Oxocarbon-based compound

Abstract

Provided is an oxocarbon-based compound represented by formula (1) or formula (2). In formula (3), ring A represents a 4- to 9-membered unsaturated hydrocarbon ring; ring B represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a condensed ring containing these ring structures; Ra represents an alkyl group or an aryl group; * represents a binding site with the 4-membered ring in formula (1) or the 5-membered ring in formula (2); when ring A has 4 to 6 members, there are three or more sp3 carbon atoms to which 1 to 3 fluorine atoms are bonded per molecule; and when ring A has 7 to 9 members, there are two or more sp3 carbon atoms to which 1 to 3 fluorine atoms are bonded per molecule.

Description

Oxocarbon compounds

[0001] The present disclosure relates to an oxocarbon compound, a resin composition containing the same, a molded article formed from the resin composition, and an optical filter.

[0002] Oxocarbon compounds are useful as dyes having an absorption range in the red to near-infrared region, and the present applicant has filed patent applications relating to various oxocarbon compounds. For example, Patent Documents 1 to 4 disclose oxocarbon compounds having a structure in which pyrrole rings are bonded to both sides of a cyclic oxocarbon skeleton via carbon atoms.

[0003] JP 2016-074649 A JP 2017-067963 A International Publication No. 2017 / 146187 JP 2018-095798 A

[0004] Oxocarbon compounds, which have an absorption range in the red to near-infrared region, are expected to be used in near-infrared cut filters, near-infrared absorbing films, security inks, and the like. When using oxocarbon compounds for such applications, it is desirable to dissolve the oxocarbon compounds in organic solvents or resins, which improves their handleability and processability. However, oxocarbon compounds generally have low solubility in organic solvents and resins. For example, when forming an optical filter from a resin composition containing an oxocarbon compound, the optical filter must be formed to a certain thickness in order to exhibit the spectral characteristics inherent to the oxocarbon compound. Meanwhile, given the demand for smaller and thinner electronic devices such as optical filters, the formation of thinner optical filters requires the presence of a higher concentration of oxocarbon compounds in the optical filter. Furthermore, when using oxocarbon compounds in security inks, it is preferable to include a high concentration of the oxocarbon compound in the ink to enhance the color development of the ink.

[0005] An object of the present disclosure is to provide an oxocarbon compound that has excellent solubility in organic solvents.

[0006] The oxocarbon compounds according to the present disclosure that can solve the above problems are as follows: [1] An oxocarbon compound represented by the following formula (1) or (2): [In formula (1) and formula (2), R １１ ~R １４ each independently represents a structural unit represented by the following formula (3): [In formula (3), ring A represents an optionally substituted 4- to 9-membered unsaturated hydrocarbon ring; ring B represents an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocycle, or a fused ring containing any of these ring structures, optionally having a substituent; R ａ represents an alkyl group or an aryl group; * represents a bonding site with the 4-membered ring in formula (1) or the 5-membered ring in formula (2).] When the ring A has 4 to 6 ring members, sp ３ When the ring A has 7 to 9 ring members, sp ３ [2] An oxocarbon compound having two or more carbon atoms in the molecule. ３ The oxocarbon compound according to [1], which contains a carbon atom.

[0007] The present disclosure also provides the following resin composition, molded article, and optical filter. [3] A resin composition containing the oxocarbon compound according to [1] or [2] and a resin component. [4] A molded article formed from the resin composition according to [3]. [5] An optical filter having a resin layer formed from the resin composition according to [3].

[0008] The oxocarbon compounds according to the present disclosure have excellent solubility in organic solvents.

[0009] 1 shows the transmission spectrum of an optical filter formed from resin composition 2 examined in the examples. 2 shows the transmission spectrum of an optical filter formed from resin composition 4 examined in the examples.

[0010] The oxocarbon compounds according to the present disclosure are squarylium compounds represented by the following formula (1) and croconium compounds represented by the following formula (2). In the following formulas (1) and (2), R １１ ~R １４ each independently represents a structural unit represented by the following formula (3):

[0011]

[0012]

[0013] In formula (3), ring A represents an optionally substituted 4- to 9-membered unsaturated hydrocarbon ring, ring B represents an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocycle, or a fused ring containing any of these ring structures, optionally having a substituent; R ａ represents an alkyl group or an aryl group, * represents a bonding site with the 4-membered ring in formula (1) or the 5-membered ring in formula (2), and when the number of ring members in ring A is 4 to 6, the oxocarbon compound is an sp ３ When the molecule has three or more carbon atoms and the ring A has 7 to 9 ring members, the oxocarbon compound has sp ３ In this way, the oxocarbon-based compound according to the present disclosure has sp ３ Since the compound has a predetermined number of carbon atoms or more, it can effectively increase the solubility in organic solvents.

[0014] Oxocarbon compounds are compounds containing a cyclic oxocarbon skeleton composed of carbon and oxygen atoms, and due to this structure, have an absorption band in the wavelength range of approximately 600 nm to 1500 nm. Therefore, they can be used as near-infrared absorbing dyes under the name or classification of oxocarbon dyes. Examples of oxocarbon skeletons include a squarylium skeleton represented by formula (1) and a croconium skeleton represented by formula (2). In the oxocarbon compounds according to the present disclosure, a group represented by formula (3) is bonded to the squarylium skeleton or croconium skeleton. In the oxocarbon compounds, the group bonded to the squarylium skeleton or croconium skeleton may contain atoms other than carbon and oxygen atoms, and in formula (3), it contains a nitrogen atom. The group represented by formula (3) may further contain other atoms depending on the substituent.

[0015] Oxocarbon compounds may contain compounds that have a resonance relationship. Examples of compounds that have a resonance relationship with the squarylium compound of formula (1) include compounds represented by the following formulas (1a) and (1b). Examples of compounds that have a resonance relationship with the croconium compound of formula (2) include compounds represented by the following formulas (2a) to (2c). In the following formulas, R in the structure of formula (3) ａ The squarylium compound represented by formula (1) and the croconium compound represented by formula (2) include compounds that are in a resonance relationship with these compounds.

[0016]

[0017]

[0018] In the squarylium compound of formula (1), R １１ and R １２ The squarylium compound of formula (1) is specifically represented by the following formula (1A): In the croconium compound of formula (2), R １３ and R １４ may be the same or different. The squarylium compound of formula (2) is specifically represented by the following formula (2A).

[0019]

[0020]

[0021] In the above formula (1A) and formula (2A), ring A １ and Ring A ２ may be the same or different, and ring B １ and Ring B ２ may be the same or different, R ａ１ and R ａ２ may be the same or different. １ and Ring A ２ For the explanation of ring A, refer to the explanation of ring B. １ and Ring B ２ For the explanation of ring B, refer to the explanation of ring B. ａ１ and R ａ２ The explanation is R ａ Please refer to the explanation in

[0022] In formula (3), ring A represents an unsaturated hydrocarbon ring having 4 to 9 members, and a substituent may be bonded to the unsaturated hydrocarbon ring. Ring A is an unsaturated hydrocarbon ring having a double bond between the carbon atom bonded to the squarylium skeleton or croconium skeleton and the carbon atom at the α-position of the pyrrole ring, and also including the carbon atoms at the α-position and the β-position of the pyrrole ring. Ring A may have an unsaturated bond (preferably a double bond) in addition to the double bond, and preferably has only one unsaturated bond (double bond). Ring A is preferably a 5- to 8-membered ring, and more preferably a 6- to 8-membered ring.

[0023] The presence of ring A in the oxocarbon compound promotes molecular association, which in turn reduces the shoulder peak on the short wavelength side of the absorption peak that has a maximum absorption in the red to near-infrared region, improving the optical properties. In addition, if the oxocarbon compound has ring A, molecular distortion can be suppressed by π-π ＊ The transition band gap is narrowed and the π electron system can be broadened by the ring B, so that the absorption wavelength can be extended to a longer wavelength.

[0024] Examples of the structure of ring A include cycloalkene structures such as cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene (e.g., 1,3-cyclohexadiene), cycloheptene, cycloheptadiene, cycloheptatriene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclononene, cyclononadiene, cyclononatriene, and cyclononatetraene. Of these, cycloalkane monoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are preferred.

