JPWO2017146187A1 - Oxocarbon compound, resin composition, and ink composition - Google Patents

Abstract

［式（１）および式（２）中、Ｒ¹〜Ｒ⁴はそれぞれ独立して、下記式（３）で示される構造単位を表す。］

［式（３）中、環Ａは、置換基を有していてもよい芳香族炭化水素環、置換基を有していてもよい芳香族複素環、または、これらの環構造を含む置換基を有していてもよい縮合環を表し；Ｒ⁵〜Ｒ⁷は、それぞれ独立して、水素原子、有機基または極性官能基を表すか、Ｒ⁵とＲ⁶は互いに連結して環を形成しており；環ＡおよびＲ⁷に含まれるπ電子の合計数は１２個以上である。］An oxocarbon compound represented by the following formula (1) or the following formula (2).

[In Formula (1) and Formula (2), R ^{1 to} R ⁴ each independently represent a structural unit represented by the following Formula (3). ]

[In Formula (3), Ring A is an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, or a substituent containing these ring structures. Each of R ^{5 to} R ⁷ independently represents a hydrogen atom, an organic group or a polar functional group, or R ⁵ and R ⁶ are connected to each other to form a ring. The total number of π electrons contained in the rings A and R ⁷ is 12 or more. ]

Description

  The present invention relates to an oxocarbon-based compound having a squarylium skeleton or a croconium skeleton, and a resin composition and an ink composition containing the oxocarbon-based compound.

  Oxocarbon compounds having a squarylium skeleton or a croconium skeleton in the compound are known as pigments having an absorption range from the visible to the near infrared region, and a raw material is squaric acid or croconic acid. It can be synthesized by introducing a group. As such oxocarbon compounds, for example, the following compounds are known.

  Patent Document 1 discloses the following squarylium compound (Example 2 of Patent Document 1).

  Patent Document 2 discloses the following squarylium compounds and croconium compounds (Examples 14 and 17 of Patent Document 2).

  Patent Document 3 discloses the following squarylium compound (Example 1 of Patent Document 3).

  Non-Patent Document 1 discloses the following squarylium compounds.

  Non-Patent Document 2 discloses the following croconium compounds.

  A dye having an absorption region in the near infrared region has been studied for various uses, and is expected to be used as a security ink, a near infrared cut filter, and the like.

  Security ink is used to print information (barcode, two-dimensional code, OCR characters, etc.) encrypted on banknotes, vouchers, securities, lottery tickets, etc. for the purpose of preventing counterfeiting, and logistics management Used to print delivery information on letters and parcels for system efficiency. As a means for reading information printed by security ink, since light emitting elements such as various lasers and LEDs having an emission wavelength in the range of 850 nm to 1300 nm are usually used, dyes used for security ink include It is required to have strong absorption in the wavelength region and to be excellent in invisibility under visible light. For example, Patent Documents 4 and 5 disclose an ink containing a phthalocyanine compound or a naphthalocyanine compound as a near infrared absorbing dye, and Patent Document 6 discloses a phthalocyanine compound having a maximum absorption wavelength around 900 nm. .

  The near-infrared cut filter is installed in an image sensor such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor), for example, thereby removing optical noise (for example, ghost or flare) that hinders image processing. Can be removed. For example, Patent Document 3 discloses a near-infrared cut filter containing a squarylium compound having a maximum absorption wavelength in the wavelength range of 660 nm to 710 nm as such an optical filter. In the case of a normal visible light image sensor, by providing an optical filter including a dye having a maximum absorption wavelength in a wavelength region around 700 nm, the dependency of the optical characteristics on the incident angle can be reduced and the viewing angle can be improved. it can.

  On the other hand, in addition to general digital cameras and video cameras, some imaging devices are required to shoot under night vision, such as surveillance cameras. Shooting under night vision such as at night is performed in a state invisible to the human eye. For example, it is performed by irradiating a light beam in the near infrared region and receiving the reflected light with an imaging device. . Even in a night vision image sensor, it is required to reduce the incident angle dependency of optical characteristics as in a normal visible light image sensor. Even when an infrared cut filter is used, it is difficult to reduce the incident angle dependency. For example, it is necessary to provide a cut filter that absorbs light in a desired wavelength range within a range of 800 nm to 1000 nm. In this case as well, it is required that the filter contains a dye having a strong absorption in such a wavelength region and having a high light transmittance in the visible light region, so that both under visible light and under night vision. A good image can be taken.

JP 2008-308602 A JP-A-6-25165 JP 2014-148567 A JP 7-164729 A JP 2002-309131 A JP 2007-56105 A

Tetrahedron Letters, vol.40, p.4067-4068 (1999) Tetrahedron Letters, vol.43, p.8391-8393 (2002)

  As described above, the application of near-infrared absorbing dyes to security inks, near-infrared cut filters, and the like has been studied, but in order to further expand the application range, for example, light rays having a wavelength range exceeding 850 nm. There is a need for dyes that can effectively absorb the above. However, no oxocarbon compounds such as squarylium compounds and croconium compounds have been known so far that can absorb light in such a long wavelength region. On the other hand, as disclosed in Patent Document 6, phthalocyanine compounds are known that can absorb light in the wavelength region around 900 nm, but absorb light in the visible light region, for example, color green, There was room for improvement in terms of invisibility.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to absorb near-infrared rays on the longer wavelength side and to have a high light transmittance in the visible light region, and a resin composition containing the same. And providing an ink composition.

  The oxocarbon compound of the present invention that has solved the above-described problems is characterized by being represented by the following formula (1) or the following formula (2).

［式（１）および式（２）中、Ｒ¹〜Ｒ⁴はそれぞれ独立して、下記式（３）で表される構造単位を表す。］

[In Formula (1) and Formula (2), R ^{1 to} R ⁴ each independently represent a structural unit represented by the following Formula (3). ]

［式（３）中、環Ａは、置換基を有していてもよい芳香族炭化水素環、置換基を有していてもよい芳香族複素環、または、これらの環構造を含む置換基を有していてもよい縮合環を表し；Ｒ⁵〜Ｒ⁷は、それぞれ独立して、水素原子、有機基または極性官能基を表すか、Ｒ⁵とＲ⁶は互いに連結して環を形成しており；＊は式（１）中の４員環または式（２）中の５員環との結合部位を表し；環ＡおよびＲ⁷に含まれるπ電子の合計数は１２個以上である。］

[In Formula (3), Ring A is an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, or a substituent containing these ring structures. Each of R ^{5 to} R ⁷ independently represents a hydrogen atom, an organic group or a polar functional group, or R ⁵ and R ⁶ are connected to each other to form a ring. * Represents a bonding site with a 4-membered ring in formula (1) or a 5-membered ring in formula (2); the total number of π electrons contained in rings A and R ⁷ is 12 or more is there. ]

The oxocarbon-based compound of the present invention has a π-electron system extending from the squarylium skeleton or the croconium skeleton to the structural unit represented by the formula (3), and the ring A and the substituent R ^{7 in} the structural unit of the formula (3). Since the total number of π electrons contained in is 12 or more, it is possible to absorb near-infrared rays on the longer wavelength side, for example, to effectively absorb light in a wavelength region exceeding 850 nm. On the other hand, the oxocarbon-based compound itself has a high light transmittance in the visible light region, and therefore has excellent invisibility under visible light.

In formula (3), R ⁵ and R ⁶ each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents an aralkyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, or an aryloxycarbonyl group which may have a substituent, or R ⁵ and R ⁶ are connected to each other. R ⁷ is preferably a hydrocarbon ring that may have a substituent and / or a condensed ring structure, or a heterocyclic ring that may have a substituent and / or a condensed ring structure, , A hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent is preferable.

  The present invention also provides a resin composition comprising the oxocarbon compound of the present invention and a resin component. The resin composition may further contain a liquid medium. The resin composition of the present invention can be suitably applied to, for example, an optical filter of an imaging device for night vision by being molded into a film, and has a high transmittance in the visible light region, so that it can be used under visible light. The present invention can also be suitably applied to an image sensor to be used. The resin composition of the present invention can also be applied to welding of a resin by a laser welding method. For example, the resin composition can be used by being included in a resin to be welded or used as an absorber of laser light.

  The present invention also provides an ink composition comprising the oxocarbon compound of the present invention and a liquid medium. Since the ink composition of the present invention absorbs light in the near-infrared region and is excellent in invisibility under visible light, it can be suitably used as a security ink.

  In the present invention, the condensed heterocyclic compound represented by the following formula (5) or the condensed heterocyclic compound represented by the following formula (5) is further reacted with squaric acid or croconic acid, and the above formula (1) or the above There is also provided a method for producing an oxocarbon compound having a step of obtaining an oxocarbon compound represented by the formula (2). The condensed heterocyclic compound represented by the following formula (5) can be suitably used as a raw material for producing the oxocarbon compound of the present invention.

［式（５）中、環Ａは、置換基を有していてもよい芳香族炭化水素環、置換基を有していてもよい芳香族複素環、または、これらの環構造を含む置換基を有していてもよい縮合環を表し；Ｒ⁵〜Ｒ⁷は、それぞれ独立して、水素原子、有機基または極性官能基を表すか、Ｒ⁵とＲ⁶は互いに連結して環を形成しており；環ＡおよびＲ⁷に含まれるπ電子の合計数は１２個以上である。］

[In Formula (5), Ring A is an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, or a substituent containing these ring structures. Each of R ^{5 to} R ⁷ independently represents a hydrogen atom, an organic group or a polar functional group, or R ⁵ and R ⁶ are connected to each other to form a ring. The total number of π electrons contained in the rings A and R ⁷ is 12 or more. ]

  The oxocarbon-based compound of the present invention and the resin composition and ink composition containing the same can absorb near-infrared rays on the longer wavelength side, and can effectively absorb, for example, light in a wavelength region exceeding 850 nm. In addition, the light transmittance in the visible light region is high and the invisibility under visible light is excellent.

The transmission spectra of the croconium compound 1, the comparative croconium compound 1, and the comparative phthalocyanine compound 1 used in the examples are shown.

[1. Oxocarbon compounds
The oxocarbon-based compound of the present invention is represented by the following formula (1) having a squarylium skeleton or the following formula (2) having a croconium skeleton.

In formula (1) and formula (2), R ^{1 to} R ⁴ each independently represents a structural unit represented by the following formula (3).

In formula (3), ring A represents an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, or a substituent containing these ring structures. R ^{5 to} R ⁷ each independently represents a hydrogen atom, an organic group or a polar functional group, or R ⁵ and R ⁶ are connected to each other to form a ring. * Represents a bonding site with the 4-membered ring in formula (1) or the 5-membered ring in formula (2), and the total number of π electrons contained in rings A and R ⁷ is 12 or more. .

In Formula (1) and Formula (2), R ¹ and R ² may be the same or different, and R ³ and R ⁴ may be the same or different. When R ¹ and R ² are different, or R ³ and R ⁴ are different, association and aggregation of molecules of the oxocarbon compound are suppressed, and improvement in solubility in solvents and resins can be expected. On the other hand, when R ¹ and R ² are the same or when R ³ and R ⁴ are the same, an improvement in durability of the oxocarbon-based compound against heat and light can be expected.

  In some cases, a compound having a squarylium skeleton (hereinafter referred to as “squarylium compound”) and a compound having a croconium skeleton (hereinafter referred to as “croconium compound”) each have a compound having a resonance relationship. Examples of the compound having a resonance relationship with the squarylium compound of the formula (1) include compounds represented by the following formulas (1a) and (1b). Examples of the compound having a resonance relationship with the croconium compound of the formula (2) include compounds represented by the following formulas (2a) to (2c). The oxocarbon-based compound of the present invention includes all these resonance-relevant compounds. Specifically, the squarylium compound of the formula (1) is represented by the following formulas (1a) and (1b). Compounds having a resonance relationship are included, and the croconium compound of the formula (2) includes compounds having a resonance relationship as represented by the following formulas (2a) to (2c).

  In the structural unit represented by the formula (3) bonded to the squarylium skeleton or the croconium skeleton, * represents a 4-membered ring of the squarylium skeleton represented by the formula (1) or a 5-membered ring of the croconium skeleton represented by the formula (2). Represents the binding site.

In the oxocarbon compound of the present invention, the total number of π electrons contained in the ring A and the substituent R ⁷ is 12 or more. By forming a π-electron system in this way, the oxocarbon-based compound can effectively absorb near-infrared rays on the longer wavelength side, for example, effectively absorbing light in a wavelength region exceeding 850 nm. be able to. On the other hand, an oxocarbon-based compound has a high light transmittance in the visible light region, and therefore has excellent invisibility under visible light. In addition, when the oxocarbon-based compound of the present invention absorbs light in a wavelength region exceeding 850 nm, it is not necessary to absorb light in the entire wavelength region exceeding 850 nm, for example, a partial wavelength region in the wavelength range of 850 nm to 1300 nm. As long as the light beam can be absorbed to a certain extent, it is sufficient.

  In formula (3), ring A represents an aromatic hydrocarbon ring, an aromatic heterocycle or a condensed ring containing these ring structures, and these rings may have a substituent. Since the oxocarbon-based compound has the ring A, the π-electron system is formed in a wide range from the squarylium skeleton or the croconium skeleton to the ring A through the pyrrole ring, and the absorption wavelength can be increased.

