KR20200071039A - 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 ray-blocking film comprising the quinoid-based ionic compound. According to the present invention, the quinoid-based ionic compound can efficiently block a near-infrared ray due to high transmittance in a visible ray region and high absorbance in a near-infrared ray region, can be easily prepared into a thin film due to high solubility in an organic solvent, and can maintain high heat-resistant and high moisture-resistant properties in a thin film state for a long time due to excellent affinity with a polymer. The near-infrared ray-blocking film containing the quinoid-based ionic compound is suitable for being applied to a protective film for protecting electronic devices, and can be used as an insulating film or a light energy absorbing layer.

Description

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}

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

Infrared is a large energy source that accounts for about 40% of the solar energy reaching the Earth, and is particularly related to thermal energy. Infrared rays having a long wavelength of 800 nm or more have high transmittance to a general visible light shielding film, and can generate excessive heat in automobiles, buildings, and electronic devices without a specific shielding film.

In addition, since most electronic devices use infrared rays for signal transmission, there is a risk of signal malfunction if the Busan-Near Infrared rays generated from the equipment are not blocked, so an efficient barrier is essential.

In order to utilize the near-infrared ray blocking film in real life, it is necessary to selectively absorb only infrared light while having high transmittance to visible light, because absorbing visible light may interfere with the field of view and deteriorate aesthetics or utility.

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 excellent infrared absorption characteristics in the region of 800 nm or more.

However, the dimonium-based materials known to date have limitations in use due to toxicity using antimonic hexafluoride containing heavy metals in anions, or there are problems in solubility in organic solvents using halogen ions such as chlorine and bromine. . In addition, since the affinity with the polymer is not good, it is easily eluted by heat after formation of the blocking film, and thus there is a problem of discoloration of the blocking film, and thus there is a problem that it is difficult to use for a long time. Therefore, there is a need to introduce new structures to cations and anions 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), a low extinction coefficient in the visible light region (especially a wavelength of 350 to 700 nm), and heat resistance. And it is to provide a quinoid-based ionic compound having high moisture resistance and a method for manufacturing the same.

Another technical problem to be solved by the present invention is to provide a high heat-resistant and high-humidity near-infrared blocking film including 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 Chemical Formula 1, n is an integer of 1 to 4, A and B are the same or different from each other, and each is nitrogen or phosphorus, and X ^- is an organic anion, substituted or unsubstituted benzene, substituted or unsubstituted Imidazole, a substituted or unsubstituted triazole, a substituted or unsubstituted tetrazole, a sulfonimide substituted with hydrogen of an alkyl group having 1 to 4 carbon atoms, or an oxalate group containing an alkyl group having 0 to 4 carbon atoms Salatoborate, R ₁ to R ₄ are the same or different from each other, and each independently a compound represented by the following 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 or different from each other, and each independently hydrogen, substituted or unsubstituted carbon atoms 1 to It is a linear or branched alkyl group of 10.

[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, and R ₃₁ and R ₃₂ are the same 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 containing the quinoid-based ionic compound and a binder; And manufacturing 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 light region and high absorbance in the near-infrared region, so that it can block efficient near-infrared rays, and has a high solubility in organic solvents, making it easy to manufacture into a thin film, as well as with a polymer. It has excellent affinity and can maintain high heat resistance and high moisture resistance for a long time in a thin film state.

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

1 is a graph showing a UV-VIS-NIR absorption spectrum of a solution phase of a quinoid-based ionic compound according to an embodiment of the present invention.
Figure 2 is a heat rise graph of the photothermal film according to the presence or absence of a near-infrared blocking film according to Example 2-2 of the present invention.
3 is a thermal image confirming the 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 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 an organic solvent and is easy to utilize, and the compound can be mixed by itself or on an organic solvent without a binder or an organic solvent to form a near infrared absorbing or blocking film. The near-infrared shielding film may be used as a protective film for protecting electronic devices or biomaterials that are vulnerable to heat and light, or may be used as an energy storage and transporter 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 Chemical Formula 1, n is an integer of 1 to 4, A and B are the same or different from each other, and each is nitrogen or phosphorus, and X ^- is an organic anion, substituted or unsubstituted benzene, substituted or unsubstituted Imidazole, a substituted or unsubstituted triazole, a substituted or unsubstituted tetrazole, a sulfonimide substituted with hydrogen of an alkyl group having 1 to 4 carbon atoms, or an oxalate group containing an alkyl group having 0 to 4 carbon atoms Salatoborate, R ₁ to R ₄ are the same or different from each other, and each independently a compound represented by the following 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 or different from each other, and each independently hydrogen, substituted or unsubstituted carbon atoms 1 to It is a linear or branched alkyl group of 10.

