Anthraquinone derivative

Abstract

To provide an anthraquinone derivative having superior light resistance and exhibiting excellent blueness.SOLUTION: An anthraquinone derivative is represented by the following formula (1). (In the formula, R1 and R2 are independently an amino group or a hydroxyl group, and Y1, Y2, and Z are 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, a piperidyl group, an aryl 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 progressing. 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 the wavelength range of 580 nm or more, which can be used 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] For pigments, it is desired that they have good lightfastness, that is, little fading due to light. As described above, although many compounds having high fastness are present in anthraquinone derivatives, in anthraquinone derivatives used as cyan dyes, lightfastness is difficult to obtain. Further, among cyan dyes, the color of a compound having an absorption maximum wavelength close to 700 nm becomes blue-green due to an increase in the green component. On the other hand, for cyan dyes used as dyes corresponding to the three primary colors of light, a strong blue tint is desired. Therefore, an anthraquinone derivative having good lightfastness and excellent blue tint is required.

Means for Solving the Problems

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

[0006]

Chemical formula

[0007] In formula (1), R 1 and R 2 are each independently an amino group or a hydroxyl group, 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, a piperidyl group, an aryl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have a substituent.

[0008] According to the above compound, the lightfastness is enhanced by the direct bonding of a substituted or unsubstituted phenyl group to the β-position of the anthraquinone skeleton. And, the presence of a phenylthio group at the α-position in such a structure suppresses the long-wavelength shift of the absorption maximum wavelength, and an excellent blue tint is obtained.

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

[0010] [Chemical formula]

[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, a piperidyl group, an aryl 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] or [Aspect 2], wherein the compound on the left side in the following reaction formula (3) 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 (3), determined by the density functional method, is -16 kcal / mol or more.

[0013] [Chemical formula]

[0014] [Aspect 4] The anthraquinone derivative according to any one of [Aspect 1] to [Aspect 3], having a 10% weight loss temperature of 350 °C or higher.

[0015] [Aspect 5] The anthraquinone derivative according to any one of [Aspect 1] to [Aspect 4], having a transition dipole moment magnitude determined by the time-dependent density functional method of 3.30 D or more and 5.00 D or less.

[0016] [Aspect 6] An anthraquinone derivative according to any one of [Aspect 1] to [Aspect 5], wherein the following formula (4) represents the anthraquinone derivative, and regarding the molecular orbital coefficient 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. Anthraquinone derivative.

[0017] [Chemical formula] [Advantages of the Invention]

[0018] According to the present disclosure, in the anthraquinone derivative, good light resistance and excellent blueness can be obtained. [Modes for Carrying Out the Invention]

[0019] An anthraquinone derivative of one embodiment will be described. In this embodiment, the anthraquinone derivative is a compound having a skeleton of 9,10-anthraquinone. 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.

[0020] 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 used in 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 used in guest-host type liquid crystal elements and polarizing films.

[0021] The anthraquinone derivative of the present embodiment is a compound represented by the following formula (1).

[0022] [Chemical formula]

[0023] In formula (1), R 1 and R 2 are each independently an amino group or a hydroxyl group. 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, a piperidyl group, an aryl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have a substituent. 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.

[0024] 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.

[0025] The action of the anthraquinone derivative of the present embodiment will be described. It is considered that one of the causes of photo-degradation in the anthraquinone derivative is that photoreduction occurs in the anthraquinone skeleton using a resin or the like existing around the anthraquinone derivative as a hydrogen source. And, as a conventional anthraquinone derivative, a structure in which a functional group such as a phenyl group is bonded to the β-position by an ether bond is known. On the other hand, in the anthraquinone derivative of the present embodiment, a phenyl group which may be substituted or unsubstituted is directly bonded to the carbon of the anthraquinone skeleton at the β-position. Due to such a structure, the progress of the photoreduction reaction is suppressed, and thus high light resistance can be obtained.

[0026] Specifically, when a phenyl group is directly bonded to the β-position, compared with the case where an ether bond exists at the β-position, the molecular structure is difficult to rotate at the bonding portion of the β-position. Therefore, the structure after photoreduction of the anthraquinone skeleton is unlikely to be a stable structure, and thus the progress of the photoreduction reaction is considered to be suppressed.

[0027] In addition, the type of substituent in the anthraquinone skeleton affects the absorption wavelength of the anthraquinone derivative. Regarding the substituent at the α-position, electron-donating substituents such as amino group, hydroxyl group, and anilino group act to shift the absorption maximum wavelength to the longer wavelength side. Also, a structure in which a phenyl group, whether substituted or unsubstituted, is directly bonded to the β-position also acts to shift the absorption maximum wavelength to the longer wavelength side.

[0028] As a conventional anthraquinone derivative of cyanine dyes, a structure is known in which one of the substituents at the α-position is an anilino group and the other three are amino groups or hydroxyl groups. In such a compound, if a structure in which a phenyl group is directly bonded to the β-position is adopted to improve light resistance, the absorption maximum wavelength will shift to the longer wavelength side, and an increase in the green component in the color exhibited by the compound is inevitable.

[0029] In contrast, the anthraquinone derivative of this embodiment has a phenylthio group, which may be substituted or unsubstituted, at the α-position. Since the phenylthio group has a smaller electron-donating property than amino group, hydroxyl group, and anilino group, the introduction of the phenylthio group at the α-position suppresses the shift of the absorption maximum wavelength to the longer wavelength side even when a phenyl group is directly bonded to the β-position as compared with the conventional structure.