  The aromatic hydrocarbon ring of ring A is not particularly limited as long as it is composed of a carbon atom and a hydrogen atom and has an aromatic property. For example, a benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, tetracene ring Fluoranthene ring, benzofluoranthene ring, cyclotetradecaheptaene ring and the like. The aromatic hydrocarbon ring may have only one ring structure or may be a condensation of two or more ring structures. The aromatic heterocycle of ring A is particularly suitable if it contains one or more atoms selected from N (nitrogen atom), O (oxygen atom) and S (sulfur atom) in the ring structure and has aromaticity. Although not limited, For example, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a purine ring, a pteridine ring, etc. are mentioned. The aromatic heterocycle may have only one ring structure, or may be a condensation of two or more ring structures. The condensed ring containing these ring structures has a structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are condensed. For example, an indole ring, an isoindole ring, a benzimidazole ring, a quinoline ring, a benzopyran ring , Acridine ring, xanthene ring, carbazole ring and the like. These ring structures should just be condensed with the pyrrole ring in Formula (3) in arbitrary positions.

  The number of π electrons contained in ring A, that is, the number of π electrons contained in the above aromatic hydrocarbon ring, aromatic heterocyclic ring or condensed ring containing these ring structures is not particularly limited. There may be six or more. Note that the number of π electrons contained in the ring A is preferably 10 or more from the viewpoint that the π-electron system of the oxocarbon-based compound is spread over a wider range and the absorption wavelength is easily increased. The number is more preferably 14, more preferably 14 or more, and even more preferably 16 or more. On the other hand, the upper limit of the number of π electrons contained in ring A is not particularly limited, but considering the ease of production of oxocarbon compounds and solvent solubility, the number of π electrons contained in ring A is preferably 26 or less, 24 or less is more preferable, and 22 or less is more preferable. The number of π electrons contained in ring A is a number including π electrons of a carbon-carbon bond shared by ring A and the pyrrole ring.

  Examples of the substituent that ring A may have (hereinafter referred to as “substituent X”) include an organic group or a polar functional group. Examples of the organic group of the substituent X include an alkyl group, an alkoxy group, an alkylthiooxy group (alkylthio group), an alkoxycarbonyl group, an alkylsulfonyl group, an aryl group, an aralkyl group, an aryloxy group, and an arylthiooxy group (arylthio group). ), Aryloxycarbonyl group, arylsulfonyl group, arylsulfinyl group, heteroaryl group, amide group, sulfonamide group, ethylene-containing group, imine-containing group, carboxy group (carboxylic acid group), benzothiazole group, halogenoalkyl group, A cyano group etc. are mentioned. Examples of the polar functional group of the substituent X include a halogeno group, a hydroxyl group, a nitro group, an amino group, and a sulfo group (sulfonic acid group).

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group. A linear or branched alkyl group such as a group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, And alicyclic alkyl groups such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group; 1-20 are preferable, as for carbon number of an alkyl group, More preferably, it is 1-10, More preferably, it is 1-6, and 3 or more are preferable especially in the case of an alicyclic alkyl group. The alkyl group may have a substituent, and examples of the substituent that the alkyl group has include a halogeno group, a hydroxyl group, a carboxy group, an alkoxy group, a cyano group, a nitro group, an amino group, and a sulfo group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. A tridecyloxy group, a tetradecyloxy group, a pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a nonadecyloxy group, an icosyloxy group, and the like. 1-20 are preferable, as for carbon number of an alkoxy group, More preferably, it is 1-10, More preferably, it is 1-5. The alkyl group in the alkoxy group may be linear or branched.

  Examples of the alkylthiooxy group (alkylthio group) include a methylthiooxy group (methylthio group), an ethylthiooxy group (ethylthio group), a propylthiooxy group (propylthio group), a butylthiooxy group (butylthio group), and pentylthio. Oxy group (pentylthio group), hexylthiooxy group (hexylthio group), heptylthiooxy group (heptylthio group), octylthiooxy group (octylthio group), nonylthiooxy group (nonylthio group), decylthiooxy group (decylthio group) ), Undecylthiooxy group (undecylthio group), dodecylthiooxy group (dodecylthio group), tridecylthiooxy group (tridecylthio group), tetradecylthiooxy group (tetradecylthio group), pentadecylthiooxy group (penta Decylthio group), f Sadecylthiooxy group (hexadecylthio group), heptadecylthiooxy group (heptadecylthio group), octadecylthiooxy group (octadecylthio group), nonadecylthiooxy group (nonadecylthio group), icosylthiooxy group (icosylthio group), etc. Is mentioned. 1-20 are preferable, as for carbon number of an alkylthiooxy group, More preferably, it is 1-10, More preferably, it is 1-5. The alkyl group in the alkylthiooxy group may be linear or branched.

  Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, In addition to unsubstituted alkoxycarbonyl groups such as octadecyloxycarbonyl group, substituted alkoxycarbonyl groups such as trifluoromethyloxycarbonyl group can be mentioned. Here, examples of the substituent include a halogeno group. 2-20 are preferable, as for carbon number of an alkoxycarbonyl group, More preferably, it is 2-10, More preferably, it is 2-5. The alkyl group in the alkoxycarbonyl group may be linear or branched.

  Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl group, an octylsulfonyl group, and a methoxymethylsulfonyl. Group, a cyanomethylsulfonyl group, a substituted or unsubstituted alkylsulfonyl group of a trifluoromethylsulfonyl group, and the like. 1-20 are preferable, as for carbon number of an alkylsulfonyl group, More preferably, it is 1-10, More preferably, it is 1-5. The alkyl group in the alkylsulfonyl group may be linear, branched or cyclic.

  Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group, an azulenyl group, a fluorenyl group, a terphenyl group, a quarterphenyl group, a pentarenyl group, a heptaenyl group, and a biphenylenyl group. Group, indacenyl group, acenaphthylenyl group, phenalenyl group and the like. 6-25 are preferable and, as for carbon number of an aryl group, More preferably, it is 6-15. The aryl group may have a substituent, and examples of the substituent of the aryl group include an alkyl group, an alkoxy group, a halogeno group, a halogenoalkyl group, a cyano group, a nitro group, a thiocyanate group, an acyl group, and an alkoxycarbonyl group. Group, aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like.

  Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylpentyl group. The aralkyl group may have a substituent, and examples of the substituent that the aralkyl group has include an alkyl group, an alkoxy group, a halogeno group, a halogenoalkyl group, a cyano group, a nitro group, a thiocyanate group, an acyl group, and an alkoxycarbonyl group. Group, aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like. 7-25 are preferable and, as for carbon number of an aralkyl group, 7-15 are more preferable.

  Examples of the aryloxy group include phenyloxy group, biphenyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, pyrenyloxy group, indenyloxy group, azulenyloxy group, fluorenyloxy group, Examples include a phenyloxy group, a quarterphenyloxy group, a pentarenyloxy group, a heptaenyloxy group, a biphenylenyloxy group, an indacenyloxy group, an acenaphthylenyloxy group, and a phenalenyloxy group. 6-25 are preferable and, as for carbon number of an aryloxy group, More preferably, it is 6-15.

  Examples of the arylthiooxy group (arylthio group) include a phenylthiooxy group, a biphenylthiooxy group, a naphthylthiooxy group, an anthrylthiooxy group, a phenanthrylthiooxy group, a pyrenylthiooxy group, and an indenylthio group. Oxy group, azulenylthiooxy group, fluorenylthiooxy group, terphenylthiooxy group, quarterphenylthiooxy group, pentarenylthiooxy group, heptalenylthiooxy group, biphenylenylthiooxy group, indacenylthiooxy group Acenaphthylenylthiooxy group, phenalenylthiooxy group and the like. 6-25 are preferable and, as for carbon number of an arylthiooxy group, 6-15 are more preferable.

  Examples of the aryloxycarbonyl group include phenoxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyl. Oxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxy A substituted or unsubstituted phenyloxycarbonyl group such as a carbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, etc .; 1-naphthyloxy Carbonyl group, a substituted or unsubstituted naphthyl oxycarbonyl group such as a 2-naphthyloxycarbonyl group; and the like. 7-25 are preferable and, as for carbon number of an aryloxycarbonyl group, More preferably, it is 7-15.

  Examples of the arylsulfonyl group include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, a 2-methoxyphenylsulfonyl group, and 2-butoxyphenylsulfonyl. Group, 2-fluorophenylsulfonyl group, 3-methylphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 3-fluorophenylsulfonyl Group, 4-methylphenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group, etc. Other unsubstituted phenylsulfonyl group; 1-naphthylsulfonyl group, 2-substituted or unsubstituted naphthylsulfonyl group such naphthylsulfonyl group; and the like. 6-25 are preferable and, as for carbon number of an arylsulfonyl group, 6-15 are more preferable.

  Examples of the arylsulfinyl group include a phenylsulfinyl group, a 2-chlorophenylsulfinyl group, a 2-methylphenylsulfinyl group, a 2-methoxyphenylsulfinyl group, a 2-butoxyphenylsulfinyl group, a 2-fluorophenylsulfinyl group, and 3-methyl. Phenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-methylphenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyano Substituted or unsubstituted phenylsulfinyl group such as phenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group; 1-naphthyls Finiru group, 2-naphthylsulfinyl substituted or unsubstituted naphthylsulfinyl group such as Le group; and the like. 6-25 are preferable and, as for carbon number of an aryl sulfinyl group, 6-15 are more preferable.

  Examples of the heteroaryl group include thienyl group, thiopyranyl group, isothiochromenyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyralidinyl group, pyrimidinyl group, pyridazinyl group, thiazolyl group, isothiazolyl group, furanyl group, A pyranyl group etc. are mentioned. 2-20 are preferable and, as for carbon number of a heteroaryl group, 3-15 are more preferable.

Examples of the amide group include those represented by the formula: —NHCOR ^a1 , wherein R ^a1 is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group include the substituents exemplified above, and a part of hydrogen atoms may be substituted with a halogen atom.

Examples of the sulfonamide group include those represented by the formula: —NHSO ₂ R ^a2 , wherein R ^a2 is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group include the substituents exemplified above, and a part of hydrogen atoms may be substituted with a halogen atom.

The ethylene-containing group is represented by the formula: —CR ^a3 = CR ^a4 —R ^a5 , and R ^{a3 to} R ^a5 are hydrogen, aliphatic hydrocarbon group, aryl group, heteroaryl group (particularly pyridyl group), cyano group , An alkoxycarbonyl group, a carboxy group, and the like, and these groups optionally have a substituent. The aliphatic hydrocarbon group represented by R ^{a3 to} R ^a5 may be either saturated or unsaturated, but is preferably unsaturated. Examples of such an aliphatic hydrocarbon group include a group having a repeating unit represented by — (CH═CH) _k — (k is an integer of 1 to 10, preferably an integer of 1 to 5). Preferably, a vinyl group is mentioned, for example. A 1,1-dicyanoethylene group, a 1-cyanoethylene group, and the like are also preferable. As an aliphatic hydrocarbon group, a C1-C20 thing is preferable, for example, More preferably, a C1-C10 thing is mentioned. Examples of the aryl group, heteroaryl group and alkoxycarbonyl group represented by R ^{a3 to} R ^a5 include the aryl group, heteroaryl group and alkoxycarbonyl group exemplified above.

Examples of the imine-containing group include those represented by the formula: —CH═N—R ^a6 , wherein R ^a6 is an amino group which may have a substituent. The amino group of R ^a6 may be substituted or unsubstituted. Examples of the amino group having a substituent include a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, and a monoalkylmonoarylamino group. Examples of the alkyl group and aryl group bonded to the amino group of R ^a6 include the alkyl groups and aryl groups exemplified above.

  Examples of the halogenoalkyl group include monohalogenoalkyl groups such as a fluoromethyl group, a 3-fluoropropyl group, a 3-chloropropyl group, a 6-fluorohexyl group, and a 4-fluorocyclohexyl group; and a dihalogeno group such as a dichloromethyl group. Alkyl group; 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 2,2-bis (trifluoro Methyl) propyl group, alkyl group having a trihalomethyl unit such as 2,2,2-trichloroethyl group; trifluoromethyl group, perfluoroethyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, etc. Perhalogenoalkyl group; and the like. 1-20 are preferable, as for carbon number of a halogenoalkyl group, More preferably, it is 1-10, More preferably, it is 1-5. The halogen of the halogenoalkyl group is preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a fluorine atom.

  Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.

  Among the above, the substituent X is preferably an alkyl group, an alkoxy group, an alkylthiooxy group, an alkoxycarbonyl group, an aryl group, an aryloxycarbonyl group, a cyano group, a halogeno group, or a nitro group, and an alkyl group, an alkoxy group, an alkylthio group. An oxy group, a halogeno group, and an aryl group are more preferable. This makes it easy to increase the solvent solubility of the oxocarbon-based compound and to finely control the maximum absorption wavelength to a desired wavelength range. Furthermore, the effect that the production of the oxocarbon-based compound is facilitated can also be obtained. In this case, the alkyl group, alkoxy group, and alkylthiooxy group preferably have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, still more preferably 1 to 2 carbon atoms, and the alkoxycarbonyl group has 2 to 6 carbon atoms. More preferably, it is 2-4, More preferably, it is 2-3, As for carbon number of an aryl group and an aryloxycarbonyl group, 6-12 are preferable and 6-10 are more preferable. Ring A may not have the substituent X. When the ring A has the substituent X, the number is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. When the ring A has a plurality of substituents X, the plurality of substituents X may be the same or different.

In formula (3), R ^{5 to} R ⁷ each independently represent a hydrogen atom, an organic group or a polar functional group, or R ⁵ and R ⁶ are connected to each other to form a ring. Examples of the organic group or polar functional group of R ^{5 to} R ⁷ include the groups exemplified as the organic group and polar functional group of the substituent X. Examples of the ring structure formed from R ⁵ and R ⁶ include a hydrocarbon ring and a heterocyclic ring, and these ring structures may or may not have aromaticity.