[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, and R ₃₁ and R ₃₂ are the same 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 Chemical Formulas 2, 3 and 3-1, * represents a bonding position with an adjacent atom.

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

As described above, X is an organic anion, an aromatic ring with or without heteroatoms, substituted or unsubstituted benzene, substituted or unsubstituted imidazole, substituted or unsubstituted triazole, substituted or unsubstituted tetra Oxalatoborate including alkyl groups having 0 to 4 carbon atoms between sol, 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 hydroxy groups, thiol groups, sulfone groups, It includes the case where 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 an alkoxy group having 1 to 10 carbon atoms. The benzene, imidazole, triazole, tetrazole may be directly connected to carbon, nitrogen, oxygen, or directly.

In the present specification, “alkyl group” or “alkoxy group” includes all branched, cyclo, straight chain, and combinations thereof, unless otherwise specified.

Examples of the substituent in the case of "substituted or unsubstituted" include an alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, aryl ether group, 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 preferred. Further, specific substituents, which are preferred in the description of each substituent, are preferred. Moreover, these substituents may be further substituted with the above-mentioned substituents.

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

The alkyl group represents, for example, a saturated aliphatic hydrocarbon group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group or tert-butyl group. The alkyl group may or may not have a substituent. The additional substituent in the case where the alkyl group is substituted is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heteroaryl group. This point is common to the following description. Moreover, although carbon number of an alkyl group is not specifically limited, From the point of ease of availability and cost, Preferably it is 1 or more and 20 or less, More preferably, it is 1 or more and 8 or less.

The cycloalkyl group represents, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl group, cyclohexyl group, norbornyl group or adamantyl group. The cycloalkyl group may or may not have a substituent. The number of carbon atoms in the alkyl group portion in the cycloalkyl group is not particularly limited, but is preferably 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, or a cyclic amide. The heterocyclic group may or may not have a substituent. The heterocycle may have one or more double bonds in the ring as long as it does not have aromaticity. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably 2 or more and 20 or less.

The alkenyl group represents, for example, an unsaturated aliphatic hydrocarbon group containing a double bond, such as a vinyl group, an allyl group, 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 2 or more and 20 or less.

The cycloalkenyl group represents, for example, an unsaturated alicyclic hydrocarbon group containing a double bond, such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexenyl group. The cycloalkenyl group may or may not have a substituent. The number of carbon atoms of the cycloalkenyl group is not particularly limited, but is preferably 4 or more and 20 or less.

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

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

The aryl ether group represents, for example, a functional group to which an aromatic hydrocarbon group via an ether bond is bonded, such as a phenoxy group. This aromatic hydrocarbon group may or may not have a substituent. The number of carbon atoms of the aryl ether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

An 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. The number of carbon atoms of the arylthioether group is not particularly limited, but is preferably 6 or more and 40 or less.

The aryl group represents, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, anthracenyl group, pyrenyl group, or fluoranthenyl group. The aryl group may or may not have a substituent. The number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 or more and 40 or less, and more preferably 6 or more and 24 or less. As a specific example of an aryl group, Preferably it is a phenyl group, 1-naphthyl group, 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 dibenzothiophenyl group and carbazolyl group. The heteroaryl group may or may not have a substituent. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably 2 or more and 30 or less. As a specific example of a heteroaryl group, Preferably it is a pyridyl group, a quinoyl group, a carbazolyl group, a dibenzofuranyl group, and a dibenzothiophenyl group.

