Dipyrromethene boron complex compound, and coloring composition and optical filter which contain that compound

Abstract

To provide a dipyrromethene boron complex compound which selectively absorbs light in the wavelength range of 480-530 nm, inhibits fluorescence, and has excellent light fastness; and a coloring composition and an optical filter which contain the compound.SOLUTION: The dipyrromethene boron complex compound is represented by the general formula (1) in the figure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to dipyrometheneboron complex compounds, colored compositions containing the compound, and optical filters. [Background technology]

[0002] In recent years, there has been a growing market demand for larger, thinner, and higher-resolution displays for image display. With the issuance of the international standard BT.2020 for ultra-high-definition (4K / 8K resolution) television (UHDTV), recommended by the International Telecommunication Union in 2012, there is a strong desire for the development of displays with wide color gamut reproduction that comply with this standard.

[0003] Display devices, starting with cathode ray tubes (CRTs), were followed by plasma displays (PDPs) and other miniaturized displays, and currently, liquid crystal displays (LCDs) and organic light-emitting diodes (OLEDs) are widely used. Furthermore, development of new display methods such as quantum dot displays and micro-LED displays is also underway.

[0004] These displays display color images by passing light emitted from a white backlight source through color filters to extract light in the respective spectral ranges of red (R), green (G), and blue (B), or by arranging light sources that emit R, G, and B light in a grid, which then form pixels. However, due to the characteristics of the backlight and emission spectrum, light in wavelengths other than pure R, G, and B is also present. Specifically, this includes the intermediate wavelength range between R and G (around 590 nm; yellow light) and the intermediate wavelength range between G and B (around 500 nm; blue-green light). Because unwanted light emission is included, the color purity decreases and color reproduction deteriorates. Therefore, such displays are equipped with filters (optical filters) to remove (absorb) light components in unwanted wavelength ranges and improve color purity.

[0005] In optical filters for displays, functional dyes are used as components that exhibit the functions described above. These dyes are required to have good absorption characteristics in the visible light region, specifically a large molar extinction coefficient, a small full width at half maximum of the absorption spectrum peak, and minimal side absorption. Furthermore, since fluorescence generated by the light absorption of the dye can cause a decrease in contrast, dyes with suppressed fluorescence and excellent lightfastness are desired.

[0006] However, there are few dye materials suitable for removing unwanted light components in the wavelength range described above (wavelength cut), and dyes with an absorption peak around 500 nm, in particular, have issues with light resistance and other aspects. For example, Patent Documents 1 and 2 describe dipyromeneboron complex compounds or pyrometenboron complex compounds as dyes that selectively absorb light around 500 nm. Many of these dyes do not sufficiently suppress fluorescence, and there are concerns that using them in optical filters will reduce the contrast of the display. On the other hand, many dyes that suppress fluorescence currently have insufficient light resistance for use in optical filters. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2006-189751 [Patent Document 2] International Publication No. 2015 / 174662 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to provide a dipyrometheneboron complex compound that selectively absorbs light in the wavelength range of 480 to 530 nm, suppresses fluorescence, and has excellent lightfastness, as well as a colored composition containing the compound and an optical filter. [Means for solving the problem]

[0009] As a result of diligent research to solve the aforementioned problems, the present inventors have discovered a dipyrometheneboron complex compound, a dye that absorbs light with a wavelength of around 500 nm, suppresses fluorescence, and exhibits excellent lightfastness. In other words, the gist of the present invention is as follows.

[0010] 1. A dipyrometheneboron complex compound represented by the following general formula (1).

[0011] [ka]

[0012] [In formula (1), R 1 ~R 3 Each of them operates independently. Hydrogen atom, halogen atom, Linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, which may have substituents. An acyl group or amide group having 1 to 20 carbon atoms, which may have substituents. A substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or This represents a heterocyclic group having 5 to 20 ring-forming atoms, which may have substituents. R 4 ~R 8 Each of them operates independently. Hydrogen atom, cyano group, nitro group, sulfonic acid group, sulfonate ion, sulfonate salt Linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, which may have substituents. An alkoxycarbonyl group having 2 to 20 carbon atoms, which may have substituents. An amino group having 0 to 20 carbon atoms, which may have substituents, or a substituted amino group, R represents an amide group or acylamino group having 1 to 20 carbon atoms, which may have substituents. 4 ~R 8 The groups may be bonded to each other to form a ring, and the ring may also be an aromatic ring. However, R4 ~R 8 At least one of them is other than a hydrogen atom, R 9 ~R 12 each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and R ~R 9 ~R 12 may combine with each other among adjacent groups to form a ring.]

[0013] 2. In the general formula (1), a dipyrromethene boron complex compound in which R 1 ~R 3 is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent.

[0014] 3. In the general formula (1), a dipyrromethene boron complex compound in which R 4 ~R 8 is a hydrogen atom, a cyano group, a nitro group, an alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, or an amino group or a substituted amino group having 0 to 20 carbon atoms.

[0015] 4. In the general formula (1), a dipyrromethene boron complex compound in which R 10 or R 11 is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0016] 5. A coloring composition containing a dipyrromethene boron complex compound in which the maximum absorption wavelength of the absorption band in the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) measured at 23 to 27 °C using a propylene glycol monomethyl ether (PGME) solution of the dipyrromethene boron complex compound is in the wavelength range of 480 to 530 nm. Measured at 23 to 27 °C Using the propylene glycol monomethyl ether (PGME) solution of the dipyrromethene boron complex compound, in the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm), the

[0017] 6. A colored composition containing a dipyrometheneboron complex compound having an absorption band with maximum absorption of 15 to 40 nm.

[0018] 7. A colorant for optical filters containing the dipyrometheneboron complex compound or coloring composition.

[0019] 8. An optical filter using the aforementioned coloring agent for optical filters. [Effects of the Invention]

[0020] The dipyrometheneboron complex compound of the present invention selectively absorbs light in the wavelength range of 480 to 530 nm, exhibits suppressed fluorescence, and has excellent lightfastness, making it useful as a colorant for optical filters. [Modes for carrying out the invention]

[0021] The embodiments of the present invention will be described in detail below. It should be noted that the present invention is not limited to the embodiments described below, and can be implemented with various modifications within the scope of its essence. First, the dipyrometheneboron complex compound, which is a dye represented by the general formula (1), will be described.

[0022] In general formula (1), R 1 ~R 3 Examples of "halogen atoms" represented by this formula include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms. Fluorine atoms, chlorine atoms, or bromine atoms are preferred as the "halogen atoms".

[0023] In general formula (1), R 1 ~R 12 In the expression "linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, which may have substituents," the "linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms" specifically refers to: Linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups; isopropyl, isobutyl, s-butyl, t-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, and 1,2-dimethylpropyl groups. Examples include branched alkyl groups such as methylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethyl-1-methylpropyl group, isooctyl group, and 2-ethylhexyl group; cyclic alkyl groups (cycloalkyl groups) such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 2-ethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group; and 1-adamantyl group and 2-adamantyl group.