[0030] Thus, the anthraquinone derivative of this embodiment has both a structure that greatly contributes to the bathochromic shift of the absorption maximum wavelength, such as an amino group or a hydroxyl group at the α-position and a phenyl group directly bonded to the β-position, and a structure that contributes little to the bathochromic shift of the absorption maximum wavelength, such as a phenylthio group at the α-position. Therefore, while realizing an absorption maximum wavelength of 580 nm or more that can be used as a cyan-based dye, it is possible to suppress the absorption maximum wavelength from becoming too large. Specifically, the absorption maximum wavelength can be in the range of 580 nm or more and 670 nm or less, and thereby, excellent blueness can be obtained. And, since excellent blueness can be obtained while having a structure in which a phenyl group is directly bonded to the β-position, it is possible to achieve both light resistance and blueness.

[0031] In the anthraquinone derivative of this embodiment, the above R 1 and R 2 are preferably hydroxyl groups. Such compounds are represented by the following formula (2).

[0032]

Chemical formula

[0033] 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 synthesis is easy. Further, when a hydroxyl group is present at the α-position, the above-mentioned photoreduction is likely to occur. However, according to the anthraquinone derivative of this embodiment, due to the structure in which a phenyl group is directly bonded to the β-position as described above, the photoreduction reaction is suppressed. Therefore, while eliminating the drawbacks of the structure having a hydroxyl group at the α-position, the advantages of the structure can be enjoyed.

[0034] The anthraquinone derivative of the present embodiment can be produced, for example, by introducing each substituent into the anthraquinone skeleton using 1,5-dihydroxy-4,8-dinitroanthraquinone or 1,5-diamino-4,8-dinitroanthraquinone as a starting material. Any known method may be used for the introduction of the substituent. For example, a desired substituent is introduced by utilizing reduction of a nitro group, substituent conversion, bromination at the β-position, and conversion of a bromo group.

[0035] [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 (3) may be -16 kcal / mol or more.

[0036] [Chemical formula]

[0037] In the above reaction formula (3), when the compound on the left side is the anthraquinone derivative of the present embodiment, X is a sulfur atom, R 2 is an amino group, R 1 and R 3 are each independently an amino group or a hydroxyl group, A 1 and A 2 are direct bonds, and Y 1 , Y 2 , and Z are defined in the same manner as in the above formula (1).

[0038] The above reaction formula (3) represents a photoreduction reaction of an 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.

[0039] The total energy difference ΔE is a 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 anthraquinone derivative P1 and hydrogen adduct K1 are determined by quantum chemical calculations using the density functional theory (DFT). The B3LYP functional is used for the functional and 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 energy Ep and Ek is the total energy of the molecule in the optimized structure obtained by the above quantum chemical calculations.

[0040] One cause of the light-induced degradation of the anthraquinone derivative is that the reaction shown in the above reaction formula (3) 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.

[0041] [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. The thermogravimetric measurement is carried out under the conditions of gas flow rate: 200 mL / min and temperature increase rate: 10 °C / min. Air is used as the gas.

[0042] 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 cause of the light degradation of the anthraquinone derivative is also radicals generated from the surroundings or itself, an anthraquinone derivative that is difficult to undergo thermal decomposition, that is, an anthraquinone derivative with a high 10% weight loss temperature, tends 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.

[0043] [Transition dipole moment] For pigments, it is desired that they have high coloring power, that is, high absorbance. The coloring power of anthraquinone derivatives varies depending on the type and position of the substituents they have. Since there are many options for substituents that can be introduced into anthraquinone derivatives, the difference in coloring power among anthraquinone derivatives is large, and many of the conventional anthraquinone derivatives have compounds with low coloring power.

[0044] The higher the coloring power, the more the amount of the pigment can be reduced, which is beneficial from the perspective of cost. Furthermore, in 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 the compounding to intensify the color. Therefore, improving the coloring power is an important issue.

[0045] In order to improve the coloring power, in 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.

[0046] The transition dipole moment of an anthraquinone derivative is the dipole moment that occurs during electronic transition in a vacuum related to 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 performed using general-purpose quantum chemical calculation programs such as Gaussian and GAMESS.

[0047] 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 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.

[0048] 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 absorbance and absorption maximum wavelength can be obtained favorably. Also, if the magnitude of the transition dipole moment is 5.00 D or less, the arrangement and structure of the substituents are less likely to become complex, so the synthesis is easy.

[0049] [Molecular orbital coefficient] For improving the coloring power, the anthraquinone derivative preferably satisfies the conditions described later regarding the molecular orbital coefficient. When the following formula (4) represents the anthraquinone derivative of the present embodiment, that is, the same compound as the above formula (1), X is a sulfur atom, and R 2 is an amino group, and R 1 and R 3 are each independently an amino group or a hydroxyl group, A 1 and A 2 are direct bonds, and Y 1 , Y 2 , and Z are defined in the same manner as in the above formula (1). In the following formula (4), C 11 , C 12 , C 21 , C 22 each represents a carbon atom.

[0050]

Chemical formula

[0051] For improving the coloring power, regarding the molecular orbital coefficient 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 (4), C 11 , C 12 , C 21 , C 22It is preferable that the average Mv, which is the square root of the sum of the squares of the coefficients corresponding to the orbitals on each carbon atom, is 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.

[0052] That is, the square root of the sum of the squares of the molecular orbital coefficients for C 11 is M 11 and the square root of the sum of the squares of the molecular orbital coefficients for C 12 is M 12 and 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 M 22 Let's assume that. At this time, M 11 , M 12 , M 21 , M 22 The average value obtained by averaging is the average Mv.

[0053] The above quantum chemical calculation can be carried out using general-purpose quantum chemical calculation programs such as Gaussian and GAMESS.

