TW202413361A - Composition, optical filter, solid-state imaging element, compound and method for producing the compound - Google Patents

Abstract

The subject of the present invention is to provide a composition that can form agglomerates to obtain a reduced optical filter. A composition contains a near-infrared absorbing pigment, an alkali-soluble resin and a solvent, wherein the near-infrared absorbing pigment contains a compound represented by formula (I).

Description

Composition, optical filter, and solid-state imaging device

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

As an example of an optical filter used in a display device such as a liquid crystal display device, an electroluminescent display device, a plasma display, and a solid-state imaging element such as a charge coupled device (CCD) and a complementary metal-oxide-semiconductor (CMOS) sensor, there is a filter that absorbs near-infrared light. As a material for making such a filter that absorbs near-infrared light, for example, a composition containing a near-infrared absorbing pigment such as a compound having a cyanine structure is known (for example, Patent Document 1). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2016-060774

[Problem to be solved by the invention] If an optical filter is formed from a previous composition containing a near-infrared absorbing pigment, agglomerates caused by the near-infrared absorbing pigment may be generated. Therefore, an object of the present invention is to provide a composition of an optical filter in which agglomerates can be reduced. In addition, an object of the present invention is also to provide a compound that can be used to prepare such a composition and a simple method for producing the compound. [Means for solving the problem]

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

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

[Chemistry 2] [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 alkyl group having 1 to 20 carbon atoms, R ^11a represents a alkyl group having 1 to 13 carbon atoms, and when there are two or more R ^{11a s} , 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 there are two or more R 11a s, they may be the same or different from each other. ¹² , these may be the same as or different from each other] [7] A method for producing a compound represented by formula (I), the method comprising 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.

[Chemistry 3] [In formula (I-x1) and formula (I-x2), R ¹ , R ⁴ , R ⁵ and R ⁸ each independently represent a alkyl 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 alkyl group having 1 to 20 carbon atoms, when there are two or more R ^11s , they may be the same or different, 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 ^{R 12} represents an alkyl group having 1 to 5 carbon atoms. When there are two or more R ¹² , they may be the same as or different from each other. Z ¹ to Z ⁴ each independently represent a bromine atom or an iodine atom.

[Chemistry 4] [In formula (I-y1) and formula (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 alkyl group having 1 to 20 carbon atoms, or an OR ¹³ group, R ¹³ represents a alkyl group having 1 to 20 carbon atoms, and when there are two or more R ¹³ groups, they may be the same or different from each other, and the OR ¹³ groups bonded to the same boron atom may bond to each other to form a ring]

[Chemistry 5] [In formula (I), R ¹ to R ¹⁰ , X ¹ to X ⁴ and Y ¹ to Y ⁸ have the same meanings as above] [Effects of the Invention]

According to the present invention, a composition capable of forming an optical filter with reduced agglomerates is provided. In addition, according to the present invention, an optical filter with reduced agglomerates and a solid-state imaging device including the optical filter are provided. Furthermore, according to the present invention, a compound that can be used to prepare the composition and a simple (more specifically, a method with a small number of steps) production method of the compound are provided.

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

The composition of the present invention contains the compound represented by the formula (I) described later as a near-infrared absorbing pigment, so it is not easy to produce agglomerates caused by the near-infrared absorbing pigment even if the film is formed. Therefore, according to the composition of the present invention, an optical filter with reduced agglomerates can be formed. The formed optical filter also has excellent light resistance. In addition, as described later, the compound represented by the formula (I) absorbs a specific wavelength in the near-infrared region, so the formed optical filter can be used as a near-infrared cutoff filter or a near-infrared transmission filter.

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

[Chemistry 6]

In formula (I), R ¹ , R ⁴ , R ⁵ , and R ⁸ each independently represent a alkyl 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 alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ⁴ , R ⁵ or R ⁸ include aliphatic alkyl groups and aromatic alkyl groups. The aliphatic alkyl group may be saturated or unsaturated, and may be chain or alicyclic.

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

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

Examples of the aromatic hydrocarbon group represented by R ¹ , R ⁴ , R ⁵ or R ⁸ include phenyl, 1-naphthyl, 2-naphthyl, phenanthrenyl, anthracenyl, pyrenyl and the like. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12.

The alkyl group represented by R ¹ , R ⁴ , R ⁵ or R ⁸ may be a group formed by combining two or more of the above-mentioned chain alkyl groups, alicyclic alkyl groups, and aromatic alkyl groups, as long as the upper limit of the carbon number is 20 or less. Such a group may be, for example, a group formed by combining an aromatic alkyl group and at least one group selected from chain alkyl groups, alicyclic alkyl groups, and aromatic alkyl groups, and in the combined alkyl group, the chain alkyl group may be combined as a divalent group (for example, an alkanediyl group). Examples of the combined alkyl groups include aralkyl groups such as benzyl, phenethyl, 1-methyl-1-phenylethyl, t-butylphenyl, t-octylphenyl, t-butylbenzyl, and t-octylbenzyl; arylalkenyl groups such as phenylvinyl (phenylvinyl); arylalkynyl groups such as phenylethynyl; o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, and 2,5-dimethylphenyl. , 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, 2,3-diisopropylphenyl, 2,4-diisopropylphenyl, 2,5-diisopropylphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-butylphenyl, o-t-butylphenyl, m-t-butylphenyl, p-t-butylphenyl, 2,6-di(t-butyl)phenyl, 3 ,5-di(tert-butyl)phenyl, 3,6-di(tert-butyl)phenyl, 4-tert-butyl-2,6-dimethylphenyl, 4-pentylphenyl, 4-octylphenyl, 4-(2,4,4-trimethyl-2-pentyl)phenyl, 2-dodecylphenyl, 3-dodecylphenyl, 4-dodecylphenyl and other alkylaryl groups; 2,3-dihydro-4-indenyl, 1,2,3,5,6,7-hexahydro-4-same-benzodiindenyl, 8-methyl-1,2,3,5,6 an aryl group formed by bonding an alkanediyl group such as 7-hexahydro-4-s-benzodiindenyl, 5,6,7,8-tetrahydro-1-naphthyl, 5,6,7,8-tetrahydro-2-naphthyl, 3-methyl-5,6,7,8-tetrahydro-2-naphthyl, 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl to form a ring; an aryl group formed by bonding more than one aryl group such as biphenyl and terphenyl; cyclohexylmethylphenyl, benzylphenyl, (dimethyl(phenyl)methyl)phenyl, etc. The alkyl group may be a alkyl group formed by a combination of a chain alkyl group and an alicyclic alkyl group, and examples thereof include 1-methylcyclopropyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3 an alicyclic alkyl group formed by bonding to one or more alkyl groups such as cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylcyclohexylmethyl, cyclohexylethyl and adamantylmethyl; and the like. The carbon number of the group consisting of two or more of the chain alkyl group, the alicyclic alkyl group and the aromatic alkyl group is preferably 6 to 18 or 7 to 18, 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 alkyl group having 1 to 20 carbon atoms. When there are two or more R ^11s in formula (I), they may be the same as or different from each other. As the alkyl group having 1 to 20 carbon atoms represented by R ¹¹ , for example, the groups exemplified as the alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ⁴ , R ⁵ or R ⁸ can be cited. As the alkyl group having 1 to 20 carbon atoms, an aromatic alkyl group is preferred, and phenyl, tolyl, methoxyphenyl, propoxyphenyl, t-butylphenyl or t-octylphenyl is more preferred, and propoxyphenyl or t-butylphenyl is most preferred. The alkyl group preferably has 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms.