An amino group is a substituted or unsubstituted amino group. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a straight chain alkyl group, and a branched alkyl group. More specifically, phenyl group, biphenyl group, naphthyl group, pyridyl group, methyl group, etc. may be mentioned, and 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, carboxyl group, oxycarbonyl group, carbamoyl group and phosphine oxide group may or may not have a substituent. Here, as a substituent, an alkyl group, cycloalkyl group, aryl group, heteroaryl group, etc. are mentioned, for example, These substituents may further be substituted.

The arylene group represents a divalent or higher group derived from aromatic hydrocarbon groups such as benzene, naphthalene, biphenyl, fluorene and phenanthrene. The arylene group may or may not have a substituent. Preferred arylene groups are divalent or trivalent arylene groups. 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, And 3,5-phenylene groups. More preferably, it is a 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, and 4,3'-biphenylene group.

A heteroarylene group is an aromatic group having one or more atoms other than carbon, such as pyridine, quinoline, pyrimidine, pyrazine, triazine, quinoxaline, quinazoline, dibenzofuran, dibenzothiophene, in a ring. It represents a group of divalent or higher derivatives. The heteroarylene group may or may not have a substituent. Preferred heteroarylene groups are divalent or trivalent heteroarylene groups. The number of carbon atoms of the heteroarylene group is not particularly limited, but is preferably 2 or more and 30 or less. As a heteroarylene group, specifically, 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. Can be.

As a more preferable substituent in the case of "substituted or unsubstituted", a hydroxy 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 1 to 10 carbon atoms. It includes the case where hydrogen is substituted or not substituted with fluorine in the alkyl group or the alkoxy group.

Rings repeatedly connected to nitrogen or phosphorus in Chemical Formula 1 may be the same or different materials.

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

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

[Formula 4]

[Formula 5]

[Formula 6]

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

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

[Formula 7]

In Formula 7, R ₅ to R ₇ are the same as or different from each other, and a hydroxy 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 an alkyl group having 1 to 10 carbon atoms. Or an alkoxy group in which hydrogen is substituted or unsubstituted with fluorine.

[Formula 8]

In Formula 8, R ₈ is the same or different from each other, and a hydroxy 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 It is 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 hydroxy 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 an alkyl group having 1 to 10 carbon atoms. Or an alkoxy group in which hydrogen is substituted or unsubstituted with fluorine.

The formulas 7 to 9 are compounds having an imidazolate or tetrazolate structure, and have been able to solve the problem of limited use due to toxicity by using anions containing heavy metals in conventional materials. In addition, the quinoid-based ionic compound containing the compound having an imidazolate or tetrazolate structure as an anion can be easily manufactured based on high solubility of an organic solvent in the production of a near-infrared barrier film incorporating the quinoid-based ionic compound. Did.

According to a preferred embodiment, X in Formula 1 is a compound represented by Formula 7, R ₅ in Formula 7 is CF ₃ , R ₆ and R ₇ are the same as each other, and are a nitro group or a cyano group. . The quinoid-based ionic compound containing the compound represented by the formula (7) satisfying the above conditions has excellent organic solvent solubility and excellent affinity with the binder polymer, so that the elution of anions due to heat after formation of the near-infrared blocking film was not observed. .

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

[Formula 10]

In Formula 10, R ₁₃ to R ₂₀ are the same or different from each other, and are alkyl groups 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 are alkyl groups having 1 to 6 carbon atoms. It was confirmed that the quinoid-based ionic compound represented by Chemical Formulas 10 or 11 had excellent transmission characteristics in the visible light region and broad and uniform absorption efficiency in all near infrared regions (wavelengths of 750 to 1300 nm).

According to a preferred embodiment, in Formula 1, A and B are 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 ensures excellent heat resistance and moisture resistance, thereby producing the quinoid-based ionic compound. It was confirmed that the near-infrared blocking film can maintain high heat and 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 Chemical Formulas 12 or 13, including organic anions, is harmless to the human body, has high solubility in organic solvents, has high transmittance in the visible light region and high absorbance in the infrared region, etc. It was confirmed that it is very suitable to be introduced into.

