WO2024070371A1

WO2024070371A1 - Composition, optical filter, and solid-state imaging element

Info

Publication number: WO2024070371A1
Application number: PCT/JP2023/030666
Authority: WO
Inventors: 悠司淺津; 裕史濱木; 拓宮澤
Original assignee: 住友化学株式会社
Priority date: 2022-09-26
Filing date: 2023-08-25
Publication date: 2024-04-04
Also published as: TW202413361A; JP2024047265A

Abstract

The present invention addresses the problem of providing a composition capable of forming an optical filter that has fewer aggregates.　The present invention relates to a composition comprising a near-infrared absorbing dye, an alkali-soluble resin, and a solvent, wherein the near-infrared absorbing dye comprises a compound represented by formula (I). (In formula (I), R1, R4, R5, and R8 each independently represent a C1-20 hydrocarbon group or the like; R2, R3, R6, and R7 each independently represent a hydrogen atom or the like; R9, R10, and R11 each independently represent a C1-20 hydrocarbon group, and if two or more R11 moieties are present, said moieties may be the same or different; X1-X4 each independently represent a hydrogen atom or the like; Y1-Y8 each independently represent a hydrogen atom or the like; and R12 represents a C1-5 alkyl group, and if two or more R12 moieties are present, said moieties may be the same or different)

Description

Composition, optical filter, and solid-state image pickup device

The present invention relates to a composition, an optical filter, and a solid-state imaging device.

One example of an optical filter used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, and in solid-state imaging devices such as CCD and CMOS sensors, is a filter that absorbs near-infrared radiation. As a material for producing such filters that absorb near-infrared radiation, for example, a composition containing a near-infrared absorbing dye such as a compound having a cyanine structure is known (for example, Patent Document 1).

JP 2016-060774 A

When an optical filter is formed from a conventional composition containing a near-infrared absorbing dye, aggregates due to the near-infrared absorbing dye may occur. Therefore, the present invention aims to provide a composition that can form an optical filter with reduced aggregates. The present invention also aims to provide a compound that can be used to prepare such a composition, and a simple method for producing the compound.

The present invention has the following aspects.
[1] A composition containing a near-infrared absorbing dye, an alkali-soluble resin, and a solvent,
The composition, wherein the near infrared absorbing dye comprises a compound represented by formula (I):

[In formula (I),
R ¹ , R ⁴ , R ⁵ , and R ⁸ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or an OR ¹¹ group;
R ² , R ³ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom or an OR ¹¹ group;
R ⁹ , R ¹⁰ , and R ¹¹ each independently represent a hydrocarbon group having 1 to 20 carbon atoms;
When two or more R ¹¹ are present, they may be the same or different from each other;
X ¹ to X ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
Y ¹ to Y ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an OR ¹² group;
R ¹² represents an alkyl group having 1 to 5 carbon atoms, and when two or more R ¹² are present, they may be the same or different.
[2] The composition according to [1], wherein X ¹ to X ⁴ and Y ¹ to Y ⁸ in formula (I) are hydrogen atoms.
[3] The composition according to [2], further comprising a polymerization initiator and a polymerizable compound.
[4] An optical filter formed from the composition according to any one of [1] to [3].
[5] A solid-state imaging device comprising the optical filter according to [4].
[6] A compound represented by formula (Ia):

[In formula (Ia),
R ^1a , R ^4a , R ^5a , and R ^8a each independently represent a halogen atom;
R ^2a , R ^3a , R ^6a , and R ^7a each independently represent a hydrogen atom, a halogen atom,
or OR ^11a group,
R ⁹ and R ¹⁰ each independently represent a hydrocarbon group having 1 to 20 carbon atoms;
R ^11a represents a hydrocarbon group having 1 to 13 carbon atoms, and when two or more R ^11a are present,
They may be the same or different from each other,
X ¹ to X ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
Y ¹ to Y ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an OR ¹² group;
R ¹² represents an alkyl group having 1 to 5 carbon atoms, and when two or more R ¹² are present, they may be the same or different.
[7] A method for producing a compound represented by formula (I), comprising a step of reacting a compound represented by formula (I-x1), a compound represented by formula (I-x2), and a compound represented by formula (I-y1) or a compound represented by formula (I-y2) in the presence of a catalyst.

[In formulas (I-x1) and (I-x2),
R ¹ , R ⁴ , R ⁵ , and R ⁸ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or an OR ¹¹ group;
R ² , R ³ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom or an OR ¹¹ group;
R ⁹ , R ¹⁰ , and R ¹¹ each independently represent a hydrocarbon group having 1 to 20 carbon atoms;
When two or more R ¹¹ are present, they may be the same or different from each other;
X ¹ to X ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
Y ¹ , Y ⁴ , Y ⁵ , and Y ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an OR ¹² group;
R ¹² represents an alkyl group having 1 to 5 carbon atoms, and when two or more R ¹² are present, they may be the same or different from each other.
Z ¹ to Z ⁴ each independently represent a bromine atom or an iodine atom.]

[In formulas (I-y1) and (I-y2),
Y ² , Y ³ , Y ⁶ , and Y ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an OR ¹² group;
A ¹ and A ² each independently represent a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, or an OR ¹³ group;
R ¹³ represents a hydrocarbon having 1 to 20 carbon atoms, and when two or more R ¹³ are present, they may be the same or different from each other;
OR ¹³ groups bonded to the same boron atom may be bonded to each other to form a ring.

[In formula (I),
R ¹ to R ¹⁰ , X ¹ to X ⁴ , and Y ¹ to Y ⁸ are as defined above.]

The present invention provides a composition capable of forming an optical filter with reduced aggregates. The present invention also provides an optical filter with reduced aggregates, and a solid-state imaging device including the optical filter. Furthermore, the present invention provides a compound that can be used to prepare the composition, and a simple (more specifically, a simple method for producing the compound with a small number of steps).

FIG. 1 is a schematic diagram showing an embodiment of a solid-state imaging device.

<Composition>
The composition according to one aspect of the present invention contains a near-infrared absorbing dye, an alkali-soluble resin, and a solvent (hereinafter, these may be referred to as the near-infrared absorbing dye (A1), the resin (B), and the solvent (E), respectively). The composition may further contain one or more of a polymerizable compound, a polymerization initiator, and a leveling agent (hereinafter, these may be referred to as the polymerizable compound (C), the polymerization initiator (D), and the leveling agent (F), respectively). In this specification, the compounds exemplified as each component may be used alone or in combination, unless otherwise specified.

The composition according to this aspect contains a compound represented by formula (I) described below as a near-infrared absorbing dye, and therefore aggregates caused by the near-infrared absorbing dye are unlikely to occur even when the composition is formed into a film. Therefore, the composition according to this aspect can form an optical filter with reduced aggregates.
The optical filter thus formed is excellent in light resistance. In addition, as described later, since the compound represented by formula (I) absorbs a specific wavelength in the near-infrared region, the optical filter thus formed can be used as a near-infrared cut filter or a near-infrared transmission filter.

<Near infrared absorbing dye (A1)>
In this specification, the near-infrared absorbing dye means a dye that absorbs wavelengths in the near-infrared region (781 nm to 3 μm). The near-infrared absorbing dye (A1) contains one or more compounds represented by formula (I). The near-infrared absorbing dye (A1) may consist of a compound represented by formula (I).

In formula (I), R ¹ , R ⁴ , R ⁵ , and R ⁸ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or an OR ¹¹ group. R ¹ , R ⁴ , R ⁵ , and R ⁸ are preferably a halogen atom or an OR ¹¹ group, and more preferably a chlorine atom or an OR ¹¹ group.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ⁴ , R ⁵ , or R ⁸ include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or alicyclic.

Examples of the saturated or unsaturated chain hydrocarbon group represented by R ¹ , R ⁴ , R ⁵ , or R ⁸ include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups; isopropyl, (1-methyl)propyl, (1-ethyl)propyl, isobutyl, sec-butyl, tert-butyl, (1-ethyl)butyl, (2-ethyl)butyl, (1-propyl)butyl, isopentyl, neopentyl, tert-pentyl, (2-methyl)pentyl, (1-ethyl)pentyl, (3-ethyl)pentyl, (1-propyl)pentyl, (1-propyl)pentyl, and (butyl)pentyl group, isohexyl group, (2-methyl)hexyl group, (5-methyl)hexyl group, (2-ethyl)hexyl group, (1-butyl)hexyl group, (1-pentyl)hexyl group, (2-methyl)heptyl group, (2-ethyl)heptyl group, (3-ethyl)heptyl group, (1-hexyl)heptyl group, (2-methyl)octyl group, (2-ethyl)octyl group, (1-heptyl) Examples of the alkyl groups include branched alkyl groups such as octyl, (2-ethyl)nonyl, and (1-octyl)nonyl; and alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), (1-methyl)ethenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1-(2-propenyl))ethenyl, (1,2-dimethyl)propenyl, and 2-pentenyl. The number of carbon atoms in the saturated chain hydrocarbon group is preferably 1 to 18, more preferably 2 to 15, and even more preferably 3 to 12. The number of carbon atoms in the unsaturated chain hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and even more preferably 3 to 12.

Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ¹ , R ⁴ , R ⁵ , or R ⁸ include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; cycloalkenyl groups such as cyclohexenyl groups (e.g., cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, and cyclooctenyl groups; norbornyl, adamantyl, and bicyclo[2.2.2]octyl groups. The number of carbon atoms in the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 15, and more preferably 3 to 12.