[0024] In general formula (1), R 1 ~R 3 The "acyl group or amide group having 1 to 20 carbon atoms, which may have substituents" is represented as "―(C=O)―R 20 R represented by " 20 It means a group that has R. 20 R may be a group containing a carbon atom or a group that does not contain a carbon atom. 20 This may be a group containing a nitrogen atom. 20 However, if the group contains carbon atoms, R 20 The number of carbon atoms may be, for example, 1 to 19, or 1 to 10. 20 If the group contains a nitrogen atom, 20 The number of carbon atoms in R can be, for example, 0 to 19. 20Examples include -H; linear, branched, or cyclic alkyl groups having 1 to 19 carbon atoms, which may have substituents; linear, branched, or cyclic alkenyl groups having 1 to 19 carbon atoms, which may have substituents; and aromatic hydrocarbon groups having 6 to 19 carbon atoms, which may have substituents. Specific examples of "acyl groups having 1 to 20 carbon atoms, which may have substituents" include formyl group, acetyl group, ethyl carbonyl group (propionyl group), propyl carbonyl group, isopropyl carbonyl group, butyl carbonyl group, isobutyl carbonyl group, s-butyl carbonyl group, t-butyl carbonyl group, pentyl carbonyl group, isopentyl carbonyl group, neopentyl carbonyl group, 2-methylbutyl carbonyl group, acryloyl group, benzoyl group, etc. 20 If it contains a nitrogen atom, R 1 ~R 3 The "acyl group having 1 to 20 carbon atoms which may have substituents" represented by R may be a primary amide group, a secondary amide group, or a tertiary amide group, 20 "-NR 21 R 22 It may be a monosubstituted amino group or a disubstituted amino group represented as ". 21 , R 22 Specifically, the above R 20 The same group as R can be cited. 20 Examples of these groups include -NH2, -NHCH3, -NHCH2CH3, dimethylamino group, diethylamino group, di(n-propyl)amino group, and di(n-butyl)amino group.

[0025] In general formula (1), R 1 ~R 3In the "aromatic hydrocarbon group having 6 to 20 carbon atoms that may have substituents" represented by , specific examples of aromatic hydrocarbon groups include phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, and triphenylenyl group (in the present invention, "aromatic hydrocarbon group" also includes aryl groups or fused polycyclic aromatic groups).

[0026] In general formula (1), R 1 ~R 3 In the expression "heterocyclic groups having 5 to 20 ring-forming atoms which may have substituents," examples of "heterocyclic groups having 5 to 20 ring-forming atoms" include, specifically, heterocyclic groups (or heteroaromatic hydrocarbon groups) such as pyridyl group, pyrimidinyl group, triazinyl group, imidazolyl group, pyrazolyl group, triazolyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, naphthylidinyl group, indolyl group, acridinyl group, phenanthrolinyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, oxazolyl group, isoxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, quinoxalyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, and carboninyl group.

[0027] In general formula (1), R 4 ~R 8 The "sulfonic acid group" represented by is the acidic form of the sulfonic acid group (-SO3H), and the "sulfonic acid ion" is the ionic form (-SO3H). - ) is a sulfonic acid group, and "sulfonate" is a sulfonic acid group in salt form (-SO3M, where M represents a metal ion, such as an alkali metal ion). In general formula (1), R 4 ~R 8In the expression "alkoxycarbonyl group having 2 to 20 carbon atoms which may have substituents," examples of "alkoxycarbonyl group having 2 to 20 carbon atoms" include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, and the like.

[0028] In general formula (1), R 4 ~R 8 In the expression "an amino group having 0 to 20 carbon atoms or a substituted amino group which may have substituents," the "amino group having 0 to 20 carbon atoms or a substituted amino group" may or may not have substituents, and if it does have substituents, it is "-NR 100 R 101 "The substituent R is expressed as " 100 and R 101 The amino group includes an amino group having a substituent, and examples include an unsubstituted amino group (-NH2), a monosubstituted amino group, and a disubstituted amino group. The number of carbon atoms in the monosubstituted or disubstituted amino group is, for example, 1 to 20, and may be 1 to 10. The amino group having 0 to 20 carbon atoms which may have substituents may be a group to which the aforementioned linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heterocyclic group having 5 to 20 ring-forming atoms is bonded via -NH-, -N<, or -N=CH-. Examples of monosubstituted amino groups include ethylamino group, butylamino group, acetylamino group, and phenylamino group. Examples of disubstituted amino groups include dialkylamino groups with 2 to 20 carbon atoms, such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, and dihexylamino group; dialkenylamino groups with 4 to 20 carbon atoms, such as diallylamino group; and diphenylamino group, N-acetyl-N-phenylamino group, and N-butyl-N-phenylamino group.

[0029] In general formula (1), R 4 ~R 8In the expression "an amide group or acylamino group having 1 to 20 carbon atoms which may have substituents," the "amide group" is "―(C=O)―NR 100 R 101 "R" is expressed as " 100 and R 101 The term "amide group having" includes unsubstituted amide groups (―(C=O)―NH2, primary amide group), monosubstituted amide groups (secondary amide group), disubstituted amide groups (tertiary amide group), etc. The number of carbon atoms in the unsubstituted amide group, monosubstituted amide group, or disubstituted amide group is, for example, 1 to 20, and may be 1 to 10. The "amide group having 1 to 20 carbon atoms which may have substituents" may be a group to which the aforementioned "linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms," "acyl group having 2 to 20 carbon atoms," "aromatic hydrocarbon group having 6 to 20 carbon atoms," or "heterocyclic group having 5 to 20 ring-forming atoms" are bonded via ―NH― or ―N<. Examples of monosubstituted amide groups include methylaminocarbonyl group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, hexylaminocarbonyl group, and phenylaminocarbonyl group. Examples of disubstituted amide groups include dialkylaminocarbonyl groups with 3 to 20 carbon atoms, such as dimethylaminocarbonyl group, diethylaminocarbonyl group, dipropylaminocarbonyl group, and dibutylaminocarbonyl group; dialkenylaminocarbonyl groups with 5 to 20 carbon atoms, such as diallylaminocarbonyl group; and diphenylaminocarbonyl group, N-acetyl-N-phenylaminocarbonyl group, and N-butyl-N-phenylaminocarbonyl group. On the other hand, in general formula (1), R 4 ~R 8 In the phrase "an amide group or acylamino group having 1 to 20 carbon atoms which may have substituents," the "acylamino group" is "-NR 100 (C=O)R 101 "Base R" is expressed as 100 and acyl group R 101 It contains an acylamino group having (C=O)- and an unsubstituted acylamino group (-NH(C=O)R 101Examples include unsubstituted acylamino groups and monosubstituted acylamino groups. The number of carbon atoms in unsubstituted acylamino groups and monosubstituted acylamino groups is, for example, 2 to 20, and may be 2 to 10. "Acylamino groups with 2 to 20 carbon atoms that may have substituents" are defined as -N(C=O)R 101 -The group may be formed by bonding the aforementioned "linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms," "acyl groups having 2 to 20 carbon atoms," "aromatic hydrocarbon groups having 6 to 20 carbon atoms," or "heterocyclic groups having 5 to 20 ring-forming atoms" via a linkage. Examples of unsubstituted acylamino groups include acetylamino group, propionylamino group, butanoylamino group, pentanoylamino group, hexanoylamino group, and benzoylamino group. Examples of monosubstituted acylamino groups include acetylmethylamino group, propionylethylamino group, and benzoylpropylamino group. However, R 4 ~R 8 At least one of them is not a hydrogen atom. More specifically, Cyano group, nitro group, sulfonic acid group, sulfonate ion, sulfonate salt Linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, which may have substituents. An alkoxycarbonyl group having 2 to 20 carbon atoms, which may have substituents. An amino group having 0 to 20 carbon atoms, which may have substituents, or a substituted amino group, This represents an amide group or acylamino group having 1 to 20 carbon atoms, which may have substituents. R 4 ~R 8 or R 9 ~R 12 The adjacent groups may bond to each other to form a ring. For example, R 4 ~R 8 The adjacent groups may be bonded to each other via single bonds, substituted or unsubstituted methylene groups, oxygen atoms, or sulfur atoms to form a ring. Also, R 4 ~R 8They may be bonded to each other between adjacent groups to form a ring, and the ring may be further an aromatic ring. For example, there is an example in which a benzene ring substituent is expanded to a naphthalene ring as described in the following (G-17). In this case, although the naphthalene ring substituent itself is unsubstituted, from the viewpoint that an extra benzene ring is condensed when viewed from the benzene ring, "R 4 ~R 8 At least one of them shall meet the requirement of "other than a hydrogen atom".

