JP6581374B2 - Method for storing or using a composition comprising an oxocarbon-based compound - Google Patents

Description

The present invention relates to a composition containing an oxocarbon-based compound as well as a method for storing or using the composition containing an oxocarbon-based compound.

An oxocarbon-based compound is a compound containing a cyclic oxocarbon group composed only of carbon and oxygen, and has an absorption band in the vicinity of a wavelength of 600 to 1500 nm derived from its structure. in use. As a product using an oxocarbon compound, for example, a filter for a plasma display panel containing a squarylium compound which is a kind of oxocarbon compound, an antioxidant and an ultraviolet absorber has been developed (Patent Document 1). The light resistance of the filter is improved by using an antioxidant.

JP 2001-350013 A

In general, as in Patent Document 1, in a product containing a pigment, degradation of the pigment by light may be a problem. In Patent Document 1, the light resistance is improved by using an antioxidant together with the squarylium compound. However, even if an antioxidant is not used, a device for suppressing deterioration of the oxocarbon compound by light is proposed. There was room.

In addition, many products placed on the market may be exposed to a high temperature environment in the manufacturing stage, and therefore, it is required that they can be stably exhibited without deterioration of various physical properties even after being exposed to a high temperature environment. In other words, although heat resistance is required, there has never been a literature or the like that has examined heat resistance of products using oxocarbon compounds. For example, Patent Document 1 does not discuss heat resistance.

The present invention has been made in view of the above situation, and includes a method that enables a composition containing an oxocarbon compound to be stably stored or used, and a stable state that includes an oxocarbon compound. An object is to provide a composition.

The inventors of the present invention have studied various products using oxocarbon compounds, and have found that the physical properties derived from oxocarbon compounds change depending on the type of solvent used during storage or use. It was found that the moment affects the stability with oxocarbon compounds. When the oxocarbon-based compound is stored or used in the presence of a solvent having a dipole moment within a predetermined range, that is, stored or used in a composition containing the oxocarbon-based compound and the solvent, light or heat It is found that the decomposition and reaction of oxocarbon compounds due to aging is sufficiently suppressed and can be stably stored or used, and that such a composition is in a stable state, and the above-mentioned problems can be solved brilliantly. The present invention was reached.

That is, the present invention is a method for storing or using a composition containing an oxocarbon-based compound, and the composition is a method for storing or using a solvent having a dipole moment of 4D or less together with an oxocarbon-based compound. is there.
The present invention is also a composition comprising an oxocarbon-based compound and a solvent having a dipole moment of 4D or less.
The present invention is described in detail below. A form in which two or three or more preferred forms of the present invention described below are combined is also a preferred form of the present invention.

In this specification, storage and use shall include storage, transport and transportation. Further, in the present invention, “stable storage or use of a composition containing an oxocarbon-based compound” means storage or use in a state in which decomposition or reaction over time of the oxocarbon-based compound is sufficiently suppressed. means.

[Method of storing or using the composition]
In the method of storage or use of the present invention (hereinafter also referred to as storage / use method), a solvent having a dipole moment of 4D or less is used. That is, the composition to be stored / used includes a solvent having a dipole moment of 4D or less together with an oxocarbon compound, but may further include a resin. Thus, the form in which the composition further contains a resin is a preferred form of the present invention. Moreover, you may further contain other components (for example, another pigment | dye, an additive, etc.) as needed.
Each component can be used alone or in combination of two or more.

Hereinafter, essential or optional components contained in the composition will be described.
-Solvent-
In the present invention, a solvent having a dipole moment of 4D (Debye) or less is used as a solvent. By using a solvent having a dipole moment of 4D or less in combination with an oxocarbon compound, the physical properties of the oxocarbon compound due to light and heat can be sufficiently suppressed, and can be stably stored or used. The dipole moment of the solvent is preferably 3.5D or less, more preferably 3D or less. Thus, it is particularly preferable that the solvent has a dipole moment of 3D or less. The lower limit of the dipole moment is not particularly limited, and is preferably 0D or more.

Examples of the solvent having a dipole moment of 4D or less include the following compounds, and one or more of these can be used.
Methyl ethyl ketone (also called 2-butanone) (dipole moment: 2.76D), methyl isobutyl ketone (also called 4-methyl-2-pentanone), cyclopentanone (dipole moment: 3.3D), cyclohexanone (dipole) Ketones such as moment: 3.01D);
PGMEA (also called 2-acetoxy-1-methoxypropane or propylene glycol monomethyl ether acetate) (dipole moment: 1.8D), ethylene glycol mono-n-butyl ether (dipole moment: 2.08D), ethylene glycol monoethyl Ethers (dipole moment: 2.08D), glycol derivatives such as ethylene glycol ethyl ether acetate (for example, ether compounds, ester compounds, ether ester compounds, etc.);
Ethers such as tetrahydrofuran (dipole moment: 1.70D), dioxane (dipole moment: 3.0D), diethyl ether (dipole moment: 1.12D), dibutyl ether (dipole moment: 1.22D);
Esters such as ethyl acetate, propyl acetate, butyl acetate;
Alcohols such as methyl cellosolve (also called 2-methoxyethanol) (dipole moment: 2.1D);
Amides such as N, N-dimethylacetamide (dipole moment: 3.72D);
Pyrrolidones such as N-methyl-pyrrolidone (more specifically, 1-methyl-2-pyrrolidone (dipole moment: 4.08D));
Aromatic hydrocarbons such as toluene (dipole moment: 0.37D), xylene (dipole moment: 1D or less);
Aliphatic hydrocarbons such as cyclohexane, ethylcyclohexane (dipole moment: 0D), heptane (dipole moment: 0.0D), limonene (dipole moment: 1D or less);
Halogen-containing aromatic hydrocarbons such as chlorobenzene and o-dichlorobenzene (dipole moment: 2.27D);

Among these, ketones containing a ring structure (referred to as cyclic ketones); ethers containing a ring structure (also referred to as cyclic ethers); chain-structured alcohols (also referred to as chain alcohols); Acetates having a structure (also referred to as chain acetate); aromatic hydrocarbons; aliphatic hydrocarbons are preferable. Thus, the embodiment in which the solvent is at least one selected from the group consisting of cyclic ketones, cyclic ethers, chain alcohols, chain acetates, aromatic hydrocarbons and aliphatic hydrocarbons is also preferable for the present invention. This is one of the forms.

