KR102449992B1 - A quinone-based ionic compound, a method for producing the same, transparent near infrared ray shielding film containing the quinone-based ionic compound and a method for producing the same - Google Patents

Abstract

The present invention relates to a quinoid-based ionic compound, a method for preparing the same, and a near-infrared blocking film comprising the quinoid-based ionic compound. The quinoid-based ionic compound according to the present invention has high transmittance in the visible region and high absorbance in the near-infrared region. It has high solubility in organic solvents and thus is easy to manufacture as a thin film, and has excellent affinity with polymers to maintain high heat and moisture resistance in a thin film state for a long time. The near-infrared blocking film containing the quinoid-based ionic compound is suitable for being applied to a protective film for protecting electronic devices, and may also be used as a heat insulating film or a light energy absorbing layer.

Description

A quinoid-based ionic compound, a method for producing the same, a transparent near-infrared blocking film containing the quinoid-based ionic compound, and a method for producing the same -based ionic compound and a method for producing the same}

The present invention relates to a quinoid-based ionic compound, a preparation method thereof, a near-infrared blocking film comprising the quinoid-based ionic compound, and a preparation method thereof.

Infrared rays are a large energy source accounting for about 40% of the solar energy reaching the earth, and are particularly closely related to thermal energy. Infrared rays with a long wavelength of 800 nm or more have high transmittance to general visible ray blocking films.

In addition, since most electronic devices use infrared for signal transmission, there is a risk of signal malfunction if the Busan-NIR generated from the device is not blocked, so an effective blocking film is essential.

In order for the near-infrared blocking film to be utilized throughout real life, it is necessary to selectively absorb only infrared light while having high transmittance to visible light.

On the other hand, the dimonium-based material is known to have a very high molar extinction coefficient compared to other materials as a material having excellent transmission characteristics in the visible light region and infrared absorption characteristics in the region of 800 nm or more.

However, dimonium-based materials known to date have limited use due to toxicity by using antimonic acid hexafluoride containing heavy metals as anions, or there is a problem in solubility in organic solvents using halogen ions such as chlorine and bromine. . In addition, due to poor affinity with the polymer, it is easily eluted by heat after the formation of the barrier film, resulting in discoloration of the barrier film, which makes it difficult to use for a long period of time. Therefore, there is a need to introduce a new structure to the cation and anion in order to compensate for the shortcomings of the existing near-infrared materials.

Korean Patent Publication No. 10-2018-0117213

Therefore, the technical problem to be solved by the present invention has a high molar extinction coefficient in the near-infrared region (especially a wavelength of 900 to 1100 nm), and a low extinction coefficient in the visible region (particularly a wavelength of 350 to 700 nm), and heat resistance and to provide a quinoid-based ionic compound having high moisture resistance and a method for preparing the same.

Another technical problem to be solved by the present invention is to provide a high heat and moisture resistant near-infrared blocking film containing the quinoid-based ionic compound and a method for manufacturing the same.

One aspect of the present invention for achieving the above object provides a quinoid-based ionic compound represented by the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 1 to 4, A and B are the same or different from each other, each is nitrogen or phosphorus, and X ^- is an organic anion, substituted or unsubstituted benzene, substituted or unsubstituted Imidazole, substituted or unsubstituted triazole, substituted or unsubstituted tetrazole, sulfonimide or oxalate in which hydrogen of an alkyl group having 1 to 4 carbon atoms is substituted with fluorine or oxalate containing an alkyl group having 0 to 4 carbon atoms and salatoborate, and R ₁ to R ₄ are the same as or different from each other, and are each independently a compound represented by Formula 2 or 3 below.

[Formula 2]

In Formula 2, A ₁ is nitrogen, phosphorus, oxygen or sulfur, A ₂ is nitrogen or phosphorus, R ₂₉ and R ₃₀ are the same as or different from each other, and each independently hydrogen, substituted or unsubstituted C 1 to 10 is a linear or branched alkyl group.

[Formula 3]

In Formula 3, A ₃ and A ₄ are the same as or different from each other, each is carbon, nitrogen, or phosphorus, A ₅ is nitrogen or phosphorus, R ₃₁ and R ₃₂ are the same as or different from each other, and each independently hydrogen, substituted or an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms.

Another aspect of the present invention provides a near-infrared blocking film comprising the quinoid-based ionic compound.

Another aspect of the present invention comprises the steps of preparing a mixed solution comprising the quinoid-based ionic compound and a binder; and preparing a near-infrared blocking film using the mixed solution.

The quinoid-based ionic compound according to the present invention has high transmittance in the visible region and high absorbance in the near-infrared region, enabling efficient near-infrared blocking, and high solubility in organic solvents, making it easy to prepare a thin film, as well as Due to its excellent affinity, it is possible to maintain high heat resistance and high moisture resistance in a thin film state for a long time.

The near-infrared blocking film containing the quinoid-based ionic compound is suitable for being applied to a protective film for protecting electronic devices, and may also be used as a heat insulating film or a light energy absorbing layer.

1 is a graph showing a solution phase UV-VIS-NIR absorption spectrum of a quinoid-based ionic compound according to an embodiment of the present invention.
2 is a graph showing the thermal rise of the photothermal film according to the presence or absence of the near-infrared blocking film according to Example 2-2 of the present invention.
3 is a thermal image showing heat generation according to the presence or absence of a near-infrared blocking film according to Example 2-2 of the present invention.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

The quinoid-based ionic compound according to the present invention has excellent heat resistance and moisture resistance, and selectively has a high molar extinction coefficient only in the near-infrared region. In addition, it has a high solubility in organic solvents, so it is easy to use, and a near-infrared absorption or blocking film can be formed by mixing the compound by itself or in an organic solvent without a binder organic or inorganic material or without a binder. The near-infrared blocking film can be used as a protective film for protecting electronic devices or biomaterials that are vulnerable to heat and light, or can be used as an energy storage and delivery system by efficiently absorbing a large amount of energy from the sun.

One aspect of the present invention provides a quinoid-based ionic compound represented by the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 1 to 4, A and B are the same or different from each other, each is nitrogen or phosphorus, and X ^- is an organic anion, substituted or unsubstituted benzene, substituted or unsubstituted Imidazole, substituted or unsubstituted triazole, substituted or unsubstituted tetrazole, sulfonimide or oxalate in which hydrogen of an alkyl group having 1 to 4 carbon atoms is substituted with fluorine or oxalate containing an alkyl group having 0 to 4 carbon atoms and salatoborate, and R ₁ to R ₄ are the same as or different from each other, and are each independently a compound represented by Formula 2 or 3 below.

[Formula 2]

In Formula 2, A ₁ is nitrogen, phosphorus, oxygen or sulfur, A ₂ is nitrogen or phosphorus, R ₂₉ and R ₃₀ are the same as or different from each other, and each independently hydrogen, substituted or unsubstituted C 1 to 10 is a linear or branched alkyl group.

[Formula 3]

In Formula 3, A ₃ and A ₄ are the same as or different from each other, each is carbon, nitrogen, or phosphorus, A ₅ is nitrogen or phosphorus, R ₃₁ and R ₃₂ are the same as or different from each other, and each independently hydrogen, substituted or an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms.

In Formulas 2, 3, and 3-1, * represents a bonding position with an adjacent atom.

Specifically, Chemical Formulas 2 and 3 may be compounds containing at least one substituted or unsubstituted thiophene, pyrrole, benzene (eg, nitrobenzene, dialkybenzene, etc.) and other aromatic groups.