[0054] Generally, the electronic transition showing the absorption maximum is the electronic transition from HOMO to LUMO. Since the probability of electronic transition is higher when the overlap of the molecular orbitals of HOMO and LUMO is larger, it is considered that high absorbance can be obtained. As a result of repeated studies by the inventor, a tendency of the spread of the molecular orbitals of HOMO and LUMO in the anthraquinone derivative was found.

[0055] That is, for the molecular orbital of LUMO of the anthraquinone derivative, the influence of the type and arrangement of the 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 the substituents. Among these, in the structure represented by the above formula (4), the molecular orbital of HOMO tends to spread toward the substituent at the α-position containing X.

[0056] Therefore, if the molecular orbital of HOMO is configured to spread toward the substituent at the β-position, that is, to spread over the benzene ring containing the substituent at the β-position, it is possible to suppress the excessive spreading of the molecular orbital of HOMO toward the α-position, and it is considered that the molecular orbital spreads well around the anthraquinone skeleton and the overlap of the molecular orbitals of HOMO and LUMO increases.

[0057] The fact that the molecular orbital of HOMO spreads over the benzene ring at the β-position can be represented by the coefficient of the orbital on the carbon atom 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 can be suppressed from becoming complicated, so the synthesis of the anthraquinone derivative is easy. In addition, it is also possible to suppress the excessive spreading of the molecular orbital of HOMO toward the substituent at the β-position and the reduction of the overlap of the molecular orbitals of HOMO and LUMO.

[0058] 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 (4), 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.

[0059] [Examples] Specific examples and comparative examples will be used to explain the above-described anthraquinone derivative. In addition, 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.

[0060] [First Example] (Synthesis of Precursor 1) To a two-necked eggplant flask, 1,5-dihydroxy-4,8-dinitroanthraquinone (5.0 parts by weight) and N,N-dimethylformamide (100 parts by weight) were added. To this, N-bromosuccinimide (5.9 parts by weight) was added at room temperature, 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. Thereafter, the precipitated solid was collected by suction filtration, and the collected product was vacuum dried at 60 °C overnight to obtain precursor 1 as a yellow solid. Precursor 1 is a compound represented by the following formula (A1).

[0061] [Chemical formula]

[0062] (Synthesis of Precursor 2) In the synthesis step of the above precursor 1, precursor 2 was obtained by performing the synthesis in the same manner except that 1,5-dihydroxy-4,8-dinitroanthraquinone was changed to 1,5-diamino-4,8-dinitroanthraquinone. Precursor 2 is a compound represented by the following formula (A2).

[0063] [Chemical formula]

[0064] (Synthesis of Precursor 3) To a two-necked round-bottom flask, add toluene (100 parts by weight), ethanol (20 parts by weight), water (10 parts by weight), precursor 1 (1 part by weight), 4-heptyloxyphenylboronic acid (1.2 parts by weight), triethylamine (0.62 parts by weight), and tris(dibenzylideneacetone)dipalladium (0.2 parts by weight). Heat and stir at 80 °C for 2 hours or more. After confirming the completion of the reaction by thin-layer chromatography, return the reaction solution to room temperature, add pure water, and extract with ethyl acetate. Add sodium sulfate to the obtained organic layer, dry it, and then remove the solvent under reduced pressure using an evaporator. Purify the obtained solid by column chromatography (developing solvent: hexane / dichloromethane = 1 / 1 to 2 / 3) to obtain precursor 3 as a dark red solid. Precursor 3 is a compound represented by the following formula (A3).

[0065] [Chemical formula]

[0066] (Synthesis of precursor 4) In the synthesis step of the above precursor 3, synthesis was carried out in the same manner except that precursor 1 was changed to precursor 2 to obtain precursor 4. Precursor 4 is a compound represented by the following formula (A4).

[0067] [Chemical formula]

[0068] (Synthesis of precursor 5) In the synthesis step of the above precursor 3, synthesis was carried out in the same manner except that 4-heptyloxyphenylboronic acid was changed to 4-pentylcyclohexylphenylboronic acid to obtain precursor 5. Precursor 5 is a compound represented by the following formula (A5).

[0069] [Chemical formula]

[0070] (Synthesis of precursor 6) In the synthesis step of the above precursor 3, synthesis was carried out in the same manner except that 4-heptyloxyphenylboronic acid was changed to 4-(dimethylamino)phenylboronic acid to obtain precursor 6. Precursor 6 is a compound represented by the following formula (A6).

[0071] [Chemical formula]

[0072] (Synthesis of precursor 7) In the synthesis step of the above precursor 3, synthesis was carried out in the same manner except that 4-heptyloxyphenylboronic acid was changed to 4-monobutylaminophenylboronic acid to obtain precursor 7. Precursor 7 is a compound represented by the following formula (A7).

[0073] [Chemical formula]

[0074] (Synthesis of precursor 8) In the synthesis step of the above precursor 3, instead of adding 1.2 parts by weight of 4-heptyloxyphenylboronic acid, 0.7 part by weight of 4-pentylcyclohexylphenylboronic acid was added and the reaction solution was stirred for 1 hour. Then, 0.5 part by weight of 4-monobutylaminophenylboronic acid was added and heating and stirring were carried out at 80 °C for 2 hours or more. Thereafter, extraction and purification were carried out in the same manner as in the synthesis step of the above precursor 3 to obtain precursor 8. Precursor 8 is a compound represented by the following formula (A8).

