Anthraquinone derivative

Abstract

To provide an anthraquinone derivative that is usable as a cyan dye and also has superior light resistance.SOLUTION: An anthraquinone derivative is represented by the following formula (1). (In the formula, A is a direct bond, an oxygen atom, or -NH-, and Y1, Y2, and Z are each independently a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a cyano group, a nitro group, a halogen atom, a C1-C10 halogenated alkyl group, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, where the aryl group and the cyclohexyl group may have a substituent.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to anthraquinone derivatives.

Background Art

[0002] Organic dyes are widely used in various printing inks and optical filters. In addition, the development of organic dyes that can be used as dichroic dyes for liquid crystal elements and polarizing films is also in progress. Among organic dyes, many anthraquinone derivatives, which are compounds having an anthraquinone skeleton, are highly stable against light, heat, temperature, etc. and have excellent fastness. Therefore, among anthraquinone derivatives, many studies have been conducted on compounds that can be used as dyes corresponding to the three primary colors of light, from the viewpoints of controlling the absorption wavelength and coloring power, solubility in solvents and resins, and improving dichroism. For example, Patent Documents 1 and 2 describe anthraquinone derivatives having an absorption maximum wavelength in a wavelength range of 580 nm or more and usable as cyan dyes.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] Dyes are desired to have good light resistance, that is, little fading due to light. Although many anthraquinone derivatives have high fastness as described above, anthraquinone derivatives used as cyan dyes tend to be difficult to obtain light resistance. Therefore, there is a demand for an anthraquinone derivative having an absorption maximum wavelength in a wavelength range of 580 nm or more and having good light resistance.

Means for Solving the Problem

[0005] Each aspect of the anthraquinone derivative for solving the above problems is described. [Aspect 1] An anthraquinone derivative represented by the following formula (1).

[0006]

Chem.

[0007] In formula (1), A is a direct bond, an oxygen atom, or -NH-, and Y 1 , Y 2 , and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents.

[0008] According to the above compound, since it has an absorption maximum wavelength in the wavelength range of 600 nm or more, it can be used as a cyan-based dye. And since the above compound does not have a hydroxyl group as a substituent at the α-position, high light resistance can be obtained.

[0009] [Aspect 2] The anthraquinone derivative according to [Aspect 1] represented by the following formula (2).

[0010]

Chem.

[0011] In formula (2), Y 1 , Y 2, and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents.

[0012] [Aspect 3] The anthraquinone derivative according to [Aspect 1] represented by the following formula (3).

[0013] [Chemical formula]

[0014] In formula (3), Y 1 , Y 2 , and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents.

[0015] [Aspect 4] The anthraquinone derivative according to any one of [Aspect 1] to [Aspect 3], wherein in the following reaction formula (4), the compound on the left side represents the anthraquinone derivative, and the difference in the total energy of the molecules before and after the reaction represented by the following reaction formula (4) obtained by the density functional method is -16 kcal / mol or more.

[0016] [Chemical formula]

[0017] [Aspect 5] The anthraquinone derivative according to any one of [Aspect 1] to [Aspect 4], wherein the 10% weight loss temperature is 350 °C or higher.

[0018] [Aspect 6] The anthraquinone derivative according to any one of [Aspect 1] to [Aspect 5], wherein the magnitude of the transition dipole moment determined by the time-dependent density functional method is 3.30 D or more and 5.00 D or less.

[0019] [Aspect 7] The anthraquinone derivative according to any one of [Aspect 1] to [Aspect 6], wherein the following formula (5) represents the anthraquinone derivative, and regarding the molecular orbital coefficient of the highest occupied molecular orbital of the anthraquinone derivative determined by the density functional method, C 11 、C 12 、C 21 、C 22 The square root of the sum of the squares of the coefficients corresponding to the orbitals on each of the carbon atoms of is obtained for each carbon atom, and the average value of the square roots for each carbon atom is 0.03 or more and 0.2 or less. Anthraquinone derivative.

[0020] [Chemical formula] [Advantages of the Invention]

[0021] According to the present disclosure, good light resistance can be obtained for anthraquinone derivatives that can be used as cyan dyes. [Modes for Carrying Out the Invention]

[0022] An anthraquinone derivative of one embodiment will be described. In this embodiment, the anthraquinone derivative is a compound having a 9,10-anthraquinone skeleton. Also, at the substitution positions of the anthraquinone skeleton, the 1,4,5,8 positions are the α positions, and the 2,3,6,7 positions are the β positions.

[0023] The anthraquinone derivative of this embodiment is used as a dye. The use as a dye is not particularly limited. For example, the anthraquinone derivative can be used as a dye for sublimation transfer printing, ink for inkjet printing, toner for laser printers and copiers, optical filters such as color filters for liquid crystal display devices and color separation filters for image pickup tubes, and ink for anti-counterfeiting printing. Further, the anthraquinone derivative can also be used as a dichroic dye for guest-host type liquid crystal elements and polarizing films.

[0024] The anthraquinone derivative of this embodiment is a compound represented by the following formula (1).

[0025]

Chemical formula

[0026] In formula (1), A is a direct bond, an oxygen atom, or -NH-. Note that when A is a direct bond, it means that a substituted or unsubstituted phenyl group is directly bonded to the carbon atom constituting the anthraquinone skeleton at the β-position of the anthraquinone derivative.

[0027] In formula (1), Y 1 , Y 2and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents. The substituent is preferably an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group. The cyclic hydrocarbon group is preferably a cyclohexyl group or a phenyl group. The halogen atom and the halogen atom contained in the halogenated alkyl group are preferably F, Cl, or Br. The alkyl group of the alkylamino group may be one or two. The carbon number of the alkyl group of the alkylamino group is preferably 1 to 10.

[0028] The type of the substituent in the anthraquinone skeleton affects the absorption wavelength of the anthraquinone derivative. The anthraquinone derivative of this embodiment has one substituted or unsubstituted anilino group and three amino groups at the α-position. Since the anthraquinone derivative having such a structure has an absorption maximum wavelength in the wavelength range of 600 nm or more, it can be used as a cyan-based dye.

[0029] One of the causes of photo-degradation in the anthraquinone derivative is considered to be that photoreduction occurs in the anthraquinone skeleton using a resin or the like existing around the anthraquinone derivative as a hydrogen source. When the anthraquinone derivative has a hydroxyl group at the α-position, such photoreduction is likely to occur. In addition, a change in the chemical structure due to the generation of radicals from the hydroxyl group also causes photo-degradation. On the other hand, since the anthraquinone derivative of this embodiment does not have a hydroxyl group at the α-position, the occurrence of photo-degradation caused by the hydroxyl group can be suppressed. Therefore, high light resistance can be obtained with the anthraquinone derivative of this embodiment.

[0030] In the anthraquinone derivative of this embodiment, it is preferable that the above A is an oxygen atom or a direct bond. The compound in the case where the above A is an oxygen atom is represented by the following formula (2), and the compound in the case where the above A is a direct bond is represented by the following formula (3).

[0031]

Chemical formula

[0032] In formula (2), Y 1 、Y 2 、and Z are defined in the same manner as in formula (1). If it is an anthraquinone derivative represented by formula (2), the solubility in solvents and resins can be enhanced.