As described above, X is an organic anion, an aromatic ring with or without a heteroatom, substituted or unsubstituted benzene, substituted or unsubstituted imidazole, substituted or unsubstituted triazole, substituted or unsubstituted tetra sol, oxalatoborate containing an alkyl group having 0 to 4 carbon atoms between sulfonimide or oxalate groups in which hydrogen of an alkyl group having 1 to 4 carbon atoms is substituted with fluorine, and the substituents include a hydroxyl group, a thiol group, a sulfone group, This includes cases in which hydrogen is not substituted with fluorine in a halogen group, a nitro group, a cyano group, a carboxy group, an amine group, an aldehyde group, or an alkyl group or alkoxy group having 1 to 10 carbon atoms. The benzene, imidazole, triazole, and tetrazole may be linked to carbon, nitrogen, oxygen, or directly and repeatedly.

In the present specification, the term "alkyl group" or "alkoxy group" includes all of branched, cyclo, linear, and complex types thereof, unless otherwise indicated.

Examples of the substituent in the case of "substituted or unsubstituted" include an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an arylether group, an arylthioether group, An aryl group, a heteroaryl group, a halogen atom, a cyano group, an amino group, a carbonyl group, a carboxy group, an oxycarbonyl group, and a carbamoyl group are preferable, and further, specific substituents that are preferable in the description of each substituent are preferable. In addition, these substituents may be further substituted by the above-mentioned substituent.

The same applies to the case of "substituted or unsubstituted" in the compound or partial structure thereof described below.

The alkyl group represents, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. The alkyl group may or may not have a substituent. There is no restriction|limiting in particular in the case of the additional substituent in case the alkyl group is substituted, For example, an alkyl group, an aryl group, heteroaryl group, etc. are mentioned, This point is common also to the following description. Moreover, carbon number of an alkyl group is although it does not specifically limit, From the point of availability and cost, Preferably it is 1 or more and 20 or less, More preferably, it is the range of 1 or more and 8 or less.

A cycloalkyl group represents saturated alicyclic hydrocarbon groups, such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group, for example. The cycloalkyl group may or may not have a substituent. Although carbon number of the alkyl group part in a cycloalkyl group is not specifically limited, Preferably it is the range of 3 or more and 20 or less.

The heterocyclic group represents, for example, an aliphatic ring having atoms other than carbon in the ring, such as a pyran ring, a piperidine ring, and a cyclic amide. The heterocyclic group may or may not have a substituent. As long as the heterocycle does not have aromaticity, it may have one or more double bonds in the ring. Although carbon number of a heterocyclic group is not specifically limited, Preferably it is the range of 2 or more and 20 or less.

An alkenyl group represents, for example, an unsaturated aliphatic hydrocarbon group containing a double bond, such as a vinyl group, an allyl group, and a butadienyl group. The alkenyl group may or may not have a substituent. Although carbon number of an alkenyl group is not specifically limited, Preferably it is the range of 2 or more and 20 or less.

A cycloalkenyl group represents, for example, an unsaturated alicyclic hydrocarbon group containing a double bond, such as a cyclopentenyl group, a cyclopentadienyl group, and a cyclohexenyl group. The cycloalkenyl group may or may not have a substituent. Although carbon number of a cycloalkenyl group is not specifically limited, Preferably it is the range of 4 or more and 20 or less.

An alkynyl group represents, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond, such as an ethynyl group. The alkynyl group may have a substituent and does not need to have it. Although carbon number of an alkynyl group is not specifically limited, Preferably it is the range of 2 or more and 20 or less.

An alkoxy group represents, for example, a functional group to which an aliphatic hydrocarbon group is bonded via an ether bond, such as a methoxy group, an ethoxy group, and a propoxy group. This aliphatic hydrocarbon group may or may not have a substituent. Although carbon number of an alkoxy group is not specifically limited, Preferably it is the range of 1 or more and 20 or less.

The alkylthio group is one in which the oxygen atom of the ether bond of the alkoxy group is substituted with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. Although carbon number of an alkylthio group is not specifically limited, Preferably it is the range of 1 or more and 20 or less.

The aryl ether group represents a functional group to which an aromatic hydrocarbon group, such as a phenoxy group, bonded through an ether bond, for example. This aromatic hydrocarbon group may or may not have a substituent. Although carbon number of an aryl ether group is not specifically limited, Preferably it is the range of 6 or more and 40 or less.

The arylthioether group is one in which the oxygen atom of the ether bond of the arylether group is substituted with a sulfur atom. The aromatic hydrocarbon group in the arylthioether group may or may not have a substituent. Although carbon number of an arylthio ether group is not specifically limited, Preferably it is the range of 6 or more and 40 or less.

An aryl group represents aromatic hydrocarbon groups, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, anthracenyl group, a pyrenyl group, and a fluoranthenyl group, for example. The aryl group may or may not have a substituent. Although carbon number of an aryl group is not specifically limited, Preferably it is the range of 6 or more and 40 or less, More preferably, it is the range of 6 or more and 24 or less. As a specific example of an aryl group, Preferably, they are a phenyl group, 1-naphthyl group, and 2-naphthyl group.

Heteroaryl group, furanyl group, thiophenyl group, pyridyl group, quinolinyl group, isoquinolinyl group, pyrazinyl group, pyrimidyl group, naphthyridyl group, benzofuranyl group, benzothiophenyl group, indolyl group, dibenzofuranyl group, A cyclic aromatic group having one or more atoms other than carbon in the ring, such as a dibenzothiophenyl group and a carbazolyl group, is represented. The heteroaryl group may or may not have a substituent. Although carbon number of a heteroaryl group is not specifically limited, Preferably it is the range of 2 or more and 30 or less. Specific examples of the heteroaryl group are preferably a pyridyl group, a quinolyl group, a carbazolyl group, a dibenzofuranyl group, and a dibenzothiophenyl group.

An amino group is a substituted or unsubstituted amino group. As a substituent in the case of substitution, an aryl group, a heteroaryl group, a linear alkyl group, and a branched alkyl group are mentioned, for example. More specifically, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a methyl group, etc. are mentioned, These substituents may be further substituted. Although carbon number of a substituent is not specifically limited, Preferably it is the range of 6 or more and 40 or less.

The halogen atom represents an atom selected from fluorine, chlorine, bromine and iodine.

The carbonyl group, carboxy group, oxycarbonyl group, carbamoyl group, and phosphine oxide group may or may not have a substituent. Here, as a substituent, an alkyl group, a cycloalkyl group, an aryl group, heteroaryl group etc. are mentioned, for example, These substituents may be further substituted.

The arylene group represents a divalent or higher group derived from an aromatic hydrocarbon group such as benzene, naphthalene, biphenyl, fluorene, or phenanthrene. The arylene group may or may not have a substituent. A preferable arylene group is a divalent or trivalent arylene group. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, and a fluorenylene group. More specifically, 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 4,4'-biphenylene group, 4,3'-biphenylene group, 3,3'-bi phenylene group, 1,4-naphthalenylene group, 1,5-naphthalenylene group, 2,5-naphthalenylene group, 2,6-naphthalenylene group, 2,7-naphthalenylene group, 1, 3,5-phenylene group etc. are mentioned. More preferably, they are a 1, 4- phenylene group, a 1, 3- phenylene group, a 4,4'- biphenylene group, and a 4,3'- biphenylene group.