[0030] In the general formula (1), R 1 ~R 12 represented by "a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent", R 1 ~R 3 represented by "an acyl group or an amide group having 1 to 20 carbon atoms which may have a substituent", "an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent", "a heterocyclic group having 5 to 20 ring-forming atoms which may have a substituent", R 4 ~R 8 represented by "an alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent", "an amino group or a substituted amino group having 0 to 20 carbon atoms which may have a substituent", or As the "substituent" in "an amide group having 1 to 20 carbon atoms which may have a substituent", specifically a deuterium atom, a hydroxyl group, a thiol group, a cyano group, a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; an amino group or a substituted amino group having 0 to 20 carbon atoms; a sulfonyl-containing group having 0 to 20 carbon atoms; a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms; Linear, branched, or cyclic alkoxy groups, or aryloxy groups, having 1 to 20 carbon atoms; Acyl groups with 2 to 20 carbon atoms; Acyloxy groups, aminooxy groups, phosphate groups, or phosphate ester groups having 0 to 20 carbon atoms; Aromatic hydrocarbon groups or condensed polycyclic aromatic groups having 6 to 20 carbon atoms; Examples include heterocyclic groups with 5 to 20 ring-forming atoms. If a "substituent" contains a carbon atom, that carbon atom is not included in the above-mentioned "0-20 carbon atoms", "1-20 carbon atoms", and "6-20 carbon atoms". There may be only one of these "substituents" or multiple of them, and if there are multiple, they may be the same or different from each other. Furthermore, these "substituents" may also have the substituents exemplified above. In addition, these substituents may be bonded to each other via single bonds, substituted or unsubstituted methylene groups, oxygen atoms (-O-), or sulfur atoms (-S-) to form a ring. However, the above-mentioned R 1 ~R 12 Each group represented by may have a maximum of 10 substituents, and the maximum number of carbon atoms in each group may be 100.

[0031] Note that in general formula (1), R 1 ~R 12 In each of the above groups having a "substituent" represented by, the "substituent" listed is (i) "Amino groups or substituted amino groups with 0 to 20 carbon atoms," (ii) "Sulfonyl-containing groups with 0 to 20 carbon atoms" (iii) "Linear, branched, or cyclic alkyl groups with 1 to 20 carbon atoms," (iv) "Linear, branched, or cyclic alkenyl groups with 2 to 20 carbon atoms," (v) "Linear, branched, or cyclic alkoxy groups or aryloxy groups having 1 to 20 carbon atoms," (vi) "Acyl groups with 2 to 20 carbon atoms" (vii) "Acyloxy groups, aminooxy groups, phosphate groups, or phosphate ester groups having 1 to 20 carbon atoms," (viii) "Aromatic hydrocarbon groups or condensed polycyclic aromatic groups with 6 to 20 carbon atoms," or (ix) Specifically, the "heterocyclic groups with 2 to 20 carbon atoms" are as follows: (i) amino group; Monosubstituted or disubstituted amino groups having linear or branched alkyl groups with 1 to 20 carbon atoms, or aromatic hydrocarbon groups with 6 to 20 carbon atoms, such as methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, di-t-butylamino group, and diphenylamino group; (ii) Groups having a sulfonyl group (―S(=O)2―) with 0 to 20 carbon atoms, such as sulfonamide groups (―S(=O)2―NH2), mesyl groups, and tosyl groups; ―SO3 - , -SO3H, -SO3M (where M is an alkali metal atom); (iii) Linear or branched alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, and decyl groups; cyclic alkyl groups (cycloalkyl groups) with 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl groups; 1-adamantyl and 2-adamantyl groups; Aryloxy groups with 6 to 20 carbon atoms, such as phenyloxy, tolyloxy, biphenylyloxy, naphthyloxy, anthracenyloxy, and phenantrenyloxy; (iv) A vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, or a linear or branched alkenyl group having 2 to 20 carbon atoms in which a plurality of these alkenyl groups are bonded; a cyclic alkenyl group having 2 to 20 carbon atoms such as a cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group (cycloalkenyl group); (v) A linear or branched alkoxy group having 1 to 20 carbon atoms such as a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group; a cyclic alkoxy group having 3 to 20 carbon atoms such as a cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclononyloxy group, cyclodecyloxy group (cycloalkoxy group); 1-adamantyloxy group, 2-adamantyloxy group; (vi) An acyl group having 2 to 20 carbon atoms such as a formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group; (vii) An acyloxy group (ester group) represented by “—O—(C═O)—R” (where R represents any alkyl group or aromatic hydrocarbon group, etc.), for example, an acetyloxy group; -ONR 31 R 32 An aminooxy group represented by (where R 31 and R 32 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group, an acyl group having 2 to 20 carbon atoms (such as an acetyl group, benzoyl group), etc.), for example,; -OP(═O)OR 33 OR 34 A phosphate group or phosphate ester group represented by (where R 33 and R 34 are each independently the above R 31 and R 32It is similar to the above. ), for example, phosphate groups, methyl phosphate groups, dimethyl phosphate groups, etc. (viii) Aromatic hydrocarbon groups or condensed polycyclic aromatic groups having 6 to 20 carbon atoms, such as phenyl groups, biphenylyl groups, terphenylyl groups, naphthyl groups, anthryl groups, phenanthryl groups, fluorenyl groups, indenyl groups, pyrenyl groups, perilenyl groups, fluoranthenyl groups, and triphenylenyl groups; (ix) Heterocyclic groups with 2 to 20 carbon atoms, such as pyridyl group, pyrimidylinyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthylidinyl group, acridinyl group, phenanthrolinyl group, benzofuranyl group, benzothienyl group, oxazolyl group, indolyl group, carbazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, and carbonyl group;

[0032] In general formula (1), R 1 ~R 3 It is preferably a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, which may have substituents, and more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, which may have substituents.