[0025] The ring A may have a substituent (hereinafter referred to as "substituent X"), and examples of the substituent X include an organic group and a polar functional group. The following formula (3A) shows a structural formula in which the substituent X is bonded to the ring A and the substituent Y described below is bonded to the ring B in the structural unit of formula (3).

[0026]

[0027] Examples of the organic group of the substituent X include an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, an aryloxycarbonyl group, an arylsulfonyl group, an arylsulfinyl group, a heteroaryl group, an amino group, an amido group, a sulfonamide group, a carboxy group (carboxylic acid group), a cyano group, etc. Examples of the polar functional group of the substituent X include a halogeno group, a hydroxyl group, a nitro group, a sulfo group (sulfonic acid group), etc.

[0028] Examples of the alkyl group for the substituent X include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl; and cyclic (alicyclic) alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. The alkyl group may have a substituent, and examples of the substituent for the alkyl group include an aryl group, a heteroaryl group, a halogeno group, a hydroxyl group, a carboxyl group, an alkoxyl group, a cyano group, a nitro group, an amino group, and a sulfo group. Examples of alkyl groups having a halogeno group include monohalogenoalkyl groups, dihalogenoalkyl groups, alkyl groups having a trihalomethyl unit, and perhalogenoalkyl groups. As the halogeno group, a fluorine atom, a chlorine atom, or a bromine atom is preferred, with a fluorine atom being particularly preferred. The number of carbon atoms in the alkyl group (the number of carbon atoms excluding substituents) is preferably 1 to 20. Specifically, if the alkyl group is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. If the alkyl group is a cyclic alkyl group (alicyclic alkyl group), the number of carbon atoms is preferably 4 to 10, and more preferably 5 to 8.

[0029] For specific examples of the alkyl group contained in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylsulfonyl group, and alkylsulfinyl group of the substituent X, see the above description of the alkyl group.

[0030] Examples of the aryl group for the substituent X include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and an indenyl group. The aryl group may have a substituent, and examples of the substituent that the aryl group has include an alkyl group, an alkoxy group, a heteroaryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. The number of carbon atoms in the aryl group (the number of carbon atoms excluding the substituent) is preferably 6 to 20, and more preferably 6 to 12.

[0031] Examples of the aralkyl group for the substituent X include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a naphthylmethyl 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, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. The number of carbon atoms in the aralkyl group (the number of carbon atoms excluding the substituent) is preferably 7 to 25, and more preferably 7 to 15.

[0032] For specific examples of the aryl group contained in the aryloxy group, arylthio group, aryloxycarbonyl group, arylsulfonyl group, and arylsulfinyl group of the substituent X, see the above description of the aryl group.

[0033] Examples of heteroaryl groups for the substituent X include a thienyl group, a thiopyranyl group, an isothiochromenyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyraridinyl group, a pyrimidinyl group, a pyridazinyl group, a thiazolyl group, an isothiazolyl group, a furanyl group, and a pyranyl group. The heteroaryl group may have a substituent, and examples of the substituent that the heteroaryl group has include an alkyl group, an alkoxy group, an aryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, an amino group, a nitro group, a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. The number of carbon atoms in the heteroaryl group (the number of carbon atoms excluding the substituent) is preferably 2 to 20, and more preferably 3 to 15.

[0034] The amino group of the substituent X is a group represented by the formula: -NR ｂ１ R ｂ２ and R ｂ１ and R ｂ２ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group are described above, and examples of the alkenyl group and the alkynyl group include the alkyl groups exemplified above in which some of the carbon-carbon single bonds have been replaced with double bonds or triple bonds. ｂ１ and R ｂ２ may be linked to each other to form a ring.

[0035] The amide group of the substituent X is an amide group represented by the formula: -NH-C(=O)-R ｂ３ and R ｂ３ is an alkyl group, an aryl group, an aralkyl group, a heteroaryl group, etc. For specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group, see the explanations for these groups above.

[0036] The sulfonamide group of the substituent X is a group represented by the formula: -NH-SO ２ -Rｂ４ and R ｂ４ is an alkyl group, an aryl group, an aralkyl group, a heteroaryl group, etc. For specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group, see the explanations for these groups above.

[0037] Examples of the halogeno group of the substituent X include a fluoro group, a chloro group, a bromo group, and an iodo group.

[0038] The number of substituents X bonded to ring A is preferably not more than the number of members of ring A minus 3. When ring A has substituents X, the number is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. When ring A has multiple substituents X, the multiple substituents X may be the same or different, and the multiple substituents X may each be bonded to different carbon atoms or to a single carbon atom. Ring A may have no substituents.

[0039] The carbon atom at the β-position of the pyrrole ring constituting a part of ring A is substituted with a substituent R ａ An alkyl group or an aryl group is bonded as R ａ For details of the alkyl group and aryl group of R, please refer to the explanation of the alkyl group and aryl group of the substituent X above. ａ The number of carbon atoms in the alkyl group of R is preferably 1 to 6, more preferably 1 to 4, if it is a linear or branched alkyl group, and is preferably 4 to 7, more preferably 5 to 6, if it is a cyclic alkyl group. ａ The alkyl group of R is more preferably a linear or branched alkyl group. ａ The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. ａ Preferred examples of the alkyl group and aryl group in R include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group. ａ In the alkyl group and aryl group, at least a portion of the hydrogen atoms may be replaced by halogen atoms (particularly fluorine atoms).

[0040] In formula (3), ring B represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a fused ring containing these ring structures, and these rings may have a substituent. By having ring B, the oxocarbon compound forms a π electron system that extends over a wide range from the squarylium skeleton or croconium skeleton to ring B via the pyrrole ring, thereby achieving a longer absorption wavelength. By appropriately setting the π conjugated system of ring B, the absorption wavelength of the oxocarbon compound can be easily adjusted, and in the short wavelength region, the maximum absorption wavelength can be adjusted to, for example, about 650 nm. By increasing the number of π electrons in ring B (widening the π conjugated system), the maximum absorption wavelength can be shifted to a longer wavelength, for example, the maximum absorption wavelength can be adjusted to about 1100 nm.

[0041] Examples of the aromatic hydrocarbon ring of ring B include those having 6 to 14 carbon atoms, such as a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluoranthene ring, a cyclotetradecaheptaene ring, etc. The aromatic hydrocarbon ring may have only one ring structure, or may be one in which two or more ring structures are condensed.

[0042] Examples of the aromatic heterocycle of ring B include a 5- or 6-membered monocyclic aromatic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and a bicyclic or tricyclic fused aromatic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, in which 3- to 8-membered rings are fused, specifically 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. The aromatic heterocycle may have only one ring structure, or may have two or more fused ring structures.

[0043] The fused ring of ring B containing an aromatic hydrocarbon ring and an aromatic heterocycle has a structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are fused together, and examples thereof include an indole ring, an isoindole ring, a benzimidazole ring, a quinoline ring, an isoquinoline ring, an acridine ring, a xanthene ring, and a carbazole ring.

[0044] Ring B may have a substituent (hereinafter referred to as "substituent Y"), and examples of the substituent Y include the organic groups and polar functional groups explained above. When ring B has substituents Y, the number of substituents Y is preferably 1 to 3, and more preferably 1 or 2. Ring B may not have a substituent.

[0045] The oxocarbon compound has an sp ３ When the molecule has 3 or more carbon atoms and the ring A has 7 to 9 ring members, sp ３ Oxocarbon compounds have two or more carbon atoms in the molecule. Oxocarbon compounds have one to three fluorine atoms in the molecule. ３ The presence of carbon atoms can increase the solubility in organic solvents.

[0046] sp ３ Carbon atoms are sp ３ It means a carbon atom having a hybrid orbital and a carbon atom having four single bonds. sp ３ The carbon atom may be a trifluoromethyl group (—CF ３ ), a carbon atom of a difluoromethyl group (—CHF ２ ), a carbon atom of a monofluoromethyl group (—CH ２ F), a difluoromethylene group (-CF ２ -), the carbon atom of a monofluoromethylene group (-CHF-), and the carbon atom of a monofluoromethine group (-CF<). ３ The carbon atom may be referred to as a "fluorine-bonded carbon atom."