Examples of the aromatic hydrocarbon group represented by R ¹ , R ⁴ , R ⁵ , or R ⁸ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group, an anthryl group, a pyrenyl group, etc. The aromatic hydrocarbon group preferably has 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms.

The hydrocarbon group represented by R ¹ , R ⁴ , R ⁵ , or R ⁸ may be a group obtained by combining two or more of the above-mentioned chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, so long as the upper limit of the carbon number is not more than 20. Such a group may be, for example, a group obtained by combining an aromatic hydrocarbon group with at least one group selected from a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and in such a combined hydrocarbon group, the chain hydrocarbon group may be combined as a divalent group (for example, an alkanediyl group). Examples of the combined hydrocarbon groups include aralkyl groups such as benzyl group, phenethyl group, 1-methyl-1-phenylethyl group, tert-butylphenyl group, tert-octylphenyl group, tert-butylbenzyl group, and tert-octylbenzyl group; arylalkenyl groups such as phenylethenyl group (phenylvinyl group); arylalkynyl groups such as phenylethynyl group; o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,7-dimethylphenyl group, 2,8-dimethylphenyl group, 2,9-dimethylphenyl group, 3,10-dimethylphenyl group, 3,11-dimethylphenyl group, 3,12-dimethylphenyl group, 3,13-dimethylphenyl group, 3,14-dimethylphenyl group, 3,15-dimethylphenyl group, 3,16-dimethylphenyl group, 3,17-dimethylphenyl group, 3,18-dimethylphenyl group, 3,19-dimethylphenyl group, 3,20-dimethylphenyl group, 3,21-dimethylphenyl group, 3,22-dimethylphenyl group, 3,23-dimethylphenyl group, 3,24-dimethylphenyl group, 3,25-dimethylphenyl group, 3,26-dimethylphenyl group, 3,27-dimethylphenyl group, 3,28-dimethylphenyl group, 3,29-dimethylphenyl group, 3,30-dimethylphenyl group, 3,31-dimethylphenyl group, 3,32-dimethylphenyl group, 3,33-dimethylphenyl group, 3,40-dimethylphenyl group, 3,41-dimethylphenyl group, 3,42-dimethylphenyl group, 3,43-dimethylphenyl group, 3,44-dimethylphenyl group, 3,45 ,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 2,3-diisopropylphenyl group, 2,4-diisopropylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-triisopropylphenyl group, 4-butylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group , alkylaryl groups such as 2,6-di(tert-butyl)phenyl group, 3,5-di(tert-butyl)phenyl group, 3,6-di(tert-butyl)phenyl group, 4-tert-butyl-2,6-dimethylphenyl group, 4-pentylphenyl group, 4-octylphenyl group, 4-(2,4,4-trimethyl-2-pentyl)phenyl group, 2-dodecylphenyl group, 3-dodecylphenyl group, and 4-dodecylphenyl group; 2,3-dihydro-4-indenyl group, 1,2,3,5,6,7-hexahydro-4-s-indacenyl group, 8-methyl-1,2,3,5,6,7 aryl groups to which alkanediyl groups are bonded to form a ring, such as -hexahydro-4-s-indacenyl group, 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro-2-naphthyl group, 3-methyl-5,6,7,8-tetrahydro-2-naphthyl group, and 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl group; aryl groups to which one or more aryl groups are bonded, such as a biphenylyl group and a terphenylyl group; cyclohexylmethylphenyl group, benzylphenyl group, and (dimethyl(phenyl)methyl)phenyl group. The hydrocarbon group may be, for example, a hydrocarbon group formed by combining a chain hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include a 1-methylcyclopropyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 1,2-dimethylcyclohexyl group, a 1,3-dimethylcyclohexyl group, a 1,4-dimethylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 2,4-dimethylcyclohexyl group, a 2,5-dimethylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 3,4-dimethylcyclohexyl group, a 3,5-dimethylcyclohexyl group, a 2,2-dimethylcyclohexyl group, a 3,3-dimethylcyclohexyl group, and the like. and alkyl groups having one or more alicyclic hydrocarbon groups bonded thereto, such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, a cyclohexylethyl group, and an adamantylmethyl group. The number of carbon atoms in a group consisting of two or more of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group is preferably 6 to 18 or 7 to 18, and more preferably 6 to 15 or 7 to 15.

The halogen atom represented by R ¹ , R ⁴ , R ⁵ or R ⁸ may be, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The halogen atom is preferably a chlorine atom.

R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms. When two or more R ¹¹ are present in formula (I), they may be the same or different from each other. Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ include the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ⁴ , R ⁵ , or R ^8. The hydrocarbon group having 1 to 20 carbon atoms is preferably an aromatic hydrocarbon group, more preferably a phenyl group, a tolyl group, a methoxyphenyl group, a propoxyphenyl group, a tert-butylphenyl group, or a tert-octylphenyl group, and most preferably a propoxyphenyl group or a tert-butylphenyl group. The number of carbon atoms in the hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and even more preferably 6 to 10.

In formula (I), R ² , R ³ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom or an OR ¹¹ group. R ¹¹ is as defined above. R ² , R ³ , R ⁶ and R ⁷ are preferably halogen atoms. The halogen atom represented by R ² , R ³ , R ⁶ or R ⁷ may be, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In formula (I), R ⁹ and R ¹⁰ each independently represent a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ or R ¹⁰ include the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ⁴ , R ⁵ or R ^8. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the groups represented by the following formulae (D-1) to (D-47) or formulae (G-1) to (G-24). In the formulae, * represents a bond.

Among these, groups represented by formula (D-12), (D-13), (D-14), (D-44), (G-3), (G-8), (G-13), (G-15), or (G-23) are preferred, and groups represented by formula (D-44) or (G-8) are more preferred.

In formula (I), X ¹ to X ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. X ¹ to X ⁴ are preferably a hydrogen atom.

Examples of the alkyl group having 1 to 10 carbon atoms represented by X ¹ to X ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, a 2-ethylhexyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

In formula (I), Y ¹ to Y ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an OR ¹² group. Y ¹ to Y ⁸ are preferably a hydrogen atom.

Examples of the alkyl group having 1 to 5 carbon atoms represented by Y ¹ to Y ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and an n-pentyl group.

R ¹² represents an alkyl group having 1 to 5 carbon atoms. When two or more R ¹² are present in formula (I), they may be the same or different from each other. Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹² include the groups exemplified as the alkyl group having 1 to 5 carbon atoms represented by Y ¹ to Y ⁸ .

The compound represented by formula (I) is preferably a compound represented by formula (Ia).

In formula (Ia), R ⁹ , R ¹⁰ , X ¹ to X ⁴ , and Y ¹ to Y ⁸ are as defined above.

In formula (Ia), R ^1a , R ^4a , R ^5a and R ^8a each independently represent a halogen atom. The halogen atom may be, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In formula (Ia), R ^2a , R ^3a , R ^6a and R ^7a each independently represent a hydrogen atom, a halogen atom or an OR ^11a group. R ^2a , R ^3a , R ^6a and R ^7a are preferably halogen atoms. The halogen atom may be, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

R ^11a represents a hydrocarbon group having 1 to 13 carbon atoms, and when two or more R ^11a are present, they may be the same or different from each other. Examples of the hydrocarbon group having 1 to 13 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, and dodecyl; aryl groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, 2,4,6-trimethylphenyl, and naphthyl; and aralkyl groups such as benzyl and phenethyl. The hydrocarbon group having 1 to 13 carbon atoms may be, for example, a propoxyphenyl group or a tert-butylphenyl group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, and more preferably 1 to 9.

Specific examples of the compound represented by formula (I) include a compound represented by the following formula: The compound represented by the following formula is a compound represented by formula (I) in which R ¹ to R ⁸ are chlorine atoms, X ¹ to X ⁴ and Y ¹ to Y ⁸ are hydrogen atoms, and R ⁹ and R ¹⁰ are diisopropylphenyl groups.

Another specific example of the compound represented by formula (I) is a compound represented by the following formula: The compound represented by the following formula is a compound represented by formula (I) in which R ¹ , R ⁴ , R ⁵ , and R ⁸ are 4-propoxyphenoxy groups, R ² , R ³ , R ⁶ , and R ⁷ are hydrogen atoms, X ¹ to X ⁴ and Y ¹ to Y ⁸ are hydrogen atoms, and R ⁹ and R ¹⁰ are 3-ethylhexyl groups.

Another specific example of the compound represented by formula (I) is a compound represented by the following formula: The compound represented by the following formula is a compound represented by formula (I) in which R ¹ to R ⁸ are each independently a 4-tert-butylphenoxy group or a chlorine atom, X ¹ to X ⁴ and Y ¹ to Y ⁸ are hydrogen atoms, and R ⁹ and R ¹⁰ are diisopropylphenyl groups.

Another specific example of the compound represented by formula (I) is a compound represented by the following formula: The compound represented by the following formula is a compound represented by formula (I) in which R ¹ , R ⁴ , R ⁵ , and R ⁸ are 4-tert-butylphenoxy groups, R ² , R ³ , R ⁶ , and R ⁷ are hydrogen atoms, X ¹ to X ⁴ and Y ¹ to Y ⁸ are hydrogen atoms, and R ⁹ and R ¹⁰ are diisopropylphenyl groups.