[0033] In general formula (1), R 4 ~R 8 It is preferably a hydrogen atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms which may have substituents, or an amino group having 0 to 20 carbon atoms which may have substituents or a substituted amino group, and more preferably a hydrogen atom, a cyano group, a nitro group, an alkoxycarbonyl group having 2 to 20 carbon atoms which may have substituents, or an amino group having 0 to 20 carbon atoms which may have substituents or a substituted amino group.

[0034] In general formula (1), R 10 or R 11 However, it is preferable that the alkyl group is a linear or branched alkyl group having 1 to 6 carbon atoms, which may have hydrogen atoms or substituents.

[0035] The dipyromethaneboron complex compound represented by general formula (1) can be synthesized and produced by, for example, the following manufacturing method. A benzaldehyde having the corresponding substituent and a pyrrole having the corresponding substituent are stirred in a solvent in the presence of an acid catalyst, and then oxidized with an oxidizing agent to obtain the dipyromethane compound of general formula (X-1) below. Subsequently, a dipyromethaneboron complex compound represented by general formula (X-2) below can be obtained by reacting it with a boron trifluoride derivative or the like in the presence of a tertiary amine. Furthermore, the compound represented by general formula (1) can be produced by stirring catechol having the substituent corresponding to general formula (X-2) below in a solvent in the presence of a Lewis acid such as aluminum chloride. However, the method for producing the dipyromethaneboron complex compound of the present invention is not limited to the above. Note that in general formulas (X-1) and (X-2) below, R 1 ~R 8 This is the same as the definition in the general formula (1) above.

[0036] [ka]

[0037] In the method for producing the dipyrometheneboron complex compound of the present invention, examples of acid catalysts include hydrochloric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, and hydrobromic acid.

[0038] In the method for producing the dipyrometheneboron complex compound of the present invention, the solvent can be any inert solvent, such as halogenated solvents like cyclomethane and dichloroethane, tetrahydrofuran (THF), and toluene.

[0039] In the method for producing the dipyrometheneboron complex compound of the present invention, examples of oxidizing agents include chloranil (2,3,5,6-tetrachloro-p-benzoquinone), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), and oxygen-containing gases (such as air).

[0040] In the method for producing the dipyrometheneboron complex compound of the present invention, examples of tertiary amines include triethylamine and N,N-diisopropylethylamine.

[0041] The isolation and purification of each product in the production method of the present invention can be carried out by appropriately combining known methods commonly used in organic synthesis, such as purification by column chromatography; adsorption purification using silica gel, activated carbon, activated clay, etc.; and recrystallization or crystallization using solvents. Furthermore, nuclear magnetic resonance analysis (NMR), absorbance measurement and ultraviolet-visible absorption spectroscopy (UV-Vis) measurement using a spectrophotometer, and thermogravimetric analysis-differential thermal analysis (TG-DTA) can be used to identify, analyze, and evaluate the optical properties, thermal properties, and other physical properties of these compounds. These analytical methods can also be used to evaluate the solubility, color, and heat resistance of the obtained compounds.

[0042] Specific examples of preferred dipyromeneboron complex compounds represented by general formula (1) are shown in formulas (G-1) to (G-21) below, but the dipyromeneboron complex compounds of the present invention are not limited to these. In the following structural formulas, some hydrogen atoms have been omitted, and all possible stereoisomers and tautomers are included, and planar structural formulas are shown.

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] The dipyromeneboron complex compound of the present invention or a colored composition containing the compound can be evaluated for its optical properties by measuring its ultraviolet-visible absorption spectrum. Specifically, the dipyromeneboron complex compound of the present invention has a maximum absorption wavelength (λ) in the visible light region (wavelength range of 350 to 700 nm) of the absorption band in its ultraviolet-visible absorption spectrum. max The wavelength range is preferably 480 nm to 530 nm, and more preferably 485 nm to 520 nm. Color reproduction tends to be better when the wavelength is within this range. A specific method for measuring the ultraviolet-visible absorption spectrum involves preparing a solution by dissolving the dipyrometheneboron complex compound in a solvent such as propylene glycol monomethyl ether (PGME), and measuring it at an appropriate temperature (e.g., room temperature around 23 to 27°C). More specific methods and detailed measurement conditions are preferably those described in the examples below.

[0051] In the ultraviolet-visible absorption spectrum of the dipyrometheneboron complex compound of the present invention or a colored composition containing the compound, when the maximum absorption wavelength of the absorption band is in the wavelength range of 480 nm to 530 nm, as described above, it is preferable that the full width at half maximum (FWHM) of the absorption band be small (narrow), specifically, preferably 40 nm or less, more preferably 30 nm or less, and usually 15 nm or more. In this specification, "full width at half maximum" means the full width at half maximum (FWHM) of the absorption band having the maximum absorption peak, and is the wavelength (nm) between two points that take half the absorbance value of the maximum absorption peak in the above absorption band.

[0052] The dipyrometheneboron complex compound of the present invention, or a colored composition containing the compound, tends to improve the color reproduction of displays because the full width at half maximum of the absorption band having the maximum absorption is in the range of 15 to 40 nm as described above. Therefore, a compound or colored composition having such an ultraviolet-visible absorption spectrum is particularly suitable for use as a colorant for optical filters, as it has a particularly sharp ultraviolet-visible absorption spectrum, and is especially suitable for fabricating optical filters (such as optical filters for displays) using the colorant.

[0053] The dipyromeneboron complex compound of the present invention preferably has a fluorescence quantum yield of 0.05 or less, more preferably 0.03 or less, and even more preferably 0.02 or less. Dipyromeneboron complex compounds with low fluorescence quantum yields can suppress fluorescence generation, thereby preventing the generation of unwanted light that affects color tone. They can also suppress a decrease in the contrast ratio of the display. The fluorescence quantum yield can be measured by mixing the dipyromeneboron complex compound with an acrylic resin solution or the like, applying it to a glass substrate to create a coating film, and then measuring the resulting coating film using an absolute quantum yield measuring device.