When R ⁵ and R ⁶ are independent groups that are not connected to each other, R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group that may have a substituent, or a substituent. An aryl group that may have a substituent, an aralkyl group that may have a substituent, an alkoxycarbonyl group that may have a substituent, or an aryloxycarbonyl group that may have a substituent. . Specific examples of these groups are the groups exemplified as the substituent X. When R ⁵ and R ⁶ are such groups, it becomes easy to improve the solvent solubility of the oxocarbon-based compound and to finely control the maximum absorption wavelength to a desired wavelength range. Furthermore, the effect that the production of the oxocarbon-based compound is facilitated can also be obtained.

When R ⁵ or R ⁶ is an alkyl group or an alkoxycarbonyl group, the carbon number of the alkyl group contained in these groups (the number of carbon atoms excluding the substituent) is 1 if it is a linear or branched alkyl group. -20 is preferable, More preferably, it is 1-12, More preferably, it is 1-10, 4-7 are preferable if it is an alicyclic alkyl group, More preferably, it is 5-6. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, etc. Is preferred. When R ⁵ or R ⁶ is an alkyl group, the substituent that the alkyl group may have does not include an aryl group. When R ⁵ or R ⁶ is an aryl group or an aryloxycarbonyl group, the number of carbon atoms (the number of carbon atoms excluding the substituent) of the aryl group contained in these groups is preferably 6-10. Preferred examples of the aryl group include a phenyl group and a naphthyl group. When R ⁵ or R ⁶ is an aralkyl group, the carbon number (the number of carbon atoms excluding the substituent) is preferably 7 to 20, and more preferably 7 to 15. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a phenylpropyl group. Preferred examples of the substituent that each R ⁵ and R ⁶ group may have include an alkoxy group, a halogeno group, a halogenoalkyl group, a cyano group, and a nitro group.

When R ⁵ and R ⁶ are connected to each other to form a ring, the structural unit of the above formula (3) is represented by the following formula (4). The ring structure formed by R ⁵ and R ⁶ , that is, ring B in the following formula (4) may be any ring structure, and ring B may have a substituent. Ring B is preferably a hydrocarbon ring that may have a substituent and / or a condensed ring structure, or a heterocyclic ring that may have a substituent and / or a condensed ring structure.

  Examples of the hydrocarbon ring of ring B include a monocyclic cycloalkane having 3 to 10 carbon atoms such as cyclopentane, cyclohexane, cycloheptane; cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene (for example, 1,3-cyclohexadiene). And monocyclic cycloalkenes having 3 to 10 carbon atoms such as cycloheptene and cycloheptadiene. As the heterocyclic ring of ring B, one or more carbon atoms constituting the hydrocarbon ring as described above are selected from N (nitrogen atom), S (sulfur atom) and O (oxygen atom). Examples include a ring structure in which at least one atom is replaced, such as a furan ring, tetrahydrofuran ring, thiophene ring, tetrahydrothiophene ring, pyrrole ring, pyrrolidine ring, pyrazole ring, oxazole ring, thiazole ring, imidazole ring, pyridine Ring, piperidine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyran ring, tetrahydropyran ring and the like. These hydrocarbon rings and heterocycles may have a condensed ring structure condensed with other rings. Examples of such ring structures include indene ring, naphthalene ring, anthracene ring, fluorene ring, benzone ring, Examples include fluorene ring, indole ring, isoindole ring, benzimidazole ring, quinoline ring, benzopyran ring, acridine ring, xanthene ring, carbazole ring, purine ring, pteridine ring and the like.

  The hydrocarbon ring or heterocyclic ring of ring B may have a substituent, such as an alkyl group, an alkoxy group, an aryl group, a thioalkoxy group, an aryloxy group, a thioaryloxy group, Examples thereof include an alkylamide group, a halogeno group, a halogenoalkyl group, a cyano group, a nitro group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, and an arylsulfonyl group. The halogenoalkyl group may be a perhalogenoalkyl group in which at least some of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. Is preferred. As the halogenoalkyl group, a fluoroalkyl group is more preferable, and a perfluoroalkyl group is more preferable. Moreover, 1-5 are preferable, as for carbon number of a halogenoalkyl group, 1-3 are more preferable, and 1-2 are more preferable.

  From the viewpoint of increasing the absorption wavelength of the oxocarbon-based compound, the ring B preferably contains a π electron. Examples of such a ring structure include a cyclohexadiene ring, a pyrrole ring, a pyran ring, an indene ring, Indole ring, isoindole ring, benzopyran ring, fluorene ring, xanthene ring and the like can be mentioned. In this case, examples of the structural unit represented by the above formula (4) include structural units represented by the following formulas (4-1) to (4-12).

In formulas (4-1) to (4-12), R ⁸ and R ⁹ represent a group or an atom bonded to the ring structure formed by R ⁵ and R ⁶ , and R ⁸ and R ⁹ are each independently From a hydrogen atom, alkyl group, alkoxy group, halogeno group, halogenoalkyl group, cyano group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, and arylsulfonyl group It preferably represents a group or atom selected from the group consisting of Details of preferred embodiments and the like of the halogenoalkyl group are as described above. The number attached to each ring of R ⁸ and R ⁹ are changed depending on the ring structure, if R ⁸ or R ⁹ are a plurality of binding a plurality of R ⁸ or R ⁹ may be different even in the same . Among these, R ⁸ and R ⁹ are preferably each independently a group or atom selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogeno group, a halogenoalkyl group, and a cyano group. And more preferably a group or an atom selected from the group consisting of a halogeno group, a halogenoalkyl group, and a cyano group. In this case, it is preferable that all of R ⁸ and R ⁹ bonded to the ring structure formed by R ⁵ and R ⁶ are not hydrogen atoms. That is, a substituent selected from the group consisting of an alkyl group, an alkoxy group, a halogeno group, a halogenoalkyl group, and a cyano group is preferably bonded to the ring structure formed by R ⁵ and R ^6. More preferably, a substituent selected from the group consisting of a group, a halogenoalkyl group, and a cyano group is bonded. As a result, the absorption wavelength of the oxocarbon-based compound can be increased.

  Ring B is preferably a hydrocarbon ring having a condensed ring structure which may have a substituent, or a heterocyclic ring having a condensed ring structure which may have a substituent, whereby an oxocarbon compound. The absorption wavelength can be further increased. The hydrocarbon ring or heterocyclic ring having a condensed ring structure is preferably formed so that the π-electron conjugated system extends to the condensed ring. From this viewpoint, the number of π electrons contained in the ring B is preferably 6 or more. 8 or more is more preferable, 10 or more is more preferable, and 12 or more is further more preferable. The upper limit of the number of π electrons contained in ring B is not particularly limited, but is preferably 20 or less, more preferably 18 or less, and even more preferably 16 or less in consideration of the ease of production of the oxocarbon-based compound and solvent solubility. The number of π electrons contained in ring B means the number of π electrons in the ring structure of ring B. When ring B has a condensed ring structure, it also includes π electrons contained in the condensed ring structure, The π electrons contained in the substituent which may have are not included.

Preferred examples of ring B include an indene ring, an indole ring, an isoindole ring, a benzopyran ring, a fluorene ring, and a xanthene ring. In the structural units represented by the above formulas (4-1) to (4-12), the formulas (4-2), (4-3), (4-4), (4-6), (4- The structural units represented by 8), (4-9), (4-11), and (4-12) are preferred. From the viewpoint of increasing the absorption wavelength, ring B is particularly preferably a fluorene ring which may have a substituent or a xanthene ring which may have a substituent, and the above formula (4-1) ) To (4-12), the structural units represented by formulas (4-4) and (4-12) are particularly preferable. In these structural units, all of R ⁸ bonded to the benzene ring included in the fluorene ring or xanthene ring are not hydrogen atoms, and all of R ⁹ are not hydrogen atoms, and the substituents listed above (particularly, halogeno). Group, halogenoalkyl group, or cyano group) is preferably bonded to each benzene ring.

R ⁷ is preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and an alkyl group which may have a substituent and For the details of the aryl group which may have a substituent, the description regarding R ⁵ and R ⁶ is referred to. If R ⁷ is an aryl group which may have a substituent, it is preferable in that the π-electron system of the oxocarbon-based compound spreads and the absorption wavelength can be shifted by a long wavelength. The number of π electrons contained in R ⁷ at this time is preferably 6 to 10 from the viewpoint of ease of production of the oxocarbon compound. Specifically, the aryl group represented by R ⁷ is preferably a phenyl group or naphthyl group which may have a substituent, and more preferably a phenyl group. R ⁷ may not have π electrons, and may be a hydrogen atom or an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms). In this case, it is preferable from the viewpoint that the solvent solubility of the oxocarbon-based compound is easily increased and the production of the oxocarbon-based compound is facilitated. Incidentally, the π electron number and contained in R ^7, means a π number electrons contained in R ⁷ of π electron system formed connected toward R ⁷ from squarylium skeleton or a croconium skeleton.

In the oxocarbon-based compound, the total number of π electrons contained in the rings A and R ⁷ is 12 or more, more preferably 14 or more, and even more preferably 16 or more. (For example, light in a wavelength range exceeding 850 nm) can be effectively absorbed. In the oxocarbon-based compound of the present invention, it is more preferable that the number of π electrons contained in ring A is in such a range, whereby the π-electron system spreads over a wider range, and the absorption wavelength is longer. It becomes easy to plan. Examples of the ring A in this case include a phenanthrene ring, an anthracene ring, a tetracene ring, a fluoranthene ring, a benzofluoranthene ring, a cyclotetradecaheptaene ring, an acridine ring, and a carbazole ring. On the other hand, the upper limit of the total number of π electrons contained in the rings A and R ⁷ is not particularly limited, but is preferably 30 or less, more preferably 28 or less in consideration of the ease of production of oxocarbon compounds and solvent solubility. The number is preferably 26 or less.

Of the structural units represented by the above formula (4), examples of structural units that are relatively easy to produce and that can give an oxocarbon compound capable of absorbing light in a longer wavelength range are shown below. The structural units shown in the following formulas (4-21) to (4-26) represent specific examples of the structural unit of the above formula (4-4), and the following formulas (4-27) to (4-32) The structural unit shown represents a specific example of the structural unit of the above formula (4-12). In the following formulas (4-21) to (4-32), the description of R ^{7 to} R ⁹ is referred to the above description. In the formulas (4-21), (4-22), (4-27), and (4-28), a fluoranthene ring is provided as the ring A, and the formulas (4-23), (4-24), (4- In 29) and (4-30), a phenanthrene ring is provided as ring A, and in formulas (4-25), (4-26), (4-31), and (4-32), an anthracene ring is provided as ring A. It has been. The mode of bonding (condensed ring) of these ring structures to the pyrrole ring is not limited to the embodiment shown in the following formula. Moreover, as ring A, things other than these ring structures may be provided.

The oxocarbon compound having the structural unit represented by the above formula (4) is preferably a croconium compound represented by the formula (2) from the viewpoint that it can absorb light in a longer wavelength region. In Formula (2), it is preferable that the ring A of R ³ and R ⁴ has the same ring structure, and the ring B of R ³ and R ⁴ preferably has the same ring structure. More preferably, in the formula (2), the ring A of R ³ and R ⁴ has the same structure (including the ring structure of the ring A and a substituent that can be bonded to it), and R ³ and R 4 Ring B of ⁴ has the same structure (a structure including a ring structure of ring B and a substituent that can be bonded to it).

  In the oxocarbon-based compound of the present invention, the maximum absorption wavelength is preferably 835 nm or more, more preferably 840 nm or more, and further preferably 845 nm or more, from the viewpoint of increasing the light absorptance in a wavelength region exceeding 850 nm. The upper limit of the maximum absorption wavelength is not particularly limited, and may be, for example, 1300 nm or less or 1100 nm or less.

  As the visible light transmittance, when the transmittance at the maximum absorption wavelength is 10% (or 10% or less), the average transmittance at a wavelength of 400 nm to 700 nm is preferably 83% or more, and more preferably 84% or more. 85% or more is more preferable.

As described above, the oxocarbon-based compound of the present invention has a π-electron system extending from the squarylium skeleton or the croconium skeleton to the ring A (or further to the substituent R ⁷ ), and the ring A and the substituent R ⁷ Since the total number of π electrons contained is 12 or more, near infrared rays on the longer wavelength side can be absorbed, and for example, light rays in a wavelength region exceeding 850 nm can be effectively absorbed. On the other hand, the oxocarbon-based compound itself has a high light transmittance in the visible light region, and therefore has excellent invisibility under visible light. For example, some phthalocyanine compounds have a maximum absorption wavelength in a wavelength region exceeding 850 nm, but phthalocyanine compounds have an absorption peak derived from a soret band in a wavelength region near 400 nm and may exhibit a green color. On the other hand, the oxocarbon compound of the present invention functions as a near-infrared absorbing dye and has excellent invisibility.

The oxocarbon compound of the present invention can be produced by reacting the condensed heterocyclic compound represented by the following formula (5) with squaric acid or croconic acid. In the following formula (5), ring A and R ^{5 to} R ⁷ have the same meaning as in the above formula (3), and the total number of π electrons contained in rings A and R ⁷ is 12 or more. The preferred embodiments of ring A and R ^{5 to} R ⁷ are also as described above.

