pellet obtained by melt-kneading a resin and a compound (Z), etc.; a method of melt-molding a resin composition containing a resin and a compound (Z); or a method of melt-molding pellets obtained by removing the solvent from a resin composition containing the compound (Z), a resin, and a solvent. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

＜＜Cast molding＞＞
The cast molding is a method in which a resin composition containing the compound (Z), a resin, and a solvent is cast onto a suitable support and the solvent is removed; It can also be carried out by casting a curable composition containing a curable resin onto a suitable support, removing the solvent, and then curing by an appropriate method such as ultraviolet irradiation or heating.

When the base material (i) is a base material made of a resin substrate (i-3) containing the compound (Z), the base material (i) is coated from the support after cast molding. It can be obtained by peeling off. Further, the base material (i) may include a resin layer such as an overcoat layer made of a curable resin containing the compound (Z) on a support such as a glass support or a base resin support. In the case of laminated base materials (i-1) and (i-2), the base material (i) can be obtained by not peeling off the coating film after cast molding.

Furthermore, an optical component made of glass plate, quartz, transparent plastic, etc. is coated with the resin composition and the solvent is dried, or the curable composition is coated, cured, and dried. A resin layer can also be formed on the component.

The amount of residual solvent in the resin layer (including the resin substrate (i-3)) obtained by the above method is preferably as small as possible. Specifically, the residual solvent amount is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably It is 0.5% by mass or less. When the amount of residual solvent is within the above range, a resin layer that is not easily deformed or changes in properties and that can easily exhibit desired functions can be formed.

The content of compound (Z) is preferably 0.01 to 2 parts by mass based on 100 parts by mass of the resin, regardless of whether the base material (i) is any of the base materials (i-1) to (i-3). 0 parts by weight, more preferably 0.02 to 1.5 parts by weight, particularly preferably 0.03 to 1.0 parts by weight.
When the content of the compound (Z) as the base material (i) is within the above range, an optical filter with excellent UV resistance that has both good near-infrared absorption characteristics and high visible light transmittance can be obtained. be able to.

The optical member of the present invention can be suitably used as an optical filter. The optical filter may be comprised only of the above-mentioned optical member, or may have the above-mentioned optical member and a dielectric multilayer film described below from the viewpoint of UV resistance and infrared shielding property.

When the optical member is used in a solid-state image sensor or the like, it is preferable that the optical member has a high visible light transmittance, and a low transmittance in the near-infrared wavelength region is preferable.
From this point of view, it is preferable that the optical member of the present invention has a dielectric multilayer film and satisfies characteristics (a) and (b).
Characteristic (a): In the wavelength range of 430 to 570 nm, the average value of transmittance when measured from the vertical direction of the optical member is preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, especially Preferably it is 83% or more, most preferably 85% or more.

Characteristic (b): In the wavelength range of 850 to 1200 nm, the average value of transmittance when measured from the vertical direction of the optical member is preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, especially Preferably it is 2% or less. If the average transmittance is within this range in this wavelength region, when the optical member of the present invention is used for a solid-state image sensor, near-infrared rays can be sufficiently cut and excellent color reproducibility can be achieved, which is preferable. .

When the optical member of the present invention is used in a solid-state imaging device having a near-infrared sensing function, the optical member has a light blocking zone Za, a light transmitting zone Zb, and a light blocking zone Zc in the wavelength range of 700 to 1100 nm. It is preferable. However, the wavelength of each band satisfies Za<Zb<Zc. Note that the above-mentioned "Za<Zb<Zc" only needs to satisfy this formula for the center wavelength of each band, and the long wavelength side or short wavelength side of each band may partially overlap with other bands. For example, the long wavelength side of Za and the short wavelength side of Zb may partially overlap. The maximum transmittance of the light (near infrared) transmission band Zb is preferably high, and the minimum transmittance of the light blocking bands Za and Zc is preferably low.

The thickness of the optical member of the present invention may be appropriately selected depending on the desired use, but according to the trend of thinning and weight reduction of solid-state imaging devices in recent years, the thickness of the optical filter of the present invention may also be thin. is preferred. Since the optical member of the present invention includes the base material (i), it can be made thinner.

In the optical member of the present invention, the thickness of the resin layer in the base materials (i-1) and (i-2) is preferably 20 μm or less, more preferably 1 to 15 μm, and even more preferably 5 to 10 μm. be.

[Other functional membranes]
The optical member of the present invention may use the base material (i) as an optical filter, but may have other functional films as long as the effects of the present invention are not impaired.
As the functional film, for example, a dielectric multilayer film may be provided.
When the optical member of the present invention includes a dielectric multilayer film, it is preferable that the dielectric multilayer film is provided on at least one surface of the optical member.

The dielectric multilayer film has the ability to reflect near-infrared rays. When a dielectric multilayer film is provided on one side of an optical member, it is excellent in manufacturing cost and ease of manufacturing. Further, when a dielectric multilayer film is provided on both sides, an optical member that has high strength and is less likely to warp or twist can be obtained. When applying the optical member to a solid-state image pickup device, it is preferable that the optical member has less warpage and twist, and therefore it is preferable to provide a dielectric multilayer film on both sides of the base material (i).