The solvent having a dipole moment of 4D or less preferably has a boiling point of 90 ° C or higher. For example, when the composition further contains a resin, volatilization at the time of coating or the like can be sufficiently suppressed and occurrence of unevenness can be suppressed by including at least the solvent having the boiling point. The boiling point is more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, particularly preferably 120 ° C. or higher, and most preferably 130 ° C. or higher. Moreover, although an upper limit is not specifically limited, For example, it is preferable that it is 250 degrees C or less.

In the present invention, in addition to a solvent having a dipole moment of 4D or less, one or more other solvents may be included. However, from the viewpoint of further enhancing the effects of the present invention, the total amount of solvent (dipole moment is 4D). The total amount of the following solvents and other solvents) is preferably 100% by mass, and the solvent having a dipole moment of 4D or less is preferably 50% by mass or more. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.
The other solvent is not particularly limited, but the water content in 100% by mass of the total solvent used in the present invention is preferably 3% by mass or less.

In the composition, the content of the solvent is not particularly limited. For example, when the composition contains a solvent, the total amount of the solvent (dipole moment is 4D or less with respect to 100 parts by mass of the resin (solid content). The total amount of the solvent and other solvents is preferably 10 to 4000 parts by mass. More preferably, it is 300-3000 mass parts, More preferably, it is 500-2000 mass parts. Moreover, when the said composition does not contain resin, it is preferable that the total amount of a solvent shall be 1-10000 mass parts with respect to 1 mass part of total amounts of an oxocarbon type compound. More preferably, it is 10-8000 mass parts, More preferably, it is 100-5000 mass parts.

-Oxocarbon compounds-
The oxocarbon-based compound is a compound containing one or more cyclic oxocarbon groups composed of only carbon and oxygen. In the present invention, the oxocarbon-based dye (used as a near-infrared absorbing dye ( It is preferable to use an organic compound). For example, what has an absorption maximum in the wavelength range of 600-1500 nm is preferable. By having an absorption maximum in this wavelength region, it is possible to reduce light absorption particularly in the region of 600 nm to 1600 nm, and it is possible to remove optical noise caused by this. As a result, the cured product containing the oxocarbon-based compound has physical properties suitable for reducing optical noise, such as high visible light transmittance and excellent blocking performance in the near infrared region. The wavelength range of the absorption maximum is more preferably 600 to 1300 nm, still more preferably 650 to 1100 nm.
In this specification, “absorption maximum” means the peak where the absorbance turns from increasing to decreasing when the relationship between wavelength and absorbance is represented by a two-dimensional graph with the X axis as the wavelength and the Y axis as the absorbance. means.

It is preferable that the oxocarbon compound is dispersed or dissolved in the composition. Among these, it is more preferable that the oxocarbon-based compound is dissolved in the composition. That is, the oxocarbon-based compound is preferably one that dissolves in other components (preferably, a resin and / or a solvent) included in the composition. Thereby, a composition or a cured product in which the oxocarbon compound is uniformly dispersed or dissolved at a high concentration can be provided, and physical properties derived from the oxocarbon compound can be more fully exhibited.

The oxocarbon-based compound is also preferably a compound having a heterocyclic ring and / or an aromatic ring in addition to a cyclic oxocarbon group. Thus, the oxocarbon-based compound includes a cyclic oxocarbon group, a heterocyclic ring and / or a heterocyclic ring. Or the form which is a compound which has an aromatic ring is one of the suitable forms of this invention. More preferred are compounds having a cyclic oxocarbon group and a nitrogen-containing ring, and even more preferred are compounds having a cyclic oxocarbon group and a nitrogen-containing heterocycle (indolenine). Thereby, it becomes possible to give the composition which was further excellent in light resistance and heat resistance.

As the oxocarbon-based compound having a heterocyclic ring and / or an aromatic ring, a squarylium-based compound and a croconium-based compound are suitable. That is, the oxocarbon compound of the present invention preferably contains at least one selected from the group consisting of squarylium compounds and croconium compounds. It is also preferable to use a mixture of two or more oxocarbon compounds having different structures. For example, the form which mixes and uses 2 or more types of squarylium compounds which have a different structure is mentioned. Thereby, it becomes possible to give the composition which was further excellent in light resistance and heat resistance.

The squarylium-based compound is also referred to as a squarylium-based dye, and the structure thereof is not particularly limited. For example, a compound represented by the following formula (1) is preferable. The croconium-based compound is also referred to as a croconium-based dye, and the structure thereof is not particularly limited. For example, a compound represented by the following formula (2) is preferable. A compound having two or more main skeletons (squarylium skeleton, croconium skeleton) in formula (1) and / or (2) in one molecule may be used.

In the above formulas (1) and (2), R ^a1 and R ^a2 are the same or different and each represents a heterocyclic ring, an aromatic ring or a hydrogen atom, and at least one of R ^a1 and R ^a2 is a heterocyclic ring or an aromatic ring Represents a ring. The heterocyclic ring and the aromatic ring may have a substituent.

Examples of the heterocyclic ring include aromatic heterocyclic rings and alicyclic heterocyclic rings.
Examples of the aromatic heterocycle include a 5-membered or 6-membered monocyclic aromatic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom; A bicyclic or tricyclic fused ring aromatic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom; and more specifically, a pyridine ring, a pyrazine ring, Pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, cinnoline ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, thiophene ring, furan ring, thiazole ring Oxazole ring, indole ring, isoindole ring, indazole ring, benzimidazole ring, benztriazole ring, Zochiazoru ring, benzoxazole ring, purine ring, carbazole ring.