  The condensed heterocyclic compound represented by the formula (5) is suitably used as a raw material for the oxocarbon compound of the present invention, whereby the oxocarbon compound of the present invention can be easily produced. That is, by a production method having a step of reacting a condensed heterocyclic compound represented by the formula (5) with squaric acid or croconic acid to obtain an oxocarbon-based compound represented by the formula (1) or the formula (2), The oxocarbon compound of the present invention can be produced. Specifically, the squarylium compound represented by the formula (1) can be obtained by reacting the condensed heterocyclic compound of the formula (5) with squaric acid, and the croconium compound represented by the formula (2) is The condensed heterocyclic compound of formula (5) can be obtained by reacting with croconic acid.

  The amount of the condensed heterocyclic compound used in the reaction of the condensed heterocyclic compound with squaric acid or croconic acid is preferably 1 mol or more, more preferably 1.5 times mol or more with respect to squaric acid or croconic acid. More preferably, it is 2 times mol or more, and 5 times mol or less is preferable, More preferably, it is 4 times mol or less, More preferably, it is 3 times mol or less.

  The reaction between squaric acid or croconic acid and the condensed heterocyclic compound is preferably carried out in the presence of a solvent. Solvents that can be used include, for example, chlorinated hydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene, xylene and trimethylbenzene; chlorinated aromatics such as chlorotoluene and dichlorobenzene; tetrahydrofuran (THF), ethers such as dioxane, cyclopentyl methyl ether, diisopropyl ether, and diethyl ether; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, and tert-amyl alcohol; These solvents may use only 1 type and may use 2 or more types together. In addition, when using alcohol as a reaction solvent, it is preferable to use tertiary alcohol. The use amount (total) of the solvent is preferably 1 mass times or more, more preferably 5 mass times or more, further preferably 10 mass times or more, and preferably 100 mass times or less with respect to squaric acid or croconic acid.

  In the reaction of squaric acid or croconic acid with the condensed heterocyclic compound, the reaction temperature may be appropriately set, for example, preferably 30 ° C or higher, more preferably 60 ° C or higher, further preferably 80 ° C or higher, and 170 ° C or lower. Preferably, 140 degrees C or less is more preferable. The reaction is preferably performed under reflux. The reaction time is not particularly limited and may be appropriately set according to the progress of the reaction. For example, 0.5 hour or more is preferable, 1 hour or more is more preferable, 48 hours or less is preferable, and 24 hours or less is preferable. More preferred. The atmosphere during the reaction is preferably an inert gas (nitrogen, argon, etc.) atmosphere.

  The squarylium compound can be synthesized by appropriately adopting a known synthesis method in which a condensed heterocyclic compound and squaric acid are reacted. For example, a squarylium compound can be synthesized by a synthesis method described in the following paper: Serguei Miltsov et al., “New Cyanine Dyes: Norindosquarocyanines”, Tetrahedron Letters, Vol. 40, Issue 21, p.4067-4068 ( 1999).

  A method for synthesizing the croconium compound is not particularly limited, but the croconium compound can be synthesized by appropriately adopting a known synthesis method in which a condensed heterocyclic compound and croconic acid are reacted. For example, a croconium compound can be synthesized by a method described in JP-A No. 2002-286931, JP-A No. 2007-31644, JP-A No. 2007-31645, and JP-A No. 2007-169315.

The condensed heterocyclic compound of the formula (5) can be synthesized by appropriately adopting known synthetic techniques, and can be produced, for example, according to the following reaction formula. In the following reaction formula, ring A and R ^{5 to} R ⁷ have the same meaning as in the above formula (3).

For example, a condensed heterocyclic compound in which ring A is a fluoranthene ring, R ⁵ and R ⁶ are methyl groups and R ⁷ is a hydrogen atom is obtained by reacting fluoranthenyl hydrazine hydrochloride with 3-methyl-2-butanone. Can be synthesized. Thus, an aromatic hydrocarbon ring, an aromatic heterocycle or a condensed ring hydrazine hydrochloride (compound of the above formula (6)) and a dimethyl ketone derivative (compound of the above formula (7)) containing these ring structures. Can be synthesized to produce a condensed heterocyclic compound of the formula (5). The synthesis of fused heterocyclic compounds can also be referred to the following paper: Sajjadifar et al., “New 3H-Indole Synthesis by Fischer's Method. Part I”, Molecules, Vol. 15, p.2491-2498 (2010).

  The oxocarbon compound obtained by reacting the condensed heterocyclic compound of formula (5) with squaric acid or croconic acid can be filtered, silica gel column chromatography, alumina column chromatography, sublimation as necessary. , And can be appropriately purified by known purification means such as recrystallization and crystallization. The chemical structure of the obtained oxocarbon-based compound can be analyzed by a known analysis method such as mass spectrometry, single crystal X-ray structure analysis, Fourier transform infrared spectroscopy, or nuclear magnetic resonance spectroscopy.

[2. Resin composition]
The oxocarbon compound of the present invention can be mixed with a resin component to form a resin composition. The resin composition contains at least the oxocarbon compound of the present invention and a resin component. Since the resin composition of the present invention can effectively absorb light in the near-infrared region, for example, light in the wavelength region exceeding 850 nm, by using a resin molded body such as a film, an imaging device for night vision It can apply suitably for optical filters, such as. The optical filter formed in this way has a reduced incident angle dependency of optical characteristics on the short wavelength side in the near infrared region, an improved viewing angle, a high transmittance in the visible light region, and a visible light. The present invention can also be suitably applied to an image sensor used under light. Resin moldings also include near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, solar cell materials that use visible light and near-infrared light, plasma display panels (PDP), and specific wavelengths for CCDs. Application to an absorption filter or the like is also possible.

  The resin composition of the present invention can also be suitably used for laser welding applications. The joining of the resin by the laser welding method can be performed by stacking a light transmitting resin that transmits laser light and a light absorbing resin that absorbs laser light, and irradiating the laser light from the light transmitting resin side. The irradiated laser light is transmitted through the light-transmitting resin, energy is absorbed on the surface of the light-absorbing resin, and heat is generated. As a result, the light-absorbing resin is melted, and the light-transmitting resin is also melted by heat conduction. Both resins can be welded. As the light absorbing resin, a colored resin containing carbon black or black dye may be used. Laser light having a wavelength of 800 nm to 1300 nm is used for laser welding (for example, semiconductor laser, YAG laser, fiber laser). Therefore, laser welding of transparent resins can be realized by forming the light absorbing resin from the resin composition of the present invention. That is, the oxocarbon-based compound of the present invention can function as a laser light absorber, that is, a heat source. In the laser welding method, the resin composition of the present invention can also be used as a laser light absorber sandwiched between two light transmissive resins.

  The oxocarbon-based compound contained in the resin composition may be a squarylium compound, a croconium compound, or both. The oxocarbon compound contained in the resin composition may be only one type or two or more types.

The resin composition may contain two or more squarylium compounds represented by the above formula (1), or may contain two or more croconium compounds represented by the above formula (2). Good. The resin composition thus formed effectively absorbs light in the near infrared region, improves the solubility of the oxocarbon compound in the resin, and contains the oxocarbon compound at a high concentration. It becomes easy to form. In this case, from the viewpoint of increasing the solubility of the oxocarbon-based compound in the resin, the resin composition preferably includes at least a squarylium compound having a structure in which R ¹ and R ² are different from each other in the above formula (1). In the above formula (2), it is preferable that R ³ and R ⁴ contain at least a croconium compound having a different structure. More preferably, the resin composition contains three or more oxocarbon-based compounds. Examples of such a resin composition include a squarylium compound in which R ¹ and R ² are both R _x in the above formula (1), and A resin composition comprising a squarylium compound in which R ¹ and R ² are both R _y and a squarylium compound in which R ¹ is R _x and R ² is R _y , or R ³ and R ⁴ in the above formula (2) are and croconium compounds are both R _x, and croconium compound R ³ and R ⁴ are both R _y, R ³ is R ⁴ is R _x is a resin composition comprising a croconium compound is R _y is shown. Such a resin composition is preferable in view of easy production while containing a plurality of oxocarbon compounds. In addition, _Rx and _{Ry demonstrated} here represent the arbitrary structural units represented by the said Formula (3), and _Rx and _Ry are not the same.

  Although the oxocarbon-based compound of the present invention can be regarded as a kind of dye, the resin composition of the present invention can be used together with the oxocarbon-based compound of the present invention as long as the desired performance according to the application is secured. May be contained. Examples of the dye that may be contained in the resin composition include a squarylium dye and a croconium dye other than the oxocarbon compound of the present invention, and copper (for example, Cu (II)) or zinc (for example, a central metal ion). , Zn (II)) and the like cyclic tetrapyrrole dyes (porphyrins, chlorins, phthalocyanines, cholines, etc.), cyanine dyes, quaterylene dyes, naphthalocyanine dyes, nickel complex systems Examples thereof include dyes, copper ion dyes, diimmonium dyes, subphthalocyanine dyes, xanthene dyes, azo dyes, and dipyrromethene dyes. These other pigments may be used alone or in combination of two or more.

  When the resin composition of the present invention also contains other dyes, the content of the other dyes is preferably 60% by weight or less with respect to 100% by weight in total of the oxocarbon compound of the present invention and the other dyes, 40 mass% or less is more preferable, 20 mass% or less is further more preferable, and it is especially preferable that other pigment | dye is not included substantially.

  The content of the oxocarbon compound of the present invention in the resin composition is preferably 0.01% by mass or more in 100% by mass of the solid content of the resin composition from the viewpoint of expressing desired performance. More preferably 3% by mass or more, and still more preferably 1% by mass or more. Moreover, from the point which improves the moldability, film formability, etc. of the resin composition, the content of the oxocarbon-based compound of the present invention in the resin composition is 25% by mass or less in 100% by mass of the solid content of the resin composition. Is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable. When the resin composition also contains other dyes, the total content of the oxocarbon compound of the present invention and the other dyes is preferably in the above range. In addition, the mass of the solid content of the resin composition means a mass obtained by removing the liquid medium from the resin composition.

  A known resin can be used as the resin component contained in the resin composition. As the resin component, those having high transparency and capable of dissolving or dispersing the oxocarbon compound of the present invention are preferable. When other dyes are used in combination, the resin component is preferably one that can also dissolve or disperse other dyes. By selecting such a resin component, it is possible to achieve both high transmittance in the wavelength range desired to be transmitted and high absorbency in the wavelength range desired to be blocked.

  The resin component is not only a resin that has been completely polymerized, but also a resin raw material (including a precursor of the resin, a raw material of the precursor, a monomer constituting the resin, and the like), and when the resin composition is molded In addition, those which are incorporated into the resin by polymerization reaction or crosslinking reaction can also be used. In the present invention, any resin is included in the resin component. In the latter case, the structure of the oxocarbon-based compound is caused by unreacted substances, reactive terminal functional groups, ionic groups, catalysts, acid / basic groups, etc. present in the reaction solution obtained by the polymerization reaction. Some or all of them may be decomposed. Therefore, when there is such a concern, it is desirable to form a resin composition by blending an oxocarbon-based compound with a resin that has been completely polymerized.

  Examples of the resin component include (meth) acrylic resins, (meth) acrylurethane resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyolefin resins (for example, polyethylene resins, polypropylene resins, etc.), cycloolefin resins. (Including cycloolefin copolymer and norbornene resin), petroleum resin, rosin resin, rosin ester resin, urea resin, melamine resin, urethane resin, styrene resin, styrene-acrylic resin, styrene-maleic acid resin , Polyvinyl acetate, ethylene-vinyl acetate resin, vinyl acetal resin, polyamide resin (for example, nylon), aramid resin, polyimide resin, polyamideimide resin, alkyd resin, phenol resin, epoxy resin, polyester resin (for example, Poly (Ethylene terephthalate resin, polyethylene terephthalate resin, polyarylate resin, etc.), polysulfone resin, butyral resin, polycarbonate resin, polyether resin, acrylonitrile butadiene styrene resin, acrylonitrile-styrene copolymer, cellulose derivative (for example, ethyl cellulose, cellulose acetate, Nitrocellulose, etc.), silicone resins, modified silicone resins (eg, (meth) acrylic silicone resins, alkylpolysiloxane resins, silicone urethane resins, silicone polyester resins, silicone acrylic resins, etc.), fluorine resins (eg, fluorinated) Aromatic polymer, polytetrafluoroethylene, perfluoroalkoxy fluororesin, fluorinated polyaryletherketone, fluorinated polyimid , Fluorinated polyamic acid, fluorinated polyether nitrile, etc.), diallyl phthalate resins, coumarone-indene resins, terpene phenol resins, xylene resins, alkyd resins, maleic acid resins and fumaric acid resins.

  The resin component preferably has high transparency, which makes it easy to suitably apply the resin composition to optical applications and laser welding applications. For example, the resin component preferably has a total light transmittance of 75% or more at a thickness of 0.1 mm, more preferably 80% or more, and still more preferably 85% or more. The upper limit of the total light transmittance of the resin component is not particularly limited, and the total light transmittance may be 100% or less, for example, 95% or less. The total light transmittance is measured based on JIS K 7105.

  The resin component preferably has a high glass transition temperature (Tg), whereby the heat resistance of the resin composition and various molded articles obtained therefrom can be increased. For example, the glass transition temperature of the resin component is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 80 ° C. or higher. Although the upper limit of the glass transition temperature of a resin component is not specifically limited, For example, 380 degrees C or less is preferable from the point which ensures the moldability of a resin composition.

  The resin composition may be a thermoplastic resin composition that can be used for molding such as injection molding and extrusion molding, such as spin coating, solvent casting, roll coating, spray coating, bar coating, dip coating. It may be a resin composition that is made into a paint so that it can be applied by a coating method, a screen printing method, a flexographic printing method, an ink jet method or the like.