The heteroarylene group is from an aromatic group having one or more atoms other than carbon in the ring, such as pyridine, quinoline, pyrimidine, pyrazine, triazine, quinoxaline, quinazoline, dibenzofuran, and dibenzothiophene. It represents a divalent or more induced group. The heteroarylene group may or may not have a substituent. A preferred heteroarylene group is a divalent or trivalent heteroarylene group. Although carbon number of hetero arylene group is not specifically limited, Preferably it is the range of 2 or more and 30 or less. Specific examples of the heteroarylene group include 2,6-pyridylene group, 2,5-pyridylene group, 2,4-pyridylene group, 3,5-pyridylene group, 3,6-pyridylene group, 2 ,4,6-pyridylene group, 2,4-pyrimidinylene group, 2,5-pyrimidinylene group, 4,6-pyrimidinylene group, 2,4,6-pyrimidinylene group, 2,4 ,6-triadinylene group, 4,6-dibenzofuranylene group, 2,6-dibenzofuranylene group, 2,8-dibenzofuranylene group, 3,7-dibenzofuranylene group, etc. are mentioned. can

As a more preferable substituent in the case of "substituted or unsubstituted", a hydroxyl group, a thiol group, a sulfone group, a halogen group, a nitro group, a cyano group, a carboxy group, an amine group, an aldehyde group, or a C1-C10 group Includes cases in which hydrogen is not substituted with fluorine in an alkyl group or an alkoxy group of

In Chemical Formula 1, the ring repeatedly connected with nitrogen or phosphorus may be the same or non-identical material.

In the formula (X), carbon, nitrogen, oxygen, or a structure directly and repeatedly connected includes all of the same or non-identical materials.

Specifically, for example, the cation of Formula 1 may be one selected from the group consisting of Formulas 4 to 6 below.

[Formula 4]

[Formula 5]

[Formula 6]

In the above formula, R ₁ to R ₄ are as defined in Formulas 1 to 3 and Formula 3-1.

According to one embodiment, X in Formula 1 may be represented by any one selected from Formulas 7 to 9 below.

[Formula 7]

In Formula 7, R ₅ to R ₇ are the same as or different from each other, and a hydroxyl group, a thiol group, a sulfone group, a halogen group, a nitro group, a cyano group, a carboxy group, an amine group, an aldehyde group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group in which hydrogen is unsubstituted or substituted with fluorine.

[Formula 8]

In Formula 8, R ₈ is the same as or different from each other, and a hydroxyl group, a thiol group, a sulfone group, a halogen group, a nitro group, a cyano group, a carboxy group, an amine group, an aldehyde group, an alkyl group having 1 to 10 carbon atoms, or hydrogen An alkoxy group unsubstituted or substituted with fluorine.

[Formula 9]

In Formula 9, R ₉ to R ₁₂ are the same as or different from each other, and a hydroxyl group, a thiol group, a sulfone group, a halogen group, a nitro group, a cyano group, a carboxy group, an amine group, an aldehyde group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group in which hydrogen is unsubstituted or substituted with fluorine.

Formulas 7 to 9 are compounds having an imidazolate or tetrazolate structure, and it was possible to solve the problem of limited use due to toxicity due to the use of anions containing heavy metals in conventional materials. In addition, the quinoid-based ionic compound containing the compound having the imidazolate or tetrazolate structure as an anion can be easily manufactured based on high organic solvent solubility in the preparation of a near-infrared blocking film incorporating the quinoid-based ionic compound. did.

According to a preferred embodiment, in Formula 1, X is a compound represented by Formula 7, in Formula 7, R ₅ is CF ₃ , R ₆ and R ₇ are the same as each other, and a nitro group or a cyano group. . The quinoid-based ionic compound containing the compound represented by Chemical Formula 7 that satisfies the above conditions has excellent solubility in organic solvents and excellent affinity with the binder polymer. .

According to another embodiment, the quinoid-based ionic compound may be a compound represented by the following Chemical Formula 10 or 11.

[Formula 10]

In Formula 10, R ₁₃ to R ₂₀ are the same as or different from each other and are an alkyl group having 1 to 6 carbon atoms.

[Formula 11]

In Formula 11, R ₂₁ to R ₂₈ are the same as or different from each other, and represent an alkyl group having 1 to 6 carbon atoms. It was confirmed that the quinoid-based ionic compound represented by Chemical Formula 10 or 11 had excellent transmission characteristics in the visible light region and had broad and even absorption efficiency in the entire near-infrared region (wavelength of 750 to 1300 nm).

According to a preferred embodiment, in Formula 1, A and B may be phosphorus, and n may be 1. When phosphorus is included in the quinoid-based cation in the ionic compound of Formula 1, it not only has a selective high molar extinction coefficient in the near-infrared region, but also has excellent heat resistance and moisture resistance. It was confirmed that the near-infrared blocking film can maintain high heat resistance and high moisture resistance for a long time even in a thin film state.

According to another embodiment, the quinoid-based ionic compound may be a compound represented by the following Chemical Formula 12 or 13.

[Formula 12]

[Formula 13]

The quinoid-based ionic compound represented by Formula 12 or 13 is harmless to the human body, including organic anions, has high solubility in organic solvents, and has high transmittance in the visible region and high absorbance in the infrared region. It was confirmed that it is very suitable for being introduced into

According to the most preferred embodiment, the quinoid-based ionic compound may be a compound represented by the following Chemical Formula 14 or 15.

[Formula 14]

[Formula 15]

The quinoid-based ionic compound represented by Formula 14 or 15 has a molar extinction coefficient of 150,000 cm ⁻¹ M ⁻¹ or more in the near-infrared region, and is thermally decomposed at a temperature of 250° C. or more to have the best near-infrared blocking performance and heat resistance. In addition, compared to quinoid-based ionic compounds under other conditions, it has equivalent near-infrared blocking performance even when a small amount is included, and the visible light transmittance is high. was confirmed to be possible.

Another aspect of the present invention provides a near-infrared blocking film comprising the quinoid-based ionic compound.

Another aspect of the present invention comprises the steps of preparing a mixed solution comprising the quinoid-based ionic compound and a binder; and preparing a near-infrared blocking film using the mixed solution.

The binder is selected from the group consisting of polyethylene, polystyrene, polymethylmethacrylate, polyethersulfone, polyimide, polyacrylate, polyamide, polyurethane, polypeptide, polyester, polycarbonate and polylactic glycolic acid. It may be one or more types of polymers.

The molecular weight of the polymer may be 4,000 to 400,000, preferably 10,000 to 100,000, more preferably 10,000 to 50,000.

In addition, the binder may be at least one inorganic material selected from the group consisting of silica, titania and boron oxide.

The solvent of the mixed solution is acetone, dichloromethane, chloroform, toluene, diethyl ether, petroleum ether, 1,1,2,2-tetrachloroethane, acetonitrile, 1,4-dioxane, tetrahydrofuran, It may be at least one selected from the group consisting of ethyl acetate, methanol, ethanol, hexane, dimethylformamide, dimethylacetamide and dimethoxysulfoxide.

The concentration of the quinoid-based ionic compound in the mixed solution may be 0.001 mg/ml to 100 mg/ml,

The quinoid-based ionic compound may be included in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1.0 to 5.0% by weight, based on the weight of the mixed solution.

The binder may be included in an amount of 3 to 97% by weight based on the weight of the mixed solution.

The step of preparing the near-infrared blocking film using the mixed solution may be performed by a dip coating method, a spin coating method, a doctor blade method, or a spray spraying method.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, these examples are for explaining the present invention in more detail, the scope of the present invention is not limited thereby, and it is common in the art that various changes and modifications are possible within the scope and spirit of the present invention. It will be self-evident to those with knowledge.

Reagents and solvents used in the following examples were purchased from Sigma-Aldrich (USA) and TCI (Japan), unless otherwise specified.