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

[Formula 14]

[Formula 15]

The quinoid-based ionic compound represented by Chemical Formulas 14 or 15 has a molar extinction coefficient in the near-infrared region of 150,000 cm ^-1 M ^-1 or higher, and has the best near-infrared blocking performance and heat resistance by thermal decomposition at a temperature of 250°C or higher. In addition, even if it contains a small amount compared to other conditions of the quinoid-based ionic compound, it has an equivalent near-infrared ray blocking performance, has high visible light transmittance, and improves processability based on a relatively small amount contained in an organic solvent, thereby producing a thin film having a thickness of 1 μm or less It was confirmed that it is 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 containing the quinoid-based ionic compound and a binder; And manufacturing a near-infrared blocking film using the mixed solution.

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

The molecular weight of the polymer may be 4,000 to 400,000, preferably 10,000 to 100,000, and 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 one or more 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 based on the weight of the mixed solution, preferably 0.5 to 10% by weight, and more preferably 1.0 to 5.0% by weight.

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

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

Hereinafter, preferred embodiments are provided to help understanding of the present invention. However, these examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited thereto, and various changes and modifications can be made within the scope and technical scope of the present invention. It will be obvious to those who have 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-based ionic compounds N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dicyano-2-trifluoromethyl imidazole Production of Late

Preparation of organoanionic sodium dicyano trifluoromethyl imidazolate

After dissolving 5.0 g of diaminomaleonitrile in 50 ml of 1,4-dioxane in a three-necked flask equipped with a reflux, 7.84 g of trifluoroacetic anhydride was added. The mixture was stirred at 60°C for 12 hours under an argon environment. After confirming whether the reaction was completed by thin film chromatography, the mixture was distilled with a vacuum distiller. The viscous liquid was dissolved in 60 ml of diethyl ether, and extracted with 60 ml of a 15% aqueous sodium carbonate solution. After extracting the extracted water layer twice with diethyl ether, activated carbon was added and stirred at 50°C for 5 hours. After filtering the mixture with a filter, the solvent was completely removed with a distiller. After removing the solvent, the mixture was dissolved in 50 ml of acetonitrile, and then filtered through a filter to remove solid precipitate. 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 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 completion of reflux, 100 ml of dichloromethane and 100 ml of water were added, and the organic solvent layer was separated and vacuum distilled to make N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenyl. 5.0 g of rendimonium bis4,5-dicyano-2-trifluoromethyl imidazolate was obtained. The chemical formula of the product is described below.

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

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

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

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 sodium 4,5-dinitro-2-trifluoromethyl imidazolate prepared above 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 completion of reflux, 100 ml of dichloromethane and 100 ml of water were added, and the organic solvent layer was separated and vacuum distilled to make N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenyl. 5.4 g of rendimonium bis4,5-dinitro-2-trifluoromethyl imidazolate was obtained. The chemical formula of the product is described below.

Example 1-3. Quinoid-based 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. 75 g of copper perchlorate hexahydrate was dissolved in 300 ml of acetonitrile, put into the above mixture, stirred at room temperature for 1 hour, 100 g of potassium carbonate 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 4-bromo-N,N-diethylbenzeneamine was dissolved in 200 ml of THF, and then slowly mixed with a 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 floating layer was decanted, 50 ml of dichloromethane was added and shaken. After filtering the mixture, it was dissolved in 50 ml of dichloromethane and passed through a gelite. After removing the solvent, recrystallization was performed with a mixed solvent of ethyl acetate and heptane to obtain 9.0 g of a 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, slowly mix the solution in 80 ml of 1.0 M DIBAL-H hexane solution and stir at room temperature for 30 minutes. gave. Then, 100 ml of methyl t-butyl ether was slowly added over 10 minutes. After lowering the mixture to 0° C., 30 mL of a 2.0 M sodium hydroxide solution was slowly added over 15 minutes, and 10 ml of saturated sodium chloride solution was added. The mixture was stirred at 0° C. for 10 minutes, and stirring was continued until the layers separated at room temperature. When the organic layer was extracted and the solvent was removed, 6.5 g of a colorless oil 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

The flask was mixed with 7.5 g of cesium carbonate and 0.37 g of copper iodide. Then, a solution of 6 g of 1,4-diiodine benzene and 5 g of 4,4-(bisN,N-diethylbenzeneamine) dissolved in 50 mL of toluene was added. After heating at 110° C. for 24 hours, 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 removing the solvent, it was purified by chromatography using hexane:dichloromethane (2:1, v:v) as 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 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 to give 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl) (4 -(Diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine bis4,5-dinitro-2-trifluoromethyl imidazolate 3.2 g was obtained. The chemical formula of the product is described below.