[0075] [Chemical formula]

[0076] (Synthesis of the dye of Example 1-1) Into a two-necked eggplant flask, precursor 3 (1.0 part by weight) was placed, and the inside of the system was purged with nitrogen. Then, tetrahydrofuran (18.0 parts by weight) was added. Subsequently, using another flask, a solution was prepared by mixing 4-heptylbenzenethiol (3.3 parts by weight) and pyridine (1.6 parts by weight) and stirring at room temperature for 30 minutes. This solution was added to the solution containing precursor 3 in the two-necked eggplant flask, and the mixture was heated and stirred 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 mixture 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 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 / dichloromethane = 1 / 1 to 1 / 3) to obtain the anthraquinone derivative of Example 1-1 as a dark blue solid. The anthraquinone derivative of Example 1-1 is a compound represented by the following formula (P1-1).

[0077] [Chemical formula]

[0078] (Synthesis of the dye of Example 1-2) In the synthesis step of the dye of Example 1-1 above, the synthesis was carried out in the same manner except that 4-heptylbenzenethiol was changed to 4-heptyloxybenzenethiol to obtain the anthraquinone derivative of Example 1-2. The anthraquinone derivative of Example 1-2 is a compound represented by the following formula (P1-2).

[0079] [Chemical formula]

[0080] (Synthesis of Dyes in Examples 1-3) In the synthesis process of the dye in Example 1-1 above, the synthesis was carried out in the same manner except that 4-heptylbenzenethiol was changed to 4-methoxybenzenethiol, and an 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).

[0081] [Chemical formula]

[0082] (Synthesis of Dyes in Example 1-4) In the synthesis process of the dye in Example 1-1 above, the synthesis was carried out in the same manner except that 4-heptylbenzenethiol was changed to 4-cyanobenzenethiol, and an 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).

[0083] [Chemical formula]

[0084] (Synthesis of Dyes in Example 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 3 was changed to precursor 4, 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).

[0085] [Chemical formula]

[0086] (Synthesis of Dyes in Example 1-6) In the synthesis process of the dye of Example 1-1 above, the synthesis was carried out in the same manner except that precursor 3 was changed to precursor 5 and 4-heptylbenzenethiol was changed to 4-heptyloxybenzenethiol, to obtain the anthraquinone derivative of Example 1-6. The anthraquinone derivative of Example 1-6 is a compound represented by the following formula (P1-6).

[0087]

Chemical formula

[0088] (Synthesis of the dye of Example 1-7) In the synthesis process of the dye of Example 1-1 above, the synthesis was carried out in the same manner except that precursor 3 was changed to precursor 6 and 4-heptylbenzenethiol was changed to 4-heptyloxybenzenethiol, to obtain the anthraquinone derivative of Example 1-7. The anthraquinone derivative of Example 1-7 is a compound represented by the following formula (P1-7).

[0089]

Chemical formula

[0090] (Synthesis of the dye of Example 1-8) In the synthesis process of the dye of Example 1-1 above, the synthesis was carried out in the same manner except that precursor 3 was changed to precursor 6 and 4-heptylbenzenethiol was changed to 4-cyanobenzenethiol, 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).

[0091]

Chemical formula

[0092] (Synthesis of the dye of Example 1-9) In the synthesis process of the dye of Example 1-1, the synthesis was carried out in the same manner except that precursor 3 was changed to precursor 7 and 4-heptylbenzenethiol was changed to 4-heptyloxybenzenethiol, to obtain the anthraquinone derivative of Example 1-9. The anthraquinone derivative of Example 1-9 is a compound represented by the following formula (P1-9).

[0093] [Chemical formula]

[0094] (Synthesis of the dye of Example 1-10) In the synthesis process of the dye of Example 1-1, the synthesis was carried out in the same manner except that precursor 3 was changed to precursor 8 and 4-heptylbenzenethiol was changed to 4-heptyloxybenzenethiol, to obtain the anthraquinone derivative of Example 1-10. The anthraquinone derivative of Example 1-10 is a compound represented by the following formula (P1-10).

[0095] [Chemical formula]

[0096] (Synthesis of the dye of Comparative Example 1-1) Into a two-necked eggplant flask, precursor 1 (1.0 part by weight) and N-methyl-2-pyrrolidone (20 parts by weight) were added. Thereto, 4-heptylaniline (0.8 part 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 reaction solution was allowed to cool to room temperature, then ethyl acetate (30 parts by weight) and 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% hydrochloric acid aqueous 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 residue was purified by silica gel column chromatography (developing solvent: hexane / dichloromethane = 2 / 1 to 2 / 3) to obtain a dark blue solid.

[0097] The above dark blue solid (0.30 parts by weight), 4-heptyloxyphenylboronic acid (0.28 parts by weight), and potassium carbonate (0.21 parts by weight) were placed in a two-necked flask, and the system was purged with nitrogen. Toluene (5 parts by weight) and water (2.5 parts by weight) were added thereto, and then tetrakistriphenylphosphine palladium (0.06 parts by weight) was added, followed by heating and stirring at 80 °C for 2 hours. After confirming the completion of the reaction by thin layer chromatography, the reaction solution 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 the anthraquinone derivative of Comparative Example 1-1. The anthraquinone derivative of Comparative Example 1-1 is a compound represented by the following formula (P1-11).

[0098]

Chemical formula

[0099] (Synthesis of the dye of Comparative Example 1-2) 4-Heptyloxyphenol (0.45 parts by weight) and potassium carbonate (0.30 parts by weight) were placed in a two-necked flask, and the system was purged with nitrogen. Dehydrated N-methyl-2-pyrrolidone (20 parts by weight) was added thereto, and the mixture was stirred at 120 °C for 3 hours. Precursor 1 (0.50 parts by weight) was added thereto, and the mixture was stirred at 80 °C for 7 hours. After the reaction solution was returned to room temperature, water / dichloromethane was added and separated. The obtained organic layer was dried over sodium sulfate and concentrated using an evaporator. Then, purification was performed by silica gel column chromatography (developing solvent: hexane / dichloromethane = 1 / 4, 1% by mass of triethylamine added), and the solid was recovered.