The compound represented by formula (I) is a compound that absorbs specific wavelengths in the near-infrared region. In other words, the compound represented by formula (I) is a compound that transmits specific wavelengths in the near-infrared region. Therefore, an optical filter formed from a composition containing the compound represented by formula (I) can be used as a near-infrared cut filter or a near-infrared transmittance filter depending on the absorption wavelength.

The absorption wavelength in the near infrared region of the compound represented by formula (I) is not particularly limited, but for example, the compound represented by formula (I) may have an absorption maximum in the range of 800 nm to 1400 nm.

From the viewpoint of using an optical filter formed from a composition containing a compound represented by formula (I) as a near-infrared transmission filter, it is preferable that the compound represented by formula (I) has high absorption in the visible region. For example, when the absorbance at a wavelength of 780 nm is expressed as Abs(780), and the absorbance at a wavelength (maximum absorption wavelength λ _max ) showing the maximum value of absorbance in the wavelength range of 300 to 1400 nm is expressed as Abs(λ _max ), the ratio Abs(780)/Abs(λ _max ) is preferably 0.50 or more, 0.60 or more, 0.70 or more, or 0.75 or more. Abs(780)/Abs(λ _max ) may be, for example, 1.0 or less. Since 780 nm is the upper limit wavelength of the visible region, it can be said that the higher the ratio, the more suitable it is for use in a near-infrared transmission filter. Furthermore, when the maximum absorbance in the wavelength range of 900 to 1400 nm is represented as Abs(900-1400), the ratio of Abs(900-1400) to Abs(λ _max ), Abs(900-1400)/Abs(λ _max ), is preferably 0.3 or less, 0.25 or less, 0.20 or less, or 0.15 or less. Abs(900-1400)/Abs(λ _max ) may be, for example, 0.01 or more, or 0.03 or more. The smaller this value is, the higher the transmittance in the near-infrared region, and the more suitable it is for use in a near-infrared transmission filter.

In this specification, the absorbance of the compound represented by formula (I) is a value measured using an ultraviolet-visible-near infrared absorption spectrometer (V-770, manufactured by JASCO Corporation). Specifically, for example, the compound represented by formula (I) is dissolved in a solvent so that its concentration becomes 10 ppm, and the absorbance can be measured in the wavelength range of 300 to 1400 nm (data sampling interval 1 nm). For example, propylene glycol monomethyl ether acetate or chloroform can be used as the solvent. The absorbance is hardly affected by the resin (B), polymerizable compound (C), polymerization initiator (D), dispersant, etc. described below. Therefore, a composition in which the compound represented by formula (I) is mixed with these components is diluted with a solvent so that the concentration of the compound represented by formula (I) becomes 10 ppm, and the absorbance of this solution is measured, and the obtained absorbance can be regarded as the absorbance of the compound represented by formula (I).

The compound represented by formula (I) may be produced according to a conventionally known method, or may be produced according to a production method according to one aspect of the present invention described below.

The content of the near-infrared absorbing dye (A1) may be 0.5 to 60 mass%, 2 to 60 mass%, 4 to 55 mass%, or 6 to 50 mass% of the total amount of solids in the composition. In this specification, the "total amount of solids" refers to the total amount of components excluding the solvent from the composition. The total amount of solids and the content of each component relative to the total amount of solids can be measured by known analytical means such as liquid chromatography and gas chromatography. The composition does not need to contain any near-infrared absorbing dye other than the compound represented by formula (I).

<Colorant (A2)>
The composition of the present invention may further contain a colorant other than the near infrared absorbing dye (A1) (hereinafter, also referred to as colorant (A2)). The colorant (A2) may be a dye or a pigment.

Dyes include, for example, compounds classified as having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Notes (Shikisensha Co., Ltd.). Xanthene dyes are preferred as dyes.

Xanthene dyes are dyes containing a compound having a xanthene skeleton. Examples of xanthene dyes include C.I. Acid Red 51, 52, 87, 92, 94, 289, and 388; C.I. Acid Violet 9, 30, and 102; C.I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, 10, and 11; C.I. Basic Violet 10 (Rhodamine B) and 11; C.I. Solvent Red 218; C.I. Mordant Red 27; C.I. Reactive Red 36 (Rose Bengal B); Sulforhodamine G; xanthene dyes described in JP-A-2010-32999; and xanthene dyes described in JP-A-4492760. The xanthene dye is preferably a xanthene dye that is soluble in an organic solvent.

As the xanthene dye, commercially available xanthene dyes such as "Chugai AminoL Fast Pink R-H/C" manufactured by Chugai Chemical Industry Co., Ltd. and "Rhodamin 6G" manufactured by Taoka Chemical Co., Ltd. can be used. In addition, as the xanthene dye, a xanthene dye synthesized according to the method described in JP-A-2010-32999 using a commercially available xanthene dye as a starting material can also be used.

Other dyes that may be used include known azo dyes, cyanine dyes, triphenylmethane dyes, thiazole dyes, oxazine dyes, phthalocyanine dyes, quinophthalone dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, etc. Examples of such dyes include C.I. solvent dyes, C.I. acid dyes, C.I. direct dyes, C.I. disperse dyes, C.I. basic dyes, C.I. reactive dyes, C.I. mordant dyes, and C.I. vat dyes.

C.I. Solvent dyes include, for example, C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, and 189; C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, and 247; C.I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, and 86; C.I. C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, and 60; C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, and 139; and C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

C.I. Acid dyes include, for example, C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157 , 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, and 251; C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 57, 66, 73, 76, 80, 88, 91, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, C.I. 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, and 426; C.I.

Acid Orange

6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, and 173; C.I. Acid Violet 6B, 7, 15, 16, 17, 19, 21, 23, 24, 25, 34, 38, 49, and 72; C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 12 C.I.6, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, and 340; Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, and 109.

C.I. direct dyes include, for example, C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, and 141; C.I. C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, and 250; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, and 107; C.I. C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104; Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, and 293; and C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and 82.

C.I. Disperse dyes include, for example, C.I. Disperse Yellow 51, 54, and 76; C.I. Disperse Violet 26 and 27; and C.I. Disperse Blue 1, 14, 56, and 60.

C.I. Basic dyes include, for example, C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, and 89; C.I. Basic Violet 2; C.I. Basic Red 9; and C.I. Basic Green 1.

C.I. reactive dyes include, for example, C.I. Reactive Yellow 2, 76, and 116; C.I. Reactive Orange 16; and C.I. Reactive Red 36.

C.I. Mordant dyes include, for example, C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65; C.I.

Mordant Red

1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, and 95; C.I. C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, and 48; C.I. Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, and 58; C.I.

Mordant Blue

1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84; and C.I. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, and .

An example of a C.I. vat dye is C.I. Vat Green 1.

Examples of pigments include those classified as pigments in the Color Index (published by the Society of Dyers and Colourists).

Pigments include, for example, green pigments, yellow pigments, orange pigments, red pigments, blue pigments, and purple pigments. Green pigments include C.I. Pigment Green 7, 36, 58, and 59. Yellow pigments include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, and 214. Orange pigments include C.I. Examples of pigments that may be used include C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73. Red pigments include C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, and 269. Blue pigments include C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 60. Purple pigments include C.I. Pigment Violet 1, 19, 23, 29, 32, 36, and 38. A single pigment or multiple pigments may be used for each color, and multiple color pigments may be combined.

If necessary, the pigment may be subjected to a treatment such as rosin treatment, surface treatment using a pigment derivative into which an acidic or basic group has been introduced, grafting treatment to the pigment surface with a polymer compound, atomization treatment using a sulfuric acid atomization method, etc., washing treatment with an organic solvent or water to remove impurities, removal treatment of ionic impurities using an ion exchange method, etc. It is preferable that the particle size of the pigment is approximately uniform.

When the composition contains colorant (A2), the content of colorant (A2) may be, for example, 0.5 to 70% by mass, 1 to 70% by mass, 2 to 65% by mass, 5 to 60% by mass, or 7 to 55% by mass of the total amount of solids in the composition. When the content of colorant (A2) is within the above range, it becomes easier to obtain the desired spectral characteristics.

The near-infrared absorbing dye (A1) and pigment can be dispersed in the dispersant solution to form a dispersion in which they are uniformly dispersed. The near-infrared absorbing dye (A1) and pigment may be dispersed individually, or multiple types of near-infrared absorbing dyes (A1) or pigments may be mixed and dispersed. When a dispersant is used, the amount of the dispersant used may be, for example, 10 to 200 parts by mass, 15 to 180 parts by mass, 20 to 160 parts by mass, or 80 to 160 parts by mass, per 100 parts by mass of the total of the near-infrared absorbing dye (A1) and pigment. When the amount of the dispersant used is within the above range, when two or more types of near-infrared absorbing dyes (A1) or pigments are used, a dispersion in which the near-infrared absorbing dye (A1) or pigment is more uniformly dispersed tends to be obtained.

Dispersants include, for example, silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, and acrylic surfactants. Surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. Commercially available dispersants include, for example, BYKLPN-6919 (manufactured by BYK), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWRENE (manufactured by Kyoeisha Chemical Co., Ltd.), Solpers (manufactured by Zeneca Corporation), EFKA (manufactured by BASF Japan Ltd.), AJISPER (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Disperbyk (manufactured by BYK-Chemie).