Such a dielectric multilayer film includes one in which high refractive index material layers and low refractive index material layers are alternately laminated. As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of 1.7 to 2.5 is usually 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 main components, and tin oxide and/or cerium oxide. Examples include those containing a small amount (for example, 0 to 10% by mass of the main component) of the like.

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

There is no particular restriction on the method of laminating the high refractive index material layer and the low refractive index material layer as long as a dielectric multilayer film is formed by laminating these material layers. For example, high refractive index material layers and low refractive index material layers are alternately laminated directly on the base material (i) by a CVD method, a sputtering method, a vacuum evaporation method, an ion-assisted evaporation method, an ion plating method, etc. A dielectric multilayer film can be formed.

The thickness of each layer of the high refractive index material layer and the low refractive index material layer is usually preferably 0.1λ to 0.5λ, where λ (nm) is the near-infrared wavelength to be blocked. The value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness is within this range, the product (n x d) of the refractive index (n) and the film thickness (d) is the optical film thickness (nd) calculated by λ/4, and the high refractive index material layer and Since the thickness of each layer of the low refractive index material layer is approximately the same, it tends to be possible to easily control the blocking and transmission of specific wavelengths due to the relationship of optical properties of reflection and refraction.

The total number of laminated layers of high refractive index material layers and low refractive index material layers in the dielectric multilayer film is preferably 6 to 70 layers, more preferably 10 to 60 layers for the entire optical filter. If the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of laminated layers are within the above ranges, sufficient manufacturing margins can be secured, and warping of the optical filter and cracks in the dielectric multilayer film can be reduced. can do.

The type of material constituting the high refractive index material layer and the low refractive index material layer, the thickness of each layer of the high refractive index material layer and the low refractive index material layer, the order of lamination, and the number of laminated layers according to the absorption characteristics of the compound (Z). If selected appropriately, it will have sufficient transmittance in the visible region, sufficient light-cutting characteristics in the near-infrared wavelength region, and reduce reflectance when near-infrared rays are incident from an oblique direction. Optical filters can be provided.

Here, in order to optimize the above conditions, for example, optical thin film design software (e.g., Essential Macleod, manufactured by Thin Film Center) is used to achieve both the antireflection effect in the visible region and the light ray cutting effect in the near-infrared region. Just set the parameters like this. In the case of the above software, for example, when designing the first optical layer, the target transmittance for the wavelength range of 400 to 700 nm is set to 100%, the Target Tolerance value is set to 1, the target transmittance for the wavelength range of 705 to 950 nm is set to 0%, Examples of parameter setting methods include setting the Target Tolerance value to 0.5. These parameters can also be used to change the Target Tolerance value by further dividing the wavelength range into smaller areas according to various characteristics of the base material (i).

In addition, as a functional film, an antireflection film, hard coat film, or antistatic film may be provided as appropriate for the purpose of improving the surface hardness of the substrate (i), improving chemical resistance, preventing static electricity, and eliminating scratches. can.

The optical member of the present invention may include one layer or two or more layers made of the functional film. When the optical member of the present invention includes two or more layers made of the functional film, it may include two or more similar layers or two or more different layers.

The method for laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent, and/or an antistatic agent is applied to the base material (i) by melt molding or cast molding in the same manner as described above. Examples include methods.

It can also be produced by applying a curable composition containing the coating agent and the like onto the substrate (i) using a bar coater or the like, and then curing it by irradiating ultraviolet rays or the like.
Examples of the coating agent include ultraviolet (UV)/electron beam (EB) curable resins and thermosetting resins, and specifically, vinyl compounds, urethane-based, urethane-acrylate-based, acrylate-based, and epoxy and epoxy acrylate resins. Examples of the curable composition containing these coating agents include vinyl-based, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based, and epoxy acrylate-based curable compositions.

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

In the curable composition, the blending ratio of the polymerization initiator is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, when the total amount of the curable composition is 100% by mass. More preferably, it is 1 to 5% by mass. When the blending ratio of the polymerization initiator is within the above range, the curing properties and handleability of the curable composition are excellent, and it is possible to obtain functional films such as antireflection films, hard coat films, and antistatic films having desired hardness. can.

Furthermore, an organic solvent may be added to the curable composition as a solvent, and known organic solvents can 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; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, and propylene. Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene, and xylene; Dimethylformamide, dimethylacetamide, N- Amides such as methylpyrrolidone can be mentioned.
These solvents may be used alone or in combination of two or more.

The thickness of the functional film is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, particularly preferably 0.7 to 5 μm.
In addition, in order to improve the adhesion between the base material (i) and various functional films and between functional films, the surface of the base material (i) or the functional film may be subjected to surface treatment such as corona treatment or plasma treatment. It's okay.