[0100] The synthesis was carried out in the same manner as the synthesis process of the dye in Example 1-1, except that the recovered solid was used in place of the precursor 3 and 4-heptylbenzenethiol was changed to 4-heptyloxybenzenethiol, 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 (P1-12).

[0101] [Chemical formula]

[0102] (Evaluation method) ><Preparation of test pieces for evaluation> Using the anthraquinone derivatives of each example and each comparative example of the first example, the following materials were mixed to prepare a dye-containing composition. · Mixture of pentaerythritol tetraacrylate and isobornyl acrylate (pentaerythritol tetraacrylate: 70% by mass, isobornyl acrylate: 30% by mass): 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

[0103] 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 was 8.0 μm to prepare a test piece for evaluation.

[0104] ><Evaluation of absorption wavelength> Regarding the test pieces for evaluation of each example and each comparative example of the first example, an ultraviolet-visible absorption spectrum was measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the maximum absorption wavelength λmax was determined.

[0105] In the evaluation of the absorption wavelength, when the absorption maximum wavelength λmax is 580 nm or more and 670 nm or less, the blue color is considered good "○", and when the absorption maximum wavelength λmax is less than 580 nm or exceeds 670 nm, the blue color is considered insufficient "×".

[0106] <Evaluation of light resistance> For the test pieces for evaluation of each example and each comparative example of the first example, a light resistance test was carried out 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 xenon lamp illuminance was 60 W / cm 2 (300 nm to 400 nm), and the test piece for evaluation was placed for 120 hours under the conditions of a temperature of 45 °C and a humidity of 50% RH.

[0107] For each test piece for evaluation before and after the light resistance test, absorbance measurement was performed 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 Abs1 and the absorbance Abs after the light resistance test is Abs2, ΔAbs (%) = {(Abs1 - Abs2) / Abs1} × 100.

[0108] In the evaluation of light resistance, when ΔAbs is 2% or less, it is considered particularly good "◎", when ΔAbs exceeds 2% and is 10% or less, it is considered good "○", and when ΔAbs exceeds 10%, it is considered bad "×".

[0109] (Evaluation results) Table 1 shows the structure of the anthraquinone derivative, the absorption maximum wavelength λmax, the evaluation results of the absorption wavelength, the absorbance change rate ΔAbs, and the evaluation results of light resistance for each example and each comparative example of the first example. The structure of the anthraquinone derivative of each example is represented by the following formula (I), and R, Y in Table 1 1 , Y 2, Z corresponds to R and Y in the following formula (I). 1 , Y 2 , Z corresponds to it.

[0110]

Chemical formula

[0111]

Table 1

[0112] Table 2 shows, for each comparative example, the structure of the anthraquinone derivative, the maximum absorption wavelength λmax, the evaluation result of the absorption wavelength, the absorbance change rate ΔAbs, and the evaluation result of light resistance. The structure of the anthraquinone derivative of each comparative example is represented by the following formula (II), and R, A, X, Y in Table 2 1 , Y 2 , Z corresponds to R, A, X, Y in the following formula (II). 1 , Y 2 , Z corresponds to it.

[0113]

Chemical formula

[0114]

Table 2

[0115] As shown in Tables 1 and 2, in Examples 1-1 to 1-10 and Comparative Example 1-1 in which a substituted phenyl group is directly bonded to the β-position of the anthraquinone skeleton, good light resistance is obtained, while in Comparative Example 1-2 in which the β-position is an ether bond, the light resistance is extremely poor. Therefore, it was confirmed that the light resistance is improved due to the structure in which a substituted phenyl group is directly bonded to the β-position.

[0116] In Examples 1-1 to 1-10 in which a substituted phenyl group is directly bonded to the β-position and a substituted phenylthio group is present at the α-position, an absorption maximum wavelength λmax in the range of 580 nm or more and 670 nm or less is obtained. On the other hand, in Comparative Example 1-1 in which a substituted phenyl group is directly bonded to the β-position and a substituted anilino group is present at the α-position, the absorption maximum wavelength λmax exceeds 680 nm. In Comparative Example 1-2 in which the β-position is an ether bond and a substituted phenylthio group is present at the α-position, the absorption maximum wavelength λmax is 570 nm or less.

[0117] Therefore, by having both the direct bonding structure of the substituted phenyl group at the β-position, which contributes greatly to the long-wavelength shift of the absorption maximum wavelength λmax, and the substituted phenylthio group at the α-position, which contributes little to the long-wavelength shift, it was confirmed that an absorption maximum wavelength λmax can be obtained within a suitable range and that both light resistance and blueness can be achieved.

[0118] [Second Example] (Synthesis of the Dye of Example 2-1) In the synthesis step of the dye of Example 1-1 of the First Example, the synthesis was carried out in the same manner except that precursor 3 was changed to precursor 5 and 4-heptylbenzenethiol was changed to 4-methoxybenzenethiol, to obtain the anthraquinone derivative of Example 2-1. The anthraquinone derivative of Example 2-1 is a compound represented by the following formula (P2-1).

[0119] [Chemical Formula]

[0120] (Example 2-2) The dye of Example 1-3 of the First Example was used as the anthraquinone derivative of Example 2-2. The anthraquinone derivative of Example 2-2 is a compound represented by the following formula (P2-2).