  When the resin composition is a thermoplastic resin composition, a molded product can be obtained by subjecting the resin composition to injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or the like. In this method, a thermoplastic resin is used as a resin component, an oxocarbon-based compound is blended in the thermoplastic resin, and a molded product is obtained by heat molding. For example, an oxocarbon compound may be added to the base resin powder or pellets, heated to about 150 ° C. to 350 ° C., dissolved, and then molded. The shape of the molded product is not particularly limited, but plate shape, sheet shape, granular shape, powder shape, lump shape, particle aggregate shape, spherical shape, elliptical spherical shape, cubic shape, column shape, rod shape, cone shape, cylindrical shape, Examples include a needle shape, a fiber shape, a hollow fiber shape, and a porous shape. The molded product may be any irregular shaped product. Moreover, when kneading | mixing resin, you may add the additive used for normal resin shaping | molding, such as a ultraviolet absorber and a plasticizer.

  When the resin composition is a coated resin composition, a liquid or paste resin composition containing an oxocarbon-based compound is applied on a transparent substrate (for example, a resin plate, a film, a glass plate, etc.). By doing so, it is possible to form a planar molded body such as a film having a thickness of 200 μm or less or a plate-like material having a thickness of more than 200 μm. The resin composition formed into a paint includes an oxocarbon compound, a resin component, and a liquid medium. For example, the oxocarbon compound is dissolved in a solvent containing the resin component, or the oxocarbon compound is dissolved in a resin. By dispersing in a dispersion medium containing components, a resin composition that has been made into a paint can be obtained.

  When the resin composition is a resin composition formed into a paint, it is preferable to use a solvent-soluble resin that is soluble in an organic solvent as the resin component. The solvent-soluble resin means a resin that is soluble in an organic solvent, and a resin that dissolves 1 part by mass or more with respect to 100 parts by mass of the organic solvent is preferable. If the resin component is a solvent-soluble resin, a thin film can be easily produced by forming a film by, for example, spin coating or solvent casting. Solvent-soluble resins are reactive groups that can undergo a crosslinking reaction (curing reaction) (for example, ring-opening polymerizable groups such as epoxy groups, oxetane rings, and ethylene sulfide groups, acrylic groups, methacrylic groups, vinyl groups, and the like). It may have a radical curable group and / or an addition curable group. Examples of the solvent-soluble resin include polyimide resin, polyamideimide resin, fluorinated aromatic polymer, (meth) acrylic resin, polyamide resin, aramid resin, polysulfone resin, cycloolefin resin, urethane resin, phenol resin, and epoxy. Examples thereof include resins, polyarylate resins, polycarbonate resins, and the like.

  As the resin, from the viewpoint of excellent transparency and heat resistance, polyimide resin, polyamideimide resin, fluorinated aromatic polymer, (meth) acrylic resin, polysulfone resin, cycloolefin resin, epoxy resin, polyarylate resin, polycarbonate Resins are preferred.

  Polyimide resin is a polymer containing an imide bond in the repeating unit of the main chain. For example, tetracarboxylic dianhydride and diamine are polymerized to obtain polyamic acid, which is dehydrated and cyclized (imidized). Can be manufactured. As the polyimide resin, it is preferable to use an aromatic polyimide in which aromatic rings are connected by an imide bond. Polyimide resins include, for example, Kapton (registered trademark) manufactured by DuPont, Aurum (registered trademark) manufactured by Mitsui Chemicals, Meldin (registered trademark) manufactured by Saint-Gobain, and TPS (registered trademark) TI3000 series manufactured by Toray Plastic Seiko Co., Ltd. Etc. can be used.

  Polyamideimide resin is a polymer containing an amide bond and an imide bond in the repeating unit of the main chain. As the polyamideimide resin, for example, Torlon (registered trademark) manufactured by Solvay Advanced Polymers, Viromax (registered trademark) manufactured by Toyobo, TPS (registered trademark) TI5000 series manufactured by Toray Plastic Seiko Co., Ltd., and the like can be used.

  The fluorinated aromatic polymer includes an aromatic ring having one or more fluorine atoms and at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. A polymer having a unit, and among these, a polymer essentially including a repeating unit containing an aromatic ring having one or more fluorine atoms and an ether bond is preferable. As the fluorinated aromatic polymer, for example, those described in JP 2008-181121 A can be used.

  The (meth) acrylic resin is a polymer having a repeating unit derived from (meth) acrylic acid or a derivative thereof, for example, a repeating unit derived from a (meth) acrylic acid ester such as a poly (meth) acrylic acid ester resin. The resin which has is used preferably. The (meth) acrylic resin preferably has a ring structure in the main chain, for example, a carbonyl group-containing ring structure such as a lactone ring structure, a glutaric anhydride structure, a glutarimide structure, a maleic anhydride structure, or a maleimide ring structure; oxetane Examples include carbonyl group-free ring structures such as a ring structure, an azetidine ring structure, a tetrahydrofuran ring structure, a pyrrolidine ring structure, a tetrahydropyran ring structure, and a piperidine ring structure. The carbonyl group-containing ring structure includes a structure containing a carbonyl group derivative group such as an imide group. Examples of (meth) acrylic resins having a carbonyl group-containing ring structure include those described in JP-A No. 2004-168882, JP-A No. 2008-179777, International Publication No. 2005/54311, JP-A No. 2007-31537, and the like. Those described can be used.

The polysulfone resin is a polymer having a repeating unit containing an aromatic ring, a sulfonyl group (—SO ₂ —), and an oxygen atom. As the polysulfone resin, for example, SUMIKAEXCEL (registered trademark) PES3600P and PES4100P manufactured by Sumitomo Chemical Co., Ltd., UDEL (registered trademark) P-1700 manufactured by Solvay Specialty Polymers, Inc., and the like can be used.

  The cycloolefin resin is a polymer obtained by polymerizing a cycloolefin as at least a part of the monomer component, and is not particularly limited as long as it has an alicyclic structure in a part of the main chain. Examples of the cycloolefin-based resin include Topas (registered trademark) manufactured by Polyplastics, Appel (registered trademark) manufactured by Mitsui Chemicals, ZEONEX (registered trademark) and ZEONOR (registered trademark) manufactured by Nippon Zeon, and JSR Arton (registered trademark) or the like made by the manufacturer can be used.

  The epoxy resin is a resin that can be cured by crosslinking an epoxy compound (prepolymer) in the presence of a curing agent or a curing catalyst. Examples of the epoxy compound include aromatic epoxy compounds, aliphatic epoxy compounds, alicyclic epoxy compounds, hydrogenated epoxy compounds, and the like, for example, fluorene epoxy (Ogsol (registered trademark) PG-100) manufactured by Osaka Gas Chemical Company. Bisphenol A type epoxy compound (JER (registered trademark) 828EL) manufactured by Mitsubishi Chemical Corporation, hydrogenated bisphenol A type epoxy compound (JER (registered trademark) YX8000), alicyclic liquid epoxy compound (celloxide (registered trademark) manufactured by Daicel Corporation) Trademark) 2021P) and the like can be used.

  A polyarylate resin is a polymer obtained by polycondensation of a dihydric phenol compound and a dibasic acid (for example, aromatic dicarboxylic acid such as phthalic acid), and an aromatic ring and an ester bond are added to the main chain repeating unit. And a repeating unit containing As the polyarylate resin, for example, Vectran (registered trademark) manufactured by Kuraray Co., Ltd., U polymer (registered trademark) manufactured by Unitika, Unifiner (registered trademark), or the like can be used.

  The polycarbonate resin is a polymer containing a carbonate group (—O— (C═O) —O—) in the repeating unit of the main chain. Polycarbonate resins include Panlite (registered trademark) manufactured by Teijin Limited, Iupilon (registered trademark) manufactured by Mitsubishi Engineering Plastics, Novalex (registered trademark), Zanta (registered trademark), SD Polycarbonate manufactured by Sumika Stylon Polycarbonate. (Registered trademark) or the like can be used.

  The resin composition may contain a liquid medium such as an organic solvent. For example, when the resin composition is a resin composition coated, the resin composition is coated by including the liquid medium. Work becomes easy. The liquid medium may function as a solvent (solvent) for the oxocarbon-based compound or may function as a dispersion medium. Examples of the liquid medium include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; glycols such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and ethylene glycol ethyl ether acetate. Derivatives (ether compounds, ester compounds, ether ester compounds, etc.); Amides such as N, N-dimethylacetamide; Esters such as ethyl acetate, propyl acetate, butyl acetate; N-methyl-pyrrolidone (specifically, Pyrrolidones such as 1-methyl-2-pyrrolidone); aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane and heptane; tetrahydrofuran, dioxane, diethyl ether, Ethers such as Petit ether; and the like. These liquid media may use only 1 type and may use 2 or more types together.

  As content of a liquid medium, it is preferable that it is 50 mass% or more in 100 mass% of resin compositions, 70 mass% or more is more preferable, less than 100 mass% is preferable, and 95 mass% or less is more preferable. By adjusting the content of the liquid medium within such a range, it becomes easy to obtain a resin composition having a high oxocarbon compound concentration.

  It should be noted that amides such as N, N-dimethylacetamide are preferably used in a smaller amount because they may decompose the oxocarbon-based compound. Therefore, the content of amides is preferably 60% by mass or less, more preferably 40% by mass or less, further preferably 20% by mass or less, still more preferably 5% by mass or less, and further preferably 0% by mass in 100% by mass of the resin composition. % Is particularly preferred (ie does not include amides).

  The resin composition may contain, for example, a compound (ultraviolet absorber) having an absorption ability in a wavelength range of 350 nm to 400 nm. Due to the presence of these compounds, it is possible to suppress deterioration of the resin composition due to light in the wavelength range of 350 nm to 400 nm. When a compound having an absorption ability in the wavelength range of 350 nm to 400 nm is used in combination, examples of the compound having an absorption ability in the wavelength range of 350 nm to 400 nm include TINUVIN (registered trademark) series manufactured by BASF, Sankyo Chemical Co., Ltd. Zithriser (registered trademark) series, Adeka's Adekastab (registered trademark) series, Sumitomo Chemical's Sumisorb (registered trademark) series, Kyodo Yakuhin Biosorb (registered trademark) series, Sipro Kasei's Seasorb (registered) Trademark) series or the like can be used.

  The resin composition may contain a surface conditioner, thereby suppressing appearance defects such as striations and dents in the resin layer when the resin composition is cured to form a resin layer. can do. The kind of surface conditioning agent is not specifically limited, A siloxane type surfactant, an acetylene glycol type surfactant, a fluorine type surfactant, an acrylic leveling agent, etc. can be used. As the surface conditioner, for example, BYK (registered trademark) series manufactured by Big Chemie, KF series manufactured by Shin-Etsu Chemical Co., Ltd., or the like can be used.

  The resin composition may contain a dispersant, whereby the dispersibility of the oxocarbon compound in the resin composition can be stabilized and reaggregation can be suppressed. The type of the dispersant is not particularly limited. The EFKA series manufactured by Fuka Additives, the BYK (registered trademark) series manufactured by Big Chemie, the Solsperse (registered trademark) series manufactured by Lubrizol Japan, and the Disparon manufactured by Enomoto Kasei Co., Ltd. (Registered trademark) series, Ajinomoto Fine Techno Co., Ltd. Ajisper (registered trademark) series, Shin-Etsu Chemical Co., Ltd. KP series, Kyoeisha Chemical Co., Ltd. polyflow series, DIC Co., Ltd. Megafak (registered trademark) series, Sannopco's Dispar Aid series and the like can be used.

  The resin composition of the present invention contains various additives such as a plasticizer, a surfactant, a viscosity modifier, an antifoaming agent, a preservative, a specific resistance modifier, and an adhesion improver as necessary. Also good.

[3. Optical filter (application example of resin composition)]
The resin composition of the present invention can be preferably used as a resin composition for forming a filter used in various applications such as an optical device application, a display device application, a machine part, and an electric / electronic part. As a filter for optical applications, it can be suitably applied particularly to an optical filter of an imaging device for night vision, thereby reducing the incident angle dependency of optical characteristics in the near-infrared region and improving the viewing angle. It can be set as the optical filter suitable for the imaging device for night vision. The filter may be formed from a single or a plurality of resin layers, or may be formed integrally with the support.

  The filter integrated with the support is, for example, the resin composition, the surface of the support (or the surface of the other layer in the case of having another layer such as a binder layer between the support and the resin layer). ) By spin coating or solvent casting, and dried or cured. Moreover, you may form a filter by thermocompression-bonding the planar molded object formed from the resin composition with respect to the support body.

  The resin layer formed from the resin composition may be provided only on one side of the support, or may be provided on both sides. The thickness of the resin layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 1 μm or more, more preferably 10 mm or less, more preferably 5 mm or less, and more preferably 3 mm from the viewpoint of ensuring desired near infrared ray cutting performance. The following is more preferable, and 1 mm or less is particularly preferable.

  As the support, a transparent substrate such as a resin plate, a resin film, or a glass plate is preferably used. As the resin plate or resin film used for the support, for example, those formed from the resin components described above are preferably used. When a glass plate is used as the support, it is preferable to provide a binder layer formed of, for example, a silane coupling agent between the support and the resin layer. Thereby, the adhesiveness of a resin layer and a glass support body can be improved. In addition, even if it includes a silane coupling agent as an adhesive improvement agent in the resin composition which forms a resin layer, the adhesiveness of a resin layer and a glass support body can be improved.

  In the resin layer formed from the resin composition, a protective layer made of the same or different resin as the resin layer may be laminated as the second resin layer. By providing the protective layer, the durability (decomposition resistance) of the oxocarbon compound contained in the resin layer can be improved. The protective layer may be provided only on one side of the resin layer, or may be provided on both sides. When the resin layer is provided on the support, the protective layer is preferably provided on the surface of the resin layer opposite to the support.