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), ^R9 and ^R10 each independently represent a alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms represented by ^R9 or ^R10 include the groups exemplified as the alkyl group having 1 to 20 carbon atoms represented by ^R1 , ^R4 , ^R5 or ^R8 . Examples of the alkyl group having 1 to 20 carbon atoms include groups represented by the following formulae (D-1) to (D-47) or (G-1) to (G-24). In the formulae, * represents a bonding bond.

[Chemistry 7]

[Chemistry 8]

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

In formula (I), X ¹ to X ⁴ each independently represents 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 ^X1 to ^X4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, neopentyl, t-pentyl, n-hexyl, cyclohexyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl and n-decyl.

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 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, and n-pentyl.

R ¹² represents an alkyl group having 1 to 5 carbon atoms. When there are two or more R ¹² groups in formula (I), they may be the same as 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).

[Chemistry 9]

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 alkyl group having 1 to 13 carbon atoms. When there are two or more R ^11a , they may be the same or different from each other. Examples of the alkyl 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 alkyl group having 1 to 13 carbon atoms may be, for example, propoxyphenyl or tert-butylphenyl. The carbon number of the alkyl group is preferably 1 to 10, and more preferably 1 to 9.

Specific examples of the compound represented by formula (I) include compounds represented by the following formula: The compound represented by the following formula is the compound represented by formula (I), wherein ^R1 to ^R8 are chlorine atoms, ^X1 to ^X4 and ^Y1 to ^Y8 are hydrogen atoms, and ^R9 and ^R10 are diisopropylphenyl groups.

[Chemistry 10]

As another specific example of the compound represented by formula (I), there can be cited a compound represented by the following formula. The compound represented by the following formula is a compound represented by formula (I), wherein 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.

[Chemistry 11]

As another specific example of the compound represented by formula (I), there can be cited a compound represented by the following formula: The compound represented by the following formula is a compound represented by formula (I), wherein ^R1 to ^R8 are independently 4-tert-butylphenoxy or a chlorine atom, ^X1 to ^X4 and ^Y1 to ^Y8 are hydrogen atoms, and ^R9 and ^R10 are diisopropylphenyl groups.

[Chemistry 12]

As another specific example of the compound represented by formula (I), there can be cited a compound represented by the following formula. The compound represented by the following formula is a compound represented by formula (I), wherein 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.

[Chemistry 13]

The compound represented by formula (I) is a compound that absorbs a specific wavelength in the near-infrared region. Conversely, the compound represented by formula (I) is a compound that transmits a specific wavelength in the near-infrared region. Therefore, an optical filter formed of a composition containing the compound represented by formula (I) can be used as a near-infrared cutoff filter or a near-infrared transmission filter depending on its absorption wavelength.

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

From the viewpoint of using an optical filter formed of a composition containing a compound represented by formula (I) as a near-infrared transmission filter, the compound represented by formula (I) preferably has high absorption in the visible region. For example, when the absorbance at a wavelength of 780 nm is represented by Abs (780) and the absorbance at a wavelength representing the maximum value of the absorbance in the wavelength range of 300 nm to 1400 nm (maximum absorption wavelength λ _max ) is represented by 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 wavelength of the visible region, it can be said that the higher the ratio, the more suitable it is for use in near-infrared transmission filters. In addition, when the maximum absorbance in the wavelength range of 900 nm to 1400 nm is expressed as Abs (900-1400), the ratio of Abs (900-1400) to 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 ) can be, for example, 0.01 or more or 0.03 or more. It can be said that the smaller the value, the higher the transmittance in the near-infrared region, and the more suitable _it is for use in near-infrared transmission filters.

In this specification, the absorbance of the compound represented by formula (I) is the 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) can be dissolved in a solvent so that its concentration becomes 10 ppm, and the absorbance can be measured in the range of wavelength 300 nm to 1400 nm (data sampling interval 1 nm). As a solvent, for example, propylene glycol monomethyl ether acetate or chloroform can be used. Furthermore, the absorbance is almost not affected by the resin (B), polymerizable compound (C), polymerization initiator (D), dispersant, etc. described later. Therefore, a composition in which the compound represented by formula (I) and these components are mixed may be diluted with a solvent so that the concentration of the compound represented by formula (I) becomes 10 ppm, the absorbance of the solution may be measured, and the obtained absorbance may be regarded as the absorbance of the compound represented by formula (I).

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

The content of the near-infrared absorbing pigment (A1) in the total amount of the solid components of the composition may be 0.5% to 60% by mass, 2% to 60% by mass, 4% to 55% by mass, or 6% to 50% by mass. The "total amount of solid components" in this specification refers to the total amount of components after removing the solvent from the composition. The total amount of solid components and the content of each component relative thereto can be measured, for example, by known analytical methods such as liquid chromatography and gas chromatography. The composition may not contain near-infrared absorbing pigments other than the compound represented by formula (I).

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

Examples of dyes include compounds classified as having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists) and known dyes listed in Dyeing Notes (published by Dyeing Co., Ltd.). Preferred dyes are oxyanthracene dyes.

Oxanthracene dyes are dyes containing compounds having an oxanthracene skeleton. Examples of oxanthracene 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 (rose red B) and 11; C.I. solvent red 218; C.I. mordant red 27; C.I. reactive red 36 (rose Bengal) bengal) B); acid rose red (sulforhodamine) G; oxyanthracene dyes described in Japanese Patent Laid-Open No. 2010-32999; and oxyanthracene dyes described in Japanese Patent No. 4492760. The oxyanthracene dyes are preferably oxyanthracene dyes dissolved in an organic solvent.

As the oxyanthracene dye, commercially available oxyanthracene dyes such as "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Chemical Co., Ltd. and "Rhodamin 6G" manufactured by TAOKA Chemical Industry Co., Ltd. can be used. In addition, as the oxyanthracene dye, an oxyanthracene dye synthesized using a commercially available oxyanthracene dye as a starting material according to the method described in Japanese Patent Laid-Open No. 2010-32999 can also be used.

As other dyes, 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. can be used. Examples of such dyes include C.I. solvent dyes, C.I. acid dyes, C.I. direct dyes, C.I. disperse dyes, C.I. alkaline dyes, C.I. reactive dyes, C.I. mordant dyes, and C.I. vat dyes.

Examples of C.I. solvent dyes include 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. .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.

Examples of C.I. acid dyes include 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, 1 8, 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, 195, 198, 20 6, 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, 2 3, 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, 1 17, 119, 120, 123, 126, 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; and C.I. 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.

As C.I. direct dyes, for example, there can be mentioned: 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. 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. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104; C.I. 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 6, 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.

As C.I. disperse dyes, 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 can be cited.