Examples of the alicyclic heterocycle include a 5-membered or 6-membered monocyclic alicyclic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom; And a condensed alicyclic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more specifically, a pyrrolidine ring, Examples include piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, homopiperidine ring, homopiperazine ring, tetrahydropyridine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydrofuran ring, tetrahydropyran ring, dihydrobenzofuran ring, tetrahydrocarbazole ring, etc. It is done.

As said aromatic ring, a C5-C14 aromatic ring is preferable, for example, a benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned.

Among the heterocyclic rings, a 5-membered or 6-membered heterocyclic ring is particularly preferable, and among the aromatic rings, a 5-membered or 6-membered aromatic ring is particularly preferable.

The heterocycle and aromatic ring may have one or more substituents, and the number of the substituents is preferably 5 or less. When each ring has two or more substituents, the same substituent or different substituents may be used. Specific examples of such a substituent include, for example, a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group, an alkyl group, an aryl group-Ar, an aralkyl group, a cyano group, a halogen atom, -R ¹ = R ¹ -Ar ( R ¹ represents N or CH Ar represents a substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group, an alkyl group optionally substituted with a halogen group, a cyano group, and a halogen atom. Represents an aryl group which may be substituted with. The alkyl group and the alkoxy group may have one or more substituents (the number of the substituents is preferably 3 or less). Examples of the substituent include a hydroxyl group, a carboxyl group, and a nitro group. Group, cyano group, alkoxy group, aryl group, halogen atom and the like.

In the above formulas (1) and (2), R ^a1 and R ^a2 are particularly preferably a structural unit represented by the following formula (3). R ^a1 and R ^a2 may be the same or different.

In the above formula (3), ring A represents an unsaturated hydrocarbon ring having 4 to 9 members. X and Y are the same or different and represent an organic group or a polar functional group. n is 0-6 and represents an integer of m or less. m is a value obtained by subtracting 3 from the number of members of ring A. * Represents a binding site to the squarylium skeleton in the above formula (1) or the croconium skeleton in the above formula (2), and is a carbon atom bonded to the squarylium skeleton or the croconium skeleton (a carbon atom indicated by an arrow in the formula (3)). Forms a hydrocarbon ring (ring A). Ring B represents an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing these ring structures, and may have a substituent.

The ring A represents an unsaturated hydrocarbon ring having 4 to 9 members, but a carbon atom (carbon atom indicated by an arrow in formula (3)) and a pyrrole ring bonded to a squarylium skeleton or a croconium skeleton. Any unsaturated hydrocarbon ring having at least one double bond between the constituent carbon atoms may be used. Ring A may have an unsaturated bond (preferably a double bond) in addition to this double bond, but ring A preferably has one double bond. Ring A is preferably a 5- to 8-membered ring, more preferably a 6- to 8-membered ring. Examples of the structure of ring A include cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cycloheptatriene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclononene, cyclononadiene, cyclononatriene, Examples include cycloalkene structures such as cyclononatetraene. Of these, cycloalkane monoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are preferable.

Examples of the organic group that can be represented by X and Y include, for example, an alkyl group, an alkoxy group, an alkylthiooxy group (alkylthio group), an alkyloxycarbonyl group, an alkylsulfonyl group, an aryl group, an aralkyl group, an aryloxy group, and an arylthiooxy group. Examples include a group (arylthio group), an aryloxycarbonyl group, an arylsulfonyl group, an amide group (—NHCOR ² ), a sulfonamide group (—NHSO ₂ R ² ), a carboxy group (carboxylic acid group), and a cyano group. R ² represents an arbitrary monovalent organic group. Moreover, as a polar functional group, a halogeno group, a hydroxyl group, a nitro group, an amino group, a sulfo group (sulfonic acid group) etc. are mentioned, for example.

The organic group or polar functional group represented by X is preferably an alkyl group, an alkyloxycarbonyl group, or an aryl group, and more preferably an alkyl group or an aryl group. In this case, the number of carbon atoms of the alkyl group is preferably 1 to 6 if it is a linear or branched alkyl group, more preferably 1 to 4, and 4 to 7 if it is an alicyclic alkyl group. Preferably, it is 5-6. 6-10 are preferable and, as for carbon number of an aryl group, More preferably, it is 6-8. Specifically, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, or the like is preferable.

The organic group or polar functional group represented by Y is preferably an alkyl group, an alkoxy group, a halogeno group, a phenyl group, an alkoxycarbonyl group (ester group), an amide group, a sulfonamide group or a hydroxyl group, more preferably an alkyl group. Or it is a hydroxyl group. In this case, 1-5 are preferable, as for carbon number of an alkyl group, More preferably, it is 1-3, More preferably, it is 1-2. Specifically, a methyl group, an ethyl group, a hydroxyl group and the like are preferable.

The n is 0 to 6 and represents an integer of m or less, preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and further preferably an integer of 0 to 2. When n is 1 or more, the hydrogen atom bonded to the carbon atom constituting the ring A is substituted with Y. When n is 2 or more and a plurality of Y are present, each Y may be the same or different. When n is 2 or more, a plurality of Ys may be bonded to different carbon atoms, or two Ys may be bonded to one carbon atom.