<Resin (B)>
Examples of the resin (B) include the following resins [K1] to [K6]:
Resin [K1] is a copolymer having a structural unit derived from at least one member (a) (hereinafter may be referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) (hereinafter may be referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
Resin [K2] is a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, may be referred to as "(c)");
Resin [K3] which is a copolymer having a structural unit derived from (a) and a structural unit derived from (c);
Resin [K4] is a copolymer having a structural unit derived from (a) to which (b) has been added, and a structural unit derived from (c);
Resin [K5] is a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b), and a structural unit derived from (c); or Resin [K6] is a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride, and a structural unit derived from (c).
Among these, resin (B) is preferably a copolymer having a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (i.e., resin K1 or K2), and more preferably resin K2.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid. unsaturated dicarboxylic acids such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; unsaturated mono[(meth)acryloyloxyalkyl]esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl]; and unsaturated acrylates containing hydroxy and carboxy groups such as α-(hydroxymethyl)acrylic acid. Of these, acrylic acid, methacrylic acid, or maleic anhydride are preferred as (a) from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

The cyclic ether structure having 2 to 4 carbon atoms contained in monomer (b) may be, for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring. (b) preferably has a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group. In this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid, "(meth)acryloyl" refers to at least one selected from the group consisting of acryloyl and methacryloyl, and "(meth)acrylate" refers to at least one selected from the group consisting of acrylate and methacrylate.

(b) may be, for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), or a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)").

(b1) may be, for example, a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized, or a monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon has been epoxidized.

(b1-1) may, for example, be glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, and 2,4,6-tris(glycidyloxymethyl)styrene.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000, manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400, manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100, manufactured by Daicel Corporation), 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyloxyethyl (meth)acrylate.

(b2) is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group, and examples of such (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, and 3-ethyl-3-acryloyloxyethyloxetane.

(b3) is preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group, and examples of such (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

From the viewpoint of improving the reliability of the optical filter in terms of heat resistance, chemical resistance, etc., it is preferable that (b) is (b1). Furthermore, from the viewpoint of obtaining a composition with excellent storage stability, it is more preferable that (b) is (b1-2).

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate (commonly known in the art as "dicyclopentanyl (meth)acrylate" and sometimes also as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ](meth)acrylic acid esters such as decene-8-yl (meth)acrylate (commonly known in the art as "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;
Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, Cyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept unsaturated compounds such as 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;
dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;
Examples of the copolymer include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo[2.2.1]hept-2-ene are preferred.

In the resin [K1], the structural unit derived from (a) accounts for 2 to 60 mol % based on the total number of moles of all structural units constituting the resin [K1], and
40 to 98 mol % of structural units derived from (b)
It is preferred that
The structural unit derived from (a) is 10 to 50 mol %, and
50 to 90 mol % of structural units derived from (b)
It is more preferable that:
When the ratio of each structural unit in the resin [K1] is within the above range, the composition tends to have excellent storage stability, developability when forming a colored pattern described below, and solvent resistance of the optical filter.

Resin [K1] can be produced, for example, by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (written by Otsu Takayuki, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the documents cited therein.

Specific examples include a method in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and the mixture is heated and kept warm while stirring, for example, under a nitrogen atmosphere. The polymerization initiator, solvent, etc. used here are not particularly limited, and polymerization initiators, solvents, etc. commonly used in the field can be used. For example, polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzoyl peroxide, etc.). The solvent is not particularly limited as long as it dissolves the monomers, and for example, the solvent described below can be used as the solvent (E) of the composition.

In the resin [K2], the total number of moles of all structural units constituting the resin [K2] is:
The structural unit derived from (a) is 2 to 45 mol %,
The structural unit derived from (b) is 2 to 95 mol % and the structural unit derived from (c) is 1 to 65 mol %
It is preferred that
The structural unit derived from (a) is 5 to 40 mol %,
The structural unit derived from (b) is 5 to 80 mol %, and
5 to 60 mol % of structural units derived from (c)
It is more preferable that:
When the ratio of each structural unit of the resin [K2] is within the above range, the composition tends to have excellent storage stability, developability when forming a colored pattern, and the optical filter tends to have excellent solvent resistance, heat resistance, and mechanical strength.

Resin [K2] can be produced in the same manner as resin [K1], except that, for example, (a), (b), and (c) are used instead of (a) and (b).

In the resin [K3], the total number of moles of all structural units constituting the resin [K3] is
The structural unit derived from (a) is 2 to 60 mol % and the structural unit derived from (c) is 40 to 98 mol %.
It is preferred that
The structural unit derived from (a) is 10 to 50 mol % and the structural unit derived from (c) is 50 to 90 mol %
It is more preferable that:

Resin [K3] can be produced in the same manner as resin [K1], except that (a) and (c) are used instead of (a) and (b).

Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and/or carboxylic anhydride of (a). First, the copolymer of (a) and (c) is produced by the same method as that for resin [K3]. The ratio of the structural units derived from (a) and the structural units derived from (c) is preferably the same as that for resin [K3]. Next, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms contained in (b). Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst for the carboxylic acid or carboxylic anhydride and the cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the mixture is reacted, for example, at 60 to 130°C for 1 to 10 hours to produce resin [K4]. The reaction conditions, such as the charging method, reaction temperature, and reaction time, can be adjusted appropriately taking into account the production equipment and the amount of heat generated by polymerization.

The amount of (b) used is preferably 5 to 80 moles, and more preferably 10 to 75 moles, per 100 moles of (a). By keeping the amount of (b) used within this range, the storage stability of the composition, the developability when forming a colored pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the optical filter tend to be good. Since the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as the (b) used in resin [K4], and (b1-1) is more preferred.

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of (a), (b), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of (a), (b), and (c).

Resin [K5] can be produced in the same manner as Resin [K4], except that (b) is used instead of (a) and (a) is used instead of (b). That is, first, a copolymer of (b) and (c) is obtained, and then the cyclic ether derived from (b) contained in the copolymer of (b) and (c) is reacted with a carboxylic acid or carboxylic anhydride derived from (a), to obtain Resin K5. However, the ratio of the structural unit derived from (b) and the structural unit derived from (c) is, relative to the total number of moles of all structural units constituting the above copolymer,
The structural unit derived from (b) is 5 to 95 mol % and the structural unit derived from (c) is 5 to 95 mol %
It is preferred that
The structural unit derived from (b) is 10 to 90 mol % and the structural unit derived from (c) is 10 to 90 mol %
It is more preferable that:
The amount of (a) reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). Since the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K5], and (b1-1) is more preferred.

Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic acid anhydride. Specifically, the hydroxyl group generated by the reaction of the cyclic ether derived from (b) with the carboxylic acid or carboxylic acid anhydride derived from (a) is reacted with the carboxylic acid anhydride. Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mole per mole of (a).

Specific examples of the resin (B) include resins [K1] such as 3,4-epoxycyclohexylmethyl(meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid copolymer, glycidyl(meth)acrylate/benzyl(meth)acrylate/(meth)acrylic acid copolymer, glycidyl(meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 3, 4-epoxy tricyclo [5.2.1.0 ^{2, 6} ] decyl acrylate copolymer resin [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer and other resins [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer to which glycidyl (meth) acrylate has been added, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer to which glycidyl (meth) acrylate has been added, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer to which glycidyl (meth) acrylate has been added, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer to which glycidyl (meth) acrylate has been added, Resins [K4] such as resins to which acrylate has been added; resins [K5] such as resins obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid, resins [K6] such as resins obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting the resulting copolymer with tetrahydrophthalic anhydride.

The resin [K2] may be, for example, a benzyl methacrylate/acrylic acid/3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate/3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl acrylate copolymer having a structural unit represented by the following formula:

The resin [K4] may be, for example, a resin in which glycidyl methacrylate is added to a tricyclodecyl methacrylate/benzyl methacrylate/methacrylic acid copolymer.

The weight average molecular weight of resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the optical filter is improved, the residual film rate is high, the solubility of the unexposed parts in the developer is good, and the resolution of the colored pattern tends to be improved.

The dispersity of resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of resin (B), calculated as solid content, is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, and even more preferably 70 to 135 mg-KOH/g. Here, the acid value is the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of resin (B) may be, for example, 7 to 65 mass%, 13 to 60 mass%, or 17 to 55 mass% relative to the total amount of solids in the composition. When the content of resin (B) is within the above range, a colored pattern can be formed well, and the resolution and remaining film rate of the colored pattern tend to be improved.

<Polymerizable Compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by the active radicals and/or acid generated from the polymerization initiator (D). The polymerizable compound (C) is, for example, a compound having a polymerizable ethylenically unsaturated bond, and is preferably a (meth)acrylic acid ester.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.), tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol Examples of the acrylate include nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, and caprolactone modified dipentaerythritol hexa(meth)acrylate. Among these, trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are preferred.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2900, and more preferably 250 to 1500.

The content of the polymerizable compound (C) is preferably 7 to 65 mass %, more preferably 13 to 60 mass %, and even more preferably 17 to 55 mass %, based on the total amount of solids in the composition. When the content of the polymerizable compound (C) is within the above range, the residual film rate during color pattern formation and the chemical resistance of the optical filter tend to improve.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by light or heat and initiate polymerization, and any known polymerization initiator can be used.

Polymerization initiators that generate active radicals include, for example, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

The above O-acyloxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bond.

Examples of O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl)phenyl]ethane-1-imine, Examples of the methyl ether ester include N-ethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine. Commercially available products such as Irgacure OXE01, OXE02 (both manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Corporation) may also be used. Among them, from the viewpoint of obtaining a high-brightness optical filter, the O-acyloxime compound is preferably at least one selected from the group consisting of N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and more preferably N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine or N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine.