The protective layer is preferably formed with a low oxygen permeability from the viewpoint of suppressing the decomposition of the oxocarbon-based compound contained in the resin layer. For example, the protective layer is measured at 23 ° C. and dry conditions measured according to the JIS K 716-2 method. Is preferably 100 cc / m ² / day or less, more preferably 70 cc / m ² / day or less, and even more preferably 50 cc / m ² / day or less. The lower limit of the oxygen transmission rate is not particularly limited, and may be 0 cc / m ² / day. Note that the oxygen permeability is measured by introducing oxygen gas into one chamber across the test piece and introducing nitrogen gas into the other chamber. Moreover, the ultraviolet absorber may be contained in the resin layer and / or the protective layer from the point which suppresses decomposition | disassembly of an oxocarbon type compound.

  In the case of forming an optical filter from the resin composition of the present invention, the optical filter is a layer having antireflection and antiglare properties (antireflection film) for reducing the reflection of a fluorescent lamp or the like, and a layer having scratch resistance. In addition, a transparent substrate having other functions may be included.

  The optical filter may have a near-infrared reflective film (for example, a reflective film having a wavelength range of 700 nm to 800 nm) on the resin layer. It is preferable that the near-infrared reflective film is provided on the light incident side with respect to the resin layer. As a near-infrared reflective film, an aluminum vapor-deposited film, a noble metal thin film, a resin film in which metal oxide fine particles mainly containing indium oxide and containing a small amount of tin oxide are dispersed, a high refractive index material layer and a low refractive index material layer, A dielectric multilayer film or the like in which the layers are alternately stacked can be used. If the optical filter is provided with a near-infrared reflective film, the near-infrared light can be further cut from the transmitted light of the optical filter. Note that the near-infrared reflective film may have an ultraviolet reflection function.

  The near-infrared reflective film or antireflection film (visible light antireflection film) can be composed of a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of 1.7 to 2.5 is usually selected. Examples of the material constituting the high refractive index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; silicon nitride Nitrides such as oxides, mixtures of the nitrides, and those doped with metals such as aluminum and copper and carbon (for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO)), etc. It is done. As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of 1.2 to 1.6 is usually selected. Examples of the material constituting the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and aluminum hexafluoride sodium.

  The optical filter can be used as one of constituent members of the image sensor. The image sensor is also referred to as a solid-state image sensor or an image sensor chip, and is an electronic component that converts light from a subject into an electrical signal or the like and outputs the electrical signal. The imaging element usually has a detection element (sensor) such as a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS), and may have a lens. The imaging element can be used for a mobile phone camera, a digital camera, a vehicle-mounted camera, a surveillance camera, a display element (LED or the like), and the like. In particular, an image sensor provided with an optical filter formed from the resin composition of the present invention can be suitably applied to a surveillance camera or the like for night vision. The image sensor includes one or more of the optical filters described above, and may further include other filters (for example, a visible light cut filter, an infrared cut filter, an ultraviolet cut filter, etc.) as necessary.

  The resin composition of the present invention can be used by coating on an arbitrary substrate other than the optical use filter described above. The base material at this time is not particularly limited as long as the resin layer can be formed by applying the resin composition. For example, steel, non-ferrous metal (light metal, noble metal, rare metal, rare earth, copper, zinc, Lead, tin, etc.), wood, glass, concrete, stone, ceramics, resin, rubber, leather, paper, cloth, hair, skin and the like. The shape of the substrate is not particularly limited, and is granular, powdery, massive, aggregated, plate-like, sheet-like, spherical, elliptical spherical, cubical, columnar, rod-like, conical, cylindrical, needle-like, Examples thereof include a fiber shape, a hollow fiber shape, and a porous shape.

[4. Ink composition]
The oxocarbon compound of the present invention can be applied to an ink composition. The ink composition contains at least the oxocarbon compound of the present invention and a liquid medium. The ink composition of the present invention can be effectively used as a security ink because it can effectively absorb, for example, light in a wavelength region exceeding 850 nm and has high visible light transmittance and excellent invisibility.

  The oxocarbon-based compound contained in the ink composition may be a squarylium compound, a croconium compound, or both. The oxocarbon-based compound contained in the ink composition may be only one type or two or more types.

The ink composition may contain two or more types of squarylium compounds represented by the above formula (1), or may contain two or more types of croconium compounds represented by the above formula (2). Good. The ink composition thus formed can effectively absorb light in the near-infrared region, improves the solubility of the oxocarbon compound in a liquid medium, and contains an oxocarbon compound at a high concentration. It becomes easy to form an object. In this case, from the viewpoint of increasing the solubility of the oxocarbon-based compound in the liquid medium, the ink composition preferably includes at least a squarylium compound having a structure in which R ¹ and R ² are different from each other in the above formula (1). In the above formula (2), it is preferable that R ³ and R ⁴ contain at least a croconium compound having a different structure. The ink composition more preferably contains three or more oxocarbon-based compounds. Examples of such an ink composition include a squarylium compound in which R ¹ and R ² are both R _x in the above formula (1), and R ^An ink composition comprising a squarylium compound in which both R ¹ and R ² are R _y and a squarylium compound in which R ¹ is R _x and R ² is R _y , and R ³ and R ⁴ are both in the above formula (2) An ink composition comprising a croconium compound having R _x , a croconium compound in which R ³ and R ⁴ are both R _y , and a croconium compound having R ³ in R _x and R ⁴ in R _y is shown. Such an ink composition is preferable in terms of easy production while containing a plurality of oxocarbon compounds. In addition, _Rx and _{Ry demonstrated} here represent the arbitrary structural units represented by the said Formula (3), and _Rx and _Ry are not the same.

  The ink composition may contain other coloring matter together with the oxocarbon compound of the present invention as long as desired performance according to the application is ensured. For details of other dyes, refer to the description of other dyes that may be included in the resin composition. When used as a security ink, the content of other pigments is preferably 50% by mass or less, and 20% by mass or less, with respect to 100% by mass in total of the oxocarbon compound of the present invention and other pigments. More preferred is 5% by mass or less.

  The content of the oxocarbon compound of the present invention in the ink composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 40% by mass or less, in 100% by mass of the ink composition. 30 mass% or less is more preferable, and 20 mass% or less is further more preferable. When the ink composition also contains other dyes, the total content of the oxocarbon compound of the present invention and the other dyes is preferably in the above range. By adjusting to such a range, it becomes easy to obtain a printing surface having a sufficient density, and it becomes easy to ensure the stability of the oxocarbon compound and other dyes in the ink composition.

  The liquid medium may function as a solvent (solvent) for the oxocarbon-based compound or may function as a dispersion medium. Examples of the liquid medium include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, alcohols such as tert-butyl alcohol, tert-amyl alcohol, n-hexanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monobutyl Glycol derivatives such as ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA) (ether compounds, ester compounds, ether ester compounds, etc.); ethyl acetate, propyl acetate, butyl acetate, ethyl lactate, 3-ethoxypropylo Examples thereof include esters such as ethyl onate; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane, methylcyclohexane and heptane; cyclic ethers such as tetrahydrofuran and dioxane; These liquid media may use only 1 type and may use 2 or more types together.

  The content of the liquid medium is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, more preferably 95% by mass or less, and preferably 90% by mass or less in 100% by mass of the ink composition. Is more preferable, and 80 mass% or less is still more preferable. By adjusting the content of the liquid medium within such a range, the solubility and dispersibility of the oxocarbon-based compound can be improved, and an ink composition having a high oxocarbon-based compound concentration can be easily obtained. Become.

  The ink composition may have a resin component in addition to the liquid medium. By blending the resin component, the viscosity and adhesion of the ink composition can be increased. As the resin component, a known resin used in the ink composition can be used. (Meth) acrylic resin, (meth) acrylic urethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyolefin resin ( For example, polyethylene resins, polypropylene resins, etc.), cycloolefin resins (including cycloolefin copolymers, norbornene resins, etc.), petroleum resins, rosin resins, rosin ester resins, urea resins, melamine resins, urethane resins, styrene resins Resin, styrene-acrylic resin, styrene-maleic acid resin, polyvinyl acetate, ethylene-vinyl acetate resin, vinyl acetal resin, polyamide resin (for example, nylon), aramid resin, polyimide resin, polyamideimide resin, alkyd Resin, phenolic resin, Xy resin, polyester resin (for example, polybutylene terephthalate resin, polyethylene terephthalate resin, polyarylate resin, etc.), polysulfone resin, butyral resin, polycarbonate resin, polyether resin, acrylonitrile butadiene styrene resin, acrylonitrile-styrene copolymer, acrylic Nitrile-butadiene copolymers, cellulose derivatives (eg, ethyl cellulose, cellulose acetate, nitrocellulose, etc.), silicone resins, modified silicone resins (eg, (meth) acryl silicone resins, alkylpolysiloxane resins, silicone urethane resins, silicones) Polyester resin, silicone acrylic resin, etc.), fluororesin (eg fluorinated aromatic polymer, polytetrafluoroethylene, perfume) Oloalkoxy fluororesin, fluorinated polyaryletherketone, fluorinated polyimide, fluorinated polyamic acid, fluorinated polyethernitrile, etc.), diallyl phthalate resin, coumarone indene resin, terpene phenol resin, xylene resin, alkyd resin, Examples thereof include maleic acid resins and fumaric acid resins. The amount of the resin component to be blended is preferably 1% by mass or more, more preferably 5% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, in 100% by mass of the ink composition.

  The ink composition may contain various additives such as an ultraviolet absorber, a surface modifier, a dispersant, a conductivity modifier, a polymerization inhibitor, a leveling agent, and an antioxidant as necessary. For details of these additives, refer to the description of the additives in the resin composition.

  The ink composition can be produced by a known method. For example, it can be prepared by mixing the dye containing the oxocarbon compound of the present invention, a liquid medium, and, if necessary, a polymerizable monomer, a polymerization initiator, and various additives using a mixer such as a sand mill. If necessary, the liquid mixture thus obtained may be filtered with a filter having a pore size of 3 μm or less or 1 μm or less.

  The ink composition of the present invention comprises a normal solvent type ink used for screen printing ink, gravure printing ink, offset printing ink, flexographic printing ink, ink jet recording ink, etc., light (ultraviolet light, visible light, red ink). It can be applied to various inks such as external light) curable ink and water-based ink.

  The ink composition can be used by printing (coating) on an arbitrary material to form a printed matter. Examples of the base material to be printed include paper, cloth, wood, glass, concrete, stone, ceramics, resin, rubber, leather, steel, non-ferrous metal (light metal, precious metal, rare metal, rare earth, copper, zinc, Lead, tin, etc.), hair, skin and the like. The shape of the substrate to be printed is also not particularly limited, and is in the form of a sheet, plate, sphere, ellipsoid, cube, column, rod, cone, cylinder, granule, powder, lump, particle aggregate , Needle shape, fiber shape, hollow fiber shape, porous shape and the like.

[5. Others]
The oxocarbon-based compound of the present invention utilizes light that is less likely to cause problems due to pressurization and heating, in addition to the resin composition, resin molded body, laser welding photothermal conversion material, and ink composition as described above. It can also be applied to materials for photofixing (electrostatic charge developing toner for flash fixing), cosmetic materials that have the function of absorbing or cutting near infrared rays, and materials for light detection and ranging (LIDAR) systems. It is.

  This application claims the benefit of priority based on Japanese Patent Application No. 2016-034756 filed on February 25, 2016 and Japanese Patent Application No. 2016-254310 filed on December 27, 2016. To do. The entire contents of the specifications of Japanese Patent Application No. 2016-034756 filed on February 25, 2016 and Japanese Patent Application No. 2016-254310 filed on December 27, 2016 are hereby incorporated by reference. Incorporated for.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, and is implemented with appropriate modifications within a range that can meet the purpose described above and below. Any of these may be included in the technical scope of the present invention.

(1) Synthesis of Dye Compound (1-1) Synthesis Example 1 (Synthesis of Croconium Compound 1)
Into a 300 mL four-necked flask, 60 mL of hydrochloric acid was put, the temperature in the flask was cooled to -10 ° C. or lower, and while keeping the temperature in the flask not exceeding 0 ° C., 5.13 g (0.1. 024 mol) was added and dissolved. After the exotherm subsided, a solution in which 1.63 g (0.024 mol) of sodium nitrite was dissolved in 11 g of distilled water was added dropwise over 1 hour while maintaining the temperature in the flask at −10 ° C. or lower. After completion of the dropwise addition, a solution of 26.63 g (0.118 mol) of tin chloride dihydrate dissolved in 27 mL of hydrochloric acid was added dropwise over 1 hour so that the temperature in the flask did not exceed 0 ° C. Proceeded. After completion of the reaction, the cake obtained by filtration was dried using a vacuum dryer at 60 ° C. for 12 hours to obtain 5.5 g of fluoranthene-3-hydrazine hydrochloride. The yield based on 3-aminofluoranthene was 87.2 mol%.