The ring B represents an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing these ring structures, and may have a substituent. When it has a substituent, the number of substituents may be one or two or more. Examples of the ring B include rings having the structures of the following formulas (A-1) to (A-12), and rings in which one or more hydrogen atoms of these rings are substituted with an arbitrary substituent. . Among these, a benzene ring (A-1), a naphthalene ring (A-2, A-3) or a ring substituted with a substituent is preferable, and the benzene ring (A-1) or the benzene ring (A-1) is substituted. A ring substituted with a group is more preferred. Here, examples of the substituent include the groups described above as the organic group represented by X and Y, and among them, an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms), an aryl group, Electron donating groups such as alkoxy groups, alkylthio groups (preferably alkylthio groups having 1 to 2 carbon atoms), amino groups, amide groups, sulfonamido groups; halogeno groups (preferably chloro groups or bromo groups), alkoxy An electron-withdrawing group such as a carbonyl group (also referred to as an ester group), a carboxy group (also referred to as a carboxylic acid group), a sulfo group (also referred to as a sulfonic acid group), or a nitro group is preferable, and an electron-withdrawing group is particularly preferable.

The above formulas (A-1) to (A-12) represent ring B including a part of a pyrrole ring. For example, formula (A-1) is represented by an arrow a in the following structural formula. The carbon atom at the β-position of the pyrrole ring shown and the carbon atom at the α-position of the pyrrole ring indicated by the arrow b in the following structural formula are shown.

Here, a tautomer exists in the oxocarbon compound in which the structural unit represented by the formula (3) is bonded to the squarylium skeleton in the formula (1) or the croconium skeleton in the formula (2). To do. Specifically, when the structural unit represented by the above formula (3) is bonded to the squarylium skeleton in the formula (1), in addition to the compound represented by the following formula (1-1), the following formula (1- 0) or a tautomer represented by (1-2) exists. When the structural unit represented by the above formula (3) is bonded to the croconium skeleton in the formula (2), in addition to the compound represented by the following formula (2-1), the following formula (2-0), ( There exists a tautomer represented by 2-2) or (2-3).
When at least the compound represented by the above formula (1) or (2) is used as the oxocarbon-based compound of the present invention, not only the compound represented by the above formula (1) or (2) but also the corresponding ones. Mutants are also included.

Although the manufacturing method of the said squarylium type compound and the croconium type compound is not specifically limited, For example, it can manufacture by making a pyrrole ring containing compound into an intermediate raw material and making this react with squaric acid or croconic acid. For this production, a known synthesis method can be appropriately employed. For example, JP 2002-286931 A, JP 2007-31644 A, JP 2007-31645 A, and JP 2007-169315 A. It can be synthesized by the method described in 1. Further, the obtained compound may be appropriately purified by known purification means such as filtration, silica gel column chromatography, alumina column chromatography, sublimation purification, recrystallization, and crystallization as necessary.

As the pyrrole ring-containing compound, for example, a compound represented by the following formula (4) is preferable. In the following formula (4), ring A, ring B, X, Y and n are the same as the symbols in formula (3).

Specific examples of the pyrrole ring-containing compound include 4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole, 6-methyl-4a-methyl-2,3,4,4a-tetrahydro-1H. -Carbazole, 6-fluoro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole, 6,8-difluoro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole, 6 -Chloro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole, 5,7-dichloro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole, 5,6,8 -Trichloro-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole, 6-bromo-4a-methyl-2,3,4,4a-tetrahydr -1H-carbazole, 6,8-dibromo-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole, 6-trifluoromethyl-4a-methyl-2,3,4,4a-tetrahydro-1H Carbazole, 4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole-8-carboxylic acid, 4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole-6-carboxylic acid, 6 -Phenyl-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole, 8-phenyl-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole, 6b-methyl-7,8 , 9,10-Tetrahydro-6bH-benzo [a] carbazole, 10a-methyl-6,7,8,9,10,10a-hexahydrocyclo Descriptor [b] indole, 11a- methyl -7,8,9,10,11,11a- hexahydro -6H- cycloocta [b] indole, and the like.

The said pyrrole ring containing compound is compoundable by employ | adopting a well-known synthetic | combination method suitably. For example, a paper written by Sami Sajjadifar et al. ("New 3H-Indole Synthesis by Fischer's Method. Part I.", Molecules 2010, Volume 15, published April 8, 2010, p. 2491-2498), Serguei Miltsov et al. It can be synthesized by the synthesis method described in a paper (“New Cyanine Dyes: Norindosquarocyanines”, Tetrahedron Letters, Volume 40, Issue 21, May 21, 1999, p. 4067-4068).

-Resin-
It is preferable that the said composition contains 1 type, or 2 or more types of resin.
It does not specifically limit as resin, Any of a thermoplastic resin and a thermosetting resin may be sufficient. Specifically, for example, poly (amide) imide resin, epoxy resin, polycycloolefin resin, fluorine resin, polysulfone resin, aramid resin, polyester resin, polyvinyl resin, polyolefin resin, polyvinyl chloride, (meth) In addition to acrylic resins, styrene resins, acrylic-styrene resins, polycarbonate resins, and the like, various other resins can be used. A resin having preferable physical properties may be selected as appropriate depending on the use and the like, but it is preferable to use a resin that can dissolve or disperse an oxocarbon compound. For example, in applications where high light resistance is required, it is preferable to use a fluorine-based resin, poly (amide) imide resin, or the like. In applications where transparency (transparency) is required, it is preferable to use a transparent resin. preferable.

In the present specification, poly (amide) imide resin means a polyimide resin in a narrow sense (resin containing an imide bond and not containing an amide bond or containing a small amount thereof, and the amide bond here is an amic acid. Means an amide bond that cannot form an imide bond by dehydration reaction), and a polyamide-imide resin (means a resin that contains an amide bond and an imide bond that cannot form an imide bond by a dehydration reaction of an amic acid) .)).