[0047] The oxocarbon compound preferably has 4 or more fluorine-bonded carbon atoms when the number of members of ring A is 4 to 6. There is no particular upper limit to the number of fluorine-bonded carbon atoms that the oxocarbon compound has, but it is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0048] The fluorine-bonded carbon atom may be a carbon atom constituting ring A. In this case, the sp３ At least one carbon atom is bonded to one or two fluorine atoms, and preferably, sp constituting ring A ３ Two fluorine atoms are bonded to at least one of the carbon atoms.

[0049] The fluorine-bonded carbon atom is R ａ In this case, R ａ is an alkyl group in which at least one hydrogen atom of the alkyl group is replaced with a fluorine atom, i.e., a fluoroalkyl group, or ａ is an aryl group to which a fluoroalkyl group-containing group is bonded. Examples of the fluoroalkyl group-containing group include alkyl groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, alkylsulfonyl groups, and alkylsulfinyl groups, in which at least one hydrogen atom of these groups has been replaced with a fluorine atom. Of these, the fluoroalkyl group-containing group is preferably a fluoroalkyl group.

[0050] The fluorine-bonded carbon atom may be a carbon atom contained in the substituent X bonded to ring A, or may be a carbon atom contained in the substituent Y bonded to ring B. In this case, the substituent X and the substituent Y may be a fluoroalkyl group-containing group. Examples of the fluoroalkyl group-containing group include an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, and an alkylsulfinyl group, and at least one of the hydrogen atoms of these groups is replaced with a fluorine atom. Among these, the fluoroalkyl group-containing group is preferably a fluoroalkyl group.

[0051] The fluoroalkyl group and the fluoroalkyl group-containing group described above preferably have the same or more fluorine atoms as the number of carbon atoms of the alkyl group contained in these groups, and are more preferably perfluoroalkyl groups and perfluoroalkyl group-containing groups. The fluoroalkyl group and the fluoroalkyl group contained in the fluoroalkyl group-containing group preferably have 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms, and are particularly preferably fluoromethyl groups. The fluoromethyl group may be a mono-, di-, or trifluoromethyl group, but is more preferably a trifluoromethyl group.

[0052] Preferred forms of the fluorine-bonded carbon atom include those in which a fluorine atom is bonded to a carbon atom constituting ring A, and those in which a fluorine atom is bonded to a carbon atom constituting ring A, ａ is a fluoroalkyl group, and one in which the substituent Y bonded to ring B contains a fluorine-bonded carbon atom. If a fluorine-bonded carbon atom is contained in such a form, it becomes easy to produce an oxocarbon compound having a fluorine-bonded carbon atom. In the oxocarbon compound, it is preferable that at least the substituent Y contains a fluorine-bonded carbon atom. In this case, all of the fluorine-bonded carbon atoms may be contained in the substituent Y, or a portion of the fluorine-bonded carbon atoms may be contained in the substituent Y, with the remaining portion being contained in a group other than the substituent Y. As the substituent Y containing a fluorine-bonded carbon atom, a fluoroalkyl group is preferable, a fluoromethyl group or a fluoroethyl group is more preferable, and a fluoromethyl group is even more preferable.

[0053] Because the oxocarbon compound according to the present disclosure has excellent solubility in solvents, the present disclosure can provide an oxocarbon compound solution containing the oxocarbon compound represented by formula (1) and a solvent. An organic solvent is preferably used as the solvent, which allows for the production of an oxocarbon compound solution containing a high concentration of the oxocarbon compound. The oxocarbon compound solution can be used as an ink composition, for example, in security inks.

[0054] Examples of solvents that can be used for the oxocarbon compound solution include ketones such as methyl ethyl ketone (dipole moment: 2.76 D), methyl isobutyl ketone (dipole moment: 2.56 D), cyclopentanone, and cyclohexanone (dipole moment: 3.01 D); glycol derivatives (e.g., ether compounds, ester compounds, and ether ester compounds) such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol mono-n-butyl ether (dipole moment: 2.08 D), ethylene glycol monoethyl ether (dipole moment: 2.08 D), and ethylene glycol ethyl ether acetate; amides such as N,N-dimethylacetamide (dipole moment: 3.72 D); ethyl acetate; and propyl acetate. esters such as butyl acetate; pyrrolidones such as N-methyl-pyrrolidone (dipole moment: 4.08 D); aromatic hydrocarbons such as benzene (dipole moment: 0 D), toluene (dipole moment: 0.37 D), and xylene (dipole moment: 0 to 0.44 D); aliphatic hydrocarbons such as cyclohexane and heptane (dipole moment: 0 D); ethers such as tetrahydrofuran (dipole moment: 1.70 D), dioxane, diethyl ether (dipole moment: 1.12 D), and dibutyl ether (dipole moment: 1.22 D); alcohols such as methanol, ethanol, and isopropanol; and halogen-containing aromatic hydrocarbons such as chlorobenzene and o-dichlorobenzene (dipole moment: 2.27 D). These solvents may be used alone or in combination of two or more. Oxocarbon compounds have high durability against solvents with small dipole moments. Therefore, a solvent having a dipole moment of 4.0 D or less is preferred, a solvent having a dipole moment of 3.5 D or less is more preferred, and a solvent having a dipole moment of 3.0 D or less is even more preferred. Specific examples of such solvents include o-dichlorobenzene, cyclopentanone, PGMEA, ethylcyclohexane, xylene, toluene, trimethylbenzene, and limonene. Among these, ketones, glycol derivatives, aliphatic hydrocarbons, and aromatic hydrocarbons are preferred.

[0055] The amount of solvent used may be appropriately set depending on the desired concentration of the oxocarbon compound in the oxocarbon compound solution. The concentration of the oxocarbon compound in the oxocarbon compound solution may be appropriately set within the range of, for example, 0.01 to 10% by mass, and may be 0.05% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, or 5% by mass or less, 3% by mass or less, or 2% by mass or less.

[0056] The oxocarbon compound solution may contain only one type of oxocarbon compound according to the present disclosure, or two or more types. The oxocarbon compound solution may contain another dye in addition to the oxocarbon compound according to the present disclosure, and may contain, for example, at least one dye selected from a near-infrared absorbing dye, a visible light absorbing dye, and an ultraviolet absorbing dye. For details of the near-infrared absorbing dye, the visible light absorbing dye, and the ultraviolet absorbing dye, see the description of the near-infrared absorbing dye, the visible light absorbing dye, and the ultraviolet absorbing dye that can be contained in the resin composition described below.

[0057] The oxocarbon compound according to the present disclosure can be mixed with a resin component to form a resin composition. The resin composition contains at least the oxocarbon compound according to the present disclosure and a resin component. The resin composition according to the present disclosure can be suitably applied to optical filters by forming it into a resin molded product such as a film. Since the oxocarbon compound according to the present disclosure can function as a near-infrared absorbing dye, an optical filter formed from the resin composition according to the present disclosure can be used as a near-infrared cut filter. The resin molded product can also be used as a near-infrared absorbing film or plate that blocks heat rays for energy conservation, a solar cell material that uses visible light and near-infrared light, a specific wavelength absorption filter for a plasma display panel (PDP) or a CCD, etc.

[0058] The resin composition may contain only one type of oxocarbon compound according to the present disclosure, or two or more types of oxocarbon compounds. The resin composition may contain, in addition to the oxocarbon compound according to the present disclosure, other dyes, for example, at least one selected from a near-infrared absorbing dye, a visible light absorbing dye, and an ultraviolet absorbing dye, as long as the desired performance according to the application is ensured.

[0059] If the resin composition further contains a near-infrared absorbing dye and / or a visible light absorbing dye, an optical filter having selective light transmission can be obtained from the resin composition. For example, when the resin composition contains the oxocarbon compound according to the present disclosure and a near-infrared absorbing dye, it can be used as a resin composition for an optical filter that suppresses transmission of light over a wide range from red to near-infrared and preferentially transmits light in the visible light range. When the resin composition contains the oxocarbon compound according to the present disclosure and a visible light absorbing dye, it can be used as a resin composition for a colored filter, a blue light reduction filter, or the like.