As the C.I. alkaline dye, for example, there can be listed: C.I. alkaline 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. alkaline violet 2; C.I. alkaline red 9; and C.I. alkaline green 1.

As C.I. reactive dyes, for example, there can be cited: C.I. Reactive Yellow 2, 76, and 116; C.I. Reactive Orange 16; and C.I. Reactive Red 36.

As C.I. mordant dyes, for example, there can be mentioned: 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. 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 .

As the C.I. vat dye, for example, C.I. vat Green 1 can be cited.

As pigments, for example, pigments classified as pigments in the Colour Index (published by The Society of Dyers and Colourists) can be cited.

Examples of pigments include green pigments, yellow pigments, orange pigments, red pigments, blue pigments, and purple pigments. Examples of green pigments include C.I. pigment green 7, 36, 58, and 59. Examples of 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. As orange pigments, there are C.I. Pigments Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73. As red pigments, there are C.I. Pigments 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. As blue pigments, there are C.I. Pigments Blue 15, 15:3, 15:4, 15:6, and 60. Examples of purple pigments include C.I. pigment purple 1, 19, 23, 29, 32, 36, and 38. One pigment or a plurality of pigments may be used for each color, and pigments of a plurality of colors may be combined.

The pigment may be treated with rosin as needed; surface treated with pigment derivatives into which acidic or alkaline groups are introduced; grafted with polymer compounds on the pigment surface; micronized by sulfuric acid micronization; cleaned with organic solvents or water to remove impurities; or treated by ion exchange to remove ionic impurities. The particle size of the pigment is preferably roughly uniform.

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

＜Dispersant＞

The near-infrared absorbing pigment (A1) and the pigment can be dispersed by adding a dispersant to prepare a dispersion uniformly dispersed in a dispersant solution. The near-infrared absorbing pigment (A1) and the pigment can be dispersed separately, or a plurality of near-infrared absorbing pigments (A1) or pigments can be mixed for dispersion. When a dispersant is used, the amount of the dispersant used can 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, relative to 100 parts by mass of the total of the near-infrared absorbing pigment (A1) and the pigment. When the amount of the dispersant used is within the above range, when two or more near-infrared absorbing dyes (A1) or pigments are used, a dispersion liquid in which the near-infrared absorbing dyes (A1) or pigments are more uniformly dispersed tends to be obtained.

Examples of dispersants include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, and acrylic-based surfactants. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Examples of commercially available dispersants include BYK LPN-6919 (manufactured by BYK), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Corporation), EFKA (manufactured by BASF Japan Co., Ltd.), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Disperbyk (manufactured by BYK-Chemie).

<Resin (B)> As resin (B), for example, the following resins [K1] to [K6] can be listed: Resin [K1]: a copolymer having structural units derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)"), and structural units derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b)"); Resin [K2]: a copolymer having structural units derived from (a), structural units derived from (b), and structural units derived from a monomer (c) copolymerizable with (a) (wherein, different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); Resin [K4]: a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c); Resin [K5]: 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]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride and a structural unit derived from (c). Among them, the 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 ethylenic unsaturated bond (i.e., resin [K1] or resin [K2]), and more preferably resin [K2].

Specific examples of (a) include: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; maleic acid, fumaric acid, citric acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid; 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, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing a carboxyl group; maleic anhydride, conic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic acid unsaturated dicarboxylic anhydrides such as 2-(meth)acryloxyethyl succinate and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; unsaturated mono[(meth)acryloxyalkyl] esters of divalent or higher polycarboxylic acids such as mono[2-(meth)acryloxyethyl] succinate and mono[2-(meth)acryloxyethyl] phthalate; unsaturated acrylic acid esters containing hydroxyl and carboxyl groups such as α-(hydroxymethyl)acrylic acid. Among these, acrylic acid, methacrylic acid or maleic anhydride is preferred as (a) from the viewpoint of copolymerization reactivity and solubility of the obtained resin in alkaline aqueous solution.

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

(b) may be, for example, a monomer having an oxycyclopropyl group and an ethylenic unsaturated bond (b1) (hereinafter sometimes referred to as "(b1)"), a monomer having an oxycyclobutyl group and an ethylenic unsaturated bond (b2) (hereinafter sometimes referred to as "(b2)"), or a monomer having a tetrahydrofuranyl group and an ethylenic unsaturated bond (b3) (hereinafter sometimes referred to as "(b3)").

Examples of (b1) include monomers having a structure in which a linear or branched chain aliphatic unsaturated hydrocarbon is epoxidized (b1-1) (hereinafter sometimes referred to as "(b1-1)") or monomers having a structure in which alicyclic unsaturated hydrocarbon is epoxidized (b1-2) (hereinafter sometimes referred to as "(b1-2)").

Examples of (b1-1) include 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(glycidyloxymethyl) Styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tri(glycidyloxymethyl)styrene, 2,3,5-tri(glycidyloxymethyl)styrene, 2,3,6-tri(glycidyloxymethyl)styrene, 3,4,5-tri(glycidyloxymethyl)styrene, and 2,4,6-tri(glycidyloxymethyl)styrene.

Examples of (b1-2) include vinylcyclohexene oxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000, manufactured by Daicel Co., Ltd.), 3,4-epoxyepoxyhexylmethyl (meth)acrylate (e.g., Cyclomer A400, manufactured by Daicel Co., Ltd.), 3,4-epoxyepoxyhexylmethyl (meth)acrylate (e.g., Cyclomer M100, manufactured by Daicel Co., Ltd.), 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.

As (b2), a monomer having an oxycyclobutyl group and a (meth)acryloxy group is preferred. Examples of such (b2) include 3-methyl-3-methacryloxymethyloxycyclobutane, 3-methyl-3-acryloxymethyloxycyclobutane, 3-ethyl-3-methacryloxymethyloxycyclobutane, 3-ethyl-3-acryloxymethyloxycyclobutane, 3-methyl-3-methacryloxyethyloxycyclobutane, 3-methyl-3-methacryloxyethyloxycyclobutane, 3-ethyl-3-methacryloxyethyloxycyclobutane, and 3-ethyl-3-acryloxyethyloxycyclobutane.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is preferred. 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 further improving the reliability of the optical filter in terms of heat resistance, chemical resistance, etc., (b) is preferably (b1). Furthermore, from the viewpoint of obtaining a composition excellent in storage stability, (b) is more preferably (b1-2).

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-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 ]decane-8-yl (meth)acrylate (in the art, it is commonly referred to as "dicyclopentyl (meth)acrylate". It is also sometimes referred to as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ] (Meth)acrylates such as decen-8-yl ester (in the art, it is commonly referred to as "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; (meth)acrylates containing a hydroxyl group 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-methoxy 5,6-di(2'-hydroxyethyl)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-2-ene, 5,6-di(2'-hydroxyethyl) ... [2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 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 Bicyclic unsaturated compounds such as bis(cyclohexyloxycarbonyl)bis(cyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbis(cyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bis(cyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bis(cyclo[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-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide; 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, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide or bicyclo[2.2.1]hept-2-ene is preferred from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [K1], relative to the total molar number of all structural units constituting the resin [K1], preferably: The structural unit derived from (a) is 2 mol% to 60 mol%, and The structural unit derived from (b) is 40 mol% to 98 mol%. More preferably: The structural unit derived from (a) is 10 mol% to 50 mol%, and The structural unit derived from (b) is 50 mol% to 90 mol%. If the ratio of each structural unit of the resin [K1] is within the above range, there is a tendency that the storage stability of the composition, the developability when forming the coloring pattern described later, and the solvent resistance of the optical filter are excellent.