[Applications of optical components]
By applying the compound (Z) having a specific structure, the optical member of the present invention has a high visible light transmittance and a high transmittance in the red region in the visible region, and has a steep and highly linear absorption curve. It can be suitably used as an optical member for an optical filter, an optical member for a solid-state imaging device, and an optical member for an optical sensor device, which has the characteristic of selectively and broadly absorbing near-infrared light.

By using such an optical filter, it is possible to obtain a good camera image with good RGB balance and reduced ghosting and color shading. Therefore, it is useful for correcting the visibility of solid-state imaging devices such as CCDs and CMOS image sensors in camera modules. In particular, digital still cameras, smartphone cameras, mobile phone cameras, digital video cameras, wearable device cameras, PC cameras, surveillance cameras, automobile cameras, televisions, car navigation systems, personal digital assistants, video game consoles, and portable game consoles. , fingerprint authentication systems, digital music players, etc. Furthermore, it is useful as a heat ray cut filter attached to glass plates of automobiles, buildings, etc.

[Solid-state imaging device]
The solid-state imaging device of the present invention includes the optical member of the present invention. Here, the solid-state imaging device is an image sensor equipped with a solid-state imaging element such as a CCD or CMOS image sensor, and specifically includes a digital still camera, a smartphone camera, a mobile phone camera, a wearable device camera, and a digital camera. It can be used for applications such as video cameras. For example, the camera module of the present invention includes the optical member of the present invention.

[Optical sensor device]
The optical sensor device according to the present invention is not particularly limited as long as it includes the above optical member, and may have a conventionally known configuration. The optical sensor device is preferably an ambient light sensor device.

Examples of the optical sensor device include devices having an optical filter, a photoelectric conversion element, a light diffusion film, and the like. Here, the optical sensor is a sensor that can sense the brightness and color tone of the surroundings (for example, strong red in the evening). It is possible to control the colors and colors.

EXAMPLES Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples at all. Note that "parts" means "parts by mass" unless otherwise specified. Moreover, the measurement method of each physical property value and the evaluation method of physical property are as follows.

<Molecular weight>
The molecular weight of the resin was measured by the method (a) or (b) below, taking into consideration the solubility of each resin in a solvent. (a) Using a gel permeation chromatography (GPC) device manufactured by WATERS (Model 150C, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene), weight average molecular weight in terms of standard polystyrene. (Mw) and number average molecular weight (Mn) were measured. (b) Weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a Tosoh GPC device (HLC-8220 model, column: TSKgelα-M, developing solvent: THF).

<Glass transition temperature (Tg)>
Measurement was performed using a differential scanning calorimeter (DSC6200) manufactured by SII Nanotechnologies Co., Ltd. at a temperature increase rate of 20° C. per minute under a nitrogen stream.

<Spectral transmittance>
The transmittance of the optical member in each wavelength range was measured using a spectrophotometer (manufactured by JASCO Corporation, model number: V-7300). The results are listed in Table 3.

(Near-infrared light shielding evaluation: 1100-1200 nm average transmittance)
Regarding the measurement results obtained using the above spectrophotometer, the average value of transmittance from 1100 to 1200 nm was determined. The results are listed in Table 3.
A material with a transmittance of 40% or less is judged to have absorbed this wavelength range well, and it can be said that the lower the transmittance, the better the shielding property of near-infrared light.

(Evaluation of average visible light transmittance)
Regarding the measurement results obtained using the above spectrophotometer, the average value of transmittance from 430 to 570 nm was determined. The results are listed in Table 3. A material with a transmittance of 70% or more is judged to have well absorbed this wavelength range, and can be said to have excellent visible light transmittance.

(Evaluation of UV resistance)
The optical filter produced below was exposed to UV light using a UV exposure machine (manufactured by Iwasaki Electric Co., Ltd., product name: Eye ultraviolet curing device US2-KO4501, illuminance: 180 mW/cm ² , irradiation amount: 560 mJ/cm ² ). was irradiated, and the transmittance in each wavelength region before and after irradiation was measured in comparison with the glass substrate using a spectrophotometer (manufactured by JASCO Corporation, model number: V-7300). At this time, the absorbance at the wavelength where the optical filter produced has the lowest transmittance in the wavelength range of 1100 to 1200 nm is (A1), the absorbance after UV irradiation at the same wavelength is (A2), and the absorbance retention rate (%) = UV resistance was evaluated using the following criteria as 100×(A2)/(A1). The results are listed in Table 3.
In addition, regarding the evaluation of the glass coating type, the light was incident from the glass surface.
When the absorbance retention rate is 95% or more, when used as an infrared shielding film, it is possible to maintain high UV resistance when used in combination with a protective film, etc., and it is presumed to be highly practical.