[0054] The dipyrometheneboron complex compound of the present invention needs to be dissolved in a solvent, particularly an organic solvent containing resin, during the process of manufacturing optical filters; therefore, high solubility in organic solvents is preferable. Organic solvents are not particularly limited, but examples include aromatic hydrocarbons such as toluene and xylene; ethers such as propylene glycol monomethyl ether acetate (PGMEA), methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether (PGME); ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and 3-heptanone; alcohols such as methanol, ethanol, and 2-propanol; esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, ethyl acetate, butyl acetate, and methyl 3-methoxypropionate; diacetone alcohol (DAA), etc.; amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO); and chloroform (trichloromethane). These solvents may be used individually or in mixtures of two or more types.

[0055] The solubility of the dipyrometheneboron complex compound of the present invention is expressed as solubility, which represents the maximum amount of a substance that can dissolve in a particular solvent, and is expressed in units such as "mass% (solvent name, temperature)". Solubility can be evaluated, for example, by mixing a sample with a specific solvent, stirring the solvent at a constant temperature for a certain period of time, and then visually checking for the presence or absence of insoluble matter. It can also be obtained by measuring the concentration of the prepared saturated solution, or by measuring the concentration of the dissolved portion using methods such as liquid chromatography (LC) or absorbance measurement.

[0056] The dipyrometheneboron complex compound of the present invention preferably dissolves at a concentration of 0.1% by mass or more in organic solvents, more preferably at a concentration of 0.5% by mass or more, and even more preferably at a concentration of 1% by mass or more. It is particularly preferable that it exhibits the above levels of solubility in organic solvents such as PGMEA, PGME, and cyclohexanone.

[0057] By performing thermogravimetric-differential thermal analysis (TG-DTA) on the dipyrometheneboron complex compound of the present invention or a colored composition containing the compound, the thermal decomposition temperature can be analyzed and used as an indicator of heat resistance. In the colored composition, the thermal decomposition temperature of the pigment compound is preferably 200°C or higher.

[0058] The dipyromeneboron complex compound of the present invention can be used as a colored composition by mixing it with a resin or the like. Any known resin can be used as long as it has the properties required for optical filter manufacturing. For example, (meth)acrylic resins, olefin resins, styrene resins, polyimide resins, polyamide resins, polyacetal resins, urethane resins, polyester resins, polypropylene resins, epoxy resins, vinyl ether resins, phenol (novolac) resins, polycarbonate resins, cellulose resins, other transparent resins, photocurable resins, thermosetting resins, thermoplastic resins, and composites of these resins can be used in appropriate combinations with their monomer or oligomer components. Copolymers of these resins can also be used in combination.

[0059] The colored composition of the present invention may contain optional components other than the dipyrometheneboron complex compound, solvent, or resin of the present invention, depending on its intended use. Examples of optional components include surfactants, dispersants, defoamers, leveling agents, antioxidants, other dyes (dyes, pigments, etc.), ultraviolet absorbers, infrared absorbers, antistatic agents, flame retardants, polymerizable monomers, polymerization initiators, and sensitizers. These optional components may be known.

[0060] The content of the dipyrometheneboron complex compound in the colored composition of the present invention is not particularly limited, but is preferably 0.001 to 30% by mass, and more preferably 0.01 to 20% by mass, relative to the total solid content.

[0061] The colorant for optical filters of the present invention contains the dipyrometheneboron complex compound of the present invention or a coloring composition containing said compound. Optical filters obtained using the colorant for optical filters of the present invention can be used, for example, as bandpass filters outside of a display configuration or as color reproduction or color gamut expansion filters inside a display configuration. Specifically, they are used in displays in the form of color correction filters, i.e., color purity improvement filters.

[0062] The specific form of the optical filter of the present invention is not particularly limited, but examples include a filter (filter A) in which a coating layer containing the dipyromethenboron complex compound of the present invention and a binder resin is applied to a resin film, a filter (filter B) in which the dipyromethenboron complex compound of the present invention is contained in the adhesive layer of the resin film, and a filter (filter C) in which the dipyromethenboron complex compound of the present invention is contained in the resin film. Furthermore, the dipyromethenboron complex compound of the present invention may be contained in two or more of the filters A to C.

[0063] When the optical filter of the present invention is used as a color correction filter, the installation position of the color correction filter is not particularly limited as long as it is positioned between the light source of the display and the viewer. For example, it may be a color correction coating layer or a color correction adhesive layer applied to the glass plate, polarizing plate, etc. of the display, or it may be a color correction film attached to the surface of the glass plate, polarizing plate, etc. of the display. It may also be a color correction coating layer or a color correction adhesive layer applied to the surface of a plate-shaped polymer molded body provided inside the display, or it may be a color correction film attached to the surface of the polymer molded body. Furthermore, the plate-shaped polymer molded body itself may contain the dipyrometheneboron complex compound of the present invention. The position of the color correction filter may be on the light source side or the viewer side of the front or back of the glass plate or polymer molded body.

[0064] The binder resin constituting the optical filter of the present invention is not particularly limited, but examples include (meth)acrylic resins (such as PMMA), polyamide resins, polyurethane resins, polyolefin resins, and polycarbonate resins. The adhesive is not particularly limited, but examples include acrylic, polyester, polyamide, polyurethane, polyolefin, polycarbonate, rubber, or silicone resin adhesives, with acrylic or silicone resin adhesives being preferred. The resin film can be any transparent plastic material. Examples include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, and polyphenylene sulfide resins.

[0065] When a color-correcting coating layer is provided by mixing the dipyromethenboron complex compound of the present invention with a binder resin, the content of the dipyromethenboron complex compound is preferably 0.001 to 20 parts by mass per 100 parts by mass of the binder resin. Furthermore, when a color-correcting adhesive layer is provided by mixing the dipyromethenboron complex compound of the present invention with an adhesive, the content of the dipyromethenboron complex compound is preferably 0.001 to 20 parts by mass per 100 parts by mass of the adhesive.

[0066] When applying a color-correcting coating layer and a color-correcting adhesive layer to a resin film or the like (including glass plates, polarizing plates, polymer molded articles, etc.), a coating solution can be prepared by dissolving and / or dispersing a composition containing a dipyrometheneboron complex compound, a binder resin and / or adhesive, and other additives as needed, in a solvent, and known application methods such as spin coating, spraying, bar coating, flow coating, gravure coating, roll coating, blade coating, and die coating can be used. [Examples]

[0067] The embodiments of the present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. The identification of compounds in the following synthesis examples is as follows: 1 H-NMR analysis (Bruker nuclear magnetic resonance spectrometer, model: Ascend) TM This was done using 400MHz.

[0068] [Synthesis Example 1] Synthesis of compound (G-1) The following reaction was carried out under a nitrogen atmosphere. In a reaction vessel equipped with a condenser, stirrer, and thermometer, 9.27 g of 2,4-dimethylpyrrole (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.00 g of 4-formylmethyl benzoate (manufactured by Alfa Aesar), and 400 mL of dichloromethane were added and stirred at room temperature (23-28°C). 0.07 mL of trifluoroacetic acid was added to this solution and stirred at the same temperature for 14 hours. A suspension of 12.0 g of p-chloranil (manufactured by Tokyo Chemical Industry Co., Ltd.) and 240 mL of dichloromethane was added to this reaction mixture and stirred at room temperature for a further 1 hour. 33.8 mL of triethylamine was added dropwise to this reaction solution, the reaction mixture was cooled to 10°C, and 42.8 mL of boron trifluoride diethyl ether complex (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After addition, the temperature was raised to room temperature and stirred for 2.5 hours, then water was added to the reaction mixture and the organic layer was extracted. The extract was concentrated under reduced pressure and purified by column chromatography (support: silica gel, solvent: dichloromethane / heptane = 6 / 4 (volume ratio)) to obtain the following intermediate (100) (4.34 g, yield 23%).