Example 1-1. Quinoid ionic compound N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dicyano-2-trifluoromethyl imidazole production of rate

Preparation of organic anionic sodium dicyano trifluoromethyl imidazolate

In a three-necked flask equipped with a reflux device, 5.0 g of diaminomaleonitrile was dissolved in 50 ml of 1,4-dioxane, and 7.84 g of trifluoroacetic anhydride was added thereto. The mixture was stirred for 12 hours at 60°C under an argon environment. After the completion of the reaction was confirmed by thin film chromatography, the mixture was distilled using a vacuum distiller. The viscous liquid was dissolved in 60 ml of diethyl ether, and extracted with 60 ml of 15% aqueous sodium carbonate solution. The extracted water layer was extracted twice with diethyl ether, activated carbon was added, and the mixture was stirred at 50° C. for 5 hours. After filtering the mixture through a filter, the solvent was completely removed with a evaporator. After removing the solvent, the mixture was dissolved in 50 ml of acetonitrile and filtered to remove solid precipitates. After passing the filtered solution through neutral aluminum oxide, the solvent was removed to obtain 7.6 g of sodium 4,5-dicyano-2-trifluoromethyl imidazolate.

¹³ C NMR (300 MHz; DMSO-d ₆ )/ppm: 114.4, 117.2, 118.8, 120.9, 147.4.

Preparation of N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dicyano-2-trifluoromethyl imidazolate

Under argon, 3.0 g of the sodium 4,5-dicyano-2-trifluoromethylimidazolate and N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4 - After dissolving 5.0 g of phenylenediamine in 100 ml of dichloromethane, 50 ml of isobutanol was added and refluxed for 2 hours. Then, 1.8 g of sodium persulfate and 100 ml of water were added and refluxed for 2 hours. After refluxing, 100 ml of dichloromethane and 100 ml of water were added, and the organic solvent layer was separated and vacuum distilled to N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenyl 5.0 g of rendiimonium bis4,5-dicyano-2-trifluoromethyl imidazolate was obtained. The formula of the product is given below.

Example 1-2. Quinoid ionic compound N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dinitro-2-trifluoromethyl imidazolate Agenda manufacturing.

Preparation of sodium 4,5-dinitro-2-trifluoromethyl imidazolate

5.4 g of 2-(trifluoromethyl)imidazole was dissolved in a mixed solution of 20 g of fuming nitric acid and 20 g of concentrated sulfuric acid, followed by heating under reflux for 10 minutes. After cooling the solution, it was poured into cold water, neutralized with 20% sodium hydroxide until the pH was 5-6, and extracted with ethyl acetate. The extracted materials were collected, water was removed using sodium sulfate, and the solvent was distilled off. The remaining material was separated by passing through 1000 ml of silica gel using ether as an eluent to obtain 4.5 g of sodium 4,5-dinitro-2-trifluoromethyl imidazolate.

¹³ C NMR (300 MHz; Acetone-d ₆ )/ppm: 121.0 (q), 138.2 (q), 140.5 (s);

Preparation of N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dinitro-2-trifluoromethyl imidazolate

Under argon, 3.1 g of the prepared sodium 4,5-dinitro-2-trifluoromethyl imidazolate and N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4 - After dissolving 5.0 g of phenylenediamine in 100 ml of dichloromethane, 50 ml of isobutanol was added and refluxed for 2 hours. Then, 1.8 g of sodium persulfate and 100 ml of water were added and refluxed for 2 hours. After refluxing, 100 ml of dichloromethane and 100 ml of water were added, and the organic solvent layer was separated and vacuum distilled to N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenyl 5.4 g of rendiimonium bis4,5-dinitro-2-trifluoromethyl imidazolate was obtained. The formula of the product is given below.

Examples 1-3. Quinoid ionic compound 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine Preparation of bis4,5-dinitro-2-trifluoromethyl imidazolate

Preparation of 4-bromo-N,N-diethylbenzeneamine

15 g of N,N-diethylaniline and 65 g of tetrabutylammonium bromide were dissolved in 500 ml of acetonitrile. After dissolving 75 g of copper perchlorate hexahydrate in 300 ml of acetonitrile, it was added to the above mixture, stirred at room temperature for 1 hour, and potassium carbonate 100 g was added and stirred for another 10 minutes. After the stirred mixture was filtered, water was removed with sodium sulfate, and the solvent was distilled off. The distilled material was dissolved in diethyl ether, passed through neutral aluminum oxide, and the solvent was removed to obtain 18 g of 4-bromo-N,N-diethylbenzeneamine.

¹ H NMR (300 MHz; CDCl ₃ ): δ7.1(d),6.5(d),3.4(q),1.2(t).

Preparation of 4,4-(bis(N,N-diethylbenzeneamine)phosphine oxide

10 g (43.8 mmol, 3.3 eq) of the 4-bromo-N,N-diethylbenzeneamine was dissolved in 200 ml of THF, and then slowly mixed with the suspension containing 1.1 g of magnesium. After mixing at room temperature for 4 hours, the temperature was lowered to 0 °C, and 1.83 g of diethylphosphite was dissolved in 10 ml of THF. The mixture was stirred at 0° C. for 20 minutes and stirred at room temperature for 2 hours. The temperature was lowered to 0 °C, and 40 ml of 0.1 M hydrogen chloride was slowly added over 5 minutes, and then 40 ml of methyl t-butyl ether was added and stirred for 10 minutes. The floating organic layer was decanted, and 50 ml of dichloromethane was added thereto and shaken. After filtering the mixture, it was dissolved in 50 ml of dichloromethane and passed through gelite. After removing the solvent, it was recrystallized using a mixed solvent of ethyl acetate and heptane to obtain 9.0 g of colorless solid 4,4-bis(N,N-diethylbenzeneamine)phosphine oxide.

Preparation of 4,4-bis(N,N-diethylbenzeneamine) phosphine

After dissolving 9.0 g of the 4,4-bis(N,N-diethylbenzeneamine)phosphine oxide in 200 ml of THF, the solution is slowly mixed with 80 ml of a 1.0 M DIBAL-H hexane solution and stirred at room temperature for 30 minutes. gave. Then, 100 ml of methyl t-butyl ether was slowly added over 10 minutes. After the mixture was lowered to 0° C., 30 mL of 2.0 M sodium hydroxide solution was slowly added over 15 minutes, and 10 ml of saturated sodium chloride solution was added thereto. The mixture was stirred at 0° C. for 10 minutes, and then stirring was continued at room temperature until the layers were separated. When the organic layer was extracted and the solvent was removed, 6.5 g of a colorless oil of 4,4-(bisN,N-diethylbenzeneamine) phosphine was obtained.

Preparation of 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine

7.5 g of cesium carbonate and 0.37 g of copper iodide were mixed in the flask. Then, a solution in which 6 g of 1,4-diiodobenzene and 5 g of 4,4-(bisN,N-diethylbenzeneamine) were dissolved in 50 mL of toluene was added. After heating at 110° C. for 24 h, the mixture was filtered through gelite and rinsed with dichloromethane (3×150 mL). The solution was then washed with water (3 x 500 mL) and dried over sodium sulfate. After removal of the solvent, it was purified by chromatography using hexane:dichloromethane (2: 1, v: v) as an eluent to obtain a white powdery substance 4-((4-(bis(4-(diethylamino)phenyl) ) phosphino)phenyl)(4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine 4.8 g was obtained.

Under argon, 3.1 g of sodium 4,5-dinitro-2-trifluoromethyl imidazolate and 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl) prepared above 4.0 g of (4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine was dissolved in 100 ml of dichloromethane, 50 ml of ethanol was added thereto, and the mixture was refluxed for 2 hours. Then, 1.8 g of sodium persulfate and 100 ml of water were added and refluxed for 2 hours. After refluxing, 100 ml of dichloromethane and 100 ml of water were added, and the organic solvent layer was separated and vacuum distilled to 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl) (4 3.2 g of -(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine bis4,5-dinitro-2-trifluoromethyl imidazolate were obtained. The formula of the product is given below.