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

Under argon state, 2.52 g of lithium bisoxalatovorate and 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phosph prepared above Fino)-N,N-diethylbenzeneamine 4.0 g was dissolved 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 to give (4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)( 4.8 g of 4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine bis(bisoxalatoborate) was obtained The chemical formula of the product is described below.

Example 1-5. Quinoid-based ionic compound 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl) (4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine ) Preparation of bistrifuromethanesulfonimide

Under argon, 4.0 g of lithium trifluoromethanesulfonimide and 4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl) prepared above (4-(diethylamino) 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 to give (4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)( 6.3 g of 4-(diethylamino)phenyl)phosphino)-N,N-diethylbenzeneamine bistrifuromethanesulfonimide was obtained The chemical formula of the product is described below.

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

Preparation of N,N-dibutylthiophen-2-amine

After adding 0.3 g of magnesium to 25 ml of tetrahydrofuran, 0.43 g of anhydrous lithium chloride was added. The solution in which 0.8 g of 2-chloropropane was placed 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 remaining solution from the remaining magnesium, it was pulled with a syringe and transferred to a new flask filled with argon. After the temperature of the flask was lowered to -15°C, 1.6 g of 2-bromothiophene was slowly mixed. The solution was mixed 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, 0.4 g of dibutylamine and 0.52 g of N-chlorosuccinimide were mixed for 1 hour in 10 ml of tetrahydrofuran, and slowly added to the solution. After slowly raising the temperature to room temperature, the reaction was carried out for 3 hours. After the reaction was terminated with a saturated potassium carbonate solution, it was filtered while pouring ethyl acetate. Washed several times with distilled water and 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), 1.63-1.55(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 NN-dibutylthiophen-2-amine was added to 15 ml of anhydrous chloroform, 1 g of N-bromosuccinimide was dissolved in 10 ml of THF, slowly added, and reacted for 3 hours while blocking light at room temperature. . After the reaction was completed, it was washed several times with water, and the solvent was removed to obtain 1.4 g of 5-bromo-N.N-dibutylthiophen-2-amine. 0.15 g of magnesium was added to 15 ml of tetrahydrofuran, and 0.22 g of anhydrous lithium chloride was added. The solution containing 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 remaining solution from the remaining magnesium, it was pulled 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. The solution was mixed 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, 0.13 g of p-phenylenediamine and 0.25 g of N-chlorosuccinimide were mixed in 10 ml of tetrahydrofuran for 1 hour, and slowly added to the solution. After slowly raising the temperature to room temperature, the reaction was carried out for 3 hours. After the reaction was terminated with saturated potassium carbonate solution, it was filtered while pouring ethyl acetate. Washed several times with distilled water and the solvent was removed to obtain 0.7 g of N,N,N,N-tetrakis-(2-(5-dibutylaminothiophenyl))-1,4-phenylenediamine.

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 sodium 4,5-dicyano-2-trifluoromethylimidazolate and N,N,N,N-tetrakis-(2-(5-dibutylaminothiophenyl) )) After dissolving 0.7 g of 1,4-phenylenediamine in 50 ml of dichloromethane, 15 ml of isobutanol was added and 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, 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 bis 4,5-dicyano-2-trifluoromethyl was obtained. The chemical formula of the product is described below.