[0069] [ka]

[0070] Next, the following reaction was carried out under a nitrogen atmosphere. 1.20 g of the intermediate (100), 120 mL of dichloromethane, and 1.05 g of aluminum chloride (Acros Organics) were placed in a reaction vessel equipped with a condenser, a stirrer, and a thermometer, and the mixture was stirred at room temperature (23-28°C) for 30 minutes. 1.04 g of catechol (Tokyo Chemical Industries, Ltd.) was added to this reaction mixture, and the mixture was stirred at room temperature for 1 hour. After filtering the reaction mixture, the filtrate was concentrated under reduced pressure and purified by column chromatography (support: silica gel, solvent: dichloromethane / heptane = 7 / 3 (volume ratio)) to obtain compound (G-1) (1.09 g, yield 77%) as an orange solid.

[0071] NMR measurements were performed on the obtained orange solid, and the following 25 hydrogen signals were detected, identifying the structure of the compound represented by compound (G-1).

[0072] 1 H-NMR (400MHz, CDCl3): δ(ppm)=8.19(2H), 7.41(2H), 6.78(4H), 5.95(2H), 3.98(3H), 2.08(6H), 1.35(6H).

[0073] [Synthesis Example 2] Synthesis of compound (G-2) The following reaction was carried out under a nitrogen atmosphere. 2.00 g of the intermediate (100), 200 mL of dichloromethane, and 1.74 g of aluminum chloride were placed in a reaction vessel equipped with a condenser, a stirrer, and a thermometer, and the mixture was stirred at room temperature (23-28°C) for 45 minutes. 2.61 g of 4-t-butylpyrocatechol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to this reaction mixture, and the mixture was stirred at room temperature for 1 hour. After filtering the reaction mixture, the filtrate was concentrated under reduced pressure and purified by column chromatography (support: silica gel, solvent: dichloromethane / heptane = 6 / 4 (volume ratio)) to obtain compound (G-2) (2.10 g, yield 79%) as an orange solid.

[0074] NMR measurements were performed on the obtained orange solid, and the following 33 hydrogen signals were detected, identifying the structure of the compound represented by compound (G-2).

[0075] 1 H-NMR (400MHz, CDCl3): δ(ppm)=8.18(2H), 7.41(2H), 6.82(1H), 6.75(1H), 6.65(1H), 5.94(2H), 3.97(3H), 2.08(6H), 1.34(6H), 1.30(9H).

[0076] [Synthesis Example 3] Synthesis of compound (G-7) The following reaction was carried out under a nitrogen atmosphere. In a reaction vessel equipped with a condenser, stirrer, and thermometer, 4.41 g of 2,4-dimethylpyrrole, 3.50 g of 4-nitrobenzaldehyde (Alfa Aesar), and 175 mL of dichloromethane were placed and stirred at room temperature (23-28°C). 0.04 mL of trifluoroacetic acid was added to this solution and stirred at the same temperature for 13 hours. A suspension of 5.12 g of p-chloranil and 100 mL of dichloromethane was added to this reaction mixture and stirred at room temperature for a further 1 hour. 12.8 mL of triethylamine was added dropwise to this reaction mixture, and the reaction mixture was cooled to 5°C. 17.5 mL of boron trifluoride diethyl ether complex was then added dropwise. After the addition, the temperature was raised to room temperature and stirred for 5 hours. 150 mL of water was then added to the reaction mixture and it was filtered. The organic layer of the filtrate was extracted, and the extract was concentrated under reduced pressure. After purification by column chromatography (support: silica gel, solvent: dichloromethane / heptane = 1 / 1 (volume ratio)), the following intermediate (101) was obtained (1.17 g, yield 14%).

[0077] [ka]

[0078] Next, the following reaction was carried out under a nitrogen atmosphere. 1.00 g of the intermediate (101), 100 mL of dichloromethane, and 0.90 g of aluminum chloride were placed in a reaction vessel equipped with a condenser, a stirrer, and a thermometer, and the mixture was stirred at room temperature (23-28°C) for 30 minutes. 1.35 g of 4-t-butylpyrocatechol was added to this reaction solution and the mixture was stirred at room temperature for 1.5 hours. After filtering the reaction solution, the filtrate was concentrated under reduced pressure and purified by column chromatography (support: silica gel, solvent: dichloromethane / heptane = 1 / 1 (volume ratio)) to obtain compound (G-7) (1.07 g, yield 80%) as an orange solid.

[0079] NMR measurements were performed on the obtained orange solid, and the following 30 hydrogen signals were detected, identifying the structure of the compound represented by compound (G-7).

[0080] 1 H-NMR (400MHz, CDCl3): δ(ppm)=8.39(2H), 7.55(2H), 6.83(1H), 6.76(1H), 6.66(1H), 5.97(2H), 2.09(6H), 1.36(6H), 1.31(9H).

[0081] [Synthesis Example 4] Synthesis of compound (G-10) The following reaction was carried out under a nitrogen atmosphere. 5.80 g of 2,4-dimethylpyrrole, 4.00 g of 4-cyanobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and 200 mL of dichloromethane were placed in a reaction vessel equipped with a condenser, stirrer, and thermometer, and the mixture was stirred at room temperature (23-28°C). 0.05 mL of trifluoroacetic acid was added to this solution, and the mixture was stirred at the same temperature for 5 hours. A suspension of 7.50 g of p-chloranil and 150 mL of dichloromethane was added to this reaction mixture, and the mixture was stirred at room temperature for a further 1 hour. 16.9 mL of triethylamine was added dropwise to this reaction mixture, and the reaction mixture was cooled to 5°C. 23.0 mL of boron trifluoride diethyl ether complex was then added dropwise. After the dropwise addition, the mixture was heated to room temperature and stirred for 2.5 hours, after which 150 mL of water was added to the reaction mixture. The organic layer was extracted, concentrated under reduced pressure, and then purified by column chromatography (support: silica gel, solvent: dichloromethane / heptane = 1 / 1 (volume ratio)) to obtain the following intermediate (102) (1.60 g, yield 15%).