Among the resins described above, a resin having a glass transition temperature of 120 ° C. or higher is particularly preferable. By including such a resin, the composition becomes a more stable state, volatilization during coating or the like is sufficiently suppressed, and occurrence of unevenness can be suppressed. Thus, the form in which the resin contains a resin having a glass transition temperature of 120 ° C. or higher is also one of the preferred forms of the present invention. The glass transition temperature is more preferably 130 ° C. or higher, still more preferably 140 ° C. or higher. Moreover, although an upper limit is not specifically limited, For example, it is preferable that it is 400 degrees C or less.
In addition, when using resin by this invention, it is preferable that resin whose glass transition temperature is 120 degreeC or more is 50 mass% or more in the total amount of 100 mass% of resin. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

Examples of the resin having a glass transition temperature of 120 ° C. or higher include poly (amide) imide resin, epoxy resin, polycycloolefin resin, fluorinated aromatic resin, polysulfone resin, polyethersulfone resin, and polyphenylsulfone resin. , Aramid resin, polyester resin, polyvinyl ester resin, polyolefin resin, polyvinyl chloride, (meth) acrylic resin, styrene resin, acrylic-styrene resin, polyarylate resin, polycarbonate resin, polyetherketone resin, polyethylene naphthalate resin, etc. Can be preferably used.

When the composition contains a resin, the content is not particularly limited. For example, the content of the oxocarbon compound is 0.05 to 30 parts by mass with respect to 100 parts by mass of the total resin (solid content). Thus, it is preferable to set the resin content. This makes it possible to obtain a cured product that has a higher visible light transmittance and is superior in blocking performance in the near infrared region. The content of the oxocarbon-based compound is more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, still more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more. Preferably it is 2 parts by mass or more, most preferably 3 parts by mass or more, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, and most preferably 10 parts by mass or less. It is.

The content of the resin is such that the total amount of the dye in the composition (the total amount of the oxocarbon-based compound and other dyes described later) is 0.05 to 35 mass with respect to 100 mass parts of the total resin (solid content). It is also preferable to set so that it becomes a part. This makes it possible to obtain a cured product that has a higher visible light transmittance and is superior in blocking performance in the near infrared region. The total amount of the dye is more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, still more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and particularly preferably 2 parts by mass. Above, most preferably 3 parts by mass or more, more preferably 30 parts by mass or less, still more preferably 25 parts by mass or less, particularly preferably 20 parts by mass or less, and most preferably 10 parts by mass or less.

-Other dyes-
The composition may also contain one or more dyes (referred to as other dyes) other than the oxocarbon compounds described above. Other dyes are not particularly limited. For example, a dye having characteristic absorption at a specific wavelength in each of the near infrared, infrared, ultraviolet, and visible light bands other than the wavelength range of 600 to 1500 nm is used depending on the application. What is necessary is just to select suitably according to the objective. Further, from the viewpoint of improving light resistance, an ultraviolet absorbing dye such as benzophenone or benzotriazole may be used.

When the other dye is included, the content is not particularly limited. For example, the content is preferably 50% by mass or less with respect to 100% by mass of the total amount of the oxocarbon compound and the other dye. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less. In other words, the oxocarbon compound is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more with respect to 100% by mass of the total amount of the oxocarbon compound and other dyes. It is.

-Additives-
The composition may also contain one or more appropriate additives as required. Although it does not specifically limit as a specific example of an additive, For example, a hardening | curing agent, a mold release agent, a leveling agent, a pigment, a pigment dispersant, a ultraviolet absorber, an antioxidant, an oxygen supplement agent, a viscosity modifier, a light-resistant stabilizer, for example , Metal deactivators, peroxide decomposers, fillers, reinforcing materials, plasticizers, lubricants, anticorrosives, rust inhibitors, emulsifiers, mold demolding agents, fluorescent whitening agents, organic flameproofing agents, Inorganic flame retardant, anti-dripping agent, melt flow modifier, antistatic agent, slipping agent, adhesion promoter, antifouling agent, surfactant, antifoaming agent, polymerization inhibitor, photosensitizer, Examples include surface improvers, (near) infrared cut agents, adhesion improvers, heat stabilizers, antibacterial / antifungal agents, flame retardants, and the like.

When the additive is included, the content is not particularly limited. For example, the total amount of the additive is 0.00001% by mass to 10% by mass with respect to 100% by mass of the total amount (solid content) of the composition. It is preferable.

The preparation method of the said composition is not specifically limited, It can obtain by mixing a content component by a normal method. When mixing the components, if necessary, each component or mixture can be heated and mixed to achieve a uniform composition. The heating temperature is preferably 20 to 160 ° C, more preferably 40 to 140 ° C. The mixing method is not particularly limited, and for example, the composition can be prepared by mixing and dispersing using various mixers and dispersers. The dispersion step and the mixing step are not particularly limited, and may be performed by a normal method, and the order of adding and mixing the components can be appropriately selected. For example, when a resin and a solvent are included in addition to the oxocarbon compound, the solvent may be added after the oxocarbon compound is added to the resin, and the resin and the oxocarbon compound are added to the solvent and mixed. May be. Further, it may further include other steps that are normally performed. In addition, when the composition is a composition for resin pellets, the composition may be prepared by kneading a pigment powder into a molten resin and extruding it.

In the above storage / use method, the above-mentioned composition can be stably stored or used without particularly limiting the atmosphere to be stored or used by using the above-mentioned predetermined solvent in combination with the oxocarbon-based compound. The present invention has an advantageous feature also in this respect, but in some cases, it is also preferable to store or use the composition in an atmosphere having an oxygen concentration of 10% by volume or less. The normal oxygen concentration in air is about 20% by volume, but storage or use in an atmosphere of 10% by volume or less can further suppress deterioration in physical properties of the oxocarbon-based compound due to light or heat. The oxygen concentration is more preferably 3% by volume or less, further preferably 1% by volume or less, particularly preferably 0.5% by volume or less, and most preferably 0.3% by volume or less.
In the present specification, the oxygen concentration can be measured with an oxygen concentration meter (for example, Cosmo Protector XPO-318, manufactured by Shin Cosmos Electric Co., Ltd.).

The means for bringing the oxygen concentration into the above-mentioned range is not particularly limited. For example, it is preferable to carry out curing in an inert gas atmosphere by replacing oxygen in the system with an inert gas. The inert gas is not particularly limited, and examples thereof include noble gases such as helium, neon, and argon in addition to nitrogen. Of these, argon and nitrogen are preferable, and nitrogen is particularly preferable. Further, it may be in any atmosphere under reduced pressure, normal pressure, or increased pressure.