[0060] The near-infrared absorbing dye preferably has an absorption maximum in the wavelength range of 600 nm to 1100 nm. More preferably, the near-infrared dye has an absorption peak in the wavelength range of 600 nm to 1100 nm in its absorption spectrum in the wavelength range of 450 nm to 1100 nm, and the absorption maximum of the absorption peak reaches its maximum value in the wavelength range of 450 nm to 1100 nm. The absorption maximum wavelength is more preferably 630 nm or longer, even more preferably 660 nm or longer, and more preferably 1000 nm or shorter, even more preferably 900 nm or shorter, and even more preferably 800 nm or shorter.

[0061] The visible light absorbing dye can be any dye having a maximum absorption wavelength of the maximum absorption peak in the visible light region (for example, a wavelength range of more than 420 nm and less than 680 nm), without any particular limitation. In particular, it is preferable to use a visible light absorbing dye having a maximum absorption wavelength of the maximum absorption peak in the wavelength range of 500 nm or more and less than 680 nm, where visibility is high.

[0062] The near-infrared absorbing dye and the visible light absorbing dye may be organic dyes, inorganic dyes, or organic-inorganic hybrid dyes (e.g., organic compounds with coordinated metal atoms or ions). Examples of near-infrared absorbing dyes and visible light absorbing dyes include squarylium dyes other than the oxocarbon compounds according to the present disclosure, croconium dyes other than the oxocarbon compounds according to the present disclosure, cyclic tetrapyrrole dyes (e.g., porphyrins, chlorins, phthalocyanines, naphthalocyanines, and cholines) that may have copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as a central metal ion, cyanine dyes, azo dyes, quinone dyes, xanthene dyes, indoline dyes, arylmethane dyes, quaterrylene dyes, diimonium dyes, perylene dyes, quinacrylonitrile dyes, oxazine dyes, dipyrromethene dyes, nickel complex dyes, and copper ion dyes. These dyes may be used alone or in combination of two or more. Among these, it is preferable to use at least one selected from the group consisting of squarylium dyes other than the oxocarbon compounds according to the present disclosure, croconium dyes other than the oxocarbon compounds according to the present disclosure, phthalocyanine dyes, cyanine dyes, and dipyrromethene dyes as the near-infrared absorbing dyes, in view of their ability to effectively absorb light of the desired wavelength. It is preferable to use at least one selected from the group consisting of squarylium dyes other than the squarylium compounds according to the present disclosure, croconium dyes other than the oxocarbon compounds according to the present disclosure, phthalocyanine dyes, and cyanine dyes as the near-infrared absorbing dyes. This makes it easy to effectively absorb light in the near-infrared region and increase the visible light transmittance. For example, squarylium compounds and croconium compounds described in JP 2016-074649 A can be used.

[0063] The resin composition may contain an ultraviolet absorbing dye. The ultraviolet absorbing dye preferably has a maximum absorption in the range of 300 nm to 400 nm, for example. By including an ultraviolet absorbing dye in the resin composition, an optical filter having selective light transmission properties in which transmission of light in the ultraviolet to purple region is suppressed can be obtained from the resin composition. Furthermore, deterioration of the resin composition caused by light in the ultraviolet to purple region can be suppressed. Even if the resin composition is exposed to ultraviolet light during storage or during the production and processing of the optical filter (e.g., vapor deposition or mounting), deterioration of the resin component and other components contained in the resin composition, such as oxocarbon-based compounds, from the ultraviolet light can be suppressed.

[0064] As the ultraviolet absorbing dye, known ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylic acid compounds, benzoxazinone compounds, cyanoacrylate compounds, benzoxazole compounds, merocyanine compounds, and triazine compounds can be used. Only one type of ultraviolet absorbing dye may be used, or two or more types may be used. As the ultraviolet absorbing dye (ultraviolet absorber), commercially available substances may be used, such as the Adekastab (registered trademark) series manufactured by ADEKA Corporation, the TINUVIN (registered trademark) series manufactured by BASF, the DiSlyzer (registered trademark) series manufactured by Sankyo Kasei Co., Ltd., the Sumisorb (registered trademark) series manufactured by Sumitomo Chemical Co., Ltd., the Biosorb (registered trademark) series manufactured by Kyodo Pharmaceutical Co., Ltd., and the Seesorb (registered trademark) series manufactured by Shipro Kasei Co., Ltd. can be used. In addition, the ethylene compounds disclosed in JP 2019-014707 A and JP 2022-158995 A can also be used as the ultraviolet absorbing dye.

[0065] In order to achieve the desired performance, the content of the oxocarbon compound in the resin composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.1% by mass or more, based on 100% by mass of the solid content of the resin composition. Furthermore, in order to improve the moldability and film-forming properties of the resin composition, the content of the oxocarbon compound in the resin composition is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on 100% by mass of the solid content of the resin composition. When the resin composition also contains other dyes, the total content of these dyes is preferably within the above range. The solid content of the resin composition refers to the amount of the resin composition excluding the solvent, when the resin composition contains a solvent.

[0066] A known resin can be used as the resin component contained in the resin composition. The resin component is preferably one that is highly transparent and capable of dissolving the oxocarbon-based compound according to the present disclosure. When other dyes are used in combination, the resin component is preferably one that can also dissolve the other dyes. By selecting such a resin component, it is possible to achieve both high transmittance in the wavelength range that is desired to be transmitted and high absorbance in the wavelength range that is desired to be blocked.

[0067] The resin component may be not only a polymerized resin but also a resin raw material (including a resin precursor, raw materials for the precursor, a monomer constituting the resin, etc.) that is incorporated into the resin through a polymerization reaction or a crosslinking reaction when the resin composition is molded; both resins are included in the resin component. In the latter case, the structure of the oxocarbon compound may be partially or completely decomposed by unreacted materials, reactive terminal functional groups, ionic groups, catalysts, acidic / basic groups, etc. present in the reaction liquid obtained by the polymerization reaction. Therefore, if such a concern exists, it is desirable to form the resin composition by blending an oxocarbon compound with a polymerized resin.

[0068] As the resin component, known resins can be used, and it is preferable to use a resin with high transparency. The resin component may be a thermoplastic resin or a thermosetting resin. Examples of the resin component include (meth)acrylic resins, (meth)acrylic urethane resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyolefin resins (e.g., polyethylene resins, polypropylene resins), cycloolefin resins, melamine resins, urethane resins, styrene resins, polyvinyl acetate, polyamide resins (e.g., nylon), aramid resins, polyimide resins, polyamideimide resins, alkyd resins, phenolic resins, epoxy resins, polyester resins (e.g., polybutylene terephthalate (PBT) resins, polyethylene terephthalate (PET) resins, polyarylate resins, etc.), polysulfone resins, butyral resins, polycarbonate resins, poly Examples of suitable resins include ether resins, ABS resins (acrylonitrile butadiene styrene resins), AS resins (acrylonitrile-styrene copolymers), silicone resins, modified silicone resins (e.g., (meth)acrylic silicone resins, alkyl polysiloxane resins, silicone urethane resins, silicone polyester resins, and silicone acrylic resins), and fluorine-based resins (e.g., fluorinated aromatic polymers, polytetrafluoroethylene (PTFE), perfluoroalkoxy fluorine resins (PFA), fluorinated polyaryl ether ketones (FPEK), fluorinated polyimides (FPI), fluorinated polyamic acids (FPAA), and fluorinated polyether nitriles (FPEN)). Among these, (meth)acrylic resins, cycloolefin resins, polyimide resins, polyamide-imide resins, polyester resins, polyarylate resins, polyamide resins, polycarbonate resins, epoxy resins, polysulfone resins, and fluorinated aromatic polymers are preferred from the viewpoints of excellent transparency and heat resistance.