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

Specifically, the following method can be cited: prescribed amounts of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction container, and the mixture is heated and kept warm while being stirred, for example, in a nitrogen atmosphere. The polymerization initiator, solvent, etc. used here are not particularly limited, and polymerization initiators, solvents, etc. commonly used in this field can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzoyl peroxide, etc.) can be cited. The solvent is not particularly limited as long as it can dissolve monomers, and for example, the solvent (E) described later as the composition can be used.

In resin [K2], relative to the total molar number of all structural units constituting resin [K2], preferably: The structural unit derived from (a) is 2 mol% to 45 mol%, The structural unit derived from (b) is 2 mol% to 95 mol%, and The structural unit derived from (c) is 1 mol% to 65 mol%, More preferably: The structural unit derived from (a) is 5 mol% to 40 mol%, The structural unit derived from (b) is 5 mol% to 80 mol%, and The structural unit derived from (c) is 5 mol% to 60 mol%. If the ratio of each structural unit of the resin [K2] is within the above range, the storage stability of the composition, the developing property when forming a colored pattern, and the solvent resistance, heat resistance and mechanical strength of the optical filter tend to be excellent.

For example, resin [K2] can be manufactured by the same method as resin [K1] except that (a), (b), and (c) are used instead of (a) and (b).

In resin [K3], relative to the total molar number of all structural units constituting resin [K3], preferably: The structural unit derived from (a) is 2 mol% to 60 mol%, and The structural unit derived from (c) is 40 mol% to 98 mol%, More preferably: The structural unit derived from (a) is 10 mol% to 50 mol%, and The structural unit derived from (c) is 50 mol% to 90 mol%.

For example, resin [K3] can be produced by the same method 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 a cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and/or carboxylic anhydride of (a). First, a copolymer of (a) and (c) is produced by the same method as that of resin [K3]. The ratio of the structural unit derived from (a) to the structural unit derived from (c) is preferably the same as that of resin [K3]. Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a portion of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer. Specifically, after the copolymer of (a) and (c) is produced, the atmosphere in the flask is replaced from nitrogen to air, (b), a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the reaction is carried out at, for example, 60°C to 130°C for 1 hour to 10 hours, thereby producing the resin [K4]. The charging method, reaction temperature, reaction time, and other reaction conditions can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization.

The amount of (b) used is preferably 5 mol to 80 mol, more preferably 10 mol to 75 mol, relative to 100 mol of (a). By setting the amount of (b) used within this range, the storage stability of the composition, the developing property 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 improved. In terms of (b) having high reactivity and being less likely to leave unreacted cyclic ether, (b1) is preferably used as the (b) for the resin [K4], and (b1-1) is more preferably used.

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

Resin [K5] can be produced by the same method 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 a carboxylic acid or carboxylic anhydride derived from (a) is reacted with a cyclic ether derived from (b) in the copolymer of (b) and (c), thereby obtaining Resin [K5]. Among them, relative to the total molar number of all structural units constituting the copolymer, the ratio of the structural unit derived from (b) and the structural unit derived from (c) is preferably: The structural unit derived from (b) is 5 mol% to 95 mol%, and The structural unit derived from (c) is 5 mol% to 95 mol%, More preferably: The structural unit derived from (b) is 10 mol% to 90 mol%, and The structural unit derived from (c) is 10 mol% to 90 mol%. In addition, relative to 100 mol of (b), the amount of (a) reacted with the copolymer is preferably 5 mol to 80 mol. As for (b) which has high reactivity of cyclic ether and is not easy to leave unreacted, (b) used as resin [K5] is preferably (b1), and more preferably (b1-1).

Resin [K6] is a resin obtained by further reacting carboxylic acid anhydride with resin [K5]. Specifically, carboxylic acid anhydride and a hydroxyl group generated by the reaction of the cyclic ether derived from (b) with the carboxylic acid or carboxylic acid anhydride derived from (a) are reacted. Examples of carboxylic acid anhydrides include maleic anhydride, ceramic 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 carboxylic anhydride used is preferably 0.5 mol to 1 mol per 1 mol of (a).

Specific examples of the resin (B) include: 3,4-epoxyhexylmethyl (meth)acrylate/(meth)acrylic acid copolymers, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid copolymers, and the like [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymers, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymers, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymers, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl(meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxycyclobutane/(meth)acrylic acid/styrene copolymer, benzyl(meth)acrylate/(meth)acrylic acid/3,4-epoxytricyclo[5.2.1.0 ^2,6 ] decyl ester copolymer and other resins [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer and other resins [K3]; resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, and resins obtained by adding glycidyl (meth)acrylate to glycidyl (meth)acrylate [K4]; a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate, etc. [K5]; a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate, and further reacting tetrahydrophthalic anhydride, etc. [K6], etc.

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

[Chemistry 14]

The resin [K4] may be, for example, a resin obtained by adding glycidyl methacrylate to a copolymer of tricyclodecyl methacrylate/benzyl methacrylate/methacrylic acid.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. 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 portion in the developer is good, and the resolution of the colored pattern is improved.

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

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

The content of the resin (B) relative to the total amount of the solid components in the composition may be, for example, 7% to 65% by mass, 13% to 60% by mass, or 17% to 55% by mass. When the content of the resin (B) is within the above range, a colored pattern can be formed well, and the resolution and residual 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 active free radicals and/or acids generated from the polymerization initiator (D). The polymerizable compound (C) is, for example, a polymerizable compound having an ethylenic unsaturated bond, preferably a (meth)acrylate.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trihydroxymethylpropane 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, Pentaerythritol 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, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. Among them, trihydroxymethylpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate is preferred.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2,900, more preferably 250 to 1,500.

The content of the polymerizable compound (C) is preferably 7% by mass to 65% by mass, more preferably 13% by mass to 60% by mass, and still more preferably 17% by mass to 55% by mass, relative to the total amount of the solid components in the composition. When the content of the polymerizable compound (C) is within the above range, the residual film rate during the formation of the colored pattern and the chemical resistance of the optical filter tend to be improved.

<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 to start polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator that generates active free radicals include alkyl phenoxide compounds, triazine compounds, acyl phosphine oxide compounds, O-acyl oxime compounds, and biimidazole compounds.

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

[Chemistry 15]

Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3, [0147] The following are the compounds selected from the group consisting of N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, and N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine. Commercially available products such as Irgacure OXE01 and OXE02 (both manufactured by BASF) and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used. Among them, from the viewpoint of obtaining an optical filter with high brightness, the O-acyl oxime compound is preferably selected from N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, At least one of the group consisting of oxadiazole-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, more preferably N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine or N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine.