Example 1-7. Quinoid-based ionic compounds 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 adding 0.53 g of sodium hydride 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 reacted, and stirred until no hydrogen gas was generated. 2.1 g of 1-bromobutane was added and refluxed and reacted for 12 hours. The reaction was terminated by adding methanol, and extracted 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

0.15 g of magnesium was added to 15 ml of tetrahydrofuran, and 0.22 g of anhydrous lithium chloride was added. The solution containing 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 remaining solution from the remaining magnesium, it was pulled 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. The solution was mixed 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, 0.13 g of p-phenylenediamine and 0.25 g of N-chlorosuccinimide were mixed in 10 ml of tetrahydrofuran for 1 hour, and slowly added to the solution. After slowly raising the temperature to room temperature, the reaction was carried out for 3 hours. After the reaction was terminated with a saturated potassium carbonate solution, it was filtered while pouring ethyl acetate. Washed several times with distilled water and the solvent was removed to obtain 0.85 g of N,N,N,N-tetrakis-(2-(5-dibutylaminothiophenyl))-1,4-phenylenediamine.

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, and 15 ml of isobutanol was added and 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, and 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 chemical formula of the product is described below.

Example 1-8. Preparation of quinoid-based ionic compounds 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 acetonitrile anhydrous, the reaction flask was placed in a cooler to lower the temperature to -80°C and stir vigorously. 10.5 g of triloacetamide and 8.3 g of pyridine were slowly mixed in a new flask connected to the flask. Stir slowly while confirming that gas was generated during the reaction. When gas evolution was stopped, the temperature of the flask containing the acetonitrile solution was raised to room temperature and reacted for 2 days. The solvent was removed by 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, 5.0 g of sodium 5-trifluoromethyl tetrazolate and 5.0 g of N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenediamine are 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 completion of reflux, 100 ml of dichloromethane and 100 ml of water were added, and the organic solvent layer was separated and vacuum distilled to make N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenyl. 4.2 g of rendimonium bis5-trifluoromethyl tetrazolate was obtained. The chemical formula of the product is described below.

Example 1-9. Quinoid-based ionic compounds 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, 2-bromo-1H-imidazole 1.5 g, 2-amino-4,5-imidazole dicarbonitrile 1.4 g, sodium butoxide 1.1 g, and toluene 25 ml were 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 filtered solid was washed several times with methanol, hexane, and water. The obtained solid was dissolved in diethyl ether and extracted several times with a 15% sodium carbonate solution. The organic solvent layer was removed by a distiller 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 which 0.95 g of sodium persulfate was added and 20 ml of water was added for 2 hours. After completion of reflux, 100 ml of dichloromethane and 100 ml of water were added, and then the organic solvent layer was separated and vacuum distilled to make N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1, 1.7 g of 4-phenylenedimonium bis((2-(1H-imidazoyl-2-amino)-4,5-dicyanoimidazolate) was obtained. The chemical formula of the product is described below.

Example 2-1. 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 at 4.0 mass%. It was coated on the glass by spray application. Thickness and permeability were controlled by the number of coatings.

Λmax: 1100 nm (thickness; 20 nm).

Example 2-2. 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 dissolve polyethersulfone (molar average molecular weight: 16,000) at 6.0 mass%. It is coated on a glass by a rotating coating method. The thickness and permeability are controlled by the rotation speed and frequency.

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 above in toluene Fluoromethyl imidazolate was dissolved at 1.0 mass%, and polymethyl methacrylate (average molecular weight: 15,000) was dissolved at 6.0 mass%. It is coated on a glass by a rotating coating method. Thickness and permeability were controlled by rotation speed and frequency.

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 membrane using dinitro-2-trifluoromethyl imidazolate

4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl) (4-(diethylamino)phenyl)phosphino)-N,N obtained in Example 1-3 above in chloroform -Diethylbenzeneamine bis4,5-dinitro-2-trifluoromethyl imidazolate was dissolved at 1.0 mass%, and polyether sulfone (molar average molecular weight: 16,000) was dissolved at 5.0 mass%. It is coated on a glass by a rotating coating method. Thickness and permeability were controlled by rotation speed and frequency.