[0069] The (meth)acrylic resin is a polymer having a repeating unit derived from (meth)acrylic acid or its derivative, and for example, a resin having a repeating unit derived from a (meth)acrylic acid ester, such as a poly(meth)acrylic acid ester resin, is preferably used. The (meth)acrylic resin is also preferably one having a ring structure in the main chain, and examples thereof include carbonyl group-containing ring structures such as lactone ring structures, glutaric anhydride structures, glutarimide structures, maleic anhydride structures, and maleimide ring structures; and carbonyl group-free ring structures such as oxetane ring structures, azetidine ring structures, tetrahydrofuran ring structures, pyrrolidine ring structures, tetrahydropyran ring structures, and piperidine ring structures. The carbonyl group-containing ring structures also include structures containing carbonyl group derivative groups such as imide groups. Examples of (meth)acrylic resins having a carbonyl group-containing ring structure that can be used include those described in JP-A Nos. 2004-168882, 2008-179677, WO 2005 / 54311, and 2007-31537.

[0070] The cycloolefin resin is a polymer obtained by polymerizing a cycloolefin as at least a part of a 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 resin include Topas (registered trademark) manufactured by Polyplastics Co., Ltd., Apel (registered trademark) manufactured by Mitsui Chemicals, Inc., Zeonex (registered trademark) and Zeonor (registered trademark) manufactured by Nippon Zeon Co., Ltd., and Arton (registered trademark) manufactured by JSR Corporation.

[0071] Polyimide resins are polymers containing imide bonds in the repeating units of the main chain, and can be produced, for example, by polymerizing tetracarboxylic dianhydride and diamine to obtain polyamic acid, which is then dehydrated and cyclized (imidized). As the polyimide resin, aromatic polyimides in which aromatic rings are linked by imide bonds are preferably used. Examples of polyimide resins that can be used include Kapton (registered trademark) manufactured by DuPont, Aurum (registered trademark) manufactured by Mitsui Chemicals, Inc., Merdin (registered trademark) manufactured by Saint-Gobain, and TPS (registered trademark) TI3000 series manufactured by Toray Plastics Seiko Co., Ltd.

[0072] The polyamide-imide resin is a polymer containing an amide bond and an imide bond in the repeating unit of the main chain. Examples of the polyamide-imide resin include Torlon (registered trademark) manufactured by Solvay Advanced Polymers, Viromax (registered trademark) manufactured by Toyobo Co., Ltd., and TPS (registered trademark) TI5000 series manufactured by Toray Plastics Seiko Co., Ltd.

[0073] The polyester resin is a polymer containing an ester bond in the repeating unit of the main chain, and can be obtained by, for example, condensation polymerization of a polycarboxylic acid (dicarboxylic acid) and a polyalcohol (diol). Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Examples of the polyester resin include the OKP series manufactured by Osaka Gas Chemical Co., Ltd., the TRN series manufactured by Teijin Limited, Teonex (registered trademark), Rynite (registered trademark) manufactured by DuPont, Novapex (registered trademark) manufactured by Mitsubishi Chemical Corporation, Novaduran (registered trademark) manufactured by Mitsubishi Engineering Plastics Corporation, and Lumirror (registered trademark) and Toraycon (registered trademark) manufactured by Toray Industries, Inc.

[0074] The polyarylate resin is a polymer obtained by condensation polymerization of a dihydric phenol compound and a dibasic acid (e.g., an aromatic dicarboxylic acid such as phthalic acid), and has a repeating unit containing an aromatic ring and an ester bond in the repeating unit of the main chain. Examples of the polyarylate resin that can be used include Vectran (registered trademark) manufactured by Kuraray Co., Ltd. and U-Polymer (registered trademark) manufactured by Unitika Ltd.

[0075] Polyamide resins are polymers containing amide bonds in the repeating units of their main chains, and can be obtained, for example, by condensation polymerization of diamines and dicarboxylic acids. Polyamide resins may have an aliphatic skeleton in their main chains, and nylon, for example, can be used as such an amide resin. Polyamide resins may have an aromatic skeleton, and aramid resins are known as such polyamide resins. Aramid resins are preferably used because of their excellent heat resistance and high mechanical strength, and examples of such aramid resins include Twaron (registered trademark) and Conex (registered trademark) manufactured by Teijin Limited, and Kevlar (registered trademark) and Nomex (registered trademark) manufactured by DuPont.

[0076] Polycarbonate resin is a polymer containing a carbonate group (—O—(C═O)—O—) in the repeating unit of the main chain. Examples of polycarbonate resins that can be used include Panlite (registered trademark) manufactured by Teijin Limited, Iupizeta (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Inc., Iupilon (registered trademark), Novarex (registered trademark), and Zanter (registered trademark) manufactured by Mitsubishi Engineering Plastics Corporation, and SD Polyca (registered trademark) manufactured by Sumika Styron Polycarbonate Co., Ltd.

[0077] Epoxy resins are resins that can be cured by crosslinking an epoxy compound (prepolymer) in the presence of a curing agent or curing catalyst. Examples of epoxy compounds include aromatic epoxy compounds, aliphatic epoxy compounds, alicyclic epoxy compounds, and hydrogenated epoxy compounds. Examples of such epoxy compounds include fluorene epoxy (Oxol (registered trademark) PG-100) manufactured by Osaka Gas Chemicals Co., Ltd., bisphenol A epoxy compound (JER (registered trademark) 828EL) and hydrogenated bisphenol A epoxy compound (JER (registered trademark) YX8000) manufactured by Mitsubishi Chemical Corporation, and alicyclic liquid epoxy compound (Celloxide (registered trademark) 2021P, EHPE-3150) manufactured by Daicel Corporation.

[0078] Polysulfone resins consist of aromatic rings and sulfonyl groups (-SO ２The polysulfone resin is a polymer having a repeating unit containing a hydroxyl group (-) and an oxygen atom. Examples of polysulfone resins that can be used include Sumikaexcel (registered trademark) PES3600P and PES4100P manufactured by Sumitomo Chemical Co., Ltd., and UDEL (registered trademark) P-1700 manufactured by Solvay Specialty Polymers.

[0079] The fluorinated aromatic polymer is a polymer having a repeating unit containing 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, and among these, a polymer essentially containing a repeating unit containing an aromatic ring having one or more fluorine atoms and an ether bond is preferred. As the fluorinated aromatic polymer, for example, those described in JP 2008-181121 A can be used.

[0080] The resin preferably has high transparency, which makes it easier to suitably apply the resin composition to optical applications. For example, the resin preferably has a total light transmittance of 75% or more at a thickness of 0.1 mm, more preferably 80% or more, and even more preferably 85% or more. The upper limit of the total light transmittance of the resin is not particularly limited, and the total light transmittance may be 100% or less, but may be, for example, 95% or less. The total light transmittance is measured based on JIS K 7105.

[0081] The glass transition temperature (Tg) of the resin is not particularly limited, but is preferably relatively high, which can improve the heat resistance of the resin layer formed from the resin composition. The glass transition temperature of the resin is, for example, preferably 110°C or higher, more preferably 120°C or higher, and even more preferably 130°C or higher. The upper limit of the glass transition temperature of the resin is not particularly limited, but is preferably, for example, 380°C or lower, from the viewpoint of improving the moldability of the resin composition.

[0082] The resin component preferably has high transparency, which makes it easier to suitably apply the resin composition to optical 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 even 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, but may be, for example, 95% or less. The total light transmittance is measured based on JIS K 7105.

[0083] The resin composition may contain a solvent. For example, when the resin composition is a paint-formed resin composition, the inclusion of a solvent makes it easier to apply the resin composition. A resin composition containing a solvent can also be used as an ink composition.

[0084] The solvent may function to dissolve each component contained in the resin composition or may function as a dispersion medium, but is preferably one that dissolves the oxocarbon-based compound according to the present disclosure. As the solvent, any of the solvents that can be used for the oxocarbon-based compound solution described above can be used.

[0085] The content of the solvent is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, and preferably less than 100% by mass, more preferably 95% by mass or less, based on 100% by mass of the resin composition. By adjusting the content of the solvent within this range, it becomes easier to obtain a resin composition with a high concentration of the oxocarbon compound.