The alkyl phenoxide 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 alkyl phenoxide compound is preferably a compound having a partial structure represented by formula (d2).

[Chemistry 16]

Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one. Commercially available products such as Omnirad (Irgacure) 369, 907, and 379 (all manufactured by IGM Resins B.V.) can also be used.

Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzoyl dimethyl ketal.

Examples of the triazine compound 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-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. Commercially available products such as Omnirad 819 (manufactured by IGM Resins B.V.) can also be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, azole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (for example, see Japanese Patent Publication No. 7-10913, etc.), and the like.

As the polymerization initiator (D), further examples include: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 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; benzoyl; methyl phenylglyoxylate; and titaniumocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (particularly an amine compound) described later.

Examples of the polymerization initiator that generates an acid include onium salts such as 4-hydroxyphenyldimethylcoppersulfonate, 4-hydroxyphenyldimethylcoppersulfonate, 4-acetoxyphenyldimethylcoppersulfonate, 4-acetoxyphenylmethylbenzylcoppersulfonate, triphenylcoppersulfonate, triphenylcoppersulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroiodonate, nitrobenzyl toluenesulfonates, and benzoin toluenesulfonates.

The polymerization initiator (D) is preferably a polymerization initiator that generates active free radicals, more preferably a polymerization initiator comprising at least one selected from the group consisting of phenylalkyl ketone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds, and biimidazole compounds, and further preferably a polymerization initiator comprising an O-acyl oxime compound.

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 relative to 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 high and the exposure time tends to be shortened, thereby improving the productivity of the optical filter.

<Polymerization initiator (D1)> The composition may further include a polymerization initiator (D1). The polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of the polymerizable compound (C) that starts polymerization by the polymerization initiator. The polymerization initiator (D1) is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiator (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 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, and 4,4'-bis(ethylmethylamino)benzophenone. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxyanthracene compound 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.

Examples of the thiothione compound include 2-isopropylthiothione, 4-isopropylthiothione, 2,4-diethylthiothione, 2,4-dichlorothiothione, and 1-chloro-4-propoxythiothione.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

When the polymerization initiator (D1) is used, the content of the polymerization initiator (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiator (D1) is within the above range, a colored pattern can be formed with high sensitivity, and the productivity of the optical filter tends to be improved.

<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 and not containing -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, cyclohexanol acetate, and γ-butyrolactone.

Examples of the ether solvent 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, phenethyl ether, methyl anisole, and the like.

Examples of the ether ester solvent 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, and the like.

Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, and the like.

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, etc.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

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

The content of the solvent (E) relative to the total amount of the composition may be, for example, 70 mass% to 95 mass% or 75 mass% to 92 mass%. In other words, the solid content of the composition may be, for example, 5 mass% to 30 mass% or 8 mass% to 25 mass%. When the content of the solvent (E) is within the above range, the flatness during coating becomes good, and thus there is a tendency that the display characteristics become good.

<Leveling agent (F)> As the leveling agent (F), silicone-based surfactants, fluorine-based surfactants, etc. can be listed. These surfactants may also have a polymerizable group in the side chain.

Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, the following can be cited: DOWSIL (registered trademark) (formerly Toray silicone) DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade 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 Co., Ltd. Japan) Co., Ltd.) as silicone-based surfactants.

Alternatively, the silicone-based surfactant may be a silicone-based surfactant having fluorine atoms. Examples of silicone-based surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) may be cited as silicone-based surfactants.

Examples of the fluorine-based surfactant include surfactants having a fluorine-carbon chain in the molecule. Specifically, they include: Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation); Eftop (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 Co., Ltd. (formerly Asahi Glass Co., Ltd.)); E5844 (manufactured by Daikin Fine Chemicals Co., Ltd.); Chemical) Research Institute Co., Ltd.) as a fluorine-based surfactant.

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

<Other ingredients> The composition of this aspect of the present invention may contain fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and other additives known in the art as needed.

<Method for producing the composition> The composition of the present invention can be prepared by, for example, mixing a near-infrared absorbing pigment (A1), a resin (B), and a solvent (E), and optionally a coloring agent (A2), a polymerizable compound (C), a polymerization initiator (D), a leveling agent (F), a polymerization initiation aid (D1), a dispersant, and other components. The mixed composition is preferably filtered using a filter with a pore size of about 0.01 μm to 10 μm.

In one embodiment, the composition can be prepared by preparing a dispersion of a near-infrared absorbing pigment (A1) and/or a coloring agent (A2) and mixing the dispersion with other components. The dispersion of the near-infrared absorbing pigment (A1) and/or a coloring agent (A2) can be prepared by mixing these with a suitable resin (B) and a dispersant and a solvent (E), and dispersing them using a bead mill or the like. The diameter of the beads can be, for example, 0.05 mm to 0.5 mm or less.

<Optical filter and method for manufacturing the same> An optical filter according to one aspect of the present invention is formed by the composition. The optical filter may include a cured product of the composition, or may also be composed of a cured product of the composition. The cured product of the composition can be obtained, for example, by irradiating a film-shaped composition with light, or by heating the film-shaped composition. The composition is unlikely to produce aggregates caused by near-infrared absorbing pigments even when formed into a film, so that in an optical filter formed of the composition, aggregates are reduced. The optical filter is also excellent in light resistance.

In addition, as described above, the composition absorbs a specific wavelength in the near-infrared region, so the optical filter formed by the composition can be used as a near-infrared cutoff filter or a near-infrared transmission filter. Therefore, the optical filter of the present invention can be used, for example, in infrared sensors and display devices (e.g., 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, further preferably 3 μm or less, further 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 further preferably 0.3 μm or more. The thickness of the optical filter may be, for example, 0.1 μm to 30 μm, 0.1 μm to 20 μm, or 0.5 μm to 6 μm.

The method for manufacturing the optical filter is not particularly limited, and the optical filter can be manufactured by a previously known method. For example, the optical filter can be formed on any substrate by photolithography, inkjet printing, or printing. Among them, photolithography is preferred.

The substrate may be, for example, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, sodium calcium glass coated with silicon dioxide on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or silicon. In addition, substrates including thin films such as aluminum, silver, silver/copper/palladium alloys on these substrates may also be used. Substrates treated with hexamethyldisilazane (HMDS) on silicon substrates may also be used. Furthermore, substrates including other optical filters, resin layers, transistors, circuits, etc. on these substrates may also be used.

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

Thereafter, the coating is exposed through a photomask having a prescribed pattern, and then a developer is brought into contact and developed, thereby forming a colored pattern of a cured product including the coating. The pattern of the photomask can be appropriately determined according to the purpose of the optical filter. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 nm to 450 nm. Light of such a wavelength can also be obtained, for example, by using a filter that cuts off the wavelength range to cut off light in a specific wavelength range (for example, less than 350 nm) from a prescribed light source, or by selectively extracting light of a specific wavelength (for example, 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. In order to evenly irradiate the entire exposure surface with parallel light and accurately align the mask with the substrate, it is preferred to use a reduced projection exposure device or a proximity exposure device such as a mask aligner and a stepper.

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

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

Furthermore, in the above-mentioned photolithography, no mask is used during exposure and/or no development is performed, thereby obtaining a cured product of a non-patterned coating film.