<Synthesis example 1: thermoplastic resin 1>
8-Methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 . ^17,10 ] 100 parts of dodec-3-ene (hereinafter also referred to as "DNM"), 18 parts of 1-hexene (molecular weight regulator), and 300 parts of toluene (solvent for ring-opening polymerization reaction) were replaced with nitrogen. A reaction vessel was charged, and the solution was heated to 80°C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol/liter) and 0.2 parts of a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol/liter) were added to the solution in the reaction vessel as polymerization catalysts. 9 parts of the solution was added, and the solution was heated and stirred at 80° C. for 3 hours to carry out a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

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

<Synthesis example 2: thermoplastic resin 2>
In a 3L four-necked flask were placed 35.12 parts (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 parts (0.250 mol) of 9,9-bis(4-hydroxyphenyl)fluorene, and 41.9 parts (0.250 mol) of potassium carbonate. 46 parts (0.300 mol), 443 parts of N,N-dimethylacetamide (hereinafter also referred to as "DMAc"), and 111 parts of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube, and a cooling tube were attached to the four-necked flask. Next, after purging the inside of the flask with nitrogen, the resulting solution was reacted at 140° C. for 3 hours, and the produced water was removed from the Dean-Stark tube as needed. When water generation was no longer observed, the temperature was gradually raised to 160° C., and the reaction was continued at that temperature for 6 hours. After cooling to room temperature (25° C.), the generated salts were removed using filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60° C. overnight to obtain a white powder (hereinafter also referred to as “resin B”) (yield: 95% by mass). Resin B obtained had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285°C.

<Thermoplastic resin 3>
・Polycarbonate resin: Manufactured by Teijin Ltd., product name: Pure Ace

<Synthesis Example 4: Thermosetting resin (1)>
A flask equipped with a cooling tube and a stirrer was charged with 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by mass of methacrylic acid, 30 parts by mass of glycidyl methacrylate, and 50 parts by mass of 3,4-epoxycyclohexyl methacrylate were charged, and after purging with nitrogen, gentle stirring was started. The temperature of the solution was raised to 70°C and this temperature was maintained for 4 hours to terminate the polymerization. Thereafter, the reaction product solution was dropped into a large amount of methanol to solidify the reaction product. After washing this coagulated product with water, it was redissolved in 200 g of tetrahydrofuran and coagulated again with a large amount of methanol. After performing this redissolution-solidification operation three times in total, the obtained solidified product was vacuum-dried at 60° C. for 48 hours to obtain the desired thermosetting resin (1).

<Synthesis Example 5: Thermosetting resin (2)>
A flask equipped with a cooling tube and a stirrer was charged with 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 15 parts by mass of glycidyl methacrylate, 35 parts by mass of 3-(methacryloyloxymethyl)-2-methyloxetane, and 50 parts by mass of tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate were charged. After purging with nitrogen, gentle stirring was started. The temperature of the solution was raised to 70°C and this temperature was maintained for 4 hours to terminate the polymerization. Thereafter, the reaction product solution was dropped into a large amount of methanol to solidify the reaction product. After washing this coagulated product with water, it was redissolved in 200 g of tetrahydrofuran and coagulated again with a large amount of methanol. After performing this redissolution-solidification operation three times in total, the obtained solidified product was vacuum-dried at 60° C. for 48 hours to obtain the desired thermosetting resin (2).

<Compound (Z) synthesis example>
[Synthesis of compound (Z-4)]
Spectrum info's S04290 (3.0 g) and lithium tetrakis(pentafluorophenyl)borate diethyl ether complex (4.0 g) were stirred in dichloromethane (30 mL)/water (30 mL) at room temperature for 8 hours, and silica gel was added. By purifying by column chromatography (mobile phase: dichloromethane), compound (Z-4) (4.6 g) represented by the following structural formula was obtained.

The maximum absorption wavelength λmax of (Z-4) in dichloromethane was 1104 nm.
The results of the mass spectrum of the obtained compound (Z-4) are shown below.
HRMS (MALDI) m/z: calculated for C ₂₄ BF ₂₀ [M] ^- 678.9779; found 678.9771, calculated for C ₅₃ H ₅₉ N ₂ O ₂ [M] ⁺ 755.4571; found: 755 .4574

[Compounds (Z-1) to (Z-3), (Z-5), (Z-8), (Z-9), (Z-12) and (Z-13)]
Compounds (Z-1) to (Z-3), (Z-5), (Z-8), (Z-9), (Z-12) and (Z-13) are the same as (Z-4) synthesized into. Structural formulas and dichloromethane of the obtained compounds (Z-1) to (Z-3), (Z-5), (Z-8), (Z-9), (Z-12) and (Z-13) The maximum absorption wavelength λmax is as follows.

-Compound (Z-1): A compound represented by the following structural formula. The maximum absorption wavelength λmax in dichloromethane was 1142 nm.

-Compound (Z-2): A compound represented by the following structural formula. The maximum absorption wavelength λmax in dichloromethane was 1145 nm.

-Compound (Z-3): A compound represented by the following structural formula. The maximum absorption wavelength λmax in dichloromethane was 1152 nm.

- Compound (Z-5): A compound represented by the following structural formula. The maximum absorption wavelength λmax in dichloromethane was 1101 nm.

- Compound (Z-8): A compound represented by the following structural formula. The maximum absorption wavelength λmax in dichloromethane was 1160 nm.