[0121] [Chemical Formula]

[0122] (Synthesis of the Dye of Example 2-3) In the synthesis process of the dye of Example 1-1 of the first example, the synthesis was carried out in the same manner except that precursor 3 was changed to precursor 7 and 4-heptylbenzenethiol was changed to 4-methoxybenzenethiol, and the anthraquinone derivative of Example 2-3 was obtained. The anthraquinone derivative of Example 2-3 is a compound represented by the following formula (P2-3).

[0123] [Chemical Formula]

[0124] (Synthesis of the Dye of Comparative Example 2-1) Precursor 1 (1.0 part by weight) and N-methyl-2-pyrrolidone (20 parts by weight) were added to a two-necked eggplant flask. 4-Heptylaniline (0.8 part by weight) was added thereto, 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 reaction solution was allowed to cool to room temperature, ethyl acetate (30 parts by weight) and 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% hydrochloric acid aqueous 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 residue was purified by silica gel column chromatography (developing solvent: hexane / dichloromethane = 2 / 1 to 2 / 3) to obtain a dark blue solid.

[0125] In a two-necked flask, 4-heptyloxyphenol (0.36 parts by weight) and potassium carbonate (0.24 parts by weight) were placed, and the flask was purged with nitrogen. Then, 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 above-mentioned dark blue solid (0.50 parts 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 the layers were separated. The obtained organic layer was dried over sodium sulfate and then concentrated using an evaporator. Then, purification was performed by silica gel column chromatography, and drying under reduced pressure at 60 °C was carried out to obtain the anthraquinone derivative of Comparative Example 2-1 as a blue powder. The anthraquinone derivative of Comparative Example 2-1 is a compound represented by the following formula (P2-4).

[0126] [Chemical formula]

[0127] (Synthesis of the dye of Comparative Example 2-2) In the synthesis step of the dye of Comparative Example 2-1 above, synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylphenol to obtain the anthraquinone derivative of Comparative Example 2-2. The anthraquinone derivative of Comparative Example 2-2 is a compound represented by the following formula (P2-5).

[0128] [Chemical formula]

[0129] (Synthesis of the dye of Comparative Example 2-3) In the synthesis step of the dye of Comparative Example 2-1 above, synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylcyclohexylphenol to obtain the anthraquinone derivative of Comparative Example 2-3. The anthraquinone derivative of Comparative Example 2-3 is a compound represented by the following formula (P2-6).

[0130] [Chemical formula]

[0131] (Evaluation method) (Evaluation of absorption wavelength and light resistance) For the anthraquinone derivatives of each example 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 performed.

[0132] (Calculation of total energy difference ΔE) For the anthraquinone derivatives of each example and each comparative example of the second embodiment, the total energy difference ΔE before and after the reaction represented by the above reaction formula (3) was calculated. The calculation of the total energy difference ΔE was performed using the quantum chemistry calculation program GAMESS with the functional B3LYP and the basis function 6-31G(d) according to the following procedure.

[0133] (1) For the anthraquinone derivative, structural optimization was carried out by SCF calculation to obtain the total energy Ep of the molecule in the optimized structure. (2) Using the structure in which hydrogen was added 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.

[0134] 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 that the most stable structure with the lowest energy is likely to 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 according to the calculation formula ΔE = Ek - Ep.

[0135] (Evaluation results) Table 3 shows the structure of the anthraquinone derivative, the absorption maximum wavelength λmax, the total energy difference ΔE, the absorbance change rate ΔAbs, and the evaluation results of light resistance for each example and each comparative example of the second example. The structures of the anthraquinone derivatives of each example and each comparative example are represented by the following formula (III), and R, A, X, Y 1 , Y 2 , Z in the following formula (III) are R, A, X, Y 1 , Y 2 , Z in the following formula (III) correspond to those of R, A, X, Y

[0136] [Chemical formula]

[0137] [Table 3]

[0138] As shown in Table 3, in Examples 2-1 to 2-3 where the total energy difference ΔE is -16 kcal / mol or more, high light resistance is obtained. Since the anthraquinone derivatives of Examples 2-1 to 2-3 have an absorption maximum wavelength in the wavelength range of 580 nm or more and 670 nm or less, excellent blueness is obtained. 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.

[0139] [Third Example] (Example 3-1) The dye of Example 1-2 of the first example was used as the anthraquinone derivative of Example 3-1. The anthraquinone derivative of Example 3-1 is a compound represented by the following formula (P3-1).

[0140] [Chemical formula]

[0141] (Example 3-2) The dyes of Examples 1-3 of the first embodiment were used as the anthraquinone derivatives of Example 3-2. The anthraquinone derivative of Example 3-2 is a compound represented by the following formula (P3-2).

[0142] [Chemical formula]

[0143] (Example 3-3) The dyes of Examples 1-6 of the first embodiment were used as the anthraquinone derivatives of Example 3-3. The anthraquinone derivative of Example 3-3 is a compound represented by the following formula (P3-3).

[0144] [Chemical formula]

[0145] (Example 3-4) The dyes of Examples 1-4 of the first embodiment were used as the anthraquinone derivatives of Example 3-4. The anthraquinone derivative of Example 3-4 is a compound represented by the following formula (P3-4).

[0146] [Chemical formula]

[0147] (Comparative Example 3-1) The dyes of Comparative Example 2-1 of the second embodiment were used as the anthraquinone derivatives of Comparative Example 3-1. The anthraquinone derivative of Comparative Example 3-1 is a compound represented by the following formula (P3-5).