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 bistrifuro Preparation of near infrared blocking membrane using romethanesulfonimide

(4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phosphino)-N obtained in Example 1-5 above to toluene, N-diethylbenzeneamine bistrifuromethanesulfonimide was dissolved at 1.0% by mass, and polyethersulfone (average molecular weight: 16,000) was dissolved at 5.0% by mass. Thickness and permeability were adjusted 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. N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis4,5-dicyano-2-trifluoromethyl imidazolate and Sol-gel Preparation of a near-infrared blocking film using a layer

3-glycidoxypropyl trimethoxy silane, methyltrimethoxy silane, tetraethyl orthosilicate, 2-propynyl[3-(triethoxysilyl)propyl]carbamate, respectively 2:1:1:10.2 (molar ratio) ) And the mixture was well mixed with water for at least 4 hours to reach 60% by mass. N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis 4,5-dicyano-2- obtained in Example 1-1 above was added to the mixed solution. Trifluoromethyl imidazolate was added in an amount of 2.0% by mass, and mixed with an aqueous hydrochloric acid solution. The mixed solution was coated with a thickness of 30 μm by a doctor blade method, and then heated to 100° C. to heat treatment.

Λmax: 998 nm

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

3-glycidoxypropyl trimethoxy silane, methyltrimethoxy silane, tetraethyl orthosilicate, 2-propynyl[3-(triethoxysilyl)propyl]carbamate, respectively 2:1:1:10.2 (molar ratio) ) And the mixture was well mixed with water for at least 4 hours so as to be 60% by mass. To the mixture, (4-((4-(bis(4-(diethylamino)phenyl)phosphino)phenyl)(4-(diethylamino)phenyl)phosphino)-N obtained in Example 1-4 above. ,N-diethylbenzeneamine bis(bisoxalatoborate) was added in an amount of 4.0% by mass and mixed with an aqueous hydrochloric acid solution The mixture was coated with a 30 μm thick layer by a doctor blade method, and then heated to 100° C. to heat treatment. .

Λmax: 1190 nm

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

N,N,N',N'-tetrakis(p-diisobutylaminophenyl)-p-phenylenediamine 5.0g, lithium bisoxalatobarate 2.5g, dichloromethane 100ml and ethanol 50ml 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 completion of reflux, 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(p-diisobutylaminophenyl)-p-phenyl 5.2 g of rendimonium bis(bisoxalatoborate) was obtained.

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

1.0, N,N,N',N,-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenedimonium bis(bisoxalatoborate) obtained in Comparative Example 1-1 was added to chloroform. It was dissolved in mass%, and polyethersulfone (molar average molecular weight: 16,000) was dissolved in 6.0 mass%. It was coated on a glass by a rotating coating method. Thickness and permeability were controlled by rotation speed and frequency.

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

1 is a graph showing a UV-VIS-NIR absorption spectrum of a solution phase 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 a transmittance of 90% or more in the visible light region, and the maximum absorption wavelength was almost similar to 1100 nm. Although not shown in Figure 1, Example 1-2 also had a spectrum similar to Example 1-1 and Comparative Example 1-1.

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

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

Near infrared blocking film 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, it was confirmed that the near-infrared blocking films according to Examples 2-1 to 2-7 exhibited a maximum absorption wavelength in the range of 998 to 1257 nm, and excellent near-infrared blocking effect.

Near infrared blocking film 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 resistance and heat resistance performance of the manufactured near-infrared blocking film were analyzed. It can be said to be a stable barrier film only when it maintains its original properties under high temperature and high humidity conditions.

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

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

FIG. 2 is a graph of thermal rise of a photothermal film according to the presence or absence of a near-infrared blocking film of Example 2-2. A poly(3,4-ethylenedioxythiophene) film having an excellent photothermal effect was installed at the bottom of the laser, and a laser was irradiated after placing a near infrared blocking film therebetween.

In addition, Figure 3 is a thermal image confirming the heat generation according to the presence or absence of the near-infrared blocking film according to Example 2-2. 2 and 3, when the near-infrared blocking film is not installed (No filter in FIG. 2), the temperature of the photothermal film is 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 to ℃.

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

Near infrared blocking film No barrier (℃) With blocking film (℃) 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

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

10 mg of the substances of Examples 1-1 and 1-2 and Comparative Example 1-1 were dissolved in 10 ml of acetonitrile, and then 10 mg of hydrazine was added and mixed for 10 minutes. After the precipitated solid was obtained by filtration, it was dried in a vacuum at 90° C. for 1 hour. After dissolving the obtained solid in deuterium-substituted chloroform, NMR was confirmed by mixing 1 mg of hydrazine. In Examples 1-1, 1-2 and Comparative Example 1-1, N,N,N,N-tetrakis(4-diisobutylaminophenyl)-1,4-phenylenediamine is used as a starting material. It showed the same peak.