[0033]

Chemical formula

[0034] In formula (3), Y 1 、Y 2 、and Z are defined in the same manner as in formula (1). In the anthraquinone derivative represented by formula (3), a phenyl group which may be substituted at the β-position is directly bonded. Due to such a structure, the light resistance is further enhanced. Specifically, when a phenyl group is directly bonded to the β-position, compared with the case where the β-position is an ether bond or a secondary amine, the molecular structure is difficult to rotate at the bonding portion of the β-position, so that the structure after photoreduction of the anthraquinone skeleton is unlikely to become a stable structure, and therefore, it is considered that the progress of the photoreduction reaction is suppressed.

[0035] The anthraquinone derivative of this embodiment can be produced, for example, by using 1,5-diaminoanthraquinone as a starting material and introducing each substituent into the anthraquinone skeleton. For the introduction of the substituent, a known method may be used. For example, a desired substituent is introduced through nitration for the α-position and bromination for the β-position.

[0036] [Total energy difference ΔE] In the anthraquinone derivative of the present embodiment, the total energy difference ΔE before and after the reaction represented by the following reaction formula (4) may be -16 kcal / mol or more.

[0037]

Chemical formula

[0038] In the above reaction formula (4), when the compound on the left side is the anthraquinone derivative of the present embodiment, X is -NH-, and R 1 , R 2 , and R 3 are all amino groups, A 1 and A 2 are defined in the same manner as A in the above formula (1), and Y 1 , Y 2 , and Z are defined in the same manner as in the above formula (1).

[0039] The above reaction formula (4) represents a photoreduction reaction of the anthraquinone derivative. In this reaction, using a resin or the like present around the anthraquinone derivative P1 as a hydrogen source, photoreduction of the anthraquinone derivative P1 occurs, and a hydrogen adduct K1, which is a compound in which hydrogen is added to the anthraquinone skeleton, is generated.

[0040] The total energy difference ΔE is the value obtained by subtracting the total energy Ep of the anthraquinone derivative P1 from the total energy Ek of the hydrogen adduct K1 (ΔE = Ek - Ep). The energies Ep and Ek of each of the anthraquinone derivative P1 and the hydrogen adduct K1 are obtained by quantum chemical calculations using the density functional theory (DFT: Density Functional Theory). The B3LYP is used for the functional, and the 6-31G(d) is used for the basis function. Such quantum chemical calculations can be performed using general-purpose quantum chemical calculation programs such as Gaussian and GAMESS. Each of the energies Ep and Ek is the total energy of the molecule in the optimized structure obtained by the above quantum chemical calculations.

[0041] One of the reasons for the light-induced degradation of anthraquinone derivatives is that the reaction shown in the above reaction formula (4) occurs. The larger the total energy difference ΔE, the less likely the above reaction is to occur. If the total energy difference ΔE is -16 kcal / mol or more, good light resistance can be obtained. Also, in order to obtain higher light resistance, the total energy difference ΔE is preferably -14 kcal / mol or more.

[0042] [10% weight loss temperature] In the anthraquinone derivative of this embodiment, the 10% weight loss temperature in thermogravimetric measurement may be 350 °C or higher. Thermogravimetric measurement is carried out under the conditions of a gas flow rate of 200 mL / min and a heating rate of 10 °C / min. Air is used as the gas.

[0043] When high heat is applied to the anthraquinone derivative, the anthraquinone derivative decomposes to generate radicals, and due to the action of these radicals, reactions such as further decomposition proceed. Since one of the causes of the light degradation of anthraquinone derivatives is also radicals generated from the surroundings or themselves, anthraquinone derivatives that are difficult to thermally decompose, that is, anthraquinone derivatives with a high 10% weight loss temperature, tend to have high light resistance. If the 10% weight loss temperature is 350 °C or higher, good light resistance can be obtained. Also, in order to obtain higher light resistance, the 10% weight loss temperature is preferably 365 °C or higher.

[0044] [Transition dipole moment] For dyes, it is desired to have high coloring power, that is, high absorbance. The coloring power of anthraquinone derivatives varies depending on the type and position of the substituents that the anthraquinone derivatives have. Since there are many options for substituents that can be introduced into anthraquinone derivatives, the difference in coloring power in anthraquinone derivatives is large, and there are many compounds with low coloring power among conventional anthraquinone derivatives.

[0045] The higher the coloring power, the more the amount of pigment can be reduced, which is beneficial from the perspective of cost. Furthermore, in the case of anthraquinone derivatives, since the planarity of the molecule is high and it is difficult to enhance solubility, there is also a limit to increasing the amount of compounding to intensify the color. Therefore, improving the coloring power is an important issue.

[0046] In order to improve the coloring power, in the case of anthraquinone derivatives, it is preferable that the magnitude of the transition dipole moment calculated by the time-dependent density functional theory (TDDFT) is 3.30 D or more and 5.00 D or less.

[0047] The transition dipole moment of the anthraquinone derivative is the electric dipole moment generated during the electronic transition in a vacuum related to light absorption. When calculating the transition dipole moment, B3LYP is used for the functional and 6-31G(d) is used for the basis function. Such quantum chemical calculations can be executed using general-purpose quantum chemical calculation programs such as Gaussian and GAMESS.

[0048] Since the molar absorption coefficient is proportional to the square of the transition dipole moment, the larger the transition dipole moment, the more likely it is to obtain a high absorbance. If the magnitude of the transition dipole moment is 3.30 D or more, sufficient absorbance can be obtained, and thus good coloring power can be obtained.

[0049] In addition, the type and position of the substituents of the anthraquinone derivative are related not only to the magnitude of the transition dipole moment but also to the magnitude of the absorption maximum wavelength. If the magnitude of the transition dipole moment is 3.30 D or more, both good absorbance and absorption maximum wavelength can be obtained. In addition, if the magnitude of the transition dipole moment is 5.00 D or less, the arrangement and structure of the substituents can be suppressed from becoming complicated, so the synthesis is easy.

[0050] [Molecular orbital coefficient] For improving the coloring power, it is preferable that the anthraquinone derivative satisfies the conditions described later regarding the molecular orbital coefficients. When the following formula (5) represents the anthraquinone derivative of the present embodiment, that is, the same compound as the above formula (1), X is -NH-, and R 1 , R 2 , and R 3 are all amino groups, and A 1 and A 2 are defined in the same manner as A in the above formula (1), and Y 1 , Y 2 , and Z are defined in the same manner as in the above formula (1). In the following formula (5), C 11 , C 12 , C 21 , C 22 are each a carbon atom.

[0051]

Chemical formula

[0052] For improving the coloring power, regarding the molecular orbital coefficients of the highest occupied molecular orbital (HOMO) obtained by quantum chemical calculation using the density functional theory (DFT) in the anthraquinone derivative represented by the above formula (5), the average Mv of the square root of the sum of the squares of the coefficients corresponding to the orbitals on each carbon atom of C 11 , C 12 , C 21 , C 22 is preferably 0.03 or more and 0.2 or less. B3LYP is used for the functional, and 6-31G(d) is used for the basis function.