- Compound (Z-9): A compound represented by the following structural formula. The maximum absorption wavelength λmax in dichloromethane was 1105 nm.

- Compound (Z-12): A compound represented by the following structural formula. The maximum absorption wavelength λmax in dichloromethane was 1104 nm.

- Compound (Z-13): A compound represented by the following structural formula. The maximum absorption wavelength λmax in dichloromethane was 1162 nm.

[Examples 1 to 3 and Comparative Examples 1 and 4]
For Examples 1 to 3 and Comparative Examples 1 and 4, a resin substrate consisting of a transparent resin layer containing the compound (Z) was prepared, and then an optical filter was prepared.

<Preparation of base material (i)>
A solution containing compound (Z) and other components with respect to 100 parts by mass of the resin in the proportions shown in Table 2 and having a resin concentration of 20% by mass was prepared by further adding dichloromethane. The obtained solution was cast onto a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100° C. for 8 hours to obtain a base material (i) consisting of a resin substrate having a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm.
The spectral transmittance measured from the vertical direction of the substrate (i) was evaluated for each of the above items, and the results are shown in Table 3.

<Production of optical filter>
A dielectric multilayer film (I) is formed as a first optical layer on one side of the obtained substrate (i) using an ion-assisted vacuum evaporation device, and a second optical layer is further formed on the other side of the substrate (i). A similar dielectric multilayer film (II) was formed as an optical layer to obtain an optical filter with a thickness of about 0.1 mm.

As shown in Table 1, the dielectric multilayer film (I) consists of a silica (SiO ₂ ) layer with a physical thickness of about 37 to 168 nm and a titania (TiO ₂ ) layer with a physical thickness of about 11 to 104 nm at a deposition temperature of 100°C. It is a laminate in which 26 layers are alternately laminated (26 layers in total). As shown in Table 1, the dielectric multilayer film (II) consists of a silica (SiO ₂ ) layer with a physical thickness of about 40 to 191 nm and a titania (TiO ₂ ) layer with a physical thickness of about 10 to 110 nm at a deposition temperature of 100°C. It is a laminate in which 22 layers are alternately laminated (22 layers in total).
In both dielectric multilayer films (I) and (II), the silica layer and the titania layer are arranged in order from the resin layer (1) side: titania layer, silica layer, titania layer, ... silica layer, titania layer, silica layer. The optical filter was layered alternately in the following order, and the outermost layer of the optical filter was a silica layer.

[Examples 4 and 5 and Comparative Example 2]
In Examples 4 and 5 and Comparative Example 2, optical members having a base material made of a transparent glass support having a thermosetting resin layer containing compound (Z) on one side were created.

A composition for forming a thermosetting resin layer (1) having the following composition was placed on a transparent glass support "OA-10G (thickness 200 μm)" (manufactured by Nippon Electric Glass Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width. It was applied using a spin coater and heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the spin coater were adjusted so that the thickness after drying was 4 μm. Next, heating was performed at 200°C for 5 minutes on a hot plate to cure the thermosetting resin layer forming composition (1), and the composition (1) for forming a thermosetting resin layer was cured. I got the material.

An optical member was produced in the same manner as in Example 1 except that a base material made of a transparent glass support having the resin layer was used, and the spectral characteristics of the obtained base material and optical member were evaluated. The results are listed in Table 3.

- Thermosetting resin layer forming composition (1): the compound (Z) and other components listed in Table 2, with respect to 100 parts by mass of the thermosetting resin (1), in the proportions listed in Table 2, and , methyl ethyl ketone (solvent), and TSC (solid content concentration): 35% by mass.

[Example 6]
In Example 6, an optical member having a base material made of a near-infrared absorbing glass support having a thermosetting resin layer containing compound (Z) on one side was created.

A thermosetting resin layer forming composition (2) having the following composition was placed on a near-infrared absorbing glass substrate "BS-6 (thickness 210 μm)" (manufactured by Matsunami Glass Industry Co., Ltd.) cut into a size of 60 mm in length and 60 mm in width. was applied using a spin coater and heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the spin coater were adjusted so that the thickness after drying was 4 μm. Next, heating was performed at 200°C for 5 minutes on a hot plate to cure the thermosetting resin layer-forming composition (2), thereby forming a near-infrared absorbing glass support having a resin layer containing the compound (Z). A base material consisting of was obtained.

An optical member was produced in the same manner as in Example 1 except that a base material made of a near-infrared absorbing glass support having the resin layer was used, and the spectral characteristics of the obtained base material and optical member were evaluated. The results are listed in Table 3.

・Thermosetting resin layer forming composition (2): Compound (Z) shown in Table 2 and other components for 100 parts by mass of thermosetting resin (2) in the proportions shown in Table 2. , and methyl ethyl ketone (solvent), and was prepared to have TSC: 35% by mass.

[Example 7]
In Example 7, an optical member having a base material made of a near-infrared absorbing glass support having a thermosetting resin layer containing compound (Z) on one side was created.