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

<Solid-state imaging element> The solid-state imaging element of one aspect of the present invention includes the optical filter. The optical filter may be a near-infrared transmission filter and/or a near-infrared cutoff filter. The parts of the solid-state imaging element other than the optical filter may be the same as those of a previously known solid-state imaging element. An example of a solid-state imaging element is shown in FIG1.

The solid-state imaging element 100 shown in FIG1 includes: a semiconductor substrate 2 having a light receiving element (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. As the near-infrared cut filter 4 and/or the near-infrared transmission filter 6, the above-mentioned optical filter can be used. The color filter 8 is not particularly limited, and for example, a color filter described in Japanese Patent Laid-Open No. 2014-043556 or other previously known color filter for forming pixels can be used. The microlens 10 and the planarization layer 12 are also not particularly limited, and known microlenses and planarization layers can be used.

Furthermore, in the solid-state imaging device 100 shown in FIG1 , the near-infrared cut filter 4, the color filter 8, and the microlens 10 are sequentially layered, but the positions of the near-infrared cut filter 4 and the color filter 8 can be replaced. In addition, another layer can be provided between the near-infrared cut filter 4 and the color filter 8.

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

<Method for producing a compound represented by formula (I)> The method for producing a compound represented by formula (I) in one aspect of the present invention comprises the step of reacting a compound represented by formula (I-x1), a compound represented by formula (I-x2), 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) are sometimes collectively referred to as "raw material compounds".

[Chemistry 17]

The reaction is a so-called Suzuki coupling reaction and a Heck reaction, and ring formation occurs through these reactions to form pentarylene. According to the method of the present invention, the number of steps required is reduced compared to the case of the conventional production method using a compound having a pentarylene skeleton, and the compound represented by formula (I) can be produced more simply.

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 described in formula (I).

In formula (I-x1) and formula (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 described in formula (I).

In formula (I-y1) and formula (I-y2), ^A1 and ^A2 each independently represent a hydroxyl group, a carbonyl group having 1 to 20 carbon atoms, or an ^OR13 group.

Examples of the carbonyl group having 1 to 20 carbon atoms represented by ^A1 and ^A2 include the groups exemplified as the carbonyl group having 1 to 20 carbon atoms represented by ^R1 , ^R4 , ^R5 or ^R8 .

R ¹³ represents a alkyl 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 as or different from each other. Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹³ include the groups exemplified as the alkyl 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.

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

[Chemistry 18]

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 according to a known method.

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

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

In addition, both the compound represented by formula (I-y1) and the compound represented by formula (I-y2) may be used. In this case, the ratio of the total molar number of the compound represented by formula (I-x1) and the compound represented by formula (I-x2) to the total molar number of the compound represented by formula (I-y1) and the compound represented by formula (I-y2) is generally 2:1, but may also be 4.0:1 to 1.5:1.

The catalyst is not particularly limited as long as it is a catalyst for Suzuki-Miyaura cross coupling and Heck-Crouki cross coupling reaction, and may be, for example, a transition metal complex such as a palladium complex or a nickel complex. Examples of the palladium complex 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 is the transition metal complex, and may also be a transition metal complex having ligands such as tricyclohexylphosphine, triphenylphosphine, tri(o-tolyl)phosphine, tri(tert-butyl)phosphine, 1,3-bis(diphenylphosphino)propane, or bipyridine. The catalyst is preferably tri(benzylideneacetone)dipalladium(0) having tricyclohexylphosphine as a ligand.

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

The 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, tripotassium phosphate, or an organic base such as tetrabutylammonium fluoride, tetraethylammonium hydroxide, or tetrabutylammonium hydroxide.

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

The solvent of the 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° C. to 200° C. or 100° C. to 180° C. The reaction time may be, for example, 0.5 hour to 50 hours or 5 hours to 30 hours.

In one embodiment, the production method may further include the step of replacing part or all of R ¹ to R ⁸ in the compound represented by formula (I) obtained in the step of reacting the raw material compound 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, by reacting R ¹¹ OH with the compound represented by formula (I), part or all of the halogen atoms can be replaced by the OR ¹¹ group. [Example]

The present invention is described in more detail below by way of examples, but the present invention is not limited to the following examples and can be implemented with appropriate modifications within the scope of the subject matter, all of which are included in the technical scope of the present invention. Furthermore, unless otherwise specified, "parts" refers to "parts by mass" and "%" refers to "% by mass".

In the following synthesis examples, the structures of the compounds were confirmed by mass spectrometry (LC: Model 1200 manufactured by Agilent, MASS: Model LC/MSD6130 manufactured by Agilent) or NMR (400-MR manufactured by Varian).

In the following synthesis examples, the maximum absorption wavelength of each compound was confirmed by 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 nm 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 Co., Ltd.) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: tetrahydrofuran Flow rate: 1.0 mL/min Solid content concentration of the analyzed sample: 0.001 mass% to 0.01 mass% Injection volume: 50 μL Detector: RI Calibration standard substances: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio of the obtained polystyrene-equivalent weight average molecular weight to the number average molecular weight (Mw/Mn) was defined as the dispersion degree.

<Synthesis Example 1: Synthesis of Compound (I-A)> In a nitrogen environment, 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 Fuji Film Co., Ltd. and Koh Jun Chemical Co., Ltd.) were added dropwise over 1 hour and stirred for 3 hours. After cooling to 10°C, 11 parts of concentrated hydrochloric acid were added dropwise, resulting in a white precipitate. The mixture containing the white precipitate was filtered, and the residue after filtration was washed with 50 parts of water and 20 parts of methanol. The obtained 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)).

[Chemistry 19]

<Synthesis Example 2: Synthesis of Compound (I-B)> In a nitrogen environment, 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 Fuji Films Wako Pure Chemical Industries, 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 a light brown precipitate. The mixture containing the 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 (I-B).

[Chemistry 20]

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

<Synthesis Example 3: Synthesis of Compound (I-C)> In a nitrogen atmosphere, 22 parts of Compound (I-B), 10 parts of 4,4,5,5-tetramethyl-2-(1-naphthyl)-1,3,2-dioxaborane, 3.6 parts of tris(dibenzylideneacetone)dipalladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.4 parts of tricyclohexylphosphine (manufactured by Fuji Film Co., Ltd. Wako Pure Chemical Industries, Ltd.), 67 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.), and 720 parts of dehydrated xylene (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 145°C for 18 hours. After cooling to 20°C, the reaction solution was filtered. The solvent was removed by distillation under reduced pressure, and the crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 9 parts of compound (I-C) as a red solid.

[Chemistry 21]

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

<Synthesis Example 4: Synthesis of Compound (I-D)> In a nitrogen environment, 10 parts of compound (I-C), 737 parts of bromine (manufactured by Fuji Film Co., Ltd.), and 700 parts of chloroform (manufactured by Nakalai Tesque Co., Ltd.) were mixed and stirred at 60°C for 48 hours. After the reaction was completed, the reaction solution was cooled to room temperature (18°C to 24°C) and 3000 parts of an aqueous sodium sulfite solution (1 M) was added. The mixture was washed with 700 parts of chloroform and the liquid separation operation was performed. The obtained organic layer was dehydrated with anhydrous sodium sulfate (manufactured by Kanto Chemical Co., Ltd.), and after filtering the sodium sulfate, the solvent was distilled off. The crude product was purified by silica gel column chromatography (solvent: chloroform/ethyl acetate = 5/1 (volume/volume)) to obtain 5.3 parts of colorless crystals of compound (I-D).