[0086] The resin composition may contain a surface conditioner, which can prevent appearance defects such as striations and dents from occurring in the resin layer when the resin composition is cured to form a resin layer. The type of surface conditioner is not particularly limited, and siloxane-based surfactants, acetylene glycol-based surfactants, fluorine-based surfactants, acrylic leveling agents, etc. can be used. Examples of surface conditioners that can be used include the BYK (registered trademark) series manufactured by BYK-Chemie and the KF series manufactured by Shin-Etsu Chemical Co., Ltd.

[0087] The resin composition may contain a dispersant, which stabilizes the dispersibility of the oxocarbon compound even when a portion of the oxocarbon compound is present in a dispersed state in the resin composition, thereby suppressing re-aggregation of the oxocarbon compound. The type of dispersant is not particularly limited, and examples that can be used include the EFKA series manufactured by EFKA Additives, the BYK (registered trademark) series manufactured by BYK-Chemie, the Solsperse (registered trademark) series manufactured by The Lubrizol Corporation of Japan, the Disparlon (registered trademark) series manufactured by Kusumoto Chemicals, Ltd., the Ajisper (registered trademark) series manufactured by Ajinomoto Fine-Techno Co., Ltd., the KP series manufactured by Shin-Etsu Chemical Co., Ltd., the Polyflow series manufactured by Kyoeisha Chemical Co., Ltd., the Megafac (registered trademark) series manufactured by DIC Corporation, and the Disper Aid series manufactured by San Nopco.

[0088] The resin composition may contain a silane coupling agent or its hydrolysate or hydrolyzed condensate, which can enhance the adhesion of the resin layer to the substrate when the resin composition is cured on a substrate to form a resin layer.

[0089] The resin composition may contain various additives such as a plasticizer, a surfactant, a viscosity modifier, an antifoaming agent, an antiseptic, and a resistivity modifier, as required.

[0090] A molded article can be obtained by forming the resin composition into a predetermined shape. The molded article may be formed by curing the resin composition by heating (softening) and cooling it, by curing it through a reaction of the resin components (e.g., a polymerization reaction or a crosslinking reaction), or by curing it by removing the solvent contained in the resin composition. Examples of the resin composition that can be used include thermoplastic resin compositions that can be molded by injection molding, extrusion molding, etc., and resin compositions that have been made into paints so that they can be applied by spin coating, solvent casting, roll coating, spray coating, bar coating, dip coating, screen printing, flexographic printing, inkjet printing, etc.

[0091] When the resin composition is a thermoplastic resin composition, a molded article 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 molded article can be obtained by blending an oxocarbon compound with a thermoplastic resin and then heat-molding the mixture. For example, the oxocarbon compound can be added to a powder or pellet of a base resin, heated to approximately 150°C to 350°C, dissolved, and then molded. The shape of the molded article is not particularly limited, and examples include plate-like, sheet-like, granular, powder-like, block-like, particle aggregate-like, spherical, oval-spherical, lenticular, cubic, columnar, rod-like, conical, cylindrical, needle-like, fibrous, hollow fiber-like, and porous shapes. Furthermore, additives commonly used in resin molding, such as plasticizers, can be added when kneading the resin.

[0092] When the resin composition is a paint-formed resin composition, a liquid or paste-like resin composition containing an oxocarbon compound can be applied to a substrate (e.g., a resin plate, a film, a glass plate, etc.) to obtain a film-like molded article having a thickness of 200 μm or less or a sheet-like molded article having a thickness of more than 200 μm. The molded article thus obtained can be peeled from the substrate and handled as a film or sheet, or can be handled integrally with the substrate.

[0093] The molded article of the resin composition may be composed of a single resin layer (a layer formed by curing the resin composition) or may be composed of multiple resin layers. When the molded article is handled as an integral part of a substrate, the molded article may be formed on only one side of the substrate, or on both sides. Note that the molded article and the substrate may also be integrated by thermocompression bonding or chemical bonding a molded article formed from the resin composition to the substrate.

[0094] The resin composition according to the present disclosure can be preferably used as a resin composition for forming filters used in various applications such as optical devices, display devices, mechanical parts, and electrical / electronic parts. The resin composition and its molded article can be suitably applied to optical filters such as near-infrared cut filters, and the optical filter thus formed has a resin layer formed from the resin composition according to the present disclosure. The optical filter may be formed from a single or multiple resin layers, or may be formed integrally with a support.

[0095] A filter integrated with a support can be formed, for example, by applying the resin composition to the surface of the support (or, if another layer such as a binder layer is present between the support and the resin layer, to the surface of the other layer) by spin coating or solvent casting, followed by drying or curing. Alternatively, a filter can be formed by thermocompression bonding a sheet-shaped molded article formed from the resin composition to the support.

[0096] The resin layer formed from the resin composition may be provided on only one side of the support, or on both sides. The thickness of the resin layer is not particularly limited, but from the viewpoint of ensuring the desired near-infrared cut performance, it is, for example, preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, and preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. When the resin layer is formed by coating a paint-formed resin composition on the support, the strength of the filter can be ensured by the support, so the thickness of the resin layer can be further reduced. When the resin layer is formed on the support, the thickness of the resin layer is, for example, preferably 50 μm or less, more preferably 20 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less.

[0097] As the support, it is preferable to use a transparent substrate such as a resin plate, resin film, or glass plate. The resin plate or resin film used as the support is preferably formed from, for example, the resin components described above. From the viewpoint of improving the heat resistance of the optical filter, it is preferable to use a glass substrate as the support, and the optical filter thus formed can be mounted on an electronic component, for example, by solder reflow. Furthermore, since glass substrates are less likely to crack or warp even when exposed to high temperatures, adhesion with the resin layer is more easily ensured. When a glass substrate is used as the support, a binder layer formed from, for example, a silane coupling agent may be provided between the support and the resin layer, thereby improving the adhesion between the resin layer and the glass substrate. Incidentally, the adhesion between the resin layer and the glass substrate can also be improved by adding a silane coupling agent as an adhesion improver to the resin composition forming the resin layer.

[0098] The thickness of the support (substrate) is, for example, preferably 0.05 mm or more, more preferably 0.1 mm or more, from the viewpoint of ensuring strength, and is preferably 0.4 mm or less, more preferably 0.3 mm or less, from the viewpoint of thinning.

[0099] A protective layer made of the same or a different resin as that of the resin layer may be laminated as a second resin layer on the resin layer formed from the resin composition. By providing a protective layer, the durability (decomposition resistance) of the oxocarbon-based compound contained in the resin layer can be increased. The protective layer may be provided on only one side of the resin layer or on both sides. When the resin layer is provided on a support, the protective layer is preferably provided on the side of the resin layer opposite the support.

[0100] When an optical filter is formed from the resin composition, the optical filter may have a layer (anti-reflection film) having anti-reflection or anti-glare properties that reduce reflections from fluorescent lights, etc., a layer having scratch resistance, a transparent substrate having other functions, etc. The optical filter may have a near-infrared reflective film or an ultraviolet reflective film. These anti-reflection films, reflective films, or other layers are preferably provided on the light incident side of the resin layer.

[0101] Near-infrared reflective films, ultraviolet reflective films, and anti-reflection films (visible light anti-reflection films) can be composed of dielectric films. The dielectric film is typically composed of a dielectric multilayer film in which high-refractive index material layers and low-refractive index material layers are alternately stacked, but it may also be composed of only one of the high-refractive index material layers and the low-refractive index material layers. The high-refractive index material layer can be composed of a material with a refractive index of 1.7 or higher. A material with a refractive index ranging from 1.7 to 2.5 is preferably selected, with a refractive index ranging from 1.8 or higher being more preferred, and a refractive index of 2.0 or higher being even more preferred. Examples of materials that can be used to compose 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; nitrides such as silicon nitride; mixtures of these oxides and nitrides, and mixtures thereof doped with metals such as aluminum and copper or carbon (e.g., tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO)). The material constituting the low refractive index material layer can be a material with a refractive index of less than 1.7, and preferably a material with a refractive index in the range of 1.2 to 1.6, and more preferably a material with a refractive index in the range of 1.3 to 1.5. Examples of materials constituting the low refractive index material layer include silicon oxide (silica, SiOx (x = 1 to 2)), alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride. Among these, the high refractive index material layer is preferably composed of titanium oxide, and the low refractive index material layer is preferably composed of silicon oxide.