In the said storage / use method, it is preferable to preserve | save or use a composition on temperature conditions of -20-100 degreeC from a viewpoint of stability improvement. More preferably, it is 0-60 degreeC, More preferably, it is 0-50 degreeC, Most preferably, it is 0-30 degreeC. Further, it is preferable to store the light shielded. This further improves the stability of the composition containing the oxocarbon-based compound.
Note that the storage period is not particularly limited, and can be arbitrarily set according to the usage mode, travel time, and the like. For example, it may be as short as 24 hours immediately after production of the composition, may be as long as 1 day to 6 months, or may be as long as 6 months or longer.

The composition stored or used by the above storage / use method can sufficiently exhibit the physical properties derived from the oxocarbon-based compound. For example, in addition to the near infrared absorber, a heat ray absorber, a heat ray shielding agent, a laser welding agent It is useful for various applications such as anti-counterfeiting agents. Specifically, for example, a near-infrared absorber (a near-infrared absorber for non-contact fixing toner such as flash fixing; a near-infrared absorber for heat-retaining and storing fibers; writing in an optical recording medium, a liquid crystal display device, an optical character reader, etc. Or near-infrared absorbing agent for reading); color toner, near-infrared absorbing ink, ink-jet ink, household ink-jet ink, anti-counterfeit ink (particularly anti-counterfeit bar code ink, anti-counterfeit offset ink) ) Etc .; Optical parts such as goggles lenses, shielding plates, photoconductive materials; Near-infrared photosensitizers; Eye strain prevention agents; Dyeing agents for sorting when recycling plastics; Photosensitivity for laser treatment Pre-heating aids during molding of PET bottles; photothermal exchange agents such as thermal transfer and thermal stencil; photothermal exchange of thermal rewritable recording Agents; anti-counterfeiting agents of the ID card; laser transmission welding of plastic: photothermal exchanger for (LTW Laser Transmission Welding); heat ray shielding agent; near infrared absorption filter; color CRT selective absorption filter; and the like.

〔Composition〕
The present invention is also a composition comprising an oxocarbon-based compound and a solvent having a dipole moment of 4D or less. Such a composition (also simply referred to as “composition”) may further contain a resin. Furthermore, other components (for example, other pigments, additives, etc.) may be included as necessary.
Each component can be used alone or in combination of two or more.

The preferred forms of the essential and optional components of the above composition, the preferred range of the content of each component, the preparation method, and the like are the same as those of the composition that is the object of the storage / use method described above.

The above composition is extremely excellent in light resistance and heat resistance, is excellent in transparency and the like, and further has an absorption maximum in a predetermined wavelength region due to the inclusion of an oxocarbon-based compound. Therefore, it is useful for various applications other than light selective transmission filters such as infrared cut filters and ultraviolet / infrared cut filters used for liquid crystal display devices, solid-state imaging devices, touch panel display devices, and the like. Specifically, the use mentioned above about the preservation | save / use method is mentioned, for example.

[Cured product]
The composition of this invention can also give the hardened | cured material which is excellent in light resistance and heat resistance. Thus, the hardened | cured material obtained by hardening | curing the composition of this invention is one of the suitable embodiment of this invention.

The manufacturing method for obtaining the said hardened | cured material is not specifically limited, It is preferable to obtain by hardening the said composition with a normal hardening method. Among these, it is preferable to cure the composition of the present invention in an atmosphere having an oxygen concentration of 10% by volume or less from the viewpoint that the physical properties derived from the oxocarbon compound are sufficiently exhibited. The preferable range of the oxygen concentration in this curing step is as described above. Moreover, the curing conditions (for example, temperature etc.) of a hardening process are not specifically limited. Specifically, as the curing step, for example, a step of thermoforming the composition; a step of irradiating the composition with active energy rays (also referred to as light irradiation); and molding the composition with a substrate (resin plate) , A film or a glass plate, etc.), followed by heating or light irradiation; Molding and coating may be performed by ordinary methods.

The shape of the cured product is not particularly limited, and includes various shapes such as a plate shape, a film shape, a sheet shape, a corrugated plate shape, a spherical shape, a dome shape, a pellet shape, and the like. It may be a cured film. For example, when the composition further contains a resin, the obtained cured product can be a resin film (also referred to as a resin layer), a resin pellet, or the like.

Since the storage or use method of the present invention comprises the above-described configuration, the oxocarbon-based compound can be stably stored or used with sufficient suppression of decomposition and reaction over time. In addition, the composition of the present invention is in a stable state in which decomposition and reaction over time of the oxocarbon compound is sufficiently suppressed. Therefore, the present invention is particularly useful in the technical field using oxocarbon compounds.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass”, and “%” means “mass%”.
In the following test examples, “nitrogen atmosphere” means that the oxygen concentration measured by an oxygen concentration meter (manufactured by Shin Cosmos Electric Co., Ltd., Cosmo Protector XPO-318) after replacing oxygen in the system with nitrogen is 1% by volume or less. It means that it was. “Air atmosphere” means a normal air atmosphere (the oxygen concentration is about 20% by volume).

Synthesis example 1
After synthesizing a pyrrole ring-containing compound according to the synthesis method described in the above-mentioned paper by Sami Sajjadifar et al., Serguei Miltsov et al., And reacting with squaric acid or croconic acid, oxocarbon compounds A to F are produced. did. The structural formulas of the oxocarbon compounds A to F are shown in Table 1.