[0148] [Chemical formula]

[0149] (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 (P3-6).

[0150] [Chemical formula]

[0151] (Evaluation method) (Evaluation of absorption wavelength and light resistance) 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 light resistance were carried out.

[0152] (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.

[0153] (Evaluation results) Table 4 shows the structure of the anthraquinone derivative, the maximum absorption wavelength λmax, the 10% weight loss temperature, the absorbance change rate ΔAbs, and the evaluation results of light resistance 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 (III), and R, A, X, Y 1 , Y 2 , Z in Table 4 are corresponding to R, A, X, Y 1 , Y 2 , Z in the following formula (III).

[0154] [Chemical formula]

[0155] [Table 4]

[0156] As shown in Table 4, in Examples 3-1 to 3-4 where the 10% weight loss temperature is 350°C or higher, high light resistance is obtained. Since the anthraquinone derivatives of Examples 3-1 to 3-4 have an absorption maximum wavelength in the wavelength range of 580 nm or more and 670 nm or less, an excellent blue color is obtained. 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.

[0157] [Fourth Embodiment] (Example 4-1) The dye of Example 1-2 of the first embodiment was used as the anthraquinone derivative of Example 4-1. The anthraquinone derivative of Example 4-1 is a compound represented by the following formula (P4-1).

[0158] [Chemical formula]

[0159] (Example 4-2) The dye of Example 2-3 of the second embodiment was used as the anthraquinone derivative of Example 4-2. The anthraquinone derivative of Example 4-2 is a compound represented by the following formula (P4-2).

[0160] [Chemical formula]

[0161] (Example 4-3) The dye of Example 1-6 of the first embodiment was used as the anthraquinone derivative of Example 4-3. The anthraquinone derivative of Example 4-3 is a compound represented by the following formula (P4-3).

[0162] [Chemical formula]

[0163] (Synthesis of Dye of Comparative Example 4-1) In the synthesis process of the dye of Comparative Example 2-1 of the second embodiment, 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 (P4-4).

[0164] [Chemical Formula]

[0165] (Comparative Example 4-2) The dye of Comparative Example 1-2 of the first embodiment was used as the anthraquinone derivative of Comparative Example 4-2. The anthraquinone derivative of Comparative Example 4-2 is a compound represented by the following formula (P4-5).

[0166] [Chemical Formula]

[0167] (Synthesis of Dye of Comparative Example 4-3) In the synthesis process of the dye of Comparative Example 2-1 of the second embodiment, 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 (P4-6).

[0168] [Chemical Formula]

[0169] (Evaluation Method) (Evaluation of Absorption Wavelength and Color Strength) For the anthraquinone derivatives of each example and each comparative example of the fourth embodiment, test pieces for evaluation were prepared in the same manner as in the first embodiment.

[0170] 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 "×".

[0171] <Calculation of transition dipole moment> For each example and each comparative example of the anthraquinone derivative in the fourth embodiment, the transition dipole moment was calculated using the time-dependent density functional method. Specifically, using the quantum chemical calculation program GAMESS, with the functional as B3LYP and the basis function as 6-31G(d), the transition dipole moment in vacuum of each anthraquinone derivative 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 ).

[0172] (Evaluation results) Table 5 shows the structure of the anthraquinone derivative, each component of the transition dipole moment and the magnitude μ of the transition dipole moment, the absorption maximum wavelength λmax, the absorbance, and the evaluation results of coloring power for each example and each comparative example of the fourth embodiment. The structure of the anthraquinone derivative of each example and each comparative example is represented by the following formula (III), and R, A, X, Y 1 ,Y 2 ,Z in Table 5 correspond to R, A, X, Y 1 ,Y 2 ,Z in the following formula (III).

[0173]

Chemical formula

[0174]

Table 5

[0175] As shown in Table 5, in Examples 4-1 to 4-3 where the magnitude μ of the transition dipole moment is 3.30 D or more, higher absorbance was obtained compared to Comparative Examples 4-1 to 4-3 where the magnitude μ of the transition dipole moment is less than 3.30 D, and the coloring power was good. Since the anthraquinone derivatives of Examples 4-1 to 4-3 have an absorption maximum wavelength in the wavelength range of 580 nm or more and 670 nm or less, excellent blueness is obtained.

[0176] From the results in Table 5, it is suggested that the direct bonding of a substituent at the β-position increases the transition dipole moment. Also, Y 1 , Y 2 When is an electron-donating group such as an alkylamino group, it was confirmed that the transition dipole moment increases and there is a tendency to obtain high absorbance.

[0177] 〔Fifth Example〕 (Example 5-1) The dye of Example 1-2 of the First Example was used as the anthraquinone derivative of Example 5-1. The anthraquinone derivative of Example 5-1 is a compound represented by the following formula (P5-1).

[0178]

Chemical formula

[0179] (Example 5-2) The dye of Example 1-6 of the First Example was used as the anthraquinone derivative of Example 5-2. The anthraquinone derivative of Example 5-2 is a compound represented by the following formula (P5-2).

[0180]

Chemical formula

[0181] (Example 5-3) The dyes of Examples 1-9 of the first embodiment were made into the anthraquinone derivative of Example 5-3. The anthraquinone derivative of Example 5-3 is a compound represented by the following formula (P5-3).