[0102] The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably adjusted to a range of 0.1λ to 0.5λ, more preferably 0.2λ to 0.3λ, of the wavelength λ (nm) of light to be blocked. By forming the dielectric film in this manner, it is possible to selectively reflect light in a desired wavelength range, and the dielectric film can be used to form a near-infrared reflective film, an ultraviolet reflective film, an anti-reflective film (visible light anti-reflective film), etc. The ultraviolet reflective film and the near-infrared reflective film may be a single film that has both ultraviolet and near-infrared reflective functions.

[0103] The number of layers in the dielectric film is not particularly limited as long as it is one or more, but from the viewpoint of exhibiting the desired optical performance as a near-infrared reflective film, an ultraviolet reflective film, an anti-reflection film, etc., it is preferably, for example, 2 to 80 layers. The number of layers in the dielectric film may be 5 or more, 10 or more, or 20 or more, and may be 70 or less, or 60 or less. The thickness of the dielectric film is not particularly limited and may be, for example, in the range of 0.01 μm to 10 μm, but from the viewpoint of sufficiently blocking the incidence of light in the desired wavelength range, it is preferably 0.02 μm or more, more preferably 0.03 μm or more, and from the viewpoint of thinning, it is preferably 5 μm or less, more preferably 3 μm or less.

[0104] The optical filter may have an aluminum vapor deposition film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as the main component and a small amount of tin oxide are dispersed, or the like.

[0105] The thickness of the optical filter is preferably, for example, 1 mm or less. This makes it possible to fully meet the demand for miniaturization of image sensors, for example. The thickness of the optical filter is more preferably 500 μm or less, even more preferably 300 μm or less, and even more preferably 150 μm or less, and is preferably 30 μm or more, and even more preferably 50 μm or more.

[0106] Optical filters can be used as one of the components of sensors such as image sensors (imaging elements), illuminance sensors, and proximity sensors. For example, image sensors are used as electronic components that convert light from a subject into an electrical signal or the like and output the signal, and examples of such sensors include CCDs (Charge Coupled Devices) and CMOSs ​​(Complementary Metal-Oxide Semiconductors). Image sensors can be used in mobile phone cameras, digital cameras, in-vehicle cameras, surveillance cameras, display elements (LEDs, etc.), and the like. The 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.) and lenses, as necessary.

[0107] This application claims the benefit of priority based on Japanese Patent Application No. 2024-125041, filed on July 31, 2024. The entire contents of the specification of Japanese Patent Application No. 2024-125041, filed on July 31, 2024, are incorporated herein by reference.

[0108] The contents of the present disclosure will be explained in more detail below using examples, but the contents of the present disclosure are not limited to the following examples, and can be implemented with appropriate modifications within the scope that is consistent with the intent described above and below, and all of these modifications are included in the technical scope of the present disclosure.

[0109] (1) Synthesis of Compounds (1-1) Synthesis Example 1: Synthesis of Squarylium Compound 1 7.21 g (0.120 mol) of potassium hydroxide and 150 mL of dimethyl sulfoxide were placed in a 300 mL four-neck flask and stirred at room temperature for 30 minutes. Next, a mixed solution of 5.68 g (0.040 mol) of iodomethane and 4.49 g (0.040 mol) of cyclooctanone was added dropwise, and the mixture was heated to an internal temperature of 40°C. The reaction was allowed to proceed with stirring for 2 hours. After completion of the reaction, the reaction solution, 200 mL of ethyl acetate, and 300 mL of water were added to a separatory funnel and vigorously stirred to extract the organic phase. Anhydrous magnesium sulfate was added to the extracted organic phase for dehydration. Solids (inorganic components) were filtered from this organic phase, and the solvent was then distilled off using an evaporator. After the solvent was distilled off, the mixture was dried at 40°C for 12 hours using a vacuum dryer, yielding 2.85 g of 2-methylcyclooctanone. The yield based on cyclooctanone was 56.5 mol %.

[0110] Next, 5.07 g (0.024 mol) of 2-trifluoromethylphenylhydrazine hydrochloride, 3.03 g (0.024 mol) of the 2-methylcyclooctanone obtained above, and 24 g of t-amyl alcohol were placed in a 300 mL four-neck flask, and the mixture was allowed to react for 7 hours at 100 °C while stirring using a magnetic stirrer under a nitrogen flow (10 mL / min). After completion of the reaction, the reaction solution, 200 mL of ethyl acetate, and 300 mL of water were added to a separatory funnel and vigorously stirred to extract the organic phase, and anhydrous magnesium sulfate was added to the extracted organic phase for dehydration. After filtering off the solids (inorganic components) from this organic phase, the solvent was distilled off using an evaporator. After distilling off the solvent, the mixture was dried at 60 °C for 12 hours using a vacuum dryer, yielding 4.33 g of Intermediate 1A. The yield relative to 2-trifluoromethylphenylhydrazine hydrochloride was 67.5 mol%.

[0111] Next, 4.43 g (0.016 mol) of the intermediate 1A obtained above, 1.82 g (0.016 mol) of squaric acid, 60 g of 1-butanol, and 60 g of toluene were placed in a 300 mL four-neck flask, and the mixture was stirred using a magnetic stirrer under a nitrogen flow (10 mL / min). The mixture was then reacted for 3 hours under reflux conditions while removing the eluted water using a Dean-Stark apparatus. After completion of the reaction, the solvent was removed using an evaporator, and then 60 g of methanol was added. Crystallization and washing were carried out while stirring for 30 minutes under reflux conditions. The solution was cooled to room temperature, and the cake obtained by filtration was dried at 60°C for 12 hours using a vacuum dryer. After that, it was appropriately purified by silica column chromatography (developing solvent: a mixture of chloroform and hexane), and 10.3 g of the target squarylium compound 1 was obtained. The yield relative to squaric acid was 62.3 mol%.

[0112]

[0113] (1-2) Synthesis Example 2: Synthesis of squarylium compound 2 The squarylium compound 2 shown in Table 1 was obtained in the same manner as in Synthesis Example 1, except that 4-trifluoromethylphenylhydrazine hydrochloride was used instead of 2-trifluoromethylphenylhydrazine hydrochloride in Synthesis Example 1. The yield based on squaric acid was 49.1 mol %.

[0114] (1-3) Synthesis Example 3: Synthesis of squarylium compound 3 The squarylium compound 3 shown in Table 1 was obtained in the same manner as in Synthesis Example 1, except that 3-trifluoromethylphenylhydrazine hydrochloride was used instead of 2-trifluoromethylphenylhydrazine hydrochloride in Synthesis Example 1. The yield based on squaric acid was 23.1 mol %.

[0115] (1-4) Synthesis Example 4: Synthesis of squarylium compound 4 The squarylium compound 4 shown in Table 1 was obtained in the same manner as in Synthesis Example 1, except that 3,5-bistrifluoromethylphenylhydrazine hydrochloride was used instead of 2-trifluoromethylphenylhydrazine hydrochloride in Synthesis Example 1. The yield based on squaric acid was 8.6 mol %.

[0116] (1-5) Synthesis Example 5: Synthesis of squarylium compound 5

[0079] The squarylium compound 5 shown in Table 1 was obtained in the same manner as in Synthesis Example 1, except that cyclohexanone was used instead of cyclooctanone and 3,5-bistrifluoromethylphenylhydrazine hydrochloride was used instead of 2-trifluoromethylphenylhydrazine hydrochloride. The yield based on squaric acid was 9.1 mol%.

[0117] (1-6) Synthesis Example 6: Synthesis of comparative squarylium compound 1 Comparative squarylium compound 1 was synthesized according to the method described in Example 1-18 of JP-A 2016-074649.

[0118] (1-7) Synthesis Example 7: Synthesis of comparative squarylium compound 2 Comparative squarylium compound 2 was synthesized according to the method described in Example 1-23 of JP-A 2016-074649.