[Chemistry 22]

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

<Synthesis Example 5: Synthesis of Compound (I-x-1)> In a nitrogen environment, 10 parts of compound (I-D), 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-pyrrolidone (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°C to 24°C), and 198 parts of concentrated hydrochloric acid (manufactured by Fuji Film Co., Ltd. Wako Pure Chemical Industries, Ltd.) and 992 parts of water were added. The precipitated solid was washed twice with 200 parts of ion exchange water, and then washed twice with 200 parts of methanol, and then decanted. The crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 8.5 parts of compound (I-x-1) as a red solid.

[Chemistry 23]

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

<Synthesis Example 6: Synthesis of Compound (I-y-1)> In a nitrogen atmosphere, 5.0 parts of 1,8-dibromonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 11 parts of bis(pinacol)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)ferrocene dichloropalladium (II) (manufactured by Fuji Film Co., Ltd. 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 obtained mixture was filtered through diatomaceous earth, and the filtrate was concentrated. The residue was washed with 18 parts of methanol. The obtained residue was dried under reduced pressure at 60°C to obtain 5.6 parts of a compound (Compound (I-y-1)).

[Chemistry 24]

Identification of compound (Iy-1): ¹ H NMR (400 MHz, CDCl ₃ , 25°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)> In a nitrogen environment, 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 Fuji Film Co., Ltd. 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 solution was cooled to room temperature and poured into 8000 parts of methanol. The precipitated solid was washed twice with 200 parts of ion exchange water and then washed twice with 200 parts of methanol, and then decanted. The crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 28 parts of dark green solid of compound (I-2).

[Chemistry 25]

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

<Synthesis Example 8: Synthesis of Compound (I-E)> In a nitrogen environment, 10 parts of 1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic anhydride (manufactured by Combi-Bloks), 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 Fuji Film Co., Ltd. and Koshun Chemical Co., 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 the reaction was completed, the reaction solution was cooled to room temperature (18°C to 24°C). The precipitated solid was filtered, washed twice with 100 parts of ion exchange water, and then washed twice with 100 parts of methanol, and then decanted. Drying under reduced pressure at 60°C yielded 10 parts of yellow crystals of compound (I-E).

[Chemistry 26]

<Synthesis Example 9: Synthesis of Compound (I-x-2)> In a nitrogen environment, 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-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 110°C for 49 hours. After the reaction was completed, the reaction solution was cooled to room temperature (18°C to 24°C) and 2500 parts of water were added. The precipitated solid was filtered and washed twice with 30 parts of ion exchange water. The crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 6.5 parts of compound (I-x-2) as a red solid.

[Chemistry 27]

Identification of compound (Ix-2): (Mass analysis) 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 Synthesis Example 7 except that 52 parts of Compound (I-x-1) (manufactured by Tokyo Chemical Industry Co., Ltd.) were replaced with 45 parts of Compound (I-x-2).

[Chemistry 28]

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

<Synthesis Example 11: Synthesis of Example Compound (I-3)> In a nitrogen environment, 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-pyrrolidone (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°C to 24°C), and 198 parts of concentrated hydrochloric acid (manufactured by Fuji Film Co., Ltd. and Koshin Chemical Co., Ltd.) and 992 parts of water were added. The precipitated solid was washed twice with 200 parts of ion exchange water, and then washed twice with 200 parts of methanol, and then decanted. 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, the mixture of compounds is referred to as compound (I-3)). The mixture of compounds represented by formula (I-3) is a mixture of three compounds containing chlorine atoms and 4-tert-butylphenoxy as substituents R in formula (I-3) in ratios of 3/5, 2/6, and 1/7, respectively.

[Chemistry 29]

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

<Synthesis Example 12: Synthesis of Compound (I-F)> 13 parts of red crystals of Compound (I-F) were obtained in the same manner as in the synthesis of Compound (I-B) in Synthesis Example 2 except that 5.0 parts of 2-ethylhexylamine was replaced with 5.2 parts of 2,6-diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.).

[Chemistry 30]

Identification of compound (IF): (Mass analysis) Ionization mode = ESI+: m/z = [M+H] ⁺ 514 Exact Mass: 513

<Synthesis Example 13: Synthesis of Compound (I-G)> Compound (I-B) was replaced with Compound (I-F), and 11 portions of red crystals of Compound (I-G) were obtained in the same manner as the synthesis of Compound (I-C) in Synthesis Example 3.

[Chemistry 31]

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

<Synthesis Example 14: Synthesis of Compound (I-H)> In a nitrogen environment, 10 parts of Compound (I-G), 183 parts of bromine (manufactured by Fuji Film Co., Ltd.), and 1860 parts of chloroform (manufactured by Nakalai Tesque Co., Ltd.) were mixed and stirred at 65°C for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature (18°C 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 to perform a liquid separation operation. The obtained organic layer was dehydrated using anhydrous sodium sulfate (manufactured by Kanto Chemical Co., Ltd.), and after filtering the sodium sulfate, 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).

[Chemistry 32]

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

<Synthesis Example 15: Synthesis of Compound (I-J)> Compound (I-D) was replaced with Compound (I-H), and 4.0 parts of 4-propoxyphenol was replaced with 4.2 parts of 4-tert-butylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.). In the same manner as the synthesis of Compound (I-x-1) in Synthesis Example 5, 7.5 parts of red crystals of Compound (I-J) were obtained.

[Chemistry 33]

Identification of compound (IJ): (Mass analysis) 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 (I-K) were obtained in the same manner as the synthesis of Compound (I-2) in Synthesis Example 7 except that 52 parts of Compound (I-x-1) were replaced with 45 parts of Compound (I-J).

[Chemistry 34]

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

<Synthesis Example 17: Synthesis of Example Compound (I-4)> In a nitrogen environment, 10 parts of compound (I-K), 6.5 parts of anhydrous iron (III) chloride (manufactured by Fuji Film Co., Ltd. Wako Pure Chemical Industries, Ltd.), 57 parts of nitromethane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 465 parts of chloroform (manufactured by Nakalai Tesque Co., Ltd.) were mixed and stirred at 20°C to 25°C for 24 hours. After the reaction was completed, the solvent was distilled off and 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°C to 24°C) and 7500 parts of water were added. The precipitated solid was filtered and washed twice with 30 parts of ion exchange water. The crude product was purified by silica gel column chromatography (solvent: chloroform) to obtain 4.8 parts of dark green solid of compound (I-4).