Test example 1
Using a measuring flask, a solution was prepared by diluting about 10 mg of oxocarbon-based compound B in dimethyl sulfoxide (DMSO) in an amount 5000 times that amount. The absorption spectrum of the solution immediately after this preparation was measured with a spectrophotometer (manufactured by Hitachi, Ltd., U-2910), and this was used as the spectrum before storage. Next, this solution was stored in an air atmosphere or a nitrogen atmosphere at 40 ° C. for 1 hour, and then the absorption spectrum of the solution was measured with a spectrophotometer, and this was stored as a spectrum. Read the maximum absorption wavelength (λmax) from these absorption spectra and calculate the residual ratio of absorbance at λmax before and after storage (= “absorbance of spectrum after storage at λmax / absorbance of spectrum before storage at λmax” × 100 ”). did. The results are shown in Table 1.
In addition, the example preserve | saved under "air atmosphere" was made into test example 1-1, and the example preserve | saved under "nitrogen atmosphere" was made into test example 1-2.

Test Examples 2-8
The residual ratio of absorbance at λmax before and after storage was calculated in the same manner as in Test Example 1 except that the solvents listed in Table 2 were used instead of DMSO. The results are shown in Table 2.

In Table 2, PGMEA is propylene glycol monomethyl ether acetate.

From Table 2, the following was confirmed.
Test Examples 1 and 2 are examples using a compound having a dipole moment exceeding 4D as a solvent, while Test Examples 3 to 8 are examples using a compound having a dipole moment of 4D or less.
Comparing the absorbance remaining ratio under such a difference, it can be seen that the absorbance remaining ratio in Test Examples 1 and 2 is extremely low, and that in Test Example 2 there is a large difference in the absorbance remaining ratio due to the difference in storage atmosphere. In contrast, in Test Examples 3 to 8, the absorbance remaining rate is remarkably high regardless of the storage atmosphere. In particular, it is clear that the smaller the dipole moment, the higher the residual absorbance, that is, the higher the stability. Moreover, since this test was conducted at a temperature of 40 ° C., it can be understood that deterioration due to heat is sufficiently suppressed when stored or used with a solvent having a dipole moment of 4D or less. Therefore, by storing or using a composition containing a solvent having a dipole moment of 4D or less together with an oxocarbon-based compound, the composition can be stably stored or used without deteriorating characteristics derived from the oxocarbon-based compound. I understood.

In the test examples described above, only six types of compounds are used as the solvent having a dipole moment of 4D or less. However, as long as a solvent having a dipole moment in this range is used, a mechanism for stabilizing the oxocarbon-based compound. Is the same. For at least one solvent selected from the group consisting of cyclic ketones, cyclic ethers, chain alcohols, chain acetates, aromatic hydrocarbons and aliphatic hydrocarbons, as the solvent having a dipole moment of 4D or less. Thus, it can be said that the advantageous effects of the present invention are sufficiently proved by the test examples described above, and the technical significance of the present invention is supported.

Synthesis example 2
Charge 5 parts of 1,2,4,5-cyclohexanetetracarboxylic acid (manufactured by Aldrich, purity 95%) and 44 parts of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) into the flask and stir the nitrogen gas inside the reactor. Replaced with. The temperature was raised to the reflux temperature of the solvent under a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. Thereafter, the mixture was cooled to room temperature with stirring to precipitate crystals. The precipitated crystals were separated into solid and liquid and dried to obtain crystals of the desired product (1,2,4,5-cyclohexanetetracarboxylic dianhydride). Subsequently, 4,4′-diaminodiphenyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, a dropping funnel with a side tube, a Dean Stark, and a cooling tube in a nitrogen stream. After 89 parts and 7.6 parts of N-methyl-2-pyrrolidone as a solvent were charged and dissolved, 1 part of 1,2,4,5-cyclohexanetetracarboxylic dianhydride remained as a solid at room temperature. The solution was added in portions over time and stirred at room temperature for 2 hours. 2.6 parts of xylene as an azeotropic dehydrating agent was added and reacted at 180 ° C. for 3 hours, and the product water refluxed by Dean Stark was azeotropically separated. Xylene was distilled off while the temperature was raised to 190 ° C., followed by cooling to obtain an N-methyl-2-pyrrolidone solution of polyimide. This N-methyl-2-pyrrolidone solution was further diluted with γ-butyrolactone to obtain a polyimide resin solution having a solid content of 3%. 1 part of this polyimide resin solution was reprecipitated with 50 parts of methanol and separated into solid and liquid. The solid-liquid separated polyimide resin was dissolved in γ-butyrolactone to obtain a polyimide resin solution having a solid content of 3% again, and re-precipitated with 50 parts of methanol in the same manner as described above, followed by solid-liquid separation. The resin obtained by reprecipitation was dried to obtain polyimide resin A.

Test Example 9
Mixed solution of oxocarbon compound A and 6% polyimide resin A solution (in 100% total amount, oxocarbon compound A: 0.3%, polyimide resin A solid content: 6.0%, cyclopentanone: 93 .7%) is filtered to remove insoluble matters, and 0.4 ml is hung on a glass substrate, and a spin coater (Mikasa 1H-DX) is used, and the rotation is 2000 rpm (rpm) over 0.2 seconds. The resin layer was formed by maintaining the number of rotations for 10 seconds and then rotating to 0 rotations (rpm) over 0.2 seconds. After the glass substrate on which the resin layer is formed is initially dried at 100 ° C. for 3 minutes using a precision thermostatic chamber (manufactured by Yamato Kagaku Co., Ltd., DH611) (this is referred to as “initially dried glass substrate”), an inert oven is used. (Yamato Scientific Co., Ltd., DN610I) was dried at 50 ° C. for 30 minutes (with nitrogen substitution), then heated to 200 ° C. in 20 minutes, and additionally dried at 200 ° C. for 30 minutes (under a nitrogen atmosphere). A glass substrate provided with a layer (referred to as a “coating glass substrate”) was obtained. The thickness of the resin layer after drying was 1 μm.
About the coating glass substrate produced in this way, the change in absorbance due to heating was confirmed according to the following test method.