Examples 1-4. Quinoid ionic compound 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl) (4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine Preparation of bis(bisoxalatoborate)

Under argon, 2.52 g of lithium bisoxalatoborate and 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phos After dissolving 4.0 g of pino)-N,N-diethylbenzeneamine in 100 ml of dichloromethane, 50 ml of ethanol was added and refluxed for 2 hours. Then, 1.8 g of sodium persulfate and 100 ml of water were added and refluxed for 2 hours. After completion of reflux, 100 ml of dichloromethane and 100 ml of water were added, and the organic solvent layer was separated and vacuum distilled (4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)( 4.8 g of 4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine bis(bisoxalatoborate) were obtained The formula of the product is given below.

Examples 1-5. Quinoid ionic compound 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl) (4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine ) Preparation of bistrifluoromethanesulfonimide

Under argon, 4.0 g of lithium trifluoromethanesulfonimide and 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino) prepared above After dissolving 4.0 g of phenyl)phosphino)-N,N-diethylbenzeneamine in 100 ml of dichloromethane, 50 ml of ethanol was added and refluxed for 2 hours. Then, 1.8 g of sodium persulfate and 100 ml of water were added and refluxed for 2 hours. After completion of reflux, 100 ml of dichloromethane and 100 ml of water were added, and the organic solvent layer was separated and vacuum distilled (4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)( Obtained 6.3 g of 4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine bistrifluoromethanesulfonimide The formula of the product is given below.

Example 1-6. Quinoid ionic compound N,N,N,N-tetrakis(5-dibutylaminothiophenyl)-1,4-phenylenedimonium bis4,5-dicyano-2-trifluoromethyl imine Preparation of dazolate

Preparation of N,N-dibutylthiophen-2-amine

0.3 g of magnesium was added to 25 ml of tetrahydrofuran, and then 0.43 g of anhydrous lithium chloride was added. A solution of 0.8 g of 2-chloropropane in 25 ml of THF was slowly added to the previous solution at room temperature and reacted for 12 hours. In order to separate the reaction solution from the residual magnesium, it was drawn with a syringe and transferred to a new flask filled with argon. After lowering the temperature of the flask to -15 °C, 1.6 g of 2-bromothiophene was slowly mixed. The solution was stirred for 3 hours. 3 g of titanium isopropoxide was added to the solution and the temperature was lowered to -40 °C. A new flask was prepared, and 0.4 g of dibutylamine and 0.52 g of N-chlorosuccinimide were mixed in 10 ml of tetrahydrofuran for 1 hour, and then slowly added to the solution. After slowly raising the temperature to room temperature, the reaction was carried out for 3 hours. After terminating the reaction with a saturated solution of potassium carbonate, ethyl acetate was poured thereto and filtered. After washing several times with distilled water, the solvent was removed to obtain 1.2 g of N.N-dibutylthiophen-2-amine.

¹ H NMR (300 MHz; CDCl ₃ ): δ6.75(t), 6.41(d), 5.84(d), 3.19(t), 1.631.55(m), 1.40-1.31(m), 0.95(t) ).

Preparation of N,N,N,N-tetrakis-2-(5-dibutylaminothiophenyl)-1,4-phenylenediamine

1.2 g of N.N-dibutylthiophen-2-amine was added to 15 ml of anhydrous chloroform, 1 g of N-bromosuccinimide was dissolved in 10 ml of THF, and slowly added, and reacted at room temperature for 3 hours while blocking light. . After the reaction was completed, the mixture was washed several times with water and the solvent was removed to obtain 1.4 g of 5-bromo-N.N-dibutylthiophen-2-amine. After 0.15 g of magnesium was added to 15 ml of tetrahydrofuran, 0.22 g of anhydrous lithium chloride was added. A solution of 0.4 g of 2-chloropropane in 15 ml of THF was slowly added to the previous solution at room temperature and reacted for 12 hours. In order to separate the reaction solution from the residual magnesium, it was drawn with a syringe and transferred to a new flask filled with argon. After lowering the temperature of the flask to -15 °C, 1.4 g of 5-bromo-N.N-dibutylthiophen-2-amine was slowly mixed thereinto. The solution was stirred for 3 hours. 1.5 g of titanium isopropoxide was added to the solution and the temperature was lowered to -40 °C. A new flask was prepared, and 0.13 g of p-phenylenediamine and 0.25 g of N-chlorosuccinimide were mixed in 10 ml of tetrahydrofuran for 1 hour, and then slowly added to the solution. After slowly raising the temperature to room temperature, the reaction was carried out for 3 hours. After terminating the reaction with a saturated solution of potassium carbonate, ethyl acetate was poured thereto and filtered. After washing several times with distilled water and removing the solvent, 0.7 g of N,N,N,N-tetrakis-(2-(5-dibutylaminothiophenyl))-1,4-phenylenediamine was obtained.

¹ H NMR (300 MHz; CDCl ₃ ): δ6.61(s), 5.66(s), 2.93(t), 1.60-1.27(m), 0.91(t).

Under argon, 0.4 g of the sodium 4,5-dicyano-2-trifluoromethylimidazolate and N,N,N,N-tetrakis-(2-(5-dibutylaminothiophenyl) )))-1,4-phenylenediamine 0.7 g was dissolved in 50 ml of dichloromethane, 15 ml of isobutanol was added, and the mixture was refluxed for 2 hours. Then, 0.23 g of sodium persulfate and 50 ml of water were added and refluxed for 2 hours. After refluxing, 100 ml of dichloromethane and 100 ml of water were added, and the organic solvent layer was separated and vacuum distilled to N,N,N,N-tetrakis-2-(5-dibutylaminothiophenyl)-1 0.9 g of ,4-phenylenedimonium bis4,5-dicyano-2-trifluoromethyl was obtained. The formula of the product is given below.

Examples 1-7. Quinoid ionic compound N,N,N,N-tetrakis-2-(5-dibutylaminopyridinyl)-1,4-phenylenedimonium bis4,5-dicyano-2-trifluoro Preparation of methyl imidazolate

Preparation of 5-bromo-N,N-dibutylpyridin-2-amine

After 0.53 g of sodium hydride was added to 20 ml of anhydrous tetrahydrofuran, 1.73 g of 2-amino-5-bromopyridine dissolved in 10 ml of tetrahydrofuran was slowly added. The temperature was raised to 50 °C, and the reaction was stirred until no hydrogen gas was generated. 2.1 g of 1-bromobutane was added, refluxed, and reacted for 12 hours. Methanol was added to terminate the reaction, and extraction was performed with diethyl ether. The solvent was removed to obtain 2.3 g of 5-bromo-N,N-dibutylpyridin-2-amine.

¹ H NMR (300 MHz; CDCl ₃ ): δ8.11(s), 7.49(d), 7.01(d), 3.56(t), 1.56-1.28(m), 0.91(t).