[0053] That is, the square root of the sum of the squares of the molecular orbital coefficients for C 11 is M 11 , the square root of the sum of the squares of the molecular orbital coefficients for C 12 is M 12 , the square root of the sum of the squares of the molecular orbital coefficients for C 21 is M 21 , and the square root of the sum of the squares of the molecular orbital coefficients for C 22 is M22 is assumed. At this time, M 11 and M 12 and M 21 and M 22 The average value of is the average Mv.

[0054] The above quantum chemical calculation can be performed using a general-purpose quantum chemical calculation program such as Gaussian or GAMESS.

[0055] Generally, the electronic transition showing the absorption maximum is the electronic transition from HOMO to LUMO. Since the larger the overlap of the molecular orbitals of HOMO and LUMO, the higher the probability of electronic transition, it is considered that a high absorbance can be obtained. As a result of repeated studies by the inventors, a tendency of the spread of the molecular orbitals of HOMO and LUMO in the anthraquinone derivative was found.

[0056] That is, with respect to the molecular orbital of LUMO of the anthraquinone derivative, the influence of the type and arrangement of substituents is small, and the molecular orbital of LUMO tends to gather around the anthraquinone skeleton. On the other hand, the molecular orbital of HOMO varies greatly under the influence of the type and arrangement of substituents. Among these, in the structure represented by the above formula (5), the molecular orbital of HOMO tends to spread toward the substituent at the α-position containing X.

[0057] Therefore, if the configuration is such that the molecular orbital of HOMO spreads toward the substituent at the β-position, that is, the configuration spreads on the benzene ring containing the substituent at the β-position, it is possible to suppress the molecular orbital of HOMO from spreading too much toward the α-position and to spread well around the anthraquinone skeleton in a balanced manner, and it is considered that the overlap of the molecular orbitals of HOMO and LUMO increases.

[0058] The fact that the molecular orbital of HOMO spreads over the benzene ring at the β-position can be represented by the orbital coefficients on the carbon atoms contained in the benzene ring. That is, the larger the above average Mv, the more the molecular orbital spreads over the benzene ring at the β-position. If the average Mv is 0.03 or more, the overlap of the molecular orbitals of HOMO and LUMO becomes large enough to obtain good absorbance at the absorption maximum wavelength, and high coloring power can be obtained. On the other hand, if the average Mv is 0.2 or less, the arrangement and structure of the substituents are suppressed from becoming complicated, so the synthesis of the anthraquinone derivative is easy. In addition, it is also possible to suppress the situation where the molecular orbital of HOMO spreads too much toward the substituent at the β-position and the overlap of the molecular orbitals of HOMO and LUMO becomes small.

[0059] In the anthraquinone derivative, in order to increase the average Mv within the range of 0.03 or more and 0.2 or less, in the above formula (5), A 1 、A 2 is preferably a direct bond, and Y 1 、Y 2 is preferably an electron-donating group, and Z is preferably an electron-withdrawing group.

[0060] [Examples] The above-described anthraquinone derivative will be described using specific examples and comparative examples. Note that the description of the parts by weight of each material below indicates the relative weight ratio of each material to be mixed with each other.

[0061] [First Example] (Example 1-1) [Synthesis of Precursor 1] Into a two-necked flask, 1,5-diaminoanthraquinone (5.0 parts by weight), N,N-dimethylformamide (397 parts by weight), and pyridine (10.3 parts by weight) were added, and nitrogen substitution was performed. This solution was sufficiently cooled in an ice bath, and acetyl chloride (19.8 parts by weight) was added dropwise thereto over 45 minutes while ice-cooling. Then, the solution was stirred for 10 minutes while ice-cooling, and then stirred at room temperature for 24 hours. And the precipitate was collected by suction filtration, and the collected product was washed with diethyl ether and dried to obtain a brown crude product. Then, into an eggplant flask, the crude product (5.5 parts by weight) and ethyl acetate (54 parts by weight) were added, heated to the reflux temperature, and subjected to suspension washing for 30 minutes. Then, the product collected by suction filtration was washed with diethyl ether and then dried under reduced pressure at 60 °C to obtain Precursor 1 as a brown powder. Precursor 1 is a compound represented by the following formula (A1).

[0062]

Chemical formula

[0063] <Synthesis of Precursor 2> Concentrated sulfuric acid (48 parts by weight) was placed in a four-necked flask equipped with a thermometer and a mechanical stirrer, and further potassium nitrate (6.0 parts by weight) was added and completely dissolved, and cooled until the internal temperature of the four-necked flask reached 0 °C. To this solution, Precursor 1 (3.0 parts by weight) was added in portions of 0.5 parts by weight six times so that the internal temperature of the four-necked flask did not exceed 5 °C. After the addition of Precursor 1, a light brown precipitate was formed after a while. Then, when the solution was stirred at an internal temperature of 0 °C to 5 °C for 6 hours, 1 Since the disappearance of the substrate was confirmed by 1H-NMR measurement (solvent: DMSO-d6), stirring was stopped. This solution was added little by little to pure water cooled to 0 °C to 5 °C, and the precipitate was collected by suction filtration, and the collected product was dried under reduced pressure at 60 °C to obtain a crude product. The crude product was dissolved in nitrobenzene and stirred at 180 °C for 30 minutes. After this solution was naturally cooled to room temperature, the precipitate collected by filtration was dried under reduced pressure at 60 °C to obtain Precursor 2 as a pale yellow powder. Precursor 2 is a compound represented by the following formula (A2).

[0064]

Chem.

[0065] <Synthesis of Precursor 3> Pure water (5.5 parts by weight) was placed in a two-necked flask, and concentrated sulfuric acid (40 parts by weight) was slowly added thereto while cooling with ice. Precursor 2 (2.2 parts by weight) was added thereto while cooling with ice. After stirring this solution at 95 °C for 2 hours, it was added to pure water (200 parts by weight) while cooling with ice. Thereafter, the precipitate was collected by suction filtration, and the recovered product was dried under reduced pressure at 60 °C to obtain Precursor 3 as a red powder. Precursor 3 is a compound represented by the following formula (A3).

[0066]

Chem.

[0067] <Synthesis of Precursor 4> Precursor 3 (1.6 parts by weight) and N-bromosuccinimide (1.9 parts by weight) were placed in a two-necked flask and purged with nitrogen. Nitrogen-bubbled N,N-dimethylformamide (30 parts by weight) was added thereto, and the mixture was stirred at room temperature for 20 hours. This reaction solution was poured into methanol (200 parts by weight), and the mixture was stirred at room temperature for 15 minutes. Thereafter, the precipitate was collected by suction filtration, and the recovered product was dried under reduced pressure at 60 °C to obtain Precursor 4 as a reddish-brown powder. Precursor 4 is a compound represented by the following formula (A4).

[0068]

Chem.