A base material and an optical member were produced in the same manner as in Example 6 except that the following thermosetting resin layer forming composition (3) was used, and the spectral characteristics of the obtained base material and optical member were evaluated. The results are listed in Table 3.

- Thermosetting resin layer forming composition (3): Compound (Z) listed in Table 2 and other components relative to 100 parts by mass of thermosetting resin (2) in the proportions listed in Table 2. , and methyl ethyl ketone (solvent), and was prepared to have TSC: 35% by mass.

[Example 8]
In Example 8, an optical member having a base material made of a thermoplastic resin support having a UV curable resin layer containing compound (Z) on one side was created.

A composition for forming a UV curable resin layer (1) having the following composition was placed on a 0.1 mm thick resin support made of Synthesis Example 1 that does not contain compound (Z) and cut into a size of 60 mm in length and 60 mm in width. It was applied using a spin coater and heated on a hot plate at 80° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the spin coater were adjusted so that the thickness after drying was 4 μm. Next, exposure (exposure amount 500 mJ/cm ² , 200 mW) is performed using a conveyor-type exposure machine to cure the composition (1) for forming a UV curable resin layer, thereby forming a resin layer containing the compound (Z). A base material made of a resin support was obtained.

An optical member was produced in the same manner as in Example 1 except that a base material made of a resin support having the resin layer was used, and the spectral characteristics of the obtained base material and optical member were evaluated. The results are listed in Table 3.

- UV curable resin layer forming composition (1): 20 parts by mass of tricyclodecane dimethanol acrylate, 80 parts by mass of dipentaerythritol hexaacrylate, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone, Compound (Z-12) 1 .35 parts by mass, methyl ethyl ketone (solvent), TSC: 35% by mass

[Example 9]
In Example 9, an optical member having a base material made of a near-infrared absorbing glass support having a UV curable resin layer containing compound (Z) on one side was created.

A near-infrared absorbing glass support having a resin layer containing compound (Z) was prepared in the same manner as in Example 8, except that the composition for forming a UV curable resin layer (2) having the following composition and the near-infrared absorbing glass support were used. A base material consisting of was obtained.

An optical member was produced in the same manner as in Example 1 except that a base material made of a near-infrared absorbing glass support having the resin layer was used, and the spectral characteristics of the obtained base material and optical member were evaluated. The results are listed in Table 3.

- UV curable resin layer forming composition (2): 20 parts by mass of tricyclodecane dimethanol acrylate, 80 parts by mass of dipentaerythritol hexaacrylate, 4 parts by mass of 1-hydroxycyclohexylphenyl ketone, compound (Z-13) 1 .5 parts by mass, methyl ethyl ketone (solvent), TSC: 35% by mass

[Example 10]
In Example 10, a resin substrate (10-1) consisting of a transparent resin layer containing the compound (Z) and a resin substrate (10-2) consisting of a transparent resin layer not containing the compound (Z) were respectively produced. Thereafter, a base material was produced by bonding the resin substrate (10-1) and the resin substrate (10-2) together.
First, a solution containing compound (Z) and other components based on 100 parts by mass of resin in the proportions shown in Table 2 and having a resin concentration of 20% by mass by further adding dichloromethane was prepared. The obtained solution was cast onto a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100° C. for 8 hours to obtain a resin substrate (10-1) with a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm.
Similarly, a solution containing other near-infrared absorbing dyes and other components with respect to 100 parts by mass of the resin and having a resin concentration of 20% by mass was prepared by adding dichloromethane. The obtained solution was cast onto a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100° C. for 8 hours to obtain a resin substrate (10-2) with a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm.
After uniformly applying methyl amyl ketone onto the resin substrate (10-1) using a wire bar (bar coater No. 3 manufactured by As One Co., Ltd.), immediately place the resin substrate (10-2) on a laminator. (manufactured by Yubon Co., Ltd., product name: Lamyman IKO-650E) and bonded together to produce a base material with a thickness of 0.2 mm.

An optical member was produced in the same manner as in Example 1, except that a base material produced by bonding the resin substrate (10-1) and the resin substrate (10-2) was used. The spectral characteristics of the base material and optical member were evaluated. The results are listed in Table 3.

[Example 11]
In Example 11, a thermosetting resin layer (11-2) containing the compound (Z) was formed on a resin substrate (11-1) consisting of a transparent resin layer not containing the compound (Z). The obtained optical member was produced.
First, a solution with a resin concentration of 20% by mass was prepared by adding other near-infrared absorbing dyes and other components to 100 parts by mass of the resin in the proportions listed in Table 2, and further adding dichloromethane. . The obtained solution was cast onto a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100° C. for 8 hours to obtain a resin substrate (11-1) with a thickness of 0.1 mm, a length of 210 mm, and a width of 210 mm.
A composition for forming a thermosetting resin layer (11-2) having the following composition was applied onto the resin substrate (11-1) using a spin coater, and heated on a hot plate at 80° C. for 2 minutes to volatilize the solvent. Removed. At this time, the coating conditions of the spin coater were adjusted so that the thickness after drying was 3.3 μm. Next, heating was performed at 200°C for 5 minutes on a hot plate to cure the thermosetting resin layer forming composition (11-2), and the resin substrate having the resin layer containing the compound (Z) was heated. A base material was obtained.