  Next, 3.01 g (0.011 mol) of the fluoranthene-3-hydrazine hydrochloride obtained above, 0.96 g (0.011 mol) of 3-methyl-2-butanone, and 1- 20 g of butanol was charged, and the mixture was reacted at 60 ° C. for 4 hours with stirring using a magnetic stirrer under nitrogen flow (5 mL / min) to obtain a condensed heterocyclic compound. After completion of the reaction, the solution containing the condensed heterocyclic compound was cooled to room temperature and filtered, and the obtained filtrate was transferred to a 200 mL four-necked flask. Then, 0.78 g (0.006 mol) of croconic acid and 20 g of toluene were added, stirred under a nitrogen flow (5 mL / min) using a magnetic stirrer, and water eluted using a Dean-Stark apparatus. While removing, the reaction was allowed to proceed for 6 hours under reflux conditions. After completion of the reaction, the obtained reaction solution is concentrated by an evaporator, the obtained solid is purified by column chromatography (developing solvent: chloroform), and the purified isolate is further recrystallized in methanol. 0.45 g of the target croconium compound 1 was obtained. The yield based on croconic acid was 12.2 mol%.

  The obtained compound was identified by a mass spectrometer (“LCMS-2020” manufactured by Shimadzu Corporation, M / Z = 50-2000, positive / negative simultaneous scan). Specifically, about 1 mg of the obtained compound was applied and adhered to a glass rod, ionized directly with an ionization unit (DART) (“DART-OS” manufactured by Shimadzu Corporation, heater temperature 500 ° C.), and mass spectrometry was performed. By introducing it into the meter, the mass spectrum of the compound was measured.

(1-2) Synthesis Example 2 (Synthesis of Croconium Compound 2)
A croconium compound 2 shown in Table 1 was obtained in the same manner as in Synthesis Example 1 except that ethyl 2-methylacetoacetate was used instead of 3-methyl-2-butanone in Synthesis Example 1. The yield based on croconic acid was 5.8 mol%.

(1-3) Synthesis Example 3 (Synthesis of Croconium Compound 3)
In a 300 mL four-necked flask, under nitrogen flow, 4.45 g (0.022 mol) of 3- (trifluoromethyl) phenylacetone was added, the temperature in the flask was cooled to −10 ° C. or lower, and the temperature in the flask was 0. While not exceeding ℃, hexamethyldisilazane lithium (1.3M tetrahydrofuran solution) 19.06 g, N, N′-dimethylpropyleneurea 8.46 g (0.066 mol), manganese chloride 2.77 g (0.022 mol) ) And 4.14 g (0.024 mol) of benzyl bromide were sequentially added, and the mixture was stirred overnight without controlling the temperature. The obtained reaction solution was quenched with dilute hydrochloric acid, extracted with ethyl acetate, and washed 3 times with brine. The obtained organic phase was dehydrated with sodium sulfate and concentrated with an evaporator, and then the obtained solid was purified by column chromatography (developing solvent: chloroform) to give 4-phenyl-3- (3- (trifluoro 5.0 g of methyl) phenyl) butan-2-one was obtained. The yield based on 3- (trifluoromethyl) phenylacetone was 78.1 mol%. The subsequent synthesis procedures were the same as those in Synthesis Example 1 except that 4-phenyl-3- (3- (trifluoromethyl) phenyl) butan-2-one was used instead of 3-methyl-2-butanone. In the same manner as in Example 1, the croconium compound 3 shown in Table 1 was obtained. The yield based on croconic acid was 10.1 mol%.

(1-4) Synthesis Example 4 (Synthesis of Croconium Compound 4)
In the same manner as in Synthesis Example 3 except that (2-iodoethyl) benzene was used instead of benzyl bromide in Synthesis Example 3, 5-phenyl-3- (3- (trifluoromethyl) phenyl) pentane-2- Got on. The yield based on 3- (trifluoromethyl) phenylacetone was 86.6 mol%. The subsequent synthesis procedures were the same as those in Synthesis Example 1 except that 5-phenyl-3- (3- (trifluoromethyl) phenyl) pentan-2-one was used instead of 3-methyl-2-butanone. In the same manner as in Example 1, the croconium compound 4 shown in Table 1 was obtained. The yield based on croconic acid was 8.3 mol%.

(1-5) Synthesis Example 5 (Synthesis of Croconium Compound 5)
Same as Synthesis Example 3 except that 3,4-dimethoxyphenylacetone was used instead of 3- (trifluoromethyl) phenylacetone and (2-iodoethyl) benzene was used instead of benzyl bromide in Synthesis Example 3. Thus, 3- (3,4-dimethoxyphenyl) -5-phenylpentan-2-one was obtained. The yield based on 3,4-dimethoxyphenylacetone was 95.1 mol%. Subsequent synthesis procedures were the same as those in Synthesis Example 1 except that 3- (3,4-dimethoxyphenyl) -5-phenylpentan-2-one was used instead of 3-methyl-2-butanone in Synthesis Example 1. In the same manner, the croconium compound 5 shown in Table 1 was obtained. The yield based on croconic acid was 15.4 mol%.

(1-6) Synthesis Example 6 (Synthesis of Croconium Compound 6)
3- (3- (trifluoromethyl) phenyl) decan-2-one was obtained in the same manner as in Synthesis Example 3, except that 1-iodoheptane was used instead of benzyl bromide in Synthesis Example 3. The yield based on 3- (trifluoromethyl) phenylacetone was 89.1 mol%. The subsequent synthesis procedures are the same as those in Synthesis Example 1 except that 3- (3- (trifluoromethyl) phenyl) decan-2-one was used instead of 3-methyl-2-butanone in Synthesis Example 1. Thus, the croconium compound 6 shown in Table 1 was obtained. The yield based on croconic acid was 9.2 mol%.

(1-7) Synthesis Example 7 (Synthesis of Croconium Compound 7)
A croconium compound 7 shown in Table 1 was obtained in the same manner as in Synthesis Example 1 except that 1,1-diphenylacetone was used instead of 3-methyl-2-butanone in Synthesis Example 1. The yield based on croconic acid was 1.8 mol%.

(1-8) Synthesis Example 8 (Synthesis of Croconium Compound 8)
In a 300 mL four-necked flask placed in a water bath, under nitrogen flow, while paying attention to heat generation, 6.73 g (0.060 mol) of potassium tert-butoxide, 35 g of ultra-dehydrated tetrahydrofuran, 3.32 g (0.020 mol) of fluorene, acetic acid After sequentially adding 3.52 g (0.040 mol) of ethyl, the mixture was stirred for 3 hours under reflux conditions while heating in a hot water bath. The resulting reaction solution was cooled, quenched with dilute hydrochloric acid, extracted with ethyl acetate, and washed 3 times with brine. The obtained organic phase was dehydrated with sodium sulfate and concentrated with an evaporator, and then the obtained solid was purified by column chromatography (developing solvent: chloroform) to obtain 4.1 g of 9-acetyl-9H-fluorene. It was. The yield based on fluorene was 97.6%. Subsequent synthetic procedures were other than using 9-acetyl-9H-fluorene instead of 3-methyl-2-butanone in Synthesis Example 1 and using tert-amyl alcohol instead of 1-butanol as a solvent. Produced the croconium compound 8 shown in Table 1 in the same manner as in Synthesis Example 1. The yield based on croconic acid was 30.5 mol%.

(1-9) Synthesis Example 9 (Synthesis of Croconium Compound 9)
In Synthesis Example 8, 2-bromo-9-acetyl-9H-fluorene was obtained in the same manner as in Synthesis Example 8, except that 2-bromo-9H-fluorene was used instead of fluorene. The yield based on 2-bromo-9H-fluorene was 97.1 mol%. The subsequent synthesis procedures are shown in Table 1 in the same manner as in Synthesis Example 1 except that 2-bromo-9-acetyl-9H-fluorene was used instead of 3-methyl-2-butanone in Synthesis Example 1. Croconium compound 9 was obtained. The yield based on croconic acid was 10.4 mol%.

(1-10) Synthesis Example 10 (Synthesis of Croconium Compound 10)
In Synthesis Example 8, 2-iodo-9-acetyl-9H-fluorene was obtained in the same manner as in Synthesis Example 8, except that 2-iodo-9H-fluorene was used instead of fluorene. The yield based on 2-iodo-9H-fluorene was 95.8 mol%. The subsequent synthesis procedures are shown in Table 1 in the same manner as in Synthesis Example 1 except that 2-iodo-9-acetyl-9H-fluorene was used instead of 3-methyl-2-butanone in Synthesis Example 1. Croconium compound 10 was obtained. The yield based on croconic acid was 18.9 mol%.

(1-11) Synthesis Example 11 (Synthesis of Croconium Compound 11)
2-Trifluoromethyl-9H-fluorene was synthesized using the method described in Organic Letters, vol. 16, p.4268-4271 (2014). Subsequently, 2-trifluoromethyl-9-acetyl-9H-fluorene was obtained in the same manner as in Synthesis Example 8 except that 2-trifluoromethyl-9H-fluorene was used instead of fluorene in Synthesis Example 8. . The yield based on 2-trifluoromethyl-9H-fluorene was 91.4 mol%. Subsequent synthesis procedures are as shown in Table 2 except that 2-trifluoromethyl-9-acetyl-9H-fluorene was used in place of 3-methyl-2-butanone in Synthesis Example 1. The croconium compound 11 shown in FIG. The yield based on croconic acid was 10.1 mol%.

(1-12) Synthesis Example 12 (Synthesis of Croconium Compound 12)
2-Cyano-9H-fluorene was synthesized using the method described in The Journal of Organic Chemistry, vol.69, p.987-990 (2004). Subsequently, 2-cyano-9-acetyl-9H-fluorene was obtained in the same manner as in Synthesis Example 8 except that 2-cyano-9H-fluorene was used instead of fluorene in Synthesis Example 8. The yield based on 2-cyano-9H-fluorene was 95.9 mol%. The subsequent synthesis procedures are shown in Table 2 in the same manner as in Synthesis Example 1 except that 2-cyano-9-acetyl-9H-fluorene was used instead of 3-methyl-2-butanone in Synthesis Example 1. Croconium compound 12 was obtained. The yield based on croconic acid was 12.4 mol%.

(1-13) Synthesis Example 13 (Synthesis of Croconium Compound 13)
In Synthesis Example 8, 9-acetyl-9H-2,7-dibromofluorene was obtained in the same manner as in Synthesis Example 8, except that 2,7-dibromofluorene was used instead of fluorene. The yield based on 2,7-dibromofluorene was 95.9 mol%. The subsequent synthesis procedures are shown in Table 2 in the same manner as in Synthesis Example 1 except that 9-acetyl-9H-2,7-dibromofluorene was used instead of 3-methyl-2-butanone in Synthesis Example 1. The indicated croconium compound 13 was obtained. The yield based on croconic acid was 18.5 mol%.

(1-14) Synthesis Example 14 (Synthesis of Croconium Compound 14)
In Synthesis Example 8, 2-bromo-7-iodo-9-acetyl-9H-fluorene was synthesized in the same manner as in Synthesis Example 8 except that 2-bromo-7-iodo-9H-fluorene was used instead of fluorene. Obtained. The yield based on 2-bromo-7-iodo-9H-fluorene was 95.9 mol%. The subsequent synthesis procedures were the same as those in Synthesis Example 1 except that 2-bromo-7-iodo-9-acetyl-9H-fluorene was used instead of 3-methyl-2-butanone in Synthesis Example 1. The croconium compound 14 shown in Table 2 was obtained. The yield based on croconic acid was 19.3 mol%.

(1-15) Synthesis Example 15 (Synthesis of Croconium Compound 15)
In Synthesis Example 8, 2,7-di-tert-butyl-9-acetyl- was used in the same manner as in Synthesis Example 8, except that 2,7-di-tert-butyl-9H-fluorene was used instead of fluorene. 9H-fluorene was obtained. The yield based on 2,7-di-tert-butyl-9H-fluorene was 97.3 mol%. The subsequent synthesis procedures were the same as those in Synthesis Example 1 except that 2,7-di-tert-butyl-9-acetyl-9H-fluorene was used instead of 3-methyl-2-butanone in Synthesis Example 1. Thus, the croconium compound 15 shown in Table 2 was obtained. The yield based on croconic acid was 9.3 mol%.

(1-16) Synthesis Example 16 (Synthesis of Croconium Compound 16)
9-Acetyl-9H-fluorene was obtained by the method described in Synthesis Example 8, and 9-acetyl-9H-2,7-dibromofluorene was obtained by the method described in Synthesis Example 13. Subsequent synthetic procedures used 9-acetyl-9H-fluorene and 9-acetyl-9H-2,7-dibromofluorene in a molar ratio of 1: 1 instead of 3-methyl-2-butanone in Synthesis Example 1. Except that, the croconium compound 16 (mixture) shown in Table 2 was obtained in the same manner as in Synthesis Example 1. The yield based on croconic acid was 12.1 mol%.

(1-17) Synthesis Example 17 (Synthesis of Croconium Compound 17)
In Synthesis Example 8, 1- (1H-inden-1-yl) ethane-1-one was obtained in the same manner as in Synthesis Example 8, except that indene was used instead of fluorene. The yield based on indene was 74.8 mol%. The subsequent synthesis procedures were the same as those in Synthesis Example 1 except that 1- (1H-inden-1-yl) ethane-1-one was used instead of 3-methyl-2-butanone in Synthesis Example 1. Thus, the croconium compound 17 shown in Table 2 was obtained. The yield based on croconic acid was 1.5 mol%.

(1-18) Synthesis Example 18 (Synthesis of Croconium Compound 18)
In Synthesis Example 8, 9-acetyl-9H-xanthene was obtained in the same manner as in Synthesis Example 8 except that xanthene was used instead of fluorene. The yield based on xanthene was 84.2 mol%. Subsequent synthesis procedures were performed in the same manner as in Synthesis Example 1 except that 9-acetyl-9H-xanthene was used instead of 3-methyl-2-butanone in Synthesis Example 1. Obtained. The yield based on croconic acid was 11.7 mol%.