The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent. From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of compounds having the partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Omnirad (formerly Irgacure) 369, 907, and 379 (all manufactured by IGM Resins B.V.) may also be used.

Examples of compounds having the partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal.

Examples of the triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6- Examples include [2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

The acylphosphine oxide compound may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Omnirad 819 (manufactured by IGM Resins B.V.) may also be used.

The above biimidazole compounds include, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) phenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl) biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913).

Further examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone; benzyl; methyl phenylglyoxylate; and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (particularly an amine compound) described below.

Examples of polymerization initiators that generate acid include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, as well as nitrobenzyl tosylates and benzoin tosylates.

As the polymerization initiator (D), a polymerization initiator that generates active radicals is preferred, a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound is more preferred, and a polymerization initiator containing an O-acyloxime compound is even more preferred.

The content of the polymerization initiator (D) may be, for example, 0.1 to 30 parts by mass or 1 to 20 parts by mass per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the optical filter.

<Polymerization Initiator Auxiliary Agent (D1)>
The composition may further include a polymerization initiation aid (D1). The polymerization initiation aid (D1) is a compound used to promote the polymerization of the polymerizable compound (C) whose polymerization has been initiated by a polymerization initiator, or a sensitizer. The polymerization initiation aid (D1) is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

The above amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc., of which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

Examples of the alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

The above thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

The above carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

When these polymerization initiation aids (D1) are used, the content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with even higher sensitivity, and the productivity of the optical filter tends to improve.

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. Examples of the solvent (E) include ester solvents (i.e., solvents containing -COO- and not containing -O- in the molecule), ether solvents (i.e., solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (i.e., solvents containing -COO- and -O- in the molecule), ketone solvents (i.e., solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and gamma-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole, etc.

　Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, etc.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, etc.

Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, etc.

Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

The solvent preferably contains one or more selected from the group consisting of ether solvents, ether ester solvents, and amide solvents, more preferably contains ether solvents, ether ester solvents, and amide solvents, and even more preferably contains diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, and N-methylpyrrolidone.

The content of the solvent (E) may be, for example, 70 to 95% by mass or 75 to 92% by mass, based on the total amount of the composition. In other words, the solid content of the composition may be, for example, 5 to 30% by mass or 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness during application is good, and the display characteristics tend to be good.

<Leveling Agent (F)>
Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, etc. These surfactants may have a polymerizable group in the side chain.

Examples of silicone-based surfactants include surfactants that have siloxane bonds in the molecule. Specific examples of silicone surfactants include DOWSIL (registered trademark) (formerly Toray Silicone) DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (product names, manufactured by DuPont Toray Specialty Materials Co., Ltd. (formerly Toray Dow Corning Co., Ltd.)); KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

Alternatively, the silicone surfactant may be a silicone surfactant having a fluorine atom. Examples of silicone surfactants having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples of silicone surfactants include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

The above-mentioned fluorosurfactants include, for example, surfactants having a fluorocarbon chain in the molecule. Specific examples of fluorosurfactants include Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited); Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation); F-top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by AGC Inc. (formerly Asahi Glass Co., Ltd.)); and E5844 (manufactured by Daikin Fine Chemicals Research Institute, Ltd.).

The content of the leveling agent (F) may be, for example, 0.001 to 0.2 mass%, 0.002 to 0.1 mass%, or 0.01 to 0.05 mass% relative to the total amount of the composition, from the viewpoint of obtaining an optical filter with good flatness. Note that this content does not include the content of the dispersant.

<Other ingredients>
The composition according to this aspect of the invention may optionally contain additives known in the art, such as fillers, other polymeric compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like.

<Production method of composition>
The composition according to this aspect can be prepared, for example, by mixing the near-infrared absorbing dye (A1), the resin (B), and the solvent (E), as well as the colorant (A2), the polymerizable compound (C), the polymerization initiator (D), the leveling agent (F), the polymerization initiator aid (D1), the dispersant, and other components that are used as needed. The mixed composition is preferably filtered through a filter having a pore size of about 0.01 to 10 μm.

In one embodiment, a dispersion of the near-infrared absorbing dye (A1) and/or colorant (A2) may be prepared, and this dispersion may be mixed with other components to prepare the composition. The dispersion of the near-infrared absorbing dye (A1) and/or colorant (A2) may be prepared by mixing them with a solvent (E) together with an appropriate resin (B) and dispersant, and dispersing them using a bead mill or the like. The diameter of the beads may be, for example, 0.05 to 0.5 mm or less.

Optical Filter and Its Manufacturing Method
An optical filter according to one aspect of the present invention is formed from the above-mentioned composition. The optical filter may include a cured product of the above-mentioned composition, or may be made of a cured product of the above-mentioned composition. The cured product of the composition can be obtained, for example, by irradiating the composition formed into a film with light, or by heating the composition formed into a film. The above-mentioned composition is unlikely to cause aggregates due to the near-infrared absorbing dye even when formed into a film, so that aggregates are reduced in the optical filter formed from the above-mentioned composition. Such an optical filter is also excellent in light resistance.

Furthermore, as described above, the above-mentioned composition absorbs specific wavelengths in the near-infrared region, so that an optical filter formed from the composition can be used as a near-infrared cut filter or a near-infrared transmission filter. Therefore, the optical filter according to this aspect can be used, for example, in infrared sensors and display devices (for example, liquid crystal display devices, organic EL devices, or electronic paper).

The thickness of the optical filter is preferably 20 μm or less, more preferably 6 μm or less, even more preferably 3 μm or less, even more preferably 1.5 μm or less, and particularly preferably 0.5 μm or less. The thickness of the optical filter is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more. The thickness of the optical filter may be, for example, 0.1 to 30 μm, 0.1 to 20 μm, or 0.5 to 6 μm.

The method for manufacturing the optical filter is not particularly limited, and it can be manufactured by a conventionally known method. For example, an optical filter can be formed on any substrate by a photolithography method, an inkjet method, or a printing method. Among these, the photolithography method is preferable.

The substrate may be, for example, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass with a silica-coated surface; a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate; or silicon. Substrates having thin films of aluminum, silver, or silver/copper/palladium alloys on these substrates may also be used. Substrates having hexamethyldisilazane (HMDS) treatment on silicon substrates may also be used. Furthermore, substrates having other optical filters, resin layers, transistors, circuits, etc. on these substrates may also be used.

In the photolithography method, the above-mentioned composition is first applied to a substrate, and the composition is dried to form a coating film. The composition can be applied by, for example, spin coating, slit coating, or slit and spin coating. The thickness of the coating film can be appropriately determined depending on the thickness of the desired optical filter. The composition can be dried by, for example, heat drying (pre-baking) and/or reduced pressure drying. The heat drying temperature is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. The reduced pressure drying is preferably performed at a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C.

Then, the coating film is exposed through a photomask having a predetermined pattern, and then developed by contacting with a developer to form a colored pattern consisting of the cured product of the coating film. The pattern of the photomask can be appropriately determined depending on the application of the optical filter. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. Light of such wavelengths can be obtained, for example, by cutting light of a specific wavelength range (e.g., less than 350 nm) from a specific light source using a filter that cuts this wavelength range, or by selectively extracting light of a specific wavelength (e.g., near 436 nm, near 408 nm, or near 365 nm) using a bandpass filter that extracts these wavelength ranges. The light source may be, for example, a mercury lamp, a light-emitting diode, a metal halide lamp, or a halogen lamp. It is preferable to use a reduction projection exposure device or a proximity exposure device such as a mask aligner and a stepper, because it is possible to uniformly irradiate the entire exposure surface with parallel light rays and to accurately align the photomask and the substrate.

The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of the alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. The developer may contain a surfactant. Development may be performed by, for example, a paddle method, a dipping method, or a spray method. The substrate may be tilted at any angle during development. By development, the unexposed parts of the coating film are dissolved in the developer and removed.

It is preferable to perform post-baking on the obtained colored pattern. The post-baking temperature may be, for example, 80 to 250°C, 100 to 245°C, 150 to 250°C, or 160 to 250°C. The post-baking time may be, for example, 1 to 120 minutes, 2 to 30 minutes, or 5 to 60 minutes.

In addition, in the above photolithography method, by not using a photomask during exposure and/or by not developing, it is possible to obtain a cured coating film that is not patterned.

The cured product of the coating and the color pattern are both included in the scope of the optical filter according to this aspect.

<Solid-state imaging element>
A solid-state imaging device according to one aspect of the present invention includes the optical filter described above. The optical filter may be a near-infrared transmission filter and/or a near-infrared cut filter. The portions of the solid-state imaging device other than the optical filter may be the same as those of a conventionally known solid-state imaging device. An example of a solid-state imaging device is shown in FIG. 1.

The solid-state imaging element 100 shown in FIG. 1 includes a semiconductor substrate 2 including a light receiving element and the like (not shown), a near-infrared cut filter 4, a near-infrared transmission filter 6, a color filter 8, a microlens 10, and a planarization layer 12. The near-infrared cut filter 4 and/or the near-infrared transmission filter 6 may be the optical filters described above. The color filter 8 is not particularly limited, and may be a conventionally known color filter for pixel formation, such as the color filter described in JP-A-2014-043556. The microlens 10 and planarization layer 12 are also not particularly limited, and may be a known microlens and planarization layer.