[0069] <Synthesis of Precursor 5> Into a two-necked flask, 4-heptyloxyphenol (0.45 parts by weight) and potassium carbonate (0.30 parts by weight) were added and nitrogen substitution was carried out. Dehydrated N-methyl-2-pyrrolidone (20 parts by weight) was added thereto, and the mixture was stirred at 120 °C for 3 hours. To this solution, precursor 4 (0.50 parts by weight) was added, and the mixture was stirred at 80 °C for 7 hours. The reaction solution was returned to room temperature, water / dichloromethane was added, and liquid separation was carried out. The organic layer obtained by liquid separation was dried over sodium sulfate and then concentrated using an evaporator. Purification was carried out by silica gel column chromatography (developing solvent: hexane / dichloromethane = 1 / 4, 1% by mass of triethylamine added), and the recovered product was dried under reduced pressure at 60 °C to obtain precursor 5 as a red powder. Precursor 5 is a compound represented by the following formula (A5).

[0070]

Chemical formula

[0071] <Synthesis of Precursor 6> Precursor 5 (0.20 parts by weight) was placed in a two-necked flask and nitrogen substitution was carried out. Nitrobenzene (4.8 parts by weight) and 4-heptylaniline (0.52 parts by weight) were added thereto, and the mixture was stirred at 200 °C for 12 hours. The reaction solution was dried under reduced pressure at 75 °C to distill off nitrobenzene and obtain a residue. Methanol was poured into this residue, and the precipitated powder was collected by suction filtration to obtain precursor 6 as a purple powder. Precursor 6 is a compound represented by the following formula (A6).

[0072]

Chemical formula

[0073] <Synthesis of the Dye of Example 1-1> 0.20 parts by weight of the precursor 6 was placed in a two-necked flask and purged with nitrogen. 3.1 parts by weight of 2-propanol was added thereto, and the mixture was heated to 80°C. Further, 0.22 parts by weight of sodium borohydride was added, and the mixture was stirred for 27 hours. The reaction solution was poured into cold water, and the precipitated powder was collected by suction filtration. Then, the powder was purified by column chromatography to obtain the anthraquinone derivative of Example 1-1 as a purple powder. The anthraquinone derivative of Example 1-1 is a compound represented by the following formula (P1-1).

[0074]

Chemical formula

[0075] (Example 1-2) (Synthesis of Precursor 7) In the synthesis step of the above precursor 5, synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylphenol to obtain precursor 7. Precursor 7 is a compound represented by the following formula (A7).

[0076]

Chemical formula

[0077] (Synthesis of Precursor 8) In the synthesis step of the above precursor 6, synthesis was carried out in the same manner except that precursor 5 was changed to precursor 7 to obtain precursor 8. Precursor 8 is a compound represented by the following formula (A8).

[0078]

Chemical formula

[0079] (Synthesis of the Dye of Example 1-2) In the synthesis process of the dye of Example 1-1, the synthesis was carried out in the same manner except that the precursor 6 was changed to the precursor 8, and the anthraquinone derivative of Example 1-2 was obtained. The anthraquinone derivative of Example 1-2 is a compound represented by the following formula (P1-2).

[0080]

Chemical formula

[0081] (Example 1-3) <Synthesis of Precursor 9> In the synthesis process of the above precursor 6, the synthesis was carried out in the same manner except that 4-heptylaniline was changed to N,N-dimethyl-1,4-phenylenediamine, and precursor 9 was obtained. Precursor 9 is a compound represented by the following formula (A9).

[0082]

Chemical formula

[0083] <Synthesis of the Dye of Example 1-3> In the synthesis process of the dye of Example 1-1, the synthesis was carried out in the same manner except that the precursor 6 was changed to the precursor 9, and the anthraquinone derivative of Example 1-3 was obtained. The anthraquinone derivative of Example 1-3 is a compound represented by the following formula (P1-3).

[0084]

Chemical formula

[0085] (Example 1-4) <Synthesis of Precursor 10> In the synthesis process of the above precursor 6, the synthesis was carried out in the same manner except that 4-heptylaniline was changed to 4-aminobenzonitrile, and precursor 10 was obtained. Precursor 10 is a compound represented by the following formula (A10).

[0086]

Chemical formula

[0087] <Synthesis of Dyes in Examples 1-4> In the synthesis process of the dye of Example 1-1, the synthesis was carried out in the same manner except that the precursor 6 was changed to the precursor 10, and the anthraquinone derivative of Example 1-4 was obtained. The anthraquinone derivative of Example 1-4 is a compound represented by the following formula (P1-4).

[0088]

Chemical formula

[0089] (Example 1-5) <Synthesis of Precursor 11> The eggplant flask equipped with a Dimroth condenser was purged with nitrogen. To this, toluene (5 parts by weight), water (2.5 parts by weight), precursor 4 (0.30 parts by weight), 4-heptyloxyphenylboronic acid (0.28 parts by weight), potassium carbonate (0.21 parts by weight), and tetrakis(triphenylphosphine)palladium (0.06 parts by weight) were added, and the mixture was heated and stirred at 80 °C for 2 hours or more. After confirming the completion of the reaction by thin-layer chromatography, the mixture was returned to room temperature, pure water was added, and extraction was performed with ethyl acetate. Sodium sulfate was added to the obtained organic layer and dried, and then the solvent was removed under reduced pressure using an evaporator. The obtained residue was purified by column chromatography (developing solvent: hexane / ethyl acetate = 10 / 1 to 5 / 1) to obtain precursor 11. Precursor 11 is a compound represented by the following formula (A11).

[0090]

Chemical formula

[0091] <Synthesis of Precursor 12> In the synthesis process of the above precursor 6, the synthesis was carried out in the same manner except that the precursor 5 was changed to the precursor 11, and precursor 12 was obtained. Precursor 12 is a compound represented by the following formula (A12).

[0092]

Chem.

[0093] <Synthesis of Dyes in Examples 1-5> In the synthesis process of the dye in Example 1-1 above, the synthesis was carried out in the same manner except that precursor 6 was changed to precursor 12, and an anthraquinone derivative of Example 1-5 was obtained. The anthraquinone derivative of Example 1-5 is a compound represented by the following formula (P1-5).

[0094]

Chem.

[0095] (Example 1-6) <Synthesis of Precursor 13> In the synthesis process of the above precursor 11, the synthesis was carried out in the same manner except that 4-heptyloxyphenylboronic acid was changed to (4-pentylcyclohexyl)phenylboronic acid, and precursor 13 was obtained. Precursor 13 is a compound represented by the following formula (A13).

[0096]

Chem.

[0097] <Synthesis of Precursor 14> In the synthesis process of the above precursor 6, the synthesis was carried out in the same manner except that precursor 5 was changed to precursor 13, and precursor 14 was obtained. Precursor 14 is a compound represented by the following formula (A14).

[0098]

Chem.

[0099] <Synthesis of Dye in Example 1-6> In the synthesis process of the dye of Example 1-1, the synthesis was carried out in the same manner except that precursor 6 was changed to precursor 14, and the anthraquinone derivative of Example 1-6 was obtained. The anthraquinone derivative of Example 1-6 is a compound represented by the following formula (P1-6).

[0100] [Chemical formula]

[0101] (Example 1-7) [Synthesis of Precursor 15] In the synthesis process of the above precursor 11, the synthesis was carried out in the same manner except that 4-heptyloxyphenylboronic acid was changed to (4-piperidyl-1-yl)phenylboronic acid, and precursor 15 was obtained. Precursor 15 is a compound represented by the following formula (A15).