Preparation of N,N,N,N-tetrakis-2-(5-dibutylaminopyridinyl)-1,4-phenylenediamine

After 0.15 g of magnesium was added to 15 ml of tetrahydrofuran, 0.22 g of anhydrous lithium chloride was added. A solution of 0.4 g of 2-chloropropane in 15 ml of THF was slowly added to the previous solution at room temperature and reacted for 12 hours. In order to separate the reaction solution from the residual magnesium, it was drawn with a syringe and transferred to a new flask filled with argon. After lowering the temperature of the flask to -15 °C, 1.4 g of 5-bromo-N.N-dibutylpyridin-2-amine was slowly mixed thereinto. The solution was stirred for 3 hours. 1.5 g of titanium isopropoxide was added to the solution and the temperature was lowered to -40 °C. A new flask was prepared, and 0.13 g of p-phenylenediamine and 0.25 g of N-chlorosuccinimide were mixed in 10 ml of tetrahydrofuran for 1 hour, and then slowly added to the solution. After slowly raising the temperature to room temperature, the reaction was carried out for 3 hours. After terminating the reaction with a saturated solution of potassium carbonate, ethyl acetate was poured in and filtered. After washing several times with distilled water and removing the solvent, 0.85 g of N,N,N,N-tetrakis-(2-(5-dibutylaminothiophenyl))-1,4-phenylenediamine was obtained.

¹ H NMR (300 MHz; CDCl ₃ ): δ7.95(s), 7.11(d), 6.83(d), 6.50(s), 3.51(t), 1.58-1.33(m), 0.94(t).

Under argon, 0.4 g of sodium 4,5-dicyano-2-trifluoromethylimidazolate and N,N,N,N-tetrakis-(2-(5-dibutylaminopyridinyl)) 0.8 g of -1,4-phenylenediamine was dissolved in 50 ml of dichloromethane, 15 ml of isobutanol was added, and the mixture was refluxed for 2 hours. Then, 0.23 g of sodium persulfate and 50 ml of water were added and refluxed for 2 hours. After completion of reflux, 100 ml of dichloromethane and 100 ml of water were added, the organic solvent layer was separated and vacuum distilled to N,N,N,N-tetrakis-2-(5-dibutylaminopyridinyl)-1, 0.9 g of 4-phenylenedimonium bis4,5-dicyano-2-trifluoromethyl was obtained. The formula of the product is given below.

Examples 1-8. Preparation of quinoid ionic compound N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis5-trifluoromethyl tetrazolate

Preparation of sodium 5-trifluoromethyl tetrazolate

After dissolving 3.2 g of sodium azide in 50 ml of anhydrous acetonitrile, the reaction flask was placed in a cooler, the temperature was lowered to -80 °C, and stirred vigorously. In a new flask connected to the flask by a tube, 10.5 g of trifluoroacetamide and 8.3 g of pyridine were slowly mixed. It was stirred slowly while confirming that gas was generated during the reaction. When gas generation stopped, the temperature of the flask containing the acetonitrile solution was raised to room temperature and reacted for 2 days. The solvent was removed with a distiller to obtain 5.2 g of sodium 5-trifluoromethyl tetrazolate.

¹³ C NMR (300 MHz; DMSO-d ₆ )/ppm: 123.6, 154.1.

Under argon, 2.5 g of the sodium 5-trifluoromethyl tetrazolate and 5.0 g of N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenediamine were dissolved in dichloromethane After dissolving in 100 ml, 50 ml of isobutanol was added and refluxed for 2 hours. Then, 1.8 g of sodium persulfate and 100 ml of water were added and refluxed for 2 hours. After refluxing, 100 ml of dichloromethane and 100 ml of water were added, and the organic solvent layer was separated and vacuum distilled to N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenyl 4.2 g of rendiimonium bis5-trifluoromethyl tetrazolate were obtained. The formula of the product is given below.

Examples 1-9. Quinoid ionic compound N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis(2-(1H-imidazoyl-2-amino)-1H Preparation of -4,5-dicyanoimidazolate

Preparation of sodium (2-(1H-imidazoyl-2-amino)-4,5-dicyanoimidazolate

In a flask filled with argon, 1.5 g of 2-bromo-1H-imidazole, 1.4 g of 2-amino-4,5-imidazole dicarbonitrile, 1.1 g of sodium butoxide, and 25 ml of toluene were added and stirred. 0.11 g of Pd(dba) ₂ palladium catalyst and 0.05 g of tributyl phosphate were added, and it was confirmed that the solution became dark purple. When the solution became purple, the temperature was raised to 100 °C and reacted for 12 hours. When the reaction was completed, it was precipitated in methanol, and the solid filtered through the filter was washed several times with methanol, hexane, and water. The obtained solid was dissolved in diethyl ether and extracted several times with 15% sodium carbonate solution. The organic solvent layer was removed with a evaporator to obtain 0.91 g of sodium (2-(1H-imidazoyl-2-amino)-4,5-dicyanoimidazolate.

¹³ C NMR (300 MHz; DMSO-d ₆ )/ppm: 112.2, 115.8, 120.2, 127.8, 134.0, 167.7.

Under argon, 0.9 g of the sodium (2-(1H-imidazoyl-2-amino)-4,5-dicyanoimidazolate and N,N,N,N-tetrakis(4-diisobutyl) After dissolving 1.6 g of aminophenyl)-1,4-phenylenediamine in 20 ml of dichloromethane, 10 ml of isobutanol was added and refluxed for 2 hours After that, 0.95 g of sodium persulfate and 20 ml of water were added thereto, followed by 2 hours After completion of the reflux, 100 ml of dichloromethane and 100 ml of water were added, the organic solvent layer was separated and vacuum distilled to obtain N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1, 1.7 g of 4-phenylenedimonium bis((2-(1H-imidazoyl-2-amino)-4,5-dicyanoimidazolate) were obtained. The formula of the product is given below.

Example 2-1. Near-infrared blocking film using N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dinitro-2-trifluoromethyl imidazolate Produce

N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dinitro-2-trifluoro obtained in Example 1-2 above in chloroform Romethyl imidazolate was dissolved in 4.0 mass%. The glass was coated by a spray coating method. The thickness and transmittance were controlled by the number of coatings.

Λmax: 1100 nm (thickness; 20 nm).

Example 2-2. Near-infrared blocking film using N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dinitro-2-trifluoromethyl imidazolate Produce

N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dinitro-2-trifluoro obtained in Example 1-2 above in chloroform Dissolve romethyl imidazolate at 1.0 mass% and polyethersulfone (molar average molecular weight: 16,000) at 6.0 mass%. It is coated on the glass by the spin coating method. The thickness and permeability are controlled by the rotation speed and number of times.

Λmax: 1132 nm (thickness; 1-3 μm).

Photothermal film temperature: 119.0 ℃ (No filter) / 31.4 ℃ (Filter).

The maximum temperature of the filter: 40.1 ℃.

Example 2-3. Near-infrared blocking film using N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dicyano-2-trifluoromethyl imidazolate manufacture of

N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dicyano-2-tri obtained in Example 1-1 in toluene Fluoromethyl imidazolate was dissolved in 1.0 mass %, and polymethyl methacrylate (average molecular weight: 15,000) was dissolved in 6.0 mass %. It is coated on the glass by the spin coating method. The thickness and transmittance were controlled by the rotation speed and number of times.

Λmax: 1098 nm (thickness; 1 - 3 μm)

Photothermal film temperature: 118.3 ℃ (No filter) / 32.4 ℃ (Filter).

The maximum temperature of the filter: 40.3 ℃.

Example 2-4. 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl) (4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine bis4,5- Preparation of near-infrared blocking film using dinitro-2-trifluoromethyl imidazolate

4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phosphino)-N,N obtained in Example 1-3 in chloroform -Diethylbenzeneamine bis4,5-dinitro-2-trifluoromethyl imidazolate was dissolved in 1.0 mass%, and polyethersulfone (molar average molecular weight: 16,000) was dissolved in 5.0 mass%. It is coated on the glass by the spin coating method. The thickness and transmittance were controlled by the rotation speed and number of times.

Λmax: 1257 nm (thickness; 1-3 μm).

Photothermal film temperature: 117.7 ℃ (No filter) / 28.8 ℃ (Filter).