[0082] [ka]

[0083] Next, the following reaction was carried out under a nitrogen atmosphere. 1.00 g of the intermediate (102), 100 mL of dichloromethane, and 0.95 g of aluminum chloride were placed in a reaction vessel equipped with a condenser, a stirrer, and a thermometer, and the mixture was stirred at room temperature (23-28°C) for 30 minutes. 1.43 g of 4-t-butylpyrocatechol was added to this reaction solution and the mixture was stirred at room temperature for 1 hour. After filtering the reaction solution, the filtrate was concentrated under reduced pressure and purified by column chromatography (support: silica gel, solvent: dichloromethane / heptane = 6 / 4 (volume ratio)) to obtain compound (G-10) (1.22 g, yield 90%) as an orange solid.

[0084] NMR measurements were performed on the obtained orange solid, and the following 30 hydrogen signals were detected, identifying the structure of the compound represented by compound (G-10).

[0085] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.82(2H), 7.48(2H), 6.82(1H), 6.76(1H), 6.65(1H), 5.96(2H), 2.09(6H), 1.35(6H), 1.30(9H).

[0086] [Synthesis Example 5] Synthesis of compound (G-22) The following reaction was carried out under a nitrogen atmosphere. In a reaction vessel equipped with a condenser, stirrer, and thermometer, 42.8 g of 2,4-dimethylpyrrole, 37.5 g of sodium 2-formylbenzenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 360 mL of DMF were placed and stirred at room temperature (23-28°C). 1.49 mL of trifluoroacetic acid was added to this solution and stirred at the same temperature for 18 hours. 40.9 g of 2,3-dichloro-5,6-dicyano-p-benzoquinone (manufactured by Alfa Aesar) was added to this reaction mixture and stirred at room temperature for 5 minutes. The mixture was then concentrated under reduced pressure and purified by column chromatography (support: silica gel, solvent: dichloromethane / methanol = 95 / 5 (volume ratio)). Under a nitrogen atmosphere, the solid obtained by purification by column chromatography, 360 mL of dichloromethane, and 220 mL of N,N-diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a reaction vessel equipped with a condenser, a stirrer, and a thermometer. Then, 273 mL of boron trifluoride diethyl ether complex was added dropwise. After addition, the mixture was stirred at room temperature for 16 hours, and then 10.0 mL of isopropanol was added. The reaction mixture was filtered, and 400 mL of water was added to the filtrate. The organic layer was extracted, concentrated under reduced pressure, and then purified by column chromatography (support: silica gel, solvent: ethyl acetate / heptane = 8 / 2 (volume ratio)) to obtain the following intermediate (103) (17.5 g, yield 18%).

[0087] [ka]

[0088] Next, the following reaction was carried out under a nitrogen atmosphere. 8.00 g of the intermediate (103), 150 mL of dichloromethane, and 5.00 g of aluminum chloride were placed in a reaction vessel equipped with a condenser, a stirrer, and a thermometer, and the mixture was stirred at room temperature (23-28°C) for 30 minutes. 4.95 g of catechol was added to this reaction solution, and the mixture was stirred at room temperature for 2 hours. 180 mL of dichloromethane and 20 mL of methanol were added to the reaction solution, and the mixture was filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography (support: silica gel, solvent: ethyl acetate / acetone = 75 / 25 (volume ratio)) to obtain compound (G-22) (6.10 g, yield 67%) as an orange solid.

[0089] NMR measurements were performed on the obtained orange solid, and the following 22 hydrogen signals were detected, identifying the structure of the compound represented by compound (G-22).

[0090] 1 H-NMR (400MHz, CDCl3): δ(ppm)=8.23(1H), 7.52(2H), 7.18(1H), 6.76-6.66(4H), 5.87(2H), 1.99(6H), 1.48(6H).

[0091] [Synthesis of comparative compound (B-2)] The following reaction was carried out under a nitrogen atmosphere. 1.00 g of the compound represented by formula (B-1) (manufactured by Tokyo Chemical Industry Co., Ltd.), 70 mL of dichloromethane, and 1.02 g of aluminum chloride were placed in a reaction vessel equipped with a condenser, a stirrer, and a thermometer, and the mixture was stirred at room temperature (23-28°C) for 30 minutes. 3.17 g of 4-t-butylpyrocatechol was added to this reaction mixture and the mixture was stirred at room temperature for 1 hour. After pouring this reaction mixture into water, it was filtered under reduced pressure, and the organic layer of the filtrate was extracted. The extract was concentrated under reduced pressure and purified by column chromatography (support: silica gel, solvent: dichloromethane / heptane = 1 / 1 (volume ratio)) to obtain compound (B-2) (0.76 g, yield 52%) as an orange solid.

[0092] NMR measurements were performed on the obtained orange solid, and signals from the following 29 hydrogen atoms were detected, identifying the structure of the compound represented by the following formula (B-2).

[0093] 1 H-NMR (300MHz, CDCl3): δ(ppm)=6.78(1H), 6.71(1H), 6.62(1H), 6.00(2H), 2.60(3H), 2.41(6H), 2.05(6H), 1.29(9H).

[0094] [ka]

[0095] [Example 1] (Evaluation of solubility) The solubility of compound (G-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA) was measured as follows. Mixtures were prepared by weighing 20 mg of compound (G-1) and PGMEA into sample bottles so that the dye concentrations were 0.5% by mass, 1% by mass, 2% by mass, 3% by mass, and 5% by mass. The sample bottles were tightly sealed and sonicated for 20 minutes, then left at room temperature (25°C) for 24 hours. The dye solutions of each concentration were visually observed at room temperature (25°C), and the highest dye concentration (by mass) in which no insoluble matter was observed was defined as the solubility. The measurement results are shown in Table 1.

[0096] (Measurement of maximum absorption wavelength and full width at half maximum) Maximum absorption wavelength (λ max The full width at half maximum (FWHM) of the absorption band with maximum absorption was measured using a UV-Vis spectrometer (JASCO Corporation, model: V-650) as follows: Compound (G-1) was dissolved in PGME, and a PGME solution was prepared by adjusting the concentration so that the absorbance of the maximum absorption wavelength in the wavelength range of 400 to 750 nm was 1. The maximum absorption wavelength was read from the measured absorption spectrum. The full width at half maximum (FWHM (nm)) was read from the maximum absorption wavelength (λ max The wavelengths A1 and A2 at which the absorbance A is half-value at (nm) were read from the absorption spectrum, and the absolute value of the difference between wavelengths A1 and A2 was defined as the full width at half maximum. The results are shown in Table 1.

[0097] (Measurement of fluorescence quantum yield) The fluorescence quantum yield was measured using an absolute PL quantum yield analyzer (Hamamatsu Photonics K.K., model: C9920) as follows. 5 mg of compound (G-1) obtained in Synthesis Example 1 and 20.0 g of a 25% by mass DMF-PGMEA mixed solution of methacrylic acid, acrylic acid ester, and styrene copolymer were placed in a sample bottle and mixed by stirring for 30 minutes. The resulting colored resin solution was filtered through a syringe filter, and 1 g of the filtrate was coated onto a glass substrate (spin coating method, 1000 rpm - 6 seconds). A thin film was prepared by heating and drying at 100°C for 5 minutes. The quantum yield of the prepared thin film was measured using the maximum absorption wavelength as the excitation light source wavelength. The results are shown in Table 1.