[0182] [Chemical formula]

[0183] (Synthesis of the dye of Comparative Example 5-1) Precursor 1 (1.0 part by weight) and N-methyl-2-pyrrolidone (20 parts by weight) were added to a two-necked eggplant flask. 4-Heptyloxyaniline (0.8 part by weight) was added thereto, and the mixture was heated and stirred in an oil bath at 180°C. After confirming the end of the reaction by thin layer chromatography, the reaction solution was allowed to cool to room temperature, ethyl acetate (30 parts by weight) and 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% hydrochloric acid aqueous solution, and saturated brine, and then anhydrous magnesium sulfate was added and dried. Then, after filtering off the desiccant, the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane / dichloromethane = 2 / 1 to 2 / 3) to obtain a dark blue solid.

[0184] 4-Heptyloxyphenol (0.36 part by weight) and potassium carbonate (0.24 part by weight) were placed in a two-necked flask, purged with nitrogen, dehydrated N-methyl-2-pyrrolidone (10 parts by weight) was added, and the mixture was stirred at 120°C for 3 hours. The above dark blue solid (0.50 part by weight) was added thereto, and the mixture was stirred at 120°C for 7 hours. The reaction solution was returned to room temperature, water / dichloromethane was added, and the layers were separated. The obtained organic layer was dried over sodium sulfate and concentrated with an evaporator. Then, purification was performed by silica gel column chromatography, and the anthraquinone derivative of Comparative Example 5-1 was obtained as a blue powder by drying under reduced pressure at 60°C. The anthraquinone derivative of Comparative Example 5-1 is a compound represented by the following formula (P5-4).

[0185] [Chemical formula]

[0186] (Comparative Example 5-2) The dye of Comparative Example 4-1 of the fourth embodiment was used as the anthraquinone derivative of Comparative Example 5-2. The anthraquinone derivative of Comparative Example 5-2 is a compound represented by the following formula (P5-5).

[0187] [Chemical formula]

[0188] (Comparative Example 5-3) The dye of Comparative Example 1-2 of the first embodiment was used as the anthraquinone derivative of Comparative Example 5-3. The anthraquinone derivative of Comparative Example 5-3 is a compound represented by the following formula (P5-6).

[0189] [Chemical formula]

[0190] (Comparative Example 5-4) In the synthesis process of Comparative Example 1-2 of the first embodiment, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-pentylcyclohexylphenol, and the anthraquinone derivative of Comparative Example 5-4 was obtained. The anthraquinone derivative of Comparative Example 5-4 is a compound represented by the following formula (P5-7).

[0191] [Chemical formula]

[0192] (Evaluation Method) (Evaluation of Absorption Wavelength and Color Strength) For the anthraquinone derivatives of each example and each comparative example of the fifth embodiment, test pieces for evaluation were prepared in the same manner as in the first embodiment. Then, the maximum absorption wavelength λmax and the absorbance at that wavelength were determined in the same manner as in the fourth embodiment, and the color strength was evaluated.

[0193] <Calculation of Molecular Orbital Coefficients> For the anthraquinone derivatives of each example and each comparative example of the fifth example, the molecular orbital coefficients were calculated using the density functional method. Specifically, using the quantum chemistry calculation program GAMESS, with the functional being B3LYP and the basis function being 6-31G(d), structural optimization was performed on the anthraquinone derivative, and the molecular orbital coefficients at the optimized structure were obtained. For C in the above formula (4) 11 , C 12 , C 21 , C 22 For each carbon atom of, the square root of the sum of the squares of the coefficients corresponding to the orbitals on the carbon atom M 11 , M 12 , M 21 , M 22 was calculated 、 M 11 , M 12 , M 21 , M 22 The average Mv of was determined. Under these calculation conditions, 15 orbits are assigned to each carbon atom, and the molecular orbital coefficients are calculated for each orbit.

[0194] (Evaluation Results) Table 6 shows the evaluation results of the structure of the anthraquinone derivative, the square root of the sum of the squares of the molecular orbital coefficients, the average Mv, the absorption maximum wavelength λmax, the absorbance, and the coloring power for each example and each comparative example of the fifth example. The structures of the anthraquinone derivatives of each example and each comparative example are represented by the following formula (III), and R, A, X, Y in Table 6 1 , Y 2 , Z are corresponding to R, A, X, Y in the following formula (III) 1 , Y 2 , Z.

[0195]

Chemical Formula

[0196]

Table 6

[0197] As shown in Table 6, in Examples 5-1 to 5-3 where the average Mv is 0.03 or more, higher absorbance was obtained compared to Comparative Examples 5-1 to 5-4 where the average Mv is less than 0.03, and the coloring power was good. Since the anthraquinone derivatives of Examples 5-1 to 5-3 have an absorption maximum wavelength in the wavelength range of 580 nm or more and 670 nm or less, an excellent blue color is obtained.

[0198] From the results in Table 6, it is suggested that the average Mv increases due to the direct bonding of a substituent at the β-position. Also, when Y 1 , Y 2 is an electron-donating group such as an alkylamino group, the average Mv increases and a tendency to obtain high absorbance was confirmed.

Claims

1. An anthraquinone derivative represented by the following formula (1). 【Chemical Formula 1】 In formula (1), R １ and R ２ are each independently an amino group or a hydroxyl group, 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, a piperidyl group, an aryl 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, a piperidyl group, an aryl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents.

3. The anthraquinone derivative according to Claim 1, wherein in the following reaction formula (3), 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 (3), determined by the density functional method, is -16 kcal / mol or more. An anthraquinone derivative. 【Chemical 3】

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

5. 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.

6. The anthraquinone derivative according to Claim 1, wherein The following formula (4) represents the anthraquinone derivative, and for 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 orbits on each of the carbon atoms of is calculated for each carbon atom, and the average value of the square roots for each of the carbon atoms is 0.03 or more and 0.2 or less. An anthraquinone derivative. [Chemical Formula 4]

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