In the solid-state imaging device 100 shown in FIG. 1, the near-infrared cut filter 4, the color filter 8, and the microlens 10 are laminated in this order, but the positions of the near-infrared cut filter 4 and the color filter 8 may be interchanged.
Between the transparent electrode 1 and the color filter 8, another further layer may be provided.

The solid-state imaging device can be used, for example, in an infrared sensor. That is, according to one aspect of the present invention, there is also provided an infrared sensor including the above-mentioned solid-state imaging device.

<Method for producing the compound represented by formula (I)>
A method for producing a compound represented by formula (I) according to one aspect of the present invention includes a step of reacting a compound represented by formula (I-x1), a compound represented by formula (I-x2), and a compound represented by formula (I-y1) or a compound represented by formula (I-y2) in the presence of a catalyst. Hereinafter, the compound represented by formula (I-x1), the compound represented by formula (I-x2), the compound represented by formula (I-y1), and the compound represented by formula (I-y2) may be collectively referred to as "raw material compounds".

This reaction is the so-called Suzuki coupling and Heck reaction, which causes ring formation and results in the formation of a pentalylene skeleton. The method according to this aspect requires fewer steps and can more easily produce the compound represented by formula (I) compared to the conventional method for producing a compound having a pentalylene skeleton.

In formula (I-x1) and formula (I-x2), R ¹ to R ¹⁰ , X ¹ to X ⁴ , and Y ¹ , Y ⁴ , Y ⁵ , and Y ⁸ are as defined and explained in formula (I).

In formulae (I-x1) and (I-x2), Z ¹ to Z ⁴ each independently represent a bromine atom or an iodine atom.

In formula (I-y1) and formula (I-y2), Y ² , Y ³ , Y ⁶ and Y ⁷ are as defined and explained in formula (I).

In formula (I-y1) and formula (I-y2), A ¹ and A ² each independently represent a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms, or an OR ¹³ group.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by A ¹ and A ² include the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ⁴ , R ⁵ or R ⁸ .

R ¹³ represents a hydrocarbon group having 1 to 20 carbon atoms. When two or more R ¹³ are present in formula (I-y1) or formula (I-y2), they may be the same or different. Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹³ include the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ⁴ , R ⁵ , or R ^8. R ¹³ may be, for example, a methyl group, an ethyl group, or an isopropyl group.

OR ¹³ groups bonded to the same boron atom may be bonded to each other to form a ring. The ring formed may be, for example, a ring represented by the following formula:

The compound represented by formula (I-x1), the compound represented by formula (I-x2), the compound represented by formula (I-y1), and the compound represented by formula (I-y2) can all be synthesized by a person skilled in the art in accordance with known methods.

The ratio of the total number of moles of the compound represented by formula (I-x1) and the compound represented by formula (I-x2) to the number of moles of the compound represented by formula (I-y1) is usually 2:1, but may be 4.0:1 to 1.5:1.

The ratio of the total number of moles of the compound represented by formula (I-x1) and the compound represented by formula (I-x2) to the number of moles of the compound represented by formula (I-y2) is usually 2:1, but may be 4.0:1 to 1.5:1.

Also, both the compound represented by formula (I-y1) and the compound represented by formula (I-y2) may be used. In that case, the ratio of the total number of moles of the compound represented by formula (I-x1) and the compound represented by formula (I-x2) to the total number of moles of the compound represented by formula (I-y1) and the compound represented by formula (I-y2) is usually 2:1, but may be 4.0:1 to 1.5:1.

The catalyst is not particularly limited as long as it is a catalyst that catalyzes the Suzuki-Miyaura cross-coupling and Heck-Mizoroki cross-coupling reactions, and may be, for example, a transition metal complex such as a palladium complex or a nickel complex. Examples of palladium complexes include tris(benzylideneacetone)dipalladium(0), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) dichloride, and palladium acetate. Examples of nickel complexes include tetrakis(triphenylphosphine)nickel(0), [1,3-bis(diphenylphosphino)propane)nickel(II) dichloride, and bis(1,4-cyclooctadiene)nickel(0). The catalyst may be the above-mentioned transition metal complex further having a ligand such as tricyclohexylphosphine, triphenylphosphine, tri(o-tolyl)phosphine, tri(tert-butyl)phosphine, 1,3-bis(diphenylphosphino)propane, bipyridyl, etc. The catalyst is preferably tris(benzylideneacetone)dipalladium(0) having tricyclohexylphosphine as a ligand.

The amount of catalyst used may be, for example, 0.001 to 0.3 mol% relative to the total number of moles of the compound represented by formula (I-y1) and the compound represented by formula (I-y2), and is preferably 0.05 to 0.3 mol%.

The above reaction is preferably carried out in the presence of a base. The base may be, for example, an inorganic base such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, or tripotassium phosphate, or an organic base such as tetrabutylammonium fluoride, tetraethylammonium hydroxide, or tetrabutylammonium hydroxide.

The amount of base used may be 1 to 100 moles, and preferably 3 to 20 moles, per mole of the compound represented by formula (I-y1) and the compound represented by formula (I-y2).

The solvent for the above reaction is not particularly limited as long as it does not adversely affect the reaction. For example, mesitylene, xylene, toluene, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, 1,4-dioxane, and cyclopentyl methyl ether can be used.

The amount of the solvent used is, for example, 1 to 100 parts by mass, preferably 5 to 50 parts by mass, per 1 part by mass of the total of the compound represented by formula (I-y1) and the compound represented by formula (I-y2).

The reaction temperature may be, for example, 40 to 200°C or 100 to 180°C. The reaction time may be, for example, 0.5 to 50 hours or 5 to 30 hours.

In one embodiment, the above production method may further include a step of substituting some or all of R ¹ to R ⁸ in the compound represented by formula (I) obtained in the above step of reacting the raw material compounds with other types of R ¹ to R ^8. For example, when R ¹ to R ⁸ in the obtained compound represented by formula (I) are halogen atoms, some or all of the halogen atoms can be substituted with OR ¹¹ groups by reacting the compound represented by formula (I) with R ¹¹ OH.

The present invention will be explained in more detail below with reference to examples. However, the present invention is not limited to the following examples, and it is of course possible to carry out the invention with appropriate modifications within the scope of the above-mentioned intent, and all such modifications are included within the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

In the following synthesis examples, the structures of the compounds were confirmed using a mass spectrometer (LC: Agilent 1200 model, MASS: Agilent LC/MSD6130 model) or NMR (Varian 400-MR).

In the following synthesis examples, the maximum absorption wavelength of each compound was confirmed using an ultraviolet-visible-near infrared absorption spectrometer (V-770, manufactured by JASCO Corporation). Specifically, a 10 ppm chloroform solution of the compound was prepared, and the absorbance was measured in the wavelength range of 300 to 1400 nm (data sampling interval 1 nm) to confirm the maximum absorption wavelength.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40°C
Solvent: tetrahydrofuran Flow rate: 1.0 mL/min Solids concentration of analytical sample: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight average molecular weight and number average molecular weight (Mw/Mn) calculated in terms of polystyrene obtained above was taken as the degree of dispersion.

<Synthesis Example 1: Synthesis of compound (IA)>
Under a nitrogen atmosphere, 5.4 parts of naphthalene-1,4,5,8-tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.), and 104 parts of water were mixed and heated to 85°C. 8.0 parts of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added dropwise over 1 hour, and the mixture was stirred for 3 hours. After cooling to 10°C, 11 parts of concentrated hydrochloric acid were added dropwise, resulting in the formation of a white precipitate. The mixture containing this white precipitate was filtered, and the residue after filtration was washed with 50 parts of water and 20 parts of methanol. The resulting residue was dried under reduced pressure at 60°C to obtain 6.8 parts of 4,5-dibromonaphthalene-1,8-dicarboxylic dianhydride (compound (I-A)).

<Synthesis Example 2: Synthesis of compound (IB)>
Under a nitrogen atmosphere, 2.5 parts of compound (I-A), 5.0 parts of 2-ethylhexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 15 parts of 1-methyl-2-pyrrolidone (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), and 15 parts of propionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 160°C for 12 hours. After cooling to 10°C, 100 parts of water were added dropwise, resulting in the formation of a light brown precipitate. The mixture containing this light brown precipitate was filtered, and the residue after filtration was washed with 50 parts of water and 10 parts of methanol. The obtained residue was purified by silica gel column chromatography (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 2.0 parts of compound (IB).

Identification of compound (IB):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 466
Exact Mass: 465

Synthesis Example 3: Synthesis of compound (IC)
Under a nitrogen atmosphere, 22 parts of compound (IB), 10 parts of 4,4,5,5-tetramethyl-2-(1-naphthyl)-1,3,2-dioxaborolane, 3.6 parts of tris(dibenzylideneacetone)dipalladium(0) (Tokyo Chemical Industry Co., Ltd.), 4.4 parts of tricyclohexylphosphine (Fujifilm Wako Pure Chemical Industries, Ltd.), 67 parts of potassium carbonate (Kanto Chemical Co., Ltd.), and 720 parts of dehydrated xylene (Kanto Chemical Co., Ltd.) were mixed and stirred at 145°C for 18 hours. After cooling to 20°C, the reaction liquid was filtered. The solvent was distilled off under reduced pressure, and the crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 9 parts of a red solid of compound (IC).