<Change in absorbance due to heating>
The absorption spectrum of the initial dry glass substrate (after the glass substrate on which the resin layer is formed is initially dried at 100 ° C. for 3 minutes) is measured with a spectrophotometer (U-2910, manufactured by Hitachi, Ltd.). A spectrum before heating was used. Next, the absorption spectrum of the coated glass substrate obtained in Test Example 9 was measured with a spectrophotometer, and this was used as a spectrum after heating. The maximum absorption wavelength (λmax) was read from these spectra, and the residual ratio of absorbance at λmax (= “absorbance of spectrum after heating at λmax / absorbance of spectrum before heating at λmax) × 100”) was calculated. The results are shown in Table 3.

<Change in absorbance due to UV irradiation>
The absorption spectrum of the coated glass substrate obtained in Test Example 9 was measured with a spectrophotometer (manufactured by Hitachi, Ltd., U-2910), and this was used as the spectrum before irradiation. Next, under a nitrogen atmosphere, UV irradiation (700 mJ) was performed 5 times under the following UV irradiation conditions, and then the absorption spectrum of each substrate was measured with a spectrophotometer to obtain a post-irradiation spectrum. The maximum absorption wavelength (λmax) was read from these spectra, and the residual ratio of absorbance at λmax (= “absorbance of the spectrum after irradiation at λmax / absorbance of the spectrum before irradiation at λmax) × 100”) was calculated. The results are shown in Table 3.
-UV irradiation conditions-
Irradiation lamp: manufactured by Fusion, Lamp D bulb conveyor speed: 1.2 m / min Illuminance: 270 mW / cm ²
Integrated dose per pass: 700 mJ / cm ²
UV illuminance meter: UIT-250 manufactured by USHIO INC.
UV sensor: manufactured by USHIO INC., UVD-S365

Test Examples 10-14
A change in absorbance due to heating and ultraviolet (UV) irradiation was confirmed in the same manner as in Test Example 9 except that oxocarbon compounds B to F were used instead of oxocarbon compound A. The results are shown in Table 3.

From Table 3, the following was confirmed.
Test Examples 9 to 14 are examples in which cured products were prepared using compositions containing various oxocarbon compounds, cyclopentanone (dipole moment: 3.3D), and resin. From Table 3, since the residual absorbance ratio before and after heating and before and after UV irradiation was high, it was found that the composition and a cured product obtained using the composition were excellent in heat resistance and light resistance.

Claims (10)

A method of storing or using a composition comprising an oxocarbon-based compound comprising:
The composition contains a solvent having a dipole moment of 1 D or less together with an oxocarbon-based compound,
The oxocarbon based compound, squarylium compound represented by the following formula (1), and is at least one selected from croconium compound or Ranaru group represented by the following formula (2),
A method for storage or use, wherein the wavelength range of the absorption maximum of the oxocarbon-based compound is 650 to 1500 nm.

(In the above formulas (1) and (2) , R ^a1 and R ^a2 are the same or different and are selected from a bicyclic or tricyclic condensed 3- to 8-membered ring, a nitrogen atom, an oxygen atom and a sulfur atom. A condensed alicyclic heterocyclic ring containing at least one atom, which may have a substituent, such as a hydroxyl group, a carboxyl group, A nitro group, an alkoxy group, an alkyl group, an aryl group —Ar, an aralkyl group, a cyano group, a halogen atom, or —R ¹ = R ¹ —Ar, wherein R ¹ represents N or CH, where Ar is a hydroxyl group; , A carboxyl group, a nitro group, an alkoxy group, an alkyl group which may be substituted with a halogen group, an aryl group which may be substituted with a substituent selected from the group consisting of a cyano group and a halogen atom. 2. The solvent according to claim 1, wherein the solvent is at least one selected from the group consisting of a cyclic ketone, a cyclic ether, a chain alcohol, a chain acetate, an aromatic hydrocarbon, and an aliphatic hydrocarbon. How to store or use. The method for storage or use according to claim 1 or 2, wherein the solvent has a boiling point of 90 ° C or higher. 4. The condensed alicyclic heterocyclic ring in the formulas (1) and (2) is a tetrahydroquinoline ring, a tetrahydroisoquinoline ring, a dihydrobenzofuran ring, or a tetrahydrocarbazole ring. The method of storage or use according to claim 1. The method for storage or use according to any one of claims 1 to 4 , wherein the composition further comprises a resin. The method for storage or use according to claim 5 , wherein the resin includes a resin having a glass transition temperature of 120 ° C or higher. The method for storage or use according to any one of claims 1 to 6, wherein the method comprises storing or using the composition in an atmosphere having an oxygen concentration of 10% by volume or less. The method for storage or use according to any one of claims 1 to 7, wherein the composition is a composition for a light selective transmission filter. An oxocarbon-based compound and a solvent having a dipole moment of 1 D or less,
The oxocarbon based compound, squarylium compound represented by the following formula (1), and is at least one selected from croconium compound or Ranaru group represented by the following formula (2),
A composition having a wavelength range of the absorption maximum of the oxocarbon-based compound of 650 to 1500 nm.

(In the above formulas (1) and (2) , R ^a1 and R ^a2 are the same or different and are selected from a bicyclic or tricyclic condensed 3- to 8-membered ring, a nitrogen atom, an oxygen atom and a sulfur atom. A condensed alicyclic heterocyclic ring containing at least one atom, which may have a substituent, such as a hydroxyl group, a carboxyl group, A nitro group, an alkoxy group, an alkyl group, an aryl group —Ar, an aralkyl group, a cyano group, a halogen atom, or —R ¹ = R ¹ —Ar, wherein R ¹ represents N or CH, where Ar is a hydroxyl group; , A carboxyl group, a nitro group, an alkoxy group, an alkyl group which may be substituted with a halogen group, an aryl group which may be substituted with a substituent selected from the group consisting of a cyano group and a halogen atom. The composition according to claim 9, wherein the composition is a light selective transmission filter composition.