The maximum temperature of the filter: 43.0 ℃.

Example 2-5. (4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine bistrifulo Preparation of near-infrared blocking film using romethanesulfonimide

(4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phosphino)-N obtained in Example 1-5 above in toluene, Dissolve N-diethylbenzeneamine bistrifluoromethanesulfonimide at 1.0 mass%, and polyether sulfone (average molecular weight: 16,000) at 5.0 mass%.Coated on glass by spin coating. The thickness and transmittance were controlled by the number of times.

Λmax: 1243 nm (thickness; 1 - 3 μm)

Photothermal film temperature: 117.5 ℃ (No filter) / 29.9 ℃ (Filter).

The maximum temperature of the filter: 41.0 ℃.

Example 2-6. Sol-gel with N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dicyano-2-trifluoromethyl imidazolate Fabrication of a near-infrared blocking film using a layer

3-glycidoxypropyl trimethoxy silane, methyltrimethoxy silane, tetraethylorthosilicate, and 2-propynyl [3- (triethoxysilyl) propyl] carbamate, respectively, in a 2 : 1 : 1 : 0.25 (molar ratio) ), and the mixture was mixed well with water for more than 4 hours so that the mixture became 60% by mass. In the mixture, N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dicyano-2-obtained in Example 1-1 above Trifluoromethyl imidazolate was added as much as 2.0% by mass, and mixed with an aqueous hydrochloric acid solution. The mixture was coated with a thickness of 30 μm by a doctor blade method, and then heat-treated by heating at 100 °C.

Λmax: 998 nm

Example 2-7. (4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine bis(bisox Preparation of near-infrared blocking film using salatoborate) and sol-gel layer

3-glycidoxypropyl trimethoxy silane, methyltrimethoxy silane, tetraethylorthosilicate, and 2-propynyl [3- (triethoxysilyl) propyl] carbamate, respectively, in a 2 : 1 : 1 : 0.25 (molar ratio) ), and the mixture was mixed well with water for more than 4 hours to make 60% by mass. (4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phosphino)-N obtained in Example 1-4 4.0% by mass of ,N-diethylbenzeneamine bis(bisoxalatoborate) was added, and mixed with an aqueous hydrochloric acid solution.The mixture was coated with a thickness of 30 μm by a doctor blade method, and then heat-treated by heating at 100 ° C. .

Λmax: 1190 nm

Comparative Example 1-1. Preparation of dimonium compound N,N,N',N,-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis(bisoxalatoborate)

Add 5.0 g of N,N,N',N'-tetrakis(p-diisobutylaminophenyl)-p-phenylenediamine, 2.5 g of lithium bisoxalatoborate, 100 ml of dichloromethane and 50 ml of ethanol 2 After refluxing for an hour, 2.0 g of sodium persulfate and 100 ml of water were added and refluxed for 2 hours. After refluxing, 100 ml of dichloromethane and 100 ml of water were added, the organic solvent layer was separated and vacuum distilled to N,N,N',N'-tetrakis(p-diisobutylaminophenyl)-p-phenyl 5.2 g of rendiimonium bis(bisoxalatoborate) were obtained.

Comparative Example 2-1. Preparation of a near-infrared blocking film using the N-dimonium-based compound N,N,N',N,-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis(bisoxalatoborate)

In chloroform, 1.0 of N,N,N',N,-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis(bisoxalatoborate) obtained in Comparative Example 1-1 above was added to chloroform. It was dissolved in mass%, and polyethersulfone (molar average molecular weight: 16,000) was dissolved in 6.0 mass%. The glass was coated by a spin coating method. The thickness and transmittance were controlled by the rotation speed and number of times.

Λmax: 1103 nm (thickness; 1-3 μm).

Photothermal film temperature: 115.2 ℃ (No filter) / 32.2 ℃ (Filter).

The maximum temperature of the filter: 39.9 ℃.

Experimental Example 1. UV/VIS spectrum analysis and heat rise

The quinoid-based compounds prepared in Examples 1-1 and 1-2 and Comparative Example 1-1 were respectively diluted in chloroform, and UV/VIS spectra were measured.

1 is a graph showing a solution phase UV-VIS-NIR absorption spectrum of a quinoid-based ionic compound according to an embodiment of the present invention. As shown in FIG. 1, Example 1-1 and Comparative Example 1-1 had transmittance of 90% or more in the visible light region, and the maximum absorption wavelength was almost similar to around 1100 nm. Although not shown in FIG. 1, Example 1-2 also had a spectrum similar to that of Example 1-1 and Comparative Example 1-1.

On the other hand, in the measurement of the molar extinction coefficient, the material of Comparative Example 1-1 had 140,000 cm ^-1 M ^-1 , while the quinoid-based compound N,N,N,N-tetrakis (4- Diisobutylaminophenyl) -1,4-phenylenedimonium bis4,5-dicyano-2-trifluoromethyl imidazolate is 200,000 cm ^-1 M ^-1 , N of Example 1-2, 210,000 N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dinitro-2-trifluoromethyl imidazolate cm ^-1 M ^-1 showed a significantly high molar extinction coefficient.

In addition, the results of measuring the maximum absorption wavelength (Λmax, nm) of the near-infrared blocking film prepared according to Examples 2-1 to 2-7 are described in Table 1 below.

near-infrared shield Maximum absorption wavelength (Λmax, nm) Example 2-1 1100 Example 2-2 1132 Example 2-3 1098 Example 2-4 1257 Example 2-5 1243 Example 2-6 998 Example 2-7 1190

As shown in Table 1, the near-infrared blocking films according to Examples 2-1 to 2-7 showed a maximum absorption wavelength in the range of 998 to 1257 nm, confirming that the near-infrared blocking effect was excellent.

near-infrared shield maximum absorption wavelength
(Λmax, nm) 80 ℃, humidity>90%, 24 hours 120 ℃, 24 hours Example 2-2 1132 + 1.0 + 7.3 Example 2-4 1257 + 0.3 + 3.1 Example 2-6 998 + 0.1 + 0.7 Comparative Example 2-1 1103 + 1.2 + 10.0

In addition, the moisture and heat resistance performance of the prepared near-infrared blocking film was analyzed. It can be said to be a stable barrier film when it maintains its original properties under high temperature and high humidity conditions.

When the near-infrared blocking film prepared in Examples 2-2, 2-4, 2-6 and Comparative Example 2-1 is stored for 24 hours under high humidity conditions (80 °C, humidity >90%) and high temperature conditions (120 °C) Changes in transmittance at the maximum absorption wavelength were confirmed, and the results are shown in Table 2 above. As shown in Table 2, when phosphorus was included in the quinoid-based compound, thermal stability was greatly improved, and it was confirmed that the transmittance hardly changed at 120 °C for a long time.

Experimental Example 2. Analysis of heat generation according to the presence or absence of a near-infrared blocking film

2 is a graph showing the thermal rise of the photothermal film according to the presence or absence of the near-infrared blocking film of Example 2-2. A poly(3,4-ethylenedioxythiophene) film having excellent photothermal effect was installed at the bottom of the laser, and a near-infrared blocking film was placed between them, and then the laser was irradiated.

Also, FIG. 3 is a thermal image showing heat generation according to the presence or absence of a near-infrared blocking film according to Example 2-2. As shown in FIGS. 2 and 3, when the near-infrared blocking film is not installed (No filter in FIG. 2), the temperature of the photothermal film increased to 119° C., but when the near-infrared blocking film is installed (filter in FIG. 2) 31.4 It was confirmed that the heat generation decreased at ℃.