Identification of compound (IC):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 434
Exact Mass: 433

<Synthesis Example 4: Synthesis of compound (ID)>
Under a nitrogen atmosphere, 10 parts of compound (IC), 737 parts of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 700 parts of chloroform (manufactured by Nacalai Tesque, Inc.) were mixed and stirred at 60°C for 48 hours. After the reaction was completed, the reaction solution was cooled to room temperature (18 to 24°C), and 3000 parts of an aqueous sodium sulfite solution (1M) was added. The mixture was washed with 700 parts of chloroform and subjected to a liquid separation operation. The obtained organic layer was dehydrated with anhydrous sodium sulfate (manufactured by Kanto Chemical Co., Ltd.), and the sodium sulfate was filtered, and the solvent was distilled off. The crude product was purified by silica gel column chromatography (solvent: chloroform/ethyl acetate = 5/1 (volume/volume)), and 5.3 parts of colorless crystals of compound (ID) were obtained.

Identification of compound (ID):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 746
Exact Mass: 745

Synthesis Example 5: Synthesis of compound (I-x-1)
Under a nitrogen atmosphere, 10 parts of compound (ID), 4.0 parts of 4-propoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.1 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.), and 323 parts of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 120°C for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature (18 to 24°C), and 198 parts of concentrated hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 992 parts of water were added. The precipitated solid was washed twice with 200 parts of ion-exchanged water and then twice with 200 parts of methanol, and decanted. The crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 8.5 parts of a red solid of compound (I-x-1).

Identification of compound (I-x-1):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 890
Exact Mass: 889

Synthesis Example 6: Synthesis of compound (I-y-1)
Under a nitrogen atmosphere, 5.0 parts of 1,8-dibromonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 11 parts of bis(pinacolato)diboron (manufactured by Tokyo Chemical Industry Co., Ltd.), 10 parts of potassium acetate (manufactured by Kanto Chemical Co., Ltd.), 1.3 parts of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 95 parts of dehydrated N,N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 90° C. for 17 hours. The resulting mixture was filtered through Celite, and the filtrate was concentrated. The residue was washed with 18 parts of methanol. The resulting residue was dried under reduced pressure at 60° C. to obtain 5.6 parts of a compound (Compound (I-y-1).

Identification of compound (I-y-1):
^1H NMR (400MHz, CDCl3, ₂₅ [deg.]C) δ 1.42 (s, 24H), 7.51 (dd, 2H), 8.02 (s, 2H), 8.75 (dd, 2H).

Synthesis Example 7: Synthesis of Example Compound (I-2)
Under a nitrogen atmosphere, 52 parts of compound (I-x-1), 10 parts of compound (I-y-1), 4.8 parts of tris(dibenzylideneacetone)dipalladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.9 parts of tricyclohexylphosphine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 45 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.), and 720 parts of mesitylene (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 160 ° C. for 18 hours. After the reaction was completed, the reaction liquid was cooled to room temperature and poured into 8000 parts of methanol. The precipitated solid was washed twice with 200 parts of ion-exchanged water, followed by washing twice with 200 parts of methanol, and decantation was performed. The crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 28 parts of a dark green solid of compound (I-2).

Identification of compound (I-2):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 1588
Exact Mass: 1587
(Absorption spectrum) 10 ppm chloroform solution Maximum absorption wavelength (λ _max ): 889 nm

<Synthesis Example 8: Synthesis of compound (IE)>
Under a nitrogen atmosphere, 10 parts of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic anhydride (manufactured by CombiBlcok), 6.8 parts of sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.), and 490 parts of water were mixed. 6.6 parts of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 4.5 parts of acetic acid (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 80°C for 2 hours. After completion of the reaction, the reaction liquid was cooled to room temperature (18 to 24°C). The precipitated solid was filtered, washed twice with 100 parts of ion-exchanged water and then twice with 100 parts of methanol, and decanted. The mixture was dried under reduced pressure at 60°C to obtain 10 parts of yellow crystals of compound (I-E).

Synthesis Example 9: Synthesis of compound (I-x-2)
Under a nitrogen atmosphere, 10 parts of compound (I-E), 5.7 parts of 2,6-diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 80 parts of acetic acid (manufactured by Kanto Chemical Co., Ltd.), and 160 parts of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 110° C. for 49 hours. After completion of the reaction, the reaction liquid was cooled to room temperature (18 to 24° C.), and 2,500 parts of water were added. The precipitated solid was filtered and washed twice with 30 parts of ion-exchanged water. The crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 6.5 parts of a red solid of compound (I-x-2).

Identification of compound (I-x-2):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 774
Exact Mass: 773

Synthesis Example 10: Synthesis of Example Compound (I-1)
13 parts of dark green crystals of compound (I-1) were obtained in the same manner as in the synthesis of compound (I-2) in Synthesis Example 7, except that 52 parts of compound (I-x-1) (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 45 parts of compound (I-x-2).

Identification of compound (I-1):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 1355
Exact Mass: 1354
(Absorption spectrum) 10 ppm chloroform solution Maximum absorption wavelength (λ _max ): 822 nm

Synthesis Example 11: Synthesis of Example Compound (I-3)
Under a nitrogen atmosphere, 10 parts of compound (I-1), 12 parts of 4-tert-butylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 12 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.), and 323 parts of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 120 ° C. for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature (18 to 24 ° C.), and 198 parts of concentrated hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 992 parts of water were added. The precipitated solid was washed twice with 200 parts of ion-exchanged water, followed by washing twice with 200 parts of methanol, and decantation was performed. The crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 13 parts of dark green crystals of a mixture of compounds represented by formula (I-3) (hereinafter, for convenience, this mixture of compounds is referred to as compound (I-3)). The mixture of compounds represented by formula (I-3) was a mixture of three types of compounds containing, as the substituent R in formula (I-3), a chlorine atom and a 4-tert-butylphenoxy group in ratios of 3/5, 2/6, and 1/7, respectively.

Identification of compound (I-3):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 1934, 2048, 2162
Exact Mass: 1933, 2047, 2161
(Absorption spectrum) 10 ppm chloroform solution Maximum absorption wavelength (λ _max ): 891 nm

Synthesis Example 12: Synthesis of compound (IF)
Thirteen parts of red crystals of compound (IF) were obtained in the same manner as in the synthesis of compound (IB) in Synthesis Example 2, except that 5.0 parts of 2-ethylhexylamine was changed to 5.2 parts of 2,6-diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.).

Identification of compound (I-F):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 514
Exact Mass: 513

<Synthesis Example 13: Synthesis of compound (IG)>
Eleven parts of red crystals of compound (IG) were obtained in the same manner as in the synthesis of compound (IC) in Synthesis Example 3, except that compound (IB) was changed to compound (IF).

Identification of compound (IG):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 482
Exact Mass: 481

<Synthesis Example 14: Synthesis of compound (I-H)>
Under a nitrogen atmosphere, 10 parts of compound (IG), 183 parts of bromine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and 1860 parts of chloroform (manufactured by Nacalai Tesque, Inc.) were mixed and stirred at 65°C for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature (18 to 24°C), and 1667 parts of water, potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.), and 8.3 parts of sodium sulfite (manufactured by Kanto Chemical Co., Ltd.) were added, and a separation operation was performed. The obtained organic layer was dehydrated with anhydrous sodium sulfate (manufactured by Kanto Chemical Co., Ltd.), and the sodium sulfate was filtered, and the solvent was distilled off. The crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 12 parts of red crystals of compound (I-H).

Identification of compound (I-H):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 716
Exact Mass: 715

Synthesis Example 15: Synthesis of compound (I-J)
7.5 parts of red crystals of compound (I-J) were obtained in the same manner as in the synthesis of compound (I-x-1) in Synthesis example 5, except that compound (ID) was changed to compound (I-H) and 4.0 parts of 4-propoxyphenol was changed to 4.2 parts of 4-tert-butylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.).

Identification of Compound (I-J):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 856
Exact Mass: 855

<Synthesis Example 16: Synthesis of compound (I-K)>
38 parts of red crystals of compound (IK) were obtained in the same manner as in the synthesis of compound (I-2) in Synthesis Example 7, except that 52 parts of compound (I-x-1) was changed to 45 parts of compound (I-J).

Identification of compound (I-K):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 1680
Exact Mass: 1679
(Absorption spectrum) 10 ppm chloroform solution Maximum absorption wavelength (λ _max ): 873 nm

Synthesis Example 17: Synthesis of Example Compound (I-4)
Under a nitrogen atmosphere, 10 parts of compound (I-K), 6.5 parts of anhydrous iron(III) chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 57 parts of nitromethane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 465 parts of chloroform (manufactured by Nacalai Tesque, Inc.) were mixed and stirred at 20 to 25 ° C. for 24 hours. After the reaction was completed, the solvent was distilled off and the mixture was washed with 300 parts of water. 17 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.) and 357 parts of ethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 130 ° C. for 16 hours. After the reaction was completed, the reaction solution was cooled to room temperature (18 to 24 ° C.), and 7,500 parts of water were added. The precipitated solid was filtered and washed twice with 30 parts of ion-exchanged water. The crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 4.8 parts of a dark green solid of compound (I-4).