- Thermosetting resin layer (11-2) forming composition: the compound (Z) listed in Table 2 and other components relative to 100 parts by mass of the thermosetting resin (1) in the proportions listed in Table 2. , and methyl ethyl ketone (solvent), and was prepared to have a TSC (solid content concentration) of 35% by mass.

In Example 11, an optical member was produced in the same manner as in Example 1, except that a base material produced by forming a thermosetting resin layer (11-2) on the resin substrate (11-1) was used. Then, the spectral characteristics of the obtained base material and optical member were evaluated. The results are listed in Table 3.

[Comparative example 3]
In Comparative Example 3, an optical member having a base material made of a near-infrared absorbing glass support having a UV curable resin layer containing compound (Z) on one side was produced.

A group consisting of a near-infrared absorbing glass support having a resin layer containing the compound (Z) was prepared in the same manner as in Example 8 except that the composition for forming a UV curable resin layer (3) and the near-infrared absorbing glass support were used. I got the material.

- UV curable resin layer forming composition (3): 20 parts by mass of tricyclodecane dimethanol acrylate, 80 parts by mass of dipentaerythritol hexaacrylate, 4 parts by mass of 1-hydroxycyclohexylphenyl ketone, compound (X-3) 1 .5 parts by mass, methyl ethyl ketone (solvent), TSC: 35% by mass

An optical member was produced in the same manner as in Example 1 except that a base material made of a near-infrared absorbing glass support having the resin layer was used, and the spectral characteristics of the obtained base material and optical member were evaluated. The results are listed in Table 3.

Using a spectrophotometer, the spectral transmittance of the optical filters obtained in Examples 1 to 11 and Comparative Examples 1 to 4 was measured from the vertical direction, and the optical characteristics in each wavelength region were evaluated. Each item was evaluated based on the obtained values, and the results are listed in Table 3.

The contents of symbols other than those mentioned above regarding the structure of the base material, various compounds, etc. in Table 2 are as follows.

・Compound (X-1): CIR-RL manufactured by Nippon Carlit (maximum absorption wavelength λmax 1095 nm)

・Compound (X-2): Compound having the following structure (maximum absorption wavelength λmax 1120 nm)

・Compound (X-3): Compound having the following structure (maximum absorption wavelength λmax 1062 nm)

<Other near-infrared absorbing dyes>
・Compound (A-1): Compound having the following structure (maximum absorption wavelength λmax 711 nm)

・Compound (A-2): Compound having the following structure (maximum absorption wavelength λmax 720 nm)

・Compound (A-3): Compound having the following structure (maximum absorption wavelength λmax 720 nm)

・Compound (B-1): Compound having the following structure (maximum absorption wavelength λmax 831 nm)

・Compound (B-2): Compound having the following structure (maximum absorption wavelength λmax 1020 nm)

・Compound (B-3): Compound having the following structure (maximum absorption wavelength λmax 870 nm)

・Compound (B-4): Compound having the following structure (maximum absorption wavelength λmax 780 nm)

・Compound (B-5): Compound having the following structure (maximum absorption wavelength λmax 725 nm)

・Compound (B-6): Compound having the following structure (maximum absorption wavelength λmax 735 nm)

・Compound (C-1): Compound having the following structure (maximum absorption wavelength λmax 732 nm)

・Compound (C-2): Compound having the following structure (maximum absorption wavelength λmax 737 nm)

<UV (ultraviolet) absorber>
・Compound (U-1): Compound having the following structure

・Compound (U-2): Compound having the following structure

・Compound (U-3): Compound having the following structure

・Compound (T-1): Thermal acid generator, manufactured by Sanshin Chemical Industry Co., Ltd., product name: Sunaid SI-150

As shown in Table 3, the optical filters obtained from the compositions of the present invention in Examples 1 to 11 had better near-infrared light shielding than the optical filters obtained from the compositions in Comparative Examples 1 to 4. It can be seen that it has excellent properties and UV resistance.

Claims (9)

The compound (Z) contains a resin (i) or a polymerizable compound (ii) and a compound (Z) represented by the following formula (I), and the compound (Z) has a wavelength range of 400 nm to 1300 nm in dichloromethane. A composition whose maximum absorption wavelength λmax satisfies the wavelength 1100 nm<λmax<1200 nm.
Cn ⁺ An ^- formula (I)
[In formula (I), Cn ⁺ represents a monovalent cation represented by the following formula (II), and An ^- represents a counter anion. ]