[0102] [Chemical formula]

[0103] [Synthesis of Precursor 16] In the synthesis process of the above precursor 6, the synthesis was carried out in the same manner except that precursor 5 was changed to precursor 15, and precursor 16 was obtained. Precursor 16 is a compound represented by the following formula (A16).

[0104] [Chemical formula]

[0105] [Synthesis of the Dye of Example 1-7] In the synthesis process of the dye of Example 1-1, the synthesis was carried out in the same manner except that precursor 6 was changed to precursor 16, and the anthraquinone derivative of Example 1-7 was obtained. The anthraquinone derivative of Example 1-7 is a compound represented by the following formula (P1-7).

[0106] [Chemical formula]

[0107] (Examples 1-8) <Synthesis of Precursor 17> Into a two-necked flask, precursor 4 (0.20 parts by weight), 4-heptyloxyaniline (1.2 parts by weight), and copper powder (0.053 parts by weight) were added and purged with nitrogen. To this, N-methyl-2-pyrrolidone (3.0 parts by weight) was added, and the mixture was stirred at 180 °C for 10 hours. The reaction solution was extracted with pure water / dichloromethane, and the obtained organic layer was dried over sodium sulfate, filtered, and then concentrated using an evaporator. Then, purification was performed by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 8 / 1) to obtain precursor 17. Precursor 17 is a compound represented by the following formula (A17).

[0108]

Chemical formula

[0109] <Synthesis of Precursor 18> In the synthesis step of precursor 6 described above, synthesis was carried out in the same manner except that precursor 5 was changed to precursor 17 to obtain precursor 18. Precursor 18 is a compound represented by the following formula (A18).

[0110]

Chemical formula

[0111] <Synthesis of Dyes in Examples 1-8> In the synthesis step of the dye in Example 1-1 described above, synthesis was carried out in the same manner except that precursor 6 was changed to precursor 18 to obtain the anthraquinone derivative of Example 1-8. The anthraquinone derivative of Example 1-8 is a compound represented by the following formula (P1-8).

[0112]

Chemical formula

[0113] (Comparative Example 1-1) (Synthesis of Precursor 19) Anthralfin (10.0 parts by weight), potassium carbonate (46.0 parts by weight), and N,N-dimethylformamide (300 parts by weight) were added to a two-necked flask. Dimethyl sulfate (52.5 parts by weight) was added dropwise thereto, and the mixture was stirred overnight at room temperature. This reaction solution was gently added to pure water (2400 parts by weight) and stirred for 15 minutes. Then, the precipitate was collected by suction filtration, and the collected product was vacuum dried at 60 °C to obtain Precursor 19 as a dull yellow solid. Precursor 19 is a compound represented by the following formula (A19).

[0114] [Chemical formula]

[0115] (Synthesis of Precursor 20) Boric acid (5.53 parts by weight) and concentrated sulfuric acid (300 parts by weight) were added to a two-necked flask. Precursor 19 (10.0 parts by weight) was added thereto, and the mixture was cooled with an ice bath until the internal temperature of the two-necked flask reached 5 °C or lower. A mixture of concentrated nitric acid (10.0 parts by weight), concentrated sulfuric acid (12.0 parts by weight), and pure water (60 parts by weight) was added dropwise thereto over about 3 hours while appropriately ice-cooling so that the internal temperature did not exceed 10 °C, and the mixture was stirred at the same temperature for 1 hour and then naturally warmed to room temperature. This reaction solution was gently added to pure water (1650 parts by weight) while ice-cooling and stirred for 10 minutes. Then, the precipitate was collected by suction filtration, and the collected product was vacuum dried at 60 °C overnight to obtain a crude product as a dull yellow solid. The crude product (12.8 parts by weight) was placed in an eggplant flask, and nitrobenzene (90 parts by weight) was added thereto. This mixture was stirred in an oil bath at 180 °C for 30 minutes and then naturally cooled to room temperature. Then, the precipitate was collected by suction filtration, and the collected product was vacuum dried at 60 °C overnight to obtain Precursor 20 as a yellow solid. Precursor 20 is a compound represented by the following formula (A20).

[0116] [Chemical formula]

[0117] <Synthesis of Precursor 21> Into a two-necked flask, precursor 20 (8.0 parts by weight) and lithium chloride (5.68 parts by weight) were added and purged with nitrogen. To this, N,N-dimethylformamide (113 parts by weight) was added, and the mixture was heated with stirring overnight in an oil bath at 120 °C. This reaction solution was gently added to 1N hydrochloric acid (360 parts by weight) and stirred for 10 minutes. Thereafter, the precipitate was collected by suction filtration, and the collected product was vacuum dried at 60 °C for 3 hours to obtain precursor 21 as a dull yellow solid. Precursor 21 is a compound represented by the following formula (A21).

[0118]

Chemical formula

[0119] <Synthesis of Precursor 22> Into a two-necked eggplant flask, precursor 21 (5.0 parts by weight) and N-bromosuccinimide (5.9 parts by weight) were placed and purged with nitrogen. To this, N,N-dimethylformamide (100 parts by weight) was added, and the mixture was stirred at room temperature for 1 hour. After confirming the completion of the reaction by thin-layer chromatography, this reaction solution was added to a sufficient amount of methanol and stirred for 15 minutes. The precipitate was collected by suction filtration, and the collected product was vacuum dried at 60 °C overnight to obtain precursor 22 as a yellow solid. Precursor 22 is a compound represented by the following formula (A22).

[0120]

Chemical formula

[0121] <Synthesis of Precursor 23> Into a two-necked eggplant flask, the precursor 22 (1.0 part by weight) and 4-heptylaniline (0.8 part by weight) were added and purged with nitrogen. To this, N-methyl-2-pyrrolidone (20 parts by weight) was added, and the mixture was heated and stirred in an oil bath at 180 °C. After confirming the completion of the reaction by thin-layer chromatography, the mixture was allowed to cool to room temperature. To this reaction solution, ethyl acetate (30 parts by weight) and pure water (10 parts by weight) were added, and the mixture was vigorously stirred at room temperature. Since insolubles were formed at this time, they were removed by filtration through celite. After separating the two layers, the organic layer was washed successively with distilled water, 5% aqueous hydrochloric acid solution, and saturated brine, and then anhydrous magnesium sulfate was added for drying. Then, after filtering off the desiccant, the filtrate was concentrated under reduced pressure. The obtained dark greenish-blue solid was purified by silica gel column chromatography (developing solvent: hexane / dichloromethane), and then dried under vacuum to obtain the precursor 23 as a dark blue solid. The precursor 23 is a compound represented by the following formula (A23).

[0122] [Chemical formula]

[0123] <Synthesis of the dye of Comparative Example 1-1> Into a two-necked flask, 4-heptyloxyphenol (0.36 part by weight) and potassium carbonate (0.24 part by weight) were placed and purged with nitrogen. To this, dehydrated N-methyl-2-pyrrolidone (10 parts by weight) was added, and the mixture was stirred at 120 °C for 3 hours. To this, the precursor 23 (0.50 part by weight) was added, and the mixture was stirred at 120 °C for 7 hours. The reaction solution was returned to room temperature, water / dichloromethane was added, and liquid separation was performed. The obtained organic layer was dried over sodium sulfate and then concentrated with an evaporator. Then, purification was carried out by silica gel column chromatography, and drying under reduced pressure at 60 °C gave the anthraquinone derivative of Comparative Example 1-1 as a blue powder. The anthraquinone derivative of Comparative Example 1-1 is a compound represented by the following formula (P1-9).