[Chemistry 35]

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

<Synthesis Example 18: Synthesis of Resin (B-1)> A nitrogen atmosphere was replaced by flowing an appropriate amount of nitrogen into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, and 340 parts of propylene glycol monomethyl ether acetate was added, and heated to 80° C. while stirring. Then, a mixed solution of 57 parts of acrylic acid, 54 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate (containing ratio of 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. On the other hand, a solution prepared by dissolving 40 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 197 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the 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 having a solid content of 37.0%. The viscosity of the copolymer solution measured by a B-type viscometer (23°C) was 127 mPa·s. The weight average molecular weight Mw of the copolymer was 9.4×10 ³ , the degree of dispersion was 1.89, and the acid value converted to solid content was 114 mg-KOH/g. Resin B-1 has the following structural units.

[Chemistry 36]

<Example 1> (1) Preparation of Composition 1 30 parts of compound (I-1), 24 parts (solid content conversion) of dispersant (propylene glycol monomethyl ether acetate 60% solution, BYK LPN-6919, manufactured by BYK), 24 parts (solid content conversion) 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 obtained mixture was shaken for 1 hour using a coating conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain Composition 1.

(2) Ultraviolet-visible-near-infrared absorption spectrometry 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 nm to 1400 nm (data sampling interval 1 nm). The maximum absorption wavelength λ _max was 830 nm. The ratio 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 of the maximum absorbance Abs(900-1400) to Abs(λ _max ) in the wavelength range of 900 nm to 1400 nm, Abs(900-1400)/Abs(λ _max ), was calculated to be _0.11 .

(3) Evaluation of viscosity of composition 1 Composition 1 was measured using a B-type viscometer (23°C) and the viscosity was evaluated in five stages. The evaluation criteria are as follows. 1: 0 mPa·s or more and less than 8 mPa·s 2: 8 mPa·s or more and less than 20 mPa·s 3: 20 mPa·s or more and less than 1,000 mPa·s 4: 1,000 mPa·s or more and less than 10,000 mPa·s 5: 10,000 mPa·s or more The high viscosity is considered to be caused by the aggregation of the pigments due to 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 dispersion has high stability and the operation in the process of manufacturing the optical filter becomes easier, so it is better.

(4) Preparation of curable composition 1 The curable composition 1 is obtained by mixing the following components. · Component 1: 720 parts · Resin (B): Resin (B-1) 73 parts (solid content conversion) · Polymerizable compound (C): Dipentaerythritol polyacrylate (trade name A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 68 parts · Polymerization initiator (D): N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine (trade name TR-PBG327, manufactured by Changzhou Qiangli 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 Special Materials Co., Ltd.) 1.4 parts

(5) Preparation of optical filter 1 and confirmation of agglomerates The curable composition 1 was applied to a 5 cm square glass substrate (Eagle 2000, manufactured by Corning Incorporated) by spin coating and pre-baked at 100°C for 3 minutes. After cooling, the obtained coating was irradiated with light at an exposure dose of 1000 mJ/ ^cm2 (365 nm reference) in an atmospheric environment using an exposure machine (TME-150RSK, manufactured by Topcon Co., Ltd.). Thereafter, the optical filter 1 was post-baked at 220°C for 5 minutes in an oven to obtain the optical filter 1. The presence of agglomerates on the obtained optical filter 1 was visually confirmed.

(6) Light resistance test of optical filter 1 An ultraviolet cut filter (Colored Optical Glass L38, manufactured by Hoya Co., Ltd.) that cuts off light below 380 nm was placed on optical filter 1, and irradiated with xenon light for 48 hours using a light resistance tester (SUNTEST CPS+, manufactured by Toyo Seiki Seisaku-sho, Ltd.). The absorbance of optical filter 1 at the maximum absorption wavelength before and after irradiation was measured, and the absorbance maintenance rate represented by the following formula was calculated. It can be said that the higher the absorbance maintenance rate, the better the light resistance of the optical filter. Absorbance maintenance rate (%) = (absorbance of the optical filter at the maximum absorption wavelength after irradiation) / (absorbance of the optical filter at the maximum absorption wavelength 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 in Example 1, except that an equal amount of Lumogen (registered trademark) F Orange 240 (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula was used instead of compound (I-1). Comparative composition 1, comparative curable composition 1, and comparative optical filter 1 were prepared in the same manner as in Example 1. Various evaluations (viscosity, presence of agglomerates, and light resistance test) were performed on comparative composition 1 and comparative optical filter 1 in the same manner as in Example 1.

[Chemistry 37]

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

[Table 1] Coloring agent Viscosity Condensate Absorbance maintenance rate (%) Embodiment 1 Compound (I-1) 1 without 99 Comparison Example 1 Lumogen F Orange240 5 have 71

<Example 2 to Example 4> Compound (I-2), compound (I-3) or compound (I-4) was used instead of compound (I-1), and compositions 2 to 4, curable compositions 2 to 4, and optical filters 2 to 4 were prepared in the same manner as composition 1, curable composition 1, and optical filter 1 of Example 1. Various evaluations (viscosity, presence of agglomerates, and light resistance tests) were 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 pigments have low viscosities, and optical filters 2 to 4 made from curable compositions 2 to 4 containing compounds (I-2) to (I-4) respectively have no aggregates and are also excellent in light resistance.

2: Semiconductor substrate 4: Near-infrared cut-off filter 6: Near-infrared transmission filter 8: Color filter 10: Microlens 12: Flattening layer 100: Solid-state imaging element

FIG1 is a schematic diagram showing an embodiment of a solid-state imaging element.

Claims (7)

A composition comprising a near-infrared absorbing pigment, an alkali-soluble resin and a solvent, wherein the near-infrared absorbing pigment comprises a compound represented by formula (I): In formula (I), R ¹ , R ⁴ , R ⁵ and R ⁸ each independently represent a alkyl 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 alkyl group having 1 to 20 carbon atoms, when there are two or more R ^11s , they may be the same as 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, when there are two or more R ^12s , they may be the same as or different from each other. The composition of claim 1, wherein X ¹ to X ⁴ and Y ¹ to Y ⁸ in the formula (I) are hydrogen atoms. The composition as described in claim 2 further contains a polymerization initiator and a polymerizable compound. An optical filter is formed from the composition as described in any one of claims 1 to 3. A solid-state imaging element comprises an optical filter as described in 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 alkyl group having 1 to 20 carbon atoms, R ^11a represents a alkyl group having 1 to 13 carbon atoms, and when there are two or more R ^{11a s} , 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 there are two or more R 11a s, they may be the same or different from each other. In the case of ¹² , these may be the same or different from each other. A method for producing a compound represented by formula (I), comprising the steps 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 formula (I-x1) and formula (I-x2), R ¹ , R ⁴ , R ⁵ and R ⁸ each independently represent a alkyl 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 alkyl group having 1 to 20 carbon atoms, when there are two or more R ^11s , they may be the same or different, 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 ^{R 12} represents an alkyl group having 1 to 5 carbon atoms. When there are two or more R ¹² , they may be the same as or different from each other. 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 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 alkyl group having 1 to 20 carbon atoms, or an OR ¹³ group, R ¹³ represents a alkyl group having 1 to 20 carbon atoms, and when there are two or more R ¹³ s, they may be the same or different from each other, and the OR ¹³ groups bonded to the same boron atom may bond 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 have the same meanings as described above.