[0119]

[0120] (2) Oxocarbon Compound Solution (2-1) Evaluation of Solubility A predetermined amount of squarylium compounds 1 to 5 and comparative squarylium compounds 1 and 2 shown in Table 1 was added to toluene placed in a 10 mL glass sample bottle, and the mixture was stirred at 25°C for 1 hour. The squarylium compounds were added to toluene so that the molar ratio of squarylium compound to toluene was 0.20 mol%:99.80 mol%. The resulting solution was visually inspected for the presence or absence of insoluble residues. When no insoluble residues were observed, the solubility was evaluated as A, and when insoluble residues were observed, the solubility was evaluated as B. The results are shown in Table 2. Squarylium compounds 1 to 5 exhibited high solubility in toluene.

[0121] (2-2) Spectroscopic Measurement Chloroform or toluene solutions of squarylium compounds 1 to 5 and comparative squarylium compounds 1 and 2 were prepared, and their absorption spectra were measured in the wavelength range of 300 nm to 1100 nm. The concentration of each squarylium compound solution was adjusted so that the transmittance at the absorption maximum wavelength was 10% (±0.05%). The light transmittance was measured at a measurement interval of 1 nm using a spectrophotometer (Shimadzu Corporation, UV-1800), and the wavelength at which absorption was maximum in the wavelength range of 300 nm to 1100 nm (maximum absorption wavelength λmax) was determined. The results are shown in Table 2.

[0122]

[0123] (3) Resin Composition (3-1) Preparation of Resin Composition 1: A 2-liter reaction vessel equipped with a stirring blade was charged with 10.01 g (0.044 mol) of 2,2'-bis(4-hydroxyphenyl)propane, 3.59 g (0.090 mol) of sodium hydroxide, and 300 g of ion-exchanged water. After dissolving, 0.89 g (0.009 mol) of triethylamine was added and dissolved. A solution of 3.57 g (0.021 mol) of terephthalic acid dichloride and 3.57 g (0.021 mol) of isophthalic acid dichloride dissolved in 500 g of methylene chloride was placed in a dropping funnel, which was then attached to the reaction vessel. The solution in the reaction vessel was stirred while maintaining the temperature at 20°C, and the methylene chloride solution was added dropwise from the dropping funnel over 60 minutes. Further, a solution of 0.71 g (0.005 mol) of benzoyl chloride dissolved in 10 g of methylene chloride was added thereto and stirred for 60 minutes. The resulting reaction solution was neutralized with an aqueous acetic acid solution, the pH of the aqueous phase was adjusted to 7, and the oil and aqueous phases were separated using a separatory funnel. The resulting oil phase was added dropwise to methanol under stirring to reprecipitate the polymer, and the precipitate was collected by filtration and dried in an oven at 80°C to obtain a white solid polyarylate resin. The yield was 11.5 g. The weight average molecular weight (Mw) of the resulting polyarylate resin was 33,780 and the number average molecular weight (Mn) was 8,130. The weight average molecular weight and number average molecular weight of the polyarylate resin were polystyrene-equivalent values ​​determined by gel permeation chromatography.

[0124] 100 parts by mass of the polyarylate resin obtained above was added to a mixed solvent of 283 parts by mass of toluene and 283 parts by mass of o-xylene, and 3.3 parts by mass of comparative squarylium compound 1 as a near-infrared absorbing dye, 1.1 parts by mass of squarylium compound A shown below, 8 parts by mass of ultraviolet absorbing dye A, and 0.52 parts by mass of BYK-330 (polyether-modified polydimethylsiloxane) manufactured by BYK-Chemie KK as a surface conditioner were added and mixed uniformly to obtain resin composition 1.

[0125]

[0126] (3-2) Preparation of Resin Composition 2 24.7 parts by weight of 3-glycidoxypropyltrimethoxysilane (Dow-Toray, OFS-6040), 32.1 parts by weight of 2-propanol, and 3.4 parts by weight of distilled water were blended and mixed uniformly at 25 ° C., and then 1.54 parts by weight of formic acid was added and mixed for 90 minutes to allow the hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane to proceed, thereby preparing a hydrolysis solution of the silane coupling agent. The resin composition 1 obtained above and the hydrolysis solution of the silane coupling agent were mixed uniformly at 25 ° C. in a mass ratio of 99:1, and the mixture was filtered through a 0.1 μm pore size filter (GL Sciences, GL Chromatodisc, non-aqueous 13N) to remove foreign matter, thereby obtaining a resin composition 2.

[0127] (3-3) Preparation of Resin Composition 3 Resin composition 3 was obtained in the same manner as in the preparation example of Resin Composition 1, except that squarylium compound 2 shown in Table 1 was used instead of comparative squarylium compound 1 in the preparation example of Resin Composition 1.

[0128] (3-4) Preparation of Resin Composition 4 Resin composition 4 was obtained in the same manner as in the preparation example of Resin Composition 2, except that Resin Composition 3 was used instead of Resin Composition 1 in the preparation example of Resin Composition 2.

[0129] (4) Optical Filter (4-1) Preparation of Optical Filter Each resin composition obtained above was dropped in 2 cc onto a glass substrate (Schott, D263Teco), and then a spin coater (Mikasa, 1H-D7) was used to rotate the resin composition at 1600 rpm over 0.2 seconds, maintain the rotation speed for 20 seconds, and then reduce the rotation speed to 0 rpm over 0.2 seconds. The resin composition was then deposited on the glass substrate. The glass substrate on which the resin composition was deposited was initially dried at 100 ° C. for 3 minutes using a precision incubator (Yamato Scientific, DH611) (before curing). Thereafter, the atmosphere was substituted with nitrogen at 50 ° C. for 30 minutes using an inert oven (Yamato Scientific, DN610I), and then heated to 190 ° C. in about 15 minutes. The resin layer (absorption layer) was formed on the glass substrate by drying at 190 ° C. for 60 minutes under a nitrogen atmosphere (after curing). The thickness of the resin layer formed on the glass substrate was 2 μm. An optical filter was produced by forming a resin layer on the glass substrate in this manner. The thickness of the resin layer was determined by measuring the thickness of the glass substrate on which the resin layer was formed and the thickness of the glass substrate alone using a micrometer, and then calculating the difference between the two.

[0130] (4-2) Measurement of Transmission Spectrum For each optical filter having a resin layer formed on a glass substrate, the transmission spectrum was measured at a measurement interval of 1 nm using a spectrophotometer (Shimadzu Corporation, UV-1800), and the transmittance of light at wavelengths of 300 nm to 900 nm was determined. The transmission spectra were measured for the optical filters before and after curing of the resin layer. The results for the optical filter formed from resin composition 2 are shown in Figure 1, and the results for the optical filter formed from resin composition 4 are shown in Figure 2.

[0131] The oxocarbon compounds according to the present disclosure can be used, for example, in electronic components such as mobile phone cameras, digital cameras, in-vehicle cameras, surveillance cameras, and display elements (LEDs, etc.), as well as in security inks.

Claims

1. An oxocarbon compound represented by the following formula (1) or (2): [In formula (1) and formula (2), R １１ ~R １４ each independently represents a structural unit represented by the following formula (3): [In formula (3), ring A represents an optionally substituted 4- to 9-membered unsaturated hydrocarbon ring, ring B represents an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocycle, or a fused ring containing any of these ring structures, optionally having a substituent, and R ａ represents an alkyl group or an aryl group, and * represents a bonding site with the 4-membered ring in formula (1) or the 5-membered ring in formula (2).] When the ring A has 4 to 6 ring members, sp ３ When the ring A has 7 to 9 ring members, sp ３ An oxocarbon compound that has two or more carbon atoms in the molecule.

2. The ring B has a substituent, and the substituent is the sp ３ The oxocarbon compound according to claim 1, which contains carbon atoms.

3. A resin composition comprising the oxocarbon compound according to claim 1 or 2 and a resin component.

4. A molded article formed from the resin composition according to claim 3.

5. An optical filter having a resin layer formed from the resin composition according to claim 3.

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