(1-19) Synthesis Example 19 (Synthesis of Comparative Croconium Compound 1)
In a 50 mL four-necked flask, 0.73 g (0.004 mol) of 2,3,3-trimethyl-4,5-benzo-3H-indole, 0.25 g (0.002 mol) of croconic acid, and 10 g of 1-butanol as a solvent. Then, 10 g of toluene was charged, stirred under a nitrogen flow (5 mL / min) using a magnetic stirrer, and reacted for 6 hours under reflux conditions while removing the eluted water using a Dean-Stark apparatus. After completion of the reaction, the obtained reaction solution is concentrated by an evaporator, the obtained solid is purified by column chromatography (developing solvent: chloroform), and the purified isolate is further recrystallized in methanol. 0.30 g of comparative croconium compound 1 shown in Table 2 was obtained. The yield based on croconic acid was 32.7 mol%.

(1-20) Synthesis Example 20 (Synthesis of Comparative Phthalocyanine Compound 1)
Comparative phthalocyanine compound 1 shown in Table 3 was obtained by the synthesis method described in Example 2 of JP-A-2007-56105.

(2) Preparation of resin (2-1) Preparation of fluorinated aromatic resin In a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirrer, 4,4′-bis (2,3, 4,5,6-pentafluorobenzoyl) diphenyl ether 16.74 parts by mass, 9,9-bis (4-hydroxyphenyl) fluorene 10.5 parts by mass, potassium carbonate 4.34 parts by mass, dimethylacetamide 90 parts by mass It is. The mixture charged in the reactor was heated to 80 ° C. and reacted for 8 hours. After completion of the reaction, the reaction solution was poured into a 1% aqueous acetic acid solution while vigorously stirring with a blender. The precipitated reaction product was filtered off, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated aromatic resin. The glass transition temperature (Tg) of the fluorinated aromatic resin was 242 ° C., and the number average molecular weight (Mn) was 70,770. The number average molecular weight was determined in terms of polystyrene using gel permeation chromatography.

(2-2) Preparation of acrylic resin 21.0 mass of methyl α-allyloxymethyl acrylate (AMA) as a monomer in a reactor equipped with a thermometer, a cooling tube, a gas introduction tube, and a stirrer Part, N-phenylmaleimide 9.0 parts by weight, and 45.0 parts by weight of ethyl acetate as a polymerization solvent were charged, and the temperature was raised with stirring under a stream of nitrogen gas. After the temperature in the reactor was stabilized at 70 ° C., 0.03 part by mass of an azo radical polymerization initiator (manufactured by Nippon Finechem Co., Ltd., ABN-V) was added to initiate the polymerization reaction. The reaction was carried out for 3.5 hours while maintaining the temperature in the reactor at 69 ° C. to 71 ° C., and then cooled to room temperature. Tetrahydrofuran was added as a diluent solvent, reprecipitation was performed using n-hexane as a poor solvent, and the precipitate was separated by suction filtration. The obtained precipitate was dried under reduced pressure at 80 ° C. for 2 hours using a vacuum dryer to obtain an acrylic resin. The weight average molecular weight of the acrylic resin measured by gel permeation chromatography was 31,600. Moreover, the glass transition temperature (Tg) of the acrylic resin measured with the differential scanning calorimeter was 152 degreeC.

(3) Manufacturing example of filter (resin laminated substrate) (3-1) Manufacturing example 1
2 parts by mass of polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Iupilon (registered trademark) E-2000), 0.02 parts by mass of croconium compound 7 and 18 parts by mass of chloroform are mixed to obtain a dye-containing resin composition. It was. After about 1 cc of this resin composition was dropped on a glass substrate (manufactured by SCHOTT, D263Teco, 60 mm × 60 mm × 0.3 mm, average transmittance 91%), a spin coater (manufactured by Mikasa, 1H-D7) was used. Applied. The resin laminated substrate which formed the resin layer on the glass substrate by drying the glass substrate which formed the resin composition into a film using nitrogen oven for 30 minutes at 100 degreeC using inert oven (the Yamato Scientific company make, DN610I) 1 was obtained. The thickness of the resin layer was about 2 μm.

(3-2) Production Example 2
Production Example 1 except that cycloolefin resin (Zeonor (registered trademark) 1410R, manufactured by Nippon Zeon Co., Ltd.) was used instead of polycarbonate resin as production resin, and dichlorobenzene was used instead of chloroform. In the same manner as in Example 1, a resin laminated substrate 2 was produced.

(3-3) Production Example 3
In Production Example 1, a norbornene resin (JSR, Arton (registered trademark) RX4500), which is a kind of cycloolefin resin, was used as the resin used instead of the polycarbonate resin, and the croconium compound 8 was used instead of the croconium compound 7. A resin laminated substrate 3 was produced in the same manner as in Production Example 1 except that toluene was used instead of chloroform.

(3-4) Production Example 4
In Production Example 1, a cycloolefin copolymer (TOPAS (registered trademark) 5013, manufactured by Polyplastics Co., Ltd.), which is a kind of cycloolefin resin, was used as the resin used instead of the polycarbonate resin, and the croconium compound 7 was used instead of the croconium compound 7. Resin laminate substrate 4 was produced in the same manner as in Production Example 1 except that methylcyclohexane was used instead of chloroform.

(3-5) Production Example 5
In Production Example 1, the fluorinated aromatic resin prepared in (2-1) above was used instead of the polycarbonate resin as the resin used, the croconium compound 8 was used instead of the croconium compound 7, and toluene was used instead of chloroform. A resin laminated substrate 5 was produced in the same manner as in Production Example 1 except that it was used.

(3-6) Production Example 6
In Production Example 1, the acrylic resin prepared in the above (2-2) was used as the resin used instead of the polycarbonate resin, the croconium compound 8 was used instead of the croconium compound 7, and toluene was used instead of chloroform. Except for this, a resin laminated substrate 6 was produced in the same manner as in Production Example 1.

(3-7) Comparative production example 1
Comparative resin laminated substrate 1 was produced in the same manner as in Production Example 1 except that Comparative Phthalocyanine Compound 1 was used instead of Croconium Compound 7 in Production Example 1.

(4) Evaluation (4-1) Spectroscopic measurement of dye compound and resin laminated substrate A chloroform solution of each dye compound obtained in Synthesis Examples 1 to 20 was prepared, and an absorption spectrum (transmission spectrum) at wavelengths of 400 nm to 1100 nm was measured. . The chloroform solution of the dye compound was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-1800) after adjusting the concentration so that the transmittance at the maximum absorption wavelength was 10% (± 0.05%). The light transmittance is measured at a pitch of 1 nm, the wavelength at which absorption is maximum in the wavelength range of 400 nm to 1100 nm (maximum absorption wavelength λmax), and the wavelength at which the transmittance is 30% on the longer wavelength side than the maximum absorption wavelength (% T30 ), An average transmittance (visible light transmittance) at a wavelength of 400 nm to 700 nm, and a transmittance (% T (400 nm)) at a wavelength of 400 nm. Moreover, also about each resin laminated substrate produced by the manufacture examples 1-6 and the comparative manufacture example 1, the absorption spectrum (transmission spectrum) in wavelength 400nm-1100nm is measured like the above, and the transmittance | permeability in maximum absorption wavelength is 10 The maximum absorption wavelength λmax,% T30, visible light transmittance, and% T (400 nm) when% (± 0.05%) were determined.

The spectral measurement results of the chloroform solution of each dye compound are summarized in Table 4, and the transmission spectra of the croconium compound 1, the comparative croconium compound 1, and the comparative phthalocyanine compound 1 are shown in FIG. In the croconium compounds 1 to 18, the total number of π electrons of the ring A and the substituent R ⁷ is 16, the maximum absorption wavelength λmax is 892 to 934 nm,% T30 is 918 to 963 nm, and the visible light average transmittance is 85.2. % To 92.2%. On the other hand, the comparative croconium compound 1 has a total number of π electrons of the ring A and the substituent R ⁷ of 10, the maximum absorption wavelength λmax is 810 nm,% T30 is 830 nm, and the visible light average transmittance is 92.8%. It was. When the relationship between the number of π electrons of the croconium compound 1 (the croconium compound in which% T30 has the lowest wavelength among the croconium compounds 1 to 18) and the comparative croconium compound 1 is linearly interpolated, the number of π electrons is 12 If the number is more than one, the wavelength of% T30 is 850 nm or more, and it can be seen that light in a wavelength region exceeding 850 nm can be effectively absorbed. If the wavelength of% T30 is 850 nm or more, it can be suitably used, for example, for security ink and laser welding applications. The comparative phthalocyanine compound 1 can absorb light in the wavelength range where the maximum absorption wavelength λmax exceeds 904 nm and 850 nm, but the visible light average transmittance is as low as 80.8%, which is slightly inferior in invisibility. It became a thing.

  Table 5 summarizes the spectroscopic measurement results of each resin laminated substrate. The resin laminated substrates 1 and 2 contain a croconium compound 7 as a dye, the resin laminated substrates 3 to 6 contain a croconium compound 8 as a dye, and the comparative resin laminated substrate 1 contains a comparative phthalocyanine compound as a dye. 1 was included, but regardless of the type of resin, the value of the maximum absorption wavelength λmax of the resin laminated substrate was almost the same as that in the chloroform solution. Further, the visible light transmittance of the resin laminated substrates 1 to 6 was higher than that of the comparative resin laminated substrate 1. The resin laminated substrates 1 to 6 can be preferably applied to, for example, an optical filter of an imaging device for night vision.

(4-2) Storage stability when used as ink composition 5 mg of the croconium compound 7 obtained in Synthesis Example 7 was weighed and diluted with chloroform to prepare 100 mL. 5 mL of the resulting chloroform solution was collected using a whole pipette, and further diluted with chloroform to prepare 50 mL. Thus, ink composition 1 was obtained. The obtained ink composition 1 was stored at room temperature for 1 month under light shielding. For the ink composition 1 immediately after preparation and after storage for 1 month, the absorption spectrum (transmission spectrum) at a wavelength of 400 nm to 1100 nm was measured in the same manner as described above, and the transmittance and the visible light transmittance at the maximum absorption wavelength were obtained. It was confirmed that the ink composition 1 containing the croconium compound 7 was excellent in storage stability without degradation in spectral characteristics even after one month.

  The oxocarbon-based compound of the present invention includes, for example, an optical filter for a semiconductor light-receiving element having a function of absorbing and cutting near infrared rays, a near-infrared absorbing film and a near-infrared absorbing plate for blocking heat rays for energy saving, security ink and invisible. Information display material as barcode ink, solar cell material using visible light and near infrared light, specific wavelength absorption filter for plasma display panel (PDP) and CCD, photothermal conversion material for laser welding, pressurization and Materials for photo-fixing methods that use light that is less likely to cause defects due to heating (static charge developing toner for flash fixing methods), cosmetic materials that have the function of absorbing or cutting near infrared rays, and light detection and ranging (LIDAR) It can be applied to system materials.

Claims (7)

An oxocarbon compound represented by the following formula (1) or the following formula (2).

[In Formula (1) and Formula (2), R ^{1 to} R ⁴ each independently represent a structural unit represented by the following Formula (3). ]

[In Formula (3),
Ring A may have an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, or a substituent containing these ring structures. Represents a fused ring,
R ^{5 to} R ⁷ each independently represent a hydrogen atom, an organic group, or a polar functional group, or R ⁵ and R ⁶ are connected to each other to form a ring,
* Represents a binding site with the 4-membered ring in formula (1) or the 5-membered ring in formula (2);
The total number of π electrons contained in rings A and R ⁷ is 12 or more. ] R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl which may have a substituent. A substituent, an alkoxycarbonyl group which may have a substituent, or an aryloxycarbonyl group which may have a substituent, or a substituent formed by linking R ⁵ and R ⁶ to each other And / or a hydrocarbon ring optionally having a condensed ring structure, or a heterocyclic ring optionally having a substituent and / or a condensed ring structure,
The oxocarbon compound according to claim 1, wherein R ⁷ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.   A resin composition comprising the oxocarbon-based compound according to claim 1 or 2 and a resin component.   Furthermore, the resin composition of Claim 3 containing a liquid medium.   An ink composition comprising the oxocarbon-based compound according to claim 1 and a liquid medium. A condensed heterocyclic compound represented by the following formula (5):

[In Formula (5),
Ring A may have an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, or a substituent containing these ring structures. Represents a fused ring,
R ^{5 to} R ⁷ each independently represent a hydrogen atom, an organic group, or a polar functional group, or R ⁵ and R ⁶ are connected to each other to form a ring,
The total number of π electrons contained in rings A and R ⁷ is 12 or more. ] It comprises a step of reacting a condensed heterocyclic compound represented by the following formula (5) with squaric acid or croconic acid to obtain an oxocarbon compound represented by the following formula (1) or the following formula (2). A process for producing an oxocarbon compound.

[In Formula (5),
Ring A may have an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, or a substituent containing these ring structures. Represents a fused ring,
R ^{5 to} R ⁷ each independently represent a hydrogen atom, an organic group, or a polar functional group, or R ⁵ and R ⁶ are connected to each other to form a ring,
The total number of π electrons contained in rings A and R ⁷ is 12 or more. ]

[In Formula (1) and Formula (2), R ^{1 to} R ⁴ each independently represent a structural unit represented by the following Formula (3). ]

[In Formula (3),
Ring A and R ^{5 to} R ⁷ have the same meaning as above,
* Represents a binding site with the 4-membered ring in formula (1) or the 5-membered ring in formula (2);
The total number of π electrons contained in rings A and R ⁷ is 12 or more. ]

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