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, so that it can block efficient near-infrared rays, and has a high solubility in organic solvents, making it easy to manufacture into a thin film, as well as polymer It has excellent affinity with and can maintain high heat and moisture resistance for a long time in a thin film state. The near-infrared blocking film containing the quinoid-based ionic compound is suitable for application to a protective film for protecting electronic devices, and can also be used as an 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. Anyone having ordinary knowledge in the technical field to which the present invention pertains will be able to implement the present invention with various modifications therefrom, and thus the technical protection scope of the present invention should be defined by the appended claims.

Claims (15)

A quinoid-based ionic compound represented by Formula 1 below:
[Formula 1]

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

In Chemical Formula 2, A ₁ is nitrogen, phosphorus, oxygen or sulfur,
A ₂ is nitrogen or phosphorus,
R ₂₉ and R ₃₀ are the same or different from each other, and 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 hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms.
According to claim 1,
X in Chemical Formula 1 is a quinoid-based ionic compound which is a compound represented by any one selected from the following Chemical Formulas 7 to 9:
[Formula 7]

In Formula 7, R ₅ to R ₇ are the same as or different from each other, and a hydroxy 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, and an alkyl group having 1 to 10 carbon atoms. Or an alkoxy group in which hydrogen is substituted or unsubstituted with fluorine.
[Formula 8]

In Formula 8, R ₈ is the same or different from each other, and a hydroxy 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 It is 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 hydroxy 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 an alkyl group having 1 to 10 carbon atoms. Or an alkoxy group in which hydrogen is substituted or unsubstituted with fluorine.
According to claim 1,
In Formula 1, X is a quinoid-based ionic compound, which is a compound represented by Formula 7 below:
[Formula 7]

R ₅ in Formula 7 is CF ₃ ,
R ₆ and R ₇ are the same as each other and are a nitro group or a cyano group.
According to claim 1,
The quinoid-based ionic compound is a quinoid-based ionic compound which is a compound represented by the following Chemical Formulas 10 or 11:
[Formula 10]

In Formula 10, R ₁₃ to R ₂₀ are the same or different from each other, and are alkyl groups 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 are alkyl groups having 1 to 6 carbon atoms.
According to claim 1,
In Formula 1, A and B are phosphorus,
n is a quinoid-based ionic compound of 1.
According to claim 1,
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]

According to claim 1,
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 1 to 7.
Preparing a mixed solution comprising the quinoid-based ionic compound and a binder according to any one of claims 1 to 7; And
A method of manufacturing a near-infrared blocking film comprising; preparing a near-infrared blocking film using the mixed solution.
The method of claim 9,
The binder is selected from the group consisting of polyethylene, polystyrene, polymethyl methacrylate, polyethersulfone, polyimide, polyacrylate, polyamide, polyurethane, polypeptide, polyester, polycarbonate and polylactic glycolic acid Method of manufacturing at least one near-infrared blocking film.
The method of claim 9,
The binder is a method of manufacturing at least one near-infrared blocking film selected from the group consisting of silica, titania and boron oxide.
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, Method for producing a near-infrared barrier film selected from the group consisting of ethyl acetate, methanol, ethanol, hexane, dimethylformamide, dimethylacetamide and dimethoxysulfoxide.
The method of claim 9,
The method of preparing a near-infrared blocking film in which the concentration of the quinoid-based ionic compound in the mixed solution is 0.001 mg/ml to 100 mg/ml.
The method of claim 9,
The quinoid-based ionic compound is a method of manufacturing a near-infrared blocking film containing 0.1 to 20% by weight based on the weight of the mixed solution.
The method of claim 9,
The manufacturing method of the near-infrared blocking film using the mixed solution is a method of manufacturing a near-infrared blocking film performed by a dip coating method, a rotation coating method, a doctor blade method, or a spray spraying method.

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