[0124] [Chemical formula]

[0125] (Comparative Example 1-2) <Synthesis of the Dye of Comparative Example 1-2> In the synthesis step of the above precursor 11, the synthesis was carried out in the same manner except that precursor 4 was changed to precursor 23 and 4-heptyloxyphenylboronic acid was changed to (4-pentylcyclohexyl)phenylboronic acid to obtain the anthraquinone derivative of Comparative Example 1-2. The anthraquinone derivative of Comparative Example 1-2 is a compound represented by the following formula (P1-10).

[0126] [Chemical formula]

[0127] (Comparative Example 1-3) <Synthesis of the Dye of Comparative Example 1-3> In the synthesis step of the above precursor 11, the synthesis was carried out in the same manner except that precursor 4 was changed to precursor 23 and 4-heptyloxyphenylboronic acid was changed to (4-piperidyl-1-yl)phenylboronic acid to obtain the anthraquinone derivative of Comparative Example 1-3. The anthraquinone derivative of Comparative Example 1-3 is a compound represented by the following formula (P1-11).

[0128] [Chemical formula]

[0129] (Comparative Example 1-4) <Synthesis of the Dye of Comparative Example 1-4> In the synthesis step of the above precursor 17, the synthesis was carried out in the same manner except that precursor 4 was changed to precursor 23 to obtain the anthraquinone derivative of Comparative Example 1-4. The anthraquinone derivative of Comparative Example 1-4 is a compound represented by the following formula (P1-12).

[0130] [Chemical formula]

[0131] (Evaluation Method) <Preparation of Test Specimens for Evaluation> Using the anthraquinone derivatives of each example and each comparative example of the first embodiment, the following materials were mixed to prepare a dye-containing composition. · Mixture of pentaerythritol tetraacrylate and isobornyl acrylate (70% by mass of pentaerythritol tetraacrylate and 30% by mass of isobornyl acrylate): 45 parts by weight · Photoinitiator (Omnirad TPO, manufactured by IGM Resins B.V.): 4.5 parts by weight · Anthraquinone derivative: 1 part by weight · Methyl ethyl ketone: 50 parts by weight

[0132] As a transparent substrate, a polyethylene terephthalate film with a thickness of 60 μm was used. The dye-containing composition was applied to the surface of the transparent substrate, and the coating film was dried in an oven at 80°C for 60 seconds. Then, using an ultraviolet irradiation device (manufactured by Fusion UV Systems Japan, light source H bulb), ultraviolet irradiation was performed at an irradiation dose of 150 mJ / cm 2 to cure the coating film. The thickness was adjusted so that the film thickness after curing would be 8.0 μm, and a test piece for evaluation was produced.

[0133] <Measurement of the absorption maximum wavelength> Regarding the test pieces for evaluation of each example and each comparative example of the first embodiment, an ultraviolet-visible absorption spectrum was measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the absorption maximum wavelength λmax was determined.

[0134] <Evaluation of light resistance> For the test pieces for evaluation of each example and each comparative example of the first embodiment, a light resistance test was performed using a xenon weather meter tester (X75, manufactured by Suga Test Instruments Co., Ltd.). In the light resistance test, a UV cut adhesive film that absorbs light of 395 nm or less was attached to the front surface of the test piece for evaluation, and the test piece for evaluation was placed under the conditions of a xenon lamp illuminance of 60 W / cm 2 (300 nm to 400 nm), a temperature of 45°C, and a humidity of 50% RH for 120 hours.

[0135] For each test piece for evaluation before and after the light resistance test, absorbance was measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the absorbance Abs at the wavelength showing the maximum absorbance in the visible light region was determined. Then, the absorbance change rate ΔAbs before and after the light resistance test was calculated. That is, when the absorbance Abs before the light resistance test is defined as absorbance Abs1 and the absorbance Abs after the light resistance test is defined as absorbance Abs2, ΔAbs (%) = {(Abs1 - Abs2) / Abs1} × 100. In the evaluation of light resistance, when ΔAbs was 2% or less, it was rated as good "○", and when ΔAbs exceeded 2%, it was rated as poor "×".

[0136] (Evaluation Results) Table 1 shows the structure of the anthraquinone derivative, the absorption maximum wavelength λmax, the absorbance change rate ΔAbs, and the evaluation results of light resistance for each example and each comparative example of the first embodiment. The structures of the anthraquinone derivatives of each example and each comparative example are represented by the following formula (I), and R, A, Y 1 , Y 2 , Z in the following formula (I) are the R, A, Y 1 , Y 2 , Z corresponding to those in the following formula (I).

[0137] [Chemical Formula]

[0138] [Table 1]

[0139] As shown in Table 1, the anthraquinone derivatives of Examples 1-1 to 1-8 have an absorption maximum wavelength in the wavelength range of 600 nm or more. Therefore, the anthraquinone derivatives of Examples 1-1 to 1-8 exhibit blue color and can be used as cyan dyes. And in Examples 1-1 to 1-8, high light resistance is obtained.

[0140] The anthraquinone derivatives of Comparative Examples 1-1 to 1-4 have a hydroxyl group at the α-position. In Comparative Examples 1-1 and 1-4 where the β-position is an ether bond or a secondary amine, the absorbance change rate ΔAbs is 25% or more, and the light resistance is extremely low. In Comparative Examples 1-2 and 1-3 where a substituted phenyl group is directly bonded to the β-position, the light resistance is greatly improved compared to Comparative Examples 1-1 and 1-4.

[0141] In Examples 1-1 to 1-8 where there is no hydroxyl group at the α-position, regardless of whether the β-position is a direct bond or not, higher light resistance than that of Comparative Examples 1-2 and 1-3 is obtained. Therefore, it is suggested that in the anthraquinone derivatives of Examples 1-1 to 1-8, high light resistance is obtained due to the structure in which the substituents at the α-position are amino groups and anilino groups.

[0142] [Second Example] (Example 2-1) The dye of Example 1-1 of the First Example was used as the anthraquinone derivative of Example 2-1. The anthraquinone derivative of Example 2-1 is a compound represented by the following formula (P2-1).

[0143] [Chemical formula]

[0144] (Comparative Example 2-1) The dye of Comparative Example 1-1 of the First Example was used as the anthraquinone derivative of Comparative Example 2-1. The anthraquinone derivative of Comparative Example 2-1 is a compound represented by the following formula (P2-2).

[0145] [Chemical formula]

[0146] (Comparative Example 2-2) [Synthesis of the dye of Comparative Example 2-2] In the synthesis process of the dye of Comparative Example 1-1 of the first embodiment, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylphenol, and the anthraquinone derivative of Comparative Example 2-2 was obtained. The anthraquinone derivative of Comparative Example 2-2 is a compound represented by the following formula (P2-3).