[In formula (II), R ¹ to R ⁶ , Y _B , Y _C , and Z _A to Z _C each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a phosphoric acid group, Silyl group, R _i , -OR _i , -C(=O)R _i , -OC(=O)R _i , -CO ₂ R _i , -NR _g R _h , -SQ ₂ , -SO ₂ Q ₃ , or -OSO ₂ R _i ,
The above R ⁴ and R ⁵ may be combined to form a fused ring containing an oxygen atom fused to a benzene ring, and R ⁷ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms. , one or more carbon atoms in the hydrocarbon group may be substituted with an oxygen atom, nitrogen atom, or sulfur atom, and Y _B , Y _C , and Z _A to Z _C represent two adjacent groups. may combine with each other to form a 5-membered ring structure, 6-membered ring structure, or 7-membered ring structure, and when Y _B , Y _C , and Z _A to Z _C form a ring, directly bond to the ring. The hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms, the ring members of the ring structure include carbon atoms, and the ring members are selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms. The ring structure may further include one type, and the ring structure may be any of a fused ring structure, a bridged ring structure, and a spiro ring structure.
The above Y _A and Y _D each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 8 carbon atoms, and the above Y _A forms a ring structure with the above R ¹ or the above Y _B. Y _D may form a ring structure with R ¹ or Y _C ,
The R _g and R _h each independently represent a hydrogen atom, R _i , or -C(=O)R _i ,
Q ₂ represents a hydrogen atom or R _i ,
Q ₃ represents a hydroxyl group or R _i ,
R _i is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O-, -NR- and -S-. It is a group represented by a bond, has a total number of carbon atoms of 1 to 20, and may have a substituent, and R represents a hydrogen atom or a monovalent organic group. ] An optical member comprising a substrate (i) formed from the composition according to claim 1 and comprising a layer containing a compound (Z). The optical member according to claim 2, wherein the base material (i) is any one of the following base materials (i-1) to (i-3).
(i-1) A base material comprising a resin support not containing the compound (Z) and a resin layer containing the compound (Z) (i-2) A glass support and the compound (Z) (i-3) A base material that is a resin support containing the compound (Z). The optical member according to claim 3, wherein the transmittance of the base material (i) satisfies the following (α) to (ε).
(α): In the wavelength range of 350 to 450 nm, there exists a wavelength where the transmittance is less than 50% to more than 50% (β): In the wavelength range of 430 to 570 nm (visible region), the average value of transmittance is 70% or more (γ ): In the wavelength range of 600 to 700 nm, there exists a wavelength where the transmittance is from more than 50% to less than 50% (δ): In the wavelength range of 700 to 800 nm, the average value of transmittance is 1% or less (ε): Wavelength of 800 to 1100 nm , the maximum transmittance is 40% or less An optical member having a dielectric multilayer film on at least one surface of the optical member according to claim 2. The optical member according to claim 5, which satisfies the following characteristics (a) and (b).
Characteristic (a): In the wavelength range of 430 to 570 nm, the average value of transmittance when measured from the vertical direction of the optical member is 70% or more. Characteristic (b): In the wavelength range of 850 to 1200 nm, the average value of transmittance is 70% or more in the vertical direction of the optical member. The average value of transmittance when measured from 5% or less A solid-state imaging device comprising the optical member according to claim 2. An optical sensor device comprising the optical member according to any one of claims 2 to 6. A compound (Z) represented by the following formula (I).
Cn ⁺ An ^- formula (I)
[In formula (I), Cn ⁺ represents a monovalent cation represented by the following formula (II), and An ^- represents a counter anion. ]

[In formula (II), R ¹ to R ⁶ , Y _B , Y _C , and Z _A to Z _C each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a phosphoric acid group, Silyl group, R _i , -OR _i , -C(=O)R _i , -OC(=O)R _i , -CO ₂ R _i , -NR _g R _h , -SQ ₂ , -SO ₂ Q ₃ , or -OSO ₂ R _i ,
The above R ⁴ and R ⁵ may be combined to form a fused ring containing an oxygen atom fused to a benzene ring, and R ⁷ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 25 carbon atoms. , one or more carbon atoms in the hydrocarbon group may be substituted with an oxygen atom, nitrogen atom, or sulfur atom, and Y _B , Y _C , and Z _A to Z _C represent two adjacent groups. may combine with each other to form a 5-membered ring structure, 6-membered ring structure, or 7-membered ring structure, and when Y _B , Y _C , and Z _A to Z _C form a ring, directly bond to the ring. The hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms, the ring members of the ring structure include carbon atoms, and the ring members are selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms. The ring structure may further include one type, and the ring structure may be any of a fused ring structure, a bridged ring structure, and a spiro ring structure.
The above Y _A and Y _D each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 8 carbon atoms, and the above Y _A forms a ring structure with the above R ¹ or the above Y _B. Y _D may form a ring structure with R ¹ or Y _C ,
The R _g and R _h each independently represent a hydrogen atom, R _i , or -C(=O)R _i ,
Q ₂ represents a hydrogen atom or R _i ,
Q ₃ represents a hydroxyl group or R _i ,
R _i is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O-, -NR- and -S-. It is a group represented by a bond, has a total number of carbon atoms of 1 to 20, and may have a substituent, and R represents a hydrogen atom or a monovalent organic group. ]