[0098] (Evaluation of lightfastness) The lightfastness test was performed using an accelerated lightfastness tester (Suga Test Instruments Co., Ltd., Model: Super Xenon Weather Meter SX75) as follows: 20 mg of compound (G-1) obtained in Synthesis Example 1 and 5 g of a 25% by mass DMF-PGMEA mixed solution of methacrylic acid, acrylic acid ester, and styrene copolymer were added to a sample bottle and stirred for 30 minutes. The resulting colored resin solution was filtered through a syringe filter, and 1 g of the filtrate was applied to a glass substrate (spin coating method, 1000 rpm - 6 seconds), and a thin film was prepared by heating and drying at 100°C for 5 minutes. The prepared thin film was then subjected to irradiance: 340 nm, 1 W / m². 2 Under test conditions of a test chamber temperature of 38°C and humidity of 50%, a xenon lamp was continuously irradiated for 16 hours. The ultraviolet-visible absorption spectra of the thin film were measured before irradiation (0 hours) and after irradiation. The absorbance of the peak of the absorption band with maximum absorption in the wavelength range of 400 nm to 550 nm was measured using a spectrophotometer, and the dye retention rate was calculated using the absorbance values ​​before and after irradiation according to the following formula (10). Pigment retention rate (%) = (Maximum absorbance after irradiation / Maximum absorbance before irradiation) × 100 Formula (10) A higher pigment retention rate indicates that the compound is less susceptible to degradation by light and therefore has higher lightfastness. Lightfastness was evaluated using the following three-stage evaluation. The results are shown in Table 1. "A": Dye residual rate 80% or more "B": Pigment retention rate of 50% or more, less than 80% "C": Pigment retention rate less than 50%

[0099] [Examples 2-4] In Example 1, compounds (G-2), (G-7), and (G-10) obtained in Synthesis Examples 2-4 were used instead of compound (G-1). Otherwise, solubility evaluation, measurement of maximum absorption wavelength and full width at half maximum, measurement of fluorescence quantum yield, and evaluation of photostability were performed in the same manner as in Example 1. The results are shown in Table 1.

[0100] [Comparative Example 1 and Comparative Example 2] In Example 1, solubility was evaluated, maximum absorption wavelength and full width at half maximum were measured, fluorescence quantum yield was measured, and photofastness was evaluated in the same manner as in Example 1, except that a compound not belonging to the present invention, which was used instead of compound (G-1), was used, along with compound (B-1) and comparative example compound (B-2). The results are shown in Table 1.

[0101] [Table 1]

[0102] As shown in Table 1, the dipyromeneboron complex compound of the present invention has a maximum absorption wavelength in the wavelength range of 480 to 530 nm, and the full width at half maximum of the absorption band with maximum absorption is 15 to 40 nm, confirming that it can selectively absorb light within this wavelength range. Furthermore, the colored composition containing the dipyromeneboron complex compound of the present invention has sufficient solubility and sufficiently suppressed fluorescence emission, making it practically usable as an optical filter without any problems. Moreover, the thin film prepared using the dipyromeneboron complex compound of the present invention has higher light resistance than the comparative example and is superior as an optical filter. Furthermore, the low fluorescence quantum efficiency and suppressed fluorescence in Examples 1-4 and Comparative Example 2, excluding Comparative Example 1, are thought to be due to coordination by catechol compounds, unlike in Comparative Example 1. [Industrial applicability]

[0103] The colored composition containing the dipyrometheneboron complex compound according to the present invention selectively absorbs visible light between blue and green (around 500 nm), exhibits excellent solubility and lightfastness of the film, and can suppress fluorescence, making it usable as a dye material for various applications such as optical filters and color filters. Furthermore, by using this colored composition as a colorant for optical filters, it is possible to provide optical filters for displays with excellent color reproduction.

Claims

1. A dipyrromethene boron complex compound represented by the following general formula (1). 【Chemical 1】 [In formula (1), R １ to R ３ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an acyl group or an amide group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 20 ring-forming atoms which may have a substituent, R ４ ~R ８ are each independently a hydrogen atom, a cyano group, a nitro group, a sulfonic acid group, a sulfonate ion, a sulfonate salt a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, an amino group or a substituted amino group having 0 to 20 carbon atoms which may have a substituent, represents an amide group or an acylamino group having 1 to 20 carbon atoms which may have a substituent, and R ４ ~R ８ may be bonded to each other between adjacent groups to form a ring, and the ring may further be an aromatic ring. However, R ４ ~R ８ at least one of which is other than a hydrogen atom, R ９ ~R １２ each independently represents a hydrogen atom, or represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and R ９ ~R １２ may be bonded to each other between adjacent groups to form a ring. ]

2. In the general formula (1), R １ ~R ３ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, The dipyrromethene boron complex compound according to claim 1.

3. In the general formula (1), R ４ ~R ８ is a hydrogen atom, a cyano group, a nitro group, a sulfonic acid group, a sulfonic acid ion, a sulfonate, an alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, or an amino group or a substituted amino group having 0 to 20 carbon atoms. The dipyrromethene boron complex compound according to claim 1.

4. In the general formula (1), R １０ or R １１ is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, the dipyrromethene boron complex compound according to claim 1.

5. When the thin film using the dipyrromethene boron complex compound is continuously irradiated with light of 340 nm and 1 W / m2 for 16 hours under the test conditions of temperature: 38°C and humidity: 50%, the dipyrromethene boron complex compound according to claim 1, wherein the dye residual rate calculated according to the following formula is 80% or more. Dye residual rate (%) = (maximum absorption absorbance after irradiation / maximum absorption absorbance before irradiation) × 100 The maximum absorption absorbance here means the absorbance of the peak of the absorption band having a maximum absorption in the wavelength range of 400 nm to 550 nm.

6. A thin film prepared by applying a solution containing the dipyrromethene boron complex compound, a methacrylic acid, an acrylate ester, and a copolymer of styrene, wherein the thin film having a content of the dipyrromethene boron complex compound in the solution of 0.1% by mass of the copolymer, the dipyrromethene boron complex compound according to claim 1, wherein the fluorescence quantum yield when the maximum absorption wavelength is measured as the wavelength of the excitation light source is 0.02 or less.

7. Using the propylene glycol monomethyl ether (PGME) solution of the dipyrromethene boron complex compound, measured at 23 to 27°C In the absorption band in the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm), the maximum absorption wavelength is in the wavelength range of 480 to 530 nm, A coloring composition containing the dipyrromethene boron complex compound according to claim 1.

8. A coloring composition containing a dipyrromethene boron complex compound having a maximum absorption band with a half-value width of 15 to 40 nm as described in claim 7.

9. A colorant for an optical filter containing the dipyrromethene boron complex compound according to any one of claims 1 to 6, or containing the coloring composition according to claim 7 or 8.

10. An optical filter using the colorant for an optical filter according to claim 9.

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