[0147] [Chemical formula]

[0148] (Comparative Example 2-3) ><Synthesis of the dye of Comparative Example 2-3> In the synthesis process of the dye of Comparative Example 1-1 of the first embodiment, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylcyclohexylphenol, and the anthraquinone derivative of Comparative Example 2-3 was obtained. The anthraquinone derivative of Comparative Example 2-3 is a compound represented by the following formula (P2-4).

[0149] [Chemical formula]

[0150] (Evaluation method) ><Evaluation of absorption wavelength and light resistance> For the anthraquinone derivatives of the examples and each comparative example of the second embodiment, test pieces for evaluation were prepared in the same manner as in the first embodiment, and the measurement of the maximum absorption wavelength and the evaluation of light resistance were carried out.

[0151] <Calculation of the total energy difference ΔE> For the anthraquinone derivatives of the examples and each comparative example of the second embodiment, the total energy difference ΔE before and after the reaction represented by the above reaction formula (4) was calculated. The calculation of the total energy difference ΔE was carried out using the quantum chemistry calculation program GAMESS, with the functional being B3LYP and the basis function being 6-31G(d), according to the following procedure.

[0152] (1) For the anthraquinone derivative, structural optimization was carried out by SCF calculation, and the total energy Ep of the molecule in the optimized structure was obtained. (2) Using the structure obtained by adding hydrogen to the anthraquinone skeleton of the anthraquinone derivative after structural optimization as the initial structure of the hydrogen adduct, structural optimization of the hydrogen adduct was carried out by SCF calculation. Then, for the hydrogen adduct, the total energy Ek of the molecule in the optimized structure was obtained.

[0153] The hydrogen adduct can have four types of stereoisomers depending on the positional relationship of the substituents at the β-position. Among the four types of stereoisomers, it is considered likely that the most stable structure, which is the structure with the lowest energy, will be generated. Therefore, the most stable structure was adopted as the three-dimensional structure of the hydrogen adduct. The most stable structure was searched by performing a Relaxed Scan calculation to rotate the dihedral angle at the position where the substituent at the β-position is bonded. (3) The total energy difference ΔE was calculated using the formula ΔE = Ek - Ep.

[0154] (Evaluation Results) Table 2 shows the structures of the anthraquinone derivatives, the absorption maximum wavelength λmax, the total energy difference ΔE, the absorbance change rate ΔAbs, and the evaluation results of light resistance for the examples and each comparative example of the second embodiment. The structures of the anthraquinone derivatives of the examples and each comparative example are represented by the following formula (II), and R, A, X, Y 1 , Y 2 , Z in Table 2 correspond to R, A, X, Y 1 , Y 2 , Z in the following formula (II).

[0155]

Chemical Formula

[0156]

Table 2

[0157] As shown in Table 2, in Example 2-1 where the total energy difference ΔE is -16 kcal / mol or more, high light resistance is obtained. Since the anthraquinone derivative of Example 2-1 has an absorption maximum wavelength in the wavelength range of 600 nm or more, it can be used as a cyan-based dye. On the other hand, in Comparative Examples 2-1 to 2-3 where the total energy difference ΔE is less than -16 kcal / mol, the light resistance was low.

[0158] 〔Example 3〕 (Example 3-1) (Synthesis of Precursor 24) In the synthesis step of Precursor 23 in the first example, synthesis was carried out in the same manner except that Precursor 22 was changed to Precursor 4 to obtain Precursor 24. Precursor 24 is a compound represented by the following formula (A24).

[0159]

Chemical formula

[0160] (Synthesis of the Dye in Example 3-1) In the synthesis step of the dye of Precursor 11 in the first example, synthesis was carried out in the same manner except that Precursor 4 was changed to Precursor 24 to obtain the anthraquinone derivative of Example 3-1. The anthraquinone derivative of Example 3-1 is a compound represented by the following formula (P3-1). Note that the anthraquinone derivative of Example 3-1 is the same compound as the anthraquinone derivative of Example 1-5 in the first example.

[0161]

Chemical formula

[0162] (Example 3-2) The dye of Example 1-1 in the first example was used as the anthraquinone derivative of Example 3-2. The anthraquinone derivative of Example 3-2 is a compound represented by the following formula (P3-2).

[0163]

Chemical formula

[0164] (Comparative Example 3-1) The dye of Comparative Example 1-1 of the first embodiment was used as the anthraquinone derivative of Comparative Example 3-1. The anthraquinone derivative of Comparative Example 3-1 is a compound represented by the following formula (P3-3).

[0165] [Chemical formula]

[0166] (Comparative Example 3-2) The dye of Comparative Example 2-2 of the second embodiment was used as the anthraquinone derivative of Comparative Example 3-2. The anthraquinone derivative of Comparative Example 3-2 is a compound represented by the following formula (P3-4).

[0167] [Chemical formula]

[0168] (Evaluation Method) (Evaluation of Absorption Wavelength and Lightfastness) For the anthraquinone derivatives of each example and each comparative example of the third embodiment, test pieces for evaluation were prepared in the same manner as in the first embodiment, and the measurement of the maximum absorption wavelength and the evaluation of lightfastness were performed.

[0169] (Thermogravimetric Measurement) For the anthraquinone derivatives of each example and each comparative example of the third embodiment, using a differential thermal thermogravimetric simultaneous measurement device (STA7200RV, manufactured by Hitachi High-Tech Science), under the conditions of a gas flow rate of 200 mL / min and a temperature increase rate of 10°C / min, the temperature was increased from 30°C to 550°C to perform weight measurement. Air was used as the gas. Based on the weight at the start of temperature increase, the 10% weight loss temperature was determined.

[0170] (Evaluation Results) Table 3 shows the structure of the anthraquinone derivative, the absorption maximum wavelength λmax, the 10% weight loss temperature, the absorbance change rate ΔAbs, and the light resistance evaluation results for each example and each comparative example of the third embodiment. The structures of the anthraquinone derivatives of each example and each comparative example are represented by the following formula (II), and R, A, X, Y 1 , Y 2 , Z in the following formula (II) are R, A, X, Y 1 , Y 2 , Z in the following formula (II) correspond to

[0171]

Chemical formula

[0172]

Table 3

[0173] As shown in Table 3, in Examples 3-1 and 3-2 where the 10% weight loss temperature is 350 °C or higher, high light resistance is obtained. Since the anthraquinone derivatives of Examples 3-1 and 3-2 have an absorption maximum wavelength in the wavelength range of 600 nm or more, they can be used as cyan dyes. On the other hand, in Comparative Examples 3-1 and 3-2 where the 10% weight loss temperature is less than 350 °C, the light resistance was low.

[0174] 〔Fourth Embodiment〕 (Example 4-1) (Synthesis of Precursor 25) In the synthesis step of Precursor 23 of the first embodiment, the synthesis was carried out in the same manner except that Precursor 22 was changed to Precursor 4 and 4-heptylaniline was changed to 4-heptyloxyaniline to obtain Precursor 25. Precursor 25 is a compound represented by the following formula (A25).