Identification of compound (I-4):
(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 1676
Exact Mass: 1675
(Absorption spectrum) 10 ppm chloroform solution Maximum absorption wavelength (λ _max ): 877 nm

Synthesis Example 18: Synthesis of Resin (B-1)
A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 340 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring. Next, a mixed solution of 57 parts of acrylic acid, 54 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl acrylate (content ratio is 1:1 in molar ratio), 239 parts of benzyl methacrylate, and 73 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a solution of 40 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 197 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition of the initiator solution was completed, the reaction solution was kept at 80°C for 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution with a solid content of 37.0%. The viscosity of the copolymer solution measured with a Brookfield viscometer (23°C) was 127 mPa·s. The weight average molecular weight Mw of the copolymer was 9.4×10 ³ , the dispersity was 1.89, and the acid value calculated as solid content was 114 mg-KOH/g. Resin B-1 has the following structural units.

Example 1
(1) Preparation of Composition 1 30 parts of compound (I-1), 24 parts (solid content equivalent) of a dispersant (propylene glycol monomethyl ether acetate 60% solution, BYKLPN-6919, manufactured by BYK Corporation), 24 parts (solid content equivalent) of resin (B-1), 522 parts of propylene glycol monomethyl ether acetate, and 900 parts of 0.2 mm zirconia beads were mixed, and the resulting mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Thereafter, the zirconia beads were removed by filtration to obtain composition 1.

(2) UV-Vis-Near-Infrared Absorption Spectroscopy of Composition 1 Composition 1 was diluted with propylene glycol monomethyl ether acetate so that the content of compound (I-1) in composition 1 was 10 ppm, and the absorbance was measured in the wavelength range of 300 to 1400 nm (data sampling interval 1 nm). The maximum absorption wavelength λ _max was 830 nm. The ratio Abs(780)/Abs(λ _{max ) of the absorbance Abs(780) at a wavelength of 780 nm to the absorbance Abs(λ max} ₎ at λ max was calculated to be 1.0. In addition, the ratio Abs(900-1400)/Abs(λ _max ) of the maximum absorbance Abs(900-1400) at a wavelength range of 900 to 1400 nm to Abs(λ _max ₎ was calculated to be 0.11.

(3) Evaluation of Viscosity of Composition 1 The viscosity of Composition 1 was measured using a Brookfield viscometer (23° C.) and evaluated on a 5-point scale. The evaluation criteria were as follows:
1: 0 or more and less than 8 mPa·s
2: 8 or more and less than 20 mPa·s
3: 20 or more and less than 1,000 mPa·s
4: 1,000 or more but less than 10,000 mPa·s
5: 10,000 or more mPas
The high viscosity is considered to be due to aggregation of the pigments caused by the low stability of the dispersion of the near-infrared absorbing pigment contained in the composition. If the viscosity of the dispersion of the near-infrared absorbing pigment is low, the stability of the dispersion is high, and it is preferable that the dispersion is easy to handle during the production process of the optical filter.

(4) Preparation of Curable Composition 1 Curable composition 1 was obtained by mixing the following components.
Composition 1: 720 parts Resin (B): Resin (B-1) 73 parts (solid equivalent)
Polymerizable compound (C): Dipentaerythritol polyacrylate (trade name A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) 68 parts Polymerization initiator (D): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (trade name TR-PBG327, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) 5.1 parts Solvent (E): Propylene glycol monomethyl ether acetate 1134 parts Leveling agent (F): Polyether modified silicone oil (trade name DOWSIL SH8400, manufactured by DuPont Toray Specialty Materials Co., Ltd.) 1.4 parts

(5) Preparation of Optical Filter 1 and Confirmation of Aggregates The curable composition 1 was applied to a 5 cm square glass substrate (Eagle 2000, Corning Incorporated) by spin coating, and then prebaked at 100°C for 3 minutes. After cooling, the obtained coating film was irradiated with light at an exposure dose of 1000 mJ/ ^cm2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK, Topcon Corporation). Thereafter, post-baking was performed in an oven at 220°C for 5 minutes to obtain an optical filter 1. The presence or absence of aggregates on the obtained optical filter 1 was visually confirmed.

(6) Lightfastness Test of Optical Filter 1 An ultraviolet cut filter (COLORED OPTICAL GLASS L38, manufactured by Hoya Co., Ltd.) that cuts light of 380 nm or less was placed on the optical filter 1, and xenon lamp light was irradiated for 48 hours using a lightfastness tester (SUNTEST CPS+, manufactured by Toyo Seiki Seisakusho Co., Ltd.). The absorbance at the maximum absorption wavelength of the optical filter 1 before and after irradiation was measured, and the absorbance maintenance rate shown in the following formula was calculated. It can be said that the higher the absorbance maintenance rate, the better the lightfastness of the optical filter.
Absorbance maintenance rate (%)=(absorbance at the maximum absorption wavelength of the optical filter after irradiation)/(absorbance at the maximum absorption wavelength of the optical filter before irradiation)×100

<Comparative Example 1>
Comparative composition 1, comparative curable composition 1, and comparative optical filter 1 were prepared in the same manner as composition 1, curable composition 1, and optical filter 1 in Example 1, respectively, except that the compound (I-1) was replaced with the same amount of Lumogen (registered trademark) F Orange 240 (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula. Comparative composition 1 and comparative optical filter 1 were subjected to various evaluations (viscosity, presence or absence of aggregates, and light resistance test) in the same manner as in Example 1.

The results of various evaluations (viscosity, presence or absence of aggregates, and light resistance test) in Example 1 and Comparative Example 1 are shown in Table 1.

<Examples 2 to 4>
Compositions 2 to 4, curable compositions 2 to 4, and optical filters 2 to 4 are prepared in the same manner as the composition 1, curable composition 1, and optical filter 1 of Example 1, respectively, except that compound (I-1) is replaced with compound (I-2), (I-3), or (I-4). Various evaluations (viscosity, presence or absence of aggregates, and light resistance test) are performed on compositions 2 to 4 and optical filters 2 to 4 in the same manner as in Example 1. Compositions 2 to 4 containing compounds (I-2) to (I-4) as near-infrared absorbing dyes have low viscosity, and optical filters 2 to 4 prepared from curable compositions 2 to 4 containing compounds (I-2) to (I-4), respectively, have no aggregates and are excellent in light resistance.

2: semiconductor substrate, 4: near-infrared cut filter, 6: near-infrared transmission filter, 8: color filter, 10: microlens, 100: solid-state imaging element.

Claims

A composition comprising a near-infrared absorbing dye, an alkali-soluble resin, and a solvent,
The composition, wherein the near infrared absorbing dye comprises a compound represented by formula (I):

[In formula (I),
R 1 , R 4 , R 5 , and R 8 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or an OR 11 group;
R 2 , R 3 , R 6 and R 7 each independently represent a hydrogen atom, a halogen atom or an OR 11 group;
R 9 , R 10 , and R 11 each independently represent a hydrocarbon group having 1 to 20 carbon atoms;
When two or more R 11 are present, they may be the same or different from each other;
X 1 to X 4 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
Y 1 to Y 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an OR 12 group;
R 12 represents an alkyl group having 1 to 5 carbon atoms, and when two or more R 12 are present, they may be the same or different.
The composition according to claim 1, wherein X 1 to X 4 and Y 1 to Y 8 in formula (I) are hydrogen atoms.
The composition according to claim 2, further comprising a polymerization initiator and a polymerizable compound.
An optical filter formed from the composition according to any one of claims 1 to 3.
A solid-state imaging device including the optical filter according to claim 4.
A compound represented by formula (Ia).

[In formula (Ia),
R 1a , R 4a , R 5a , and R 8a each independently represent a halogen atom;
R 2a , R 3a , R 6a and R 7a each independently represent a hydrogen atom, a halogen atom or an OR 11a group;
R 9 and R 10 each independently represent a hydrocarbon group having 1 to 20 carbon atoms;
R 11a represents a hydrocarbon group having 1 to 13 carbon atoms, and when two or more R 11a are present, they may be the same or different from each other.
X 1 to X 4 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
Y 1 to Y 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an OR 12 group;
R 12 represents an alkyl group having 1 to 5 carbon atoms, and when two or more R 12 are present, they may be the same or different.
A method for producing a compound represented by formula (I), comprising a step of reacting a compound represented by formula (I-x1), a compound represented by formula (I-x2), and a compound represented by formula (I-y1) or a compound represented by formula (I-y2) in the presence of a catalyst.

[In formulas (I-x1) and (I-x2),
R 1 , R 4 , R 5 , and R 8 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or an OR 11 group;
R 2 , R 3 , R 6 and R 7 each independently represent a hydrogen atom, a halogen atom or an OR 11 group;
R 9 , R 10 , and R 11 each independently represent a hydrocarbon group having 1 to 20 carbon atoms;
When two or more R 11 are present, they may be the same or different from each other;
X 1 to X 4 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
Y 1 , Y 4 , Y 5 , and Y 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an OR 12 group;
R 12 represents an alkyl group having 1 to 5 carbon atoms, and when two or more R 12 are present, they may be the same or different from each other.
Z 1 to Z 4 each independently represent a bromine atom or an iodine atom.]

[In formulas (I-y1) and (I-y2),
Y 2 , Y 3 , Y 6 , and Y 7 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an OR 12 group;
A 1 and A 2 each independently represent a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, or an OR 13 group;
R 13 represents a hydrocarbon having 1 to 20 carbon atoms, and when two or more R 13 are present, they may be the same or different from each other;
OR 13 groups bonded to the same boron atom may be bonded to each other to form a ring.

[In formula (I),
R 1 to R 10 , X 1 to X 4 , and Y 1 to Y 8 are as defined above.]