Table 2 shows the results of analyzing the temperature of the photothermal film according to the presence or absence of the near-infrared blocking film of Examples 2-2, 2-3, and 2-5.

near-infrared shield No barrier (℃) With barrier (°C) Example 2-2 119.0 31.4 Example 2-3 118.3 32.4 Example 2-4 117.7 28.8 Example 2-5 117.5 29.9 Comparative Example 2-1 115.2 32.2

As shown in Table 2, when the near-infrared blocking films of Examples 2-2, 2-3 and 2-5 were installed, it was confirmed that heat generation was significantly reduced.

Experimental Example 3. NMR spectrum analysis

The Example 1-1. The quinoid-based compounds prepared in 1-2 and Comparative Example 1-1 are ionic substances, and it is difficult to accurately identify peaks in NMR. Therefore, to confirm the success of the synthesis, hydrazine was added as a reducing agent to confirm whether it returned to the original starting material.

After dissolving 10 mg of the material of Examples 1-1 and 1-2 and Comparative Example 1-1 in 10 ml of acetonitrile, 10 mg of hydrazine was added and mixed for 10 minutes. After filtering the precipitated solid with a filter, it was dried at 90° C. under vacuum for 1 hour. After dissolving the obtained solid in deuterium-substituted chloroform, check NMR with 1 mg of hydrazine mixed. Examples 1-1 and 1-2 and Comparative Example 1-1 all used N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenediamine as a starting material. Therefore, the same peak was shown.

¹ HNMR (CDCl _3, 400 MHz): 6.92-6.49 (m, 20H), 3.00 (d, J=7.2 Hz, 16H), 2.03-1.96 (m, 8H), and 0.85 (d, J=6.8 Hz, 48H).

Therefore, the quinoid-based ionic compound according to the present invention has high transmittance in the visible light region and high absorbance in the near-infrared region, enabling efficient near-infrared blocking, and high solubility in organic solvents, making it easy to prepare a thin film, as well as a polymer It has excellent compatibility with and can maintain high heat resistance and high moisture resistance in a thin film state for a long time. The near-infrared blocking film containing the quinoid-based ionic compound is suitable for being applied to a protective film for protecting electronic devices, and may also be used as a heat insulating film or a light energy absorbing layer.

The above-described Examples and Comparative Examples are examples for explaining the present invention, and the present invention is not limited thereto. Those of ordinary skill in the art to which the present invention pertains will be able to practice the present invention with various modifications therefrom, so the technical protection scope of the present invention should be defined by the appended claims.

Claims (15)

delete A quinoid-based ionic compound represented by the following formula (1):
[Formula 1]

In Formula 1,
n is an integer from 1 to 4,
A and B are the same as or different from each other and each is nitrogen or phosphorus,
R ₁ To R ₄ Are the same as or different from each other, and are each independently a compound represented by Formula 2 or 3,
[Formula 2]

In Formula 2, A ₁ is nitrogen, phosphorus, oxygen or sulfur,
A ₂ is nitrogen or phosphorus,
R ₂₉ and R ₃₀ are the same as or different from each other, and are each independently hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms,
[Formula 3]

In Formula 3, A ₃ and A ₄ are the same as or different from each other, and each is carbon, nitrogen, or phosphorus;
A ₅ is nitrogen or phosphorus,
R ₃₁ and R ₃₂ are the same or different from each other, and each independently represent hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, and X in Formula 1 is any one selected from the following formulas 7 to 9 It is a compound represented by one,
[Formula 7]

In Formula 7, R ₅ to R ₇ are the same as or different from each other, and a hydroxyl group, a thiol group, a sulfone group, a halogen group, a nitro group, a cyano group, a carboxy group, an amine group, an aldehyde group, an alkyl group having 1 to 10 carbon atoms Or hydrogen is an alkoxy group unsubstituted or substituted with fluorine,
[Formula 8]

In Formula 8, R ₈ is the same as or different from each other, and a hydroxyl group, a thiol group, a sulfone group, a halogen group, a nitro group, a cyano group, a carboxy group, an amine group, an aldehyde group, an alkyl group having 1 to 10 carbon atoms, or hydrogen an alkoxy group unsubstituted or substituted with fluorine;
[Formula 9]

In Formula 9, R ₉ to R ₁₂ are the same as or different from each other, and a hydroxyl group, a thiol group, a sulfone group, a halogen group, a nitro group, a cyano group, a carboxy group, an amine group, an aldehyde group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group in which hydrogen is unsubstituted or substituted with fluorine.
A quinoid-based ionic compound represented by the following formula (1):
[Formula 1]

In Formula 1,
n is an integer from 1 to 4,
A and B are the same as or different from each other and each is nitrogen or phosphorus,
R ₁ To R ₄ Are the same as or different from each other, and are each independently a compound represented by Formula 2 or 3,
[Formula 2]

In Formula 2, A ₁ is nitrogen, phosphorus, oxygen or sulfur,
A ₂ is nitrogen or phosphorus,
R ₂₉ and R ₃₀ are the same as or different from each other, and are each independently hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms,
[Formula 3]

In Formula 3, A ₃ and A ₄ are the same as or different from each other, and each is carbon, nitrogen, or phosphorus;
A ₅ is nitrogen or phosphorus,
R ₃₁ and R ₃₂ are the same as or different from each other, and each independently represent hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms,
In Formula 1, X is a compound represented by Formula 7,
[Formula 7]

In Formula 7, R ₅ is CF ₃ ,
R ₆ and R ₇ are the same as each other and represent a nitro group or a cyano group.
delete delete 3. The method of claim 2,
The quinoid-based ionic compound is a quinoid-based ionic compound, which is a compound represented by the following Chemical Formula 12 or 13:
[Formula 12]

[Formula 13]

3. The method of claim 2,
The quinoid-based ionic compound is a quinoid-based ionic compound, which is a compound represented by the following Chemical Formula 14 or 15:
[Formula 14]

[Formula 15]

A near-infrared blocking film comprising the quinoid-based ionic compound according to any one of claims 2, 3, 6, and 7
Preparing a mixed solution comprising the quinoid-based ionic compound according to any one of claims 2, 3, 6, and 7 and a binder; and
A method of manufacturing a near-infrared blocking film comprising; preparing a near-infrared blocking film by using the mixed solution.
10. The method of claim 9,
The binder is selected from the group consisting of polyethylene, polystyrene, polymethylmethacrylate, polyethersulfone, polyimide, polyacrylate, polyamide, polyurethane, polypeptide, polyester, polycarbonate and polylactic glycolic acid. A method for producing at least one near-infrared blocking film.
10. The method of claim 9,
The binder is a method of manufacturing at least one kind of near-infrared blocking film selected from the group consisting of silica, titania and boron oxide.
10. The method of claim 9,
The solvent of the mixed solution is acetone, dichloromethane, chloroform, toluene, diethyl ether, petroleum ether, 1,1,2,2-tetrachloroethane, acetonitrile, 1,4-dioxane, tetrahydrofuran, A method for producing at least one near-infrared blocking film selected from the group consisting of ethyl acetate, methanol, ethanol, hexane, dimethylformamide, dimethylacetamide and dimethoxysulfoxide.
10. The method of claim 9,
The concentration of the quinoid-based ionic compound in the mixed solution is 0.001 mg/ml to 100 mg/ml of a method for producing a near-infrared blocking film.
10. The method of claim 9,
The method for producing a near-infrared blocking film, wherein the quinoid-based ionic compound is contained in an amount of 0.1 to 20% by weight based on the weight of the mixed solution.
10. The method of claim 9,
The manufacturing method of the near-infrared blocking film using the mixed solution is performed by a dip coating method, a spin coating method, a doctor blade method, or a spray spraying method.

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