[0175]

Chemical formula

[0176] (Synthesis of the Dye of Example 4-1) In the synthesis step of the precursor 11 of the first embodiment, the synthesis was carried out in the same manner except that the precursor 4 was changed to the precursor 25 to obtain the anthraquinone derivative of Example 4-1. The anthraquinone derivative of Example 4-1 is a compound represented by the following formula (P4-1).

[0177]

Chemical formula

[0178] (Comparative Example 4-1) <Synthesis of the dye of Comparative Example 4-1> In the synthesis step of the dye of Comparative Example 1-1 of the first embodiment, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-(trans-4-pentylcyclohexyl)phenol to obtain the anthraquinone derivative of Comparative Example 4-1. The anthraquinone derivative of Comparative Example 4-1 is a compound represented by the following formula (P4-2).

[0179]

Chemical formula

[0180] (Comparative Example 4-2) <Synthesis of Precursor 26> In the synthesis step of the precursor 5 of the first embodiment, the synthesis was carried out in the same manner except that the precursor 4 was changed to the precursor 22 to obtain the precursor 26. The precursor 26 is a compound represented by the following formula (A26).

[0181]

Chemical formula

[0182] <Synthesis of the dye of Comparative Example 4-2> Into a two-necked eggplant flask, the precursor 26 (1.0 part by weight) was placed, and after purging the inside of the system with nitrogen, tetrahydrofuran (18.0 parts by weight) was added. Subsequently, using another flask, a solution prepared by mixing 4-heptyloxybenzenethiol (3.3 parts by weight) and pyridine (1.6 parts by weight) and stirring at room temperature for 30 minutes was prepared, and this solution was added to the solution containing the precursor 26 in the two-necked eggplant flask, followed by heating and stirring at 50 °C. After confirming the completion of the reaction by thin-layer chromatography, the reaction solution was allowed to cool to room temperature, and then dilute hydrochloric acid (a mixed solution of 35% hydrochloric acid (20.0 parts by weight) and pure water (80.0 parts by weight)) was added, and the precipitated solid was collected by filtration. The collected solid (1.0 part by weight) and zinc powder (0.5 part by weight) were placed in a two-necked flask, and the inside of the system was purged with nitrogen. Dichloromethane (200.0 parts by weight) and acetic acid (18.0 parts by weight) were added thereto, and the mixture was stirred at room temperature. After confirming the completion of the reaction by thin-layer chromatography, the reaction solution was filtered, pure water was added to the filtrate, and extraction was performed with dichloromethane. Sodium sulfate was added to the obtained organic layer, dried, and then the solvent was removed under reduced pressure using an evaporator. The obtained residue was purified by column chromatography (developing solvent: hexane / dichloromethane = 1 / 1 to 1 / 3) to obtain the anthraquinone derivative of Comparative Example 4-2 as a dark blue solid. The anthraquinone derivative of Comparative Example 4-2 is a compound represented by the following formula (P4-3).

[0183] [Chemical formula]

[0184] (Comparative Example 4-3) ><Synthesis of the dye of Comparative Example 4-3> In the synthesis process of the dye of Comparative Example 1-1 of the first embodiment, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-monobutylaminophenol to obtain the anthraquinone derivative of Comparative Example 4-3. The anthraquinone derivative of Comparative Example 4-3 is a compound represented by the following formula (P4-4).

[0185] [Chemical formula]

[0186] (Evaluation method) (Evaluation of absorption wavelength and coloring power) For the examples of the fourth embodiment and the anthraquinone derivatives of each comparative example, test pieces for evaluation were prepared in the same manner as in the first embodiment.

[0187] For each test piece for evaluation, an ultraviolet-visible absorption spectrum was measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.). Then, for wavelengths in the measurement range of 360 nm or more and 800 nm or less, the absorption maximum wavelength λmax and the absorbance at that wavelength were determined. In the evaluation of coloring power, when the absorbance was 0.40 or more, it was rated as good "○", and when the absorbance was less than 0.40, it was rated as poor "×".

[0188] (Calculation of transition dipole moment) For the examples of the fourth embodiment and the anthraquinone derivatives of each comparative example, the transition dipole moment was calculated using the time-dependent density functional theory method. Specifically, using the quantum chemistry calculation program GAMESS, with the functional being B3LYP and the basis function being 6-31G(d), the transition dipole moment of each anthraquinone derivative in vacuum was calculated. The transition dipole moment is a vector consisting of the x-component, y-component, and z-component. The value obtained by taking the square root of the sum of the squares of each component was taken as the magnitude μ of the transition dipole moment (μ = (x 2 + y 2 + z 2 ) 1 / 2 )

[0189] (Evaluation results) Table 4 shows the structure of the anthraquinone derivative, each component of the transition dipole moment, the magnitude μ of the transition dipole moment, the absorption maximum wavelength λmax, the absorbance, and the evaluation results of coloring power for the examples of the fourth embodiment and each comparative example. The structures of the anthraquinone derivatives of the examples and each comparative example are represented by the following formula (II), and R, A, X, Y 1 , Y 2 , Z in Table 4 are R, A, X, Y 1 , Y2 , corresponding to Z.

[0190]

Chemical formula

[0191]

Table 4

[0192] As shown in Table 4, in Example 4-1 where the magnitude μ of the transition dipole moment is 3.30 D or more, a higher absorbance was obtained and the coloring power was good compared to Comparative Examples 4-1 to 4-3 where the magnitude μ of the transition dipole moment is less than 3.30 D. Since the anthraquinone derivative of Example 4-1 has an absorption maximum wavelength in the wavelength range of 600 nm or more, it can be used as a cyan-based dye.

Claims

1. An anthraquinone derivative represented by the following formula (1). 【Chemical 1】 In formula (1), A is a direct bond, an oxygen atom, or -NH-, and Y １ , Y ２ , and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents.

2. The anthraquinone derivative according to Claim 1, represented by the following formula (2). [Chemical 2] In formula (2), Y １ , Y ２ , and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents.

3. The anthraquinone derivative according to Claim 1, represented by the following formula (3). 【Chemical Formula 3】 In formula (3), Y １ , Y ２ , and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents.

4. The anthraquinone derivative according to Claim 1, wherein in the following reaction formula (4), the compound on the left side represents the anthraquinone derivative, and the difference in the total energy of the molecules before and after the reaction represented by the following reaction formula (4), determined by the density functional method, is -16 kcal / mol or more. An anthraquinone derivative. 【Chemical Formula 4】

5. The anthraquinone derivative according to Claim 1, having a 10% weight loss temperature of 350°C or higher.

6. The anthraquinone derivative according to Claim 1, wherein the magnitude of the transition dipole moment determined by the time-dependent density functional method is 3.30 D or more and 5.00 D or less.

7. The anthraquinone derivative according to Claim 1, wherein The following formula (5) represents the anthraquinone derivative, and regarding the molecular orbital coefficients of the highest occupied molecular orbital of the anthraquinone derivative obtained by the density functional method, C １１ , C １２ , C ２１ , C ２２ The square root of the sum of the squares of the coefficients corresponding to the orbitals on each carbon atom of is obtained for each carbon atom, and the average value of the square roots for each carbon atom is 0.03 or more and 0.2 or less. An anthraquinone derivative. 【Chemical Formula 5】

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