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 (1-1). (In the formula, R1, R2, and R3 are an amino group or a hydroxyl group; at least one of Y1 and Y2 is an electron-donating group; in a case where only one of Y1 and Y2 is an electron-donating group, the other of Y1 and Y2 is H, a C1-C10 alkyl group, a C1-C10 alkoxy group, an aryl group, or a cyclohexyl group; Z is H, a C1-C10 alkyl group, a C1-C10 alkoxy group, a cyano group, a nitro group, a halogen atom, an amino group, or an alkylamino group.)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 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 anthraquinone derivatives having an absorption maximum wavelength in a wavelength range of 580 nm or more and having good light resistance.

Means for Solving the Problems

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

[0006]

Chemical formula

[0007] In formula (1-1), R 1 , R 2 , and R 3 are each independently an amino group or a hydroxyl group. At least one of Y 1 and Y 2 is an electron-donating group. When only one of Y 1 and Y 2 is an electron-donating group, the other of Y 1 and Y 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents. Z is 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, an amino group, or an alkylamino group.

[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. Further, since a phenyl group is directly bonded to the β-position of the anthraquinone skeleton, the light resistance is enhanced. And in such a structure, since the substituent at the para-position of the phenyl group at the β-position is an electron-donating group, the absorbance is enhanced and a high coloring power is obtained.

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

[0010]

Chemical formula

[0011] In formula (1-2), Y 1 and Y 2 at least one of which is an electron-donating group, and when only one of Y 1 and Y 2 is an electron-donating group, the other of Y 1 and Y 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents. Z is 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, an amino group, or an alkylamino group.

[0012] [Aspect 3] The anthraquinone derivative according to [Aspect 1] or [Aspect 2], wherein the electron-donating group is an alkylamino group, an amino group, a piperidyl group, an acetamido group, or a hydroxyl group.

[0013] [Aspect 4] In the formula (1-2), Y 1 and Y 2 are each independently an alkylamino group, an amino group, or a piperidyl group, which is the anthraquinone derivative according to [Aspect 2].

[0014] [Aspect 5] An anthraquinone derivative represented by the following formula (2-1).

[0015] [Chemical formula]

[0016] In formula (2-1), R 1 , R 2 , and R 3 are each independently an amino group or a hydroxyl group. Y 1 and Y 2is, independently, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, a cyano group, a nitro group, a halogen atom, an amino group, an alkylamino group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents. Z is an electron-withdrawing group.

[0017] 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 cyanine dye. Further, due to the direct bonding of a phenyl group which may be substituted or unsubstituted at the β-position of the anthraquinone skeleton, the light resistance is enhanced. And in such a structure, since the substituent at the para-position of the anilino group at the α-position is an electron-withdrawing group, the absorbance is enhanced and a high coloring power is obtained.

[0018] [Aspect 6] The anthraquinone derivative according to [Aspect 5] represented by the following formula (2-2).

[0019]

Chemical formula

[0020] In formula (2-2), Y 1 and Y 2 are, independently, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, a cyano group, a nitro group, a halogen atom, an amino group, an alkylamino group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents. Z is an electron-withdrawing group.

[0021] [Aspect 7] The anthraquinone derivative according to [Aspect 5] or [Aspect 6] represented by the following formula (2-3).

[0022]

Chemical formula

[0023] In formula (2-3), R 4 and R5 Each is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cyclic hydrocarbon group, and Z is an electron-withdrawing group.

[0024] [Aspect 8] The anthraquinone derivative according to any one of [Aspects 5] to [Aspect 7], wherein the electron-withdrawing group is a cyano group, an aldehyde group, an ester group, an acetyl group, a sulfo group, a nitro group, or a halogenated alkyl group.

[0025] [Aspect 9] An anthraquinone derivative represented by the following formula (3-1).

[0026]

Chemical formula

[0027] In formula (3-1), R 1 , R 2 , and R 3 are each independently an amino group or a hydroxyl group. At least one of Y 1 and Y 2 is a cyclohexyl group, and the cyclohexyl group may have a substituent. When only one of Y 1 and Y 2 is a cyclohexyl group, the other of Y 1 and Y 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, a cyano group, a nitro group, a halogen atom, an amino group, or an alkylamino group, and the aryl group may have a substituent. Z is 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, an amino group, or an alkylamino group.

[0028] 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. Further, since a phenyl group is directly bonded to the β-position of the anthraquinone skeleton, the light resistance is enhanced. And in such a structure, since the substituent at the para-position of the phenyl group at the β-position is a substituted or unsubstituted cyclohexyl group, the absorption in the short wavelength region is suppressed and an excellent blue color is obtained.

[0029] [Aspect 10] The anthraquinone derivative according to [Aspect 9] represented by the following formula (3-2).

[0030]

Chemical formula

[0031] In formula (3-2), Y 1 and Y 2 at least one of them is a cyclohexyl group, and the cyclohexyl group may have a substituent. When only one of Y 1 and Y 2 is a cyclohexyl group, the other of Y 1 and Y 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, a cyano group, a nitro group, a halogen atom, an amino group, or an alkylamino group, and the aryl group may have a substituent. Z is 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, an amino group, or an alkylamino group.

[0032] [Aspect 11] The anthraquinone derivative according to [Aspect 10] represented by the following formula (3-3).

[0033]

Chemical formula

[0034] In formula (3-3), R 4 and R 5is, independently of one another, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cyclic hydrocarbon group, and Z is 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, an amino group, or an alkylamino group.

[0035] [Aspect 12] An anthraquinone derivative according to any one of [Aspect 1], [Aspect 5], and [Aspect 9], wherein the compound on the left side in the following reaction formula (4-2) represents the anthraquinone derivative, and the difference in the total energy of the molecule after and before the reaction represented by the following reaction formula (4-2), obtained by the density functional method, is -16 kcal / mol or more.

[0036] [Chemical formula]

[0037] [Aspect 13] An anthraquinone derivative according to any one of [Aspect 1], [Aspect 5], and [Aspect 9], wherein the 10% weight loss temperature is 350°C or higher.

[0038] [Aspect 14] An anthraquinone derivative according to any one of [Aspect 1], [Aspect 5], and [Aspect 9], wherein the magnitude of the transition dipole moment obtained by the time-dependent density functional method is 3.30 D or more and 5.00 D or less.

[0039] [Aspect 15] An anthraquinone derivative according to any one of [Aspect 1], [Aspect 5], and [Aspect 9], wherein the following formula (7-1) 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, the square root of the sum of the squares of the coefficients corresponding to the orbits on each carbon atom of C 11 , C 12 , C 21 , C 22 is obtained for each carbon atom, and the average value of the square root of the sum of the squares for each carbon atom is 0.03 or more and 0.2 or less.

[0040] [Chemical formula] [Advantages of the Invention]

[0041] 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]

[0042] Hereinafter, the anthraquinone derivatives of the first to seventh embodiments will be described. In each 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.

[0043] The anthraquinone derivatives of each embodiment are used as dyes. 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 used in 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.

[0044] (First Embodiment) The anthraquinone derivative of the first embodiment will be described. The anthraquinone derivative of the first embodiment is a compound represented by the following formula (1-1).

[0045] [Chemical formula]

[0046] In formula (1-1), R 1 , R2 and R 3 are each independently an amino group or a hydroxyl group. In formula (1-1), Y 1 and Y 2 at least one of which is an electron-donating group, and when only one of Y 1 and Y 2 is an electron-donating group, the other of Y 1 and Y 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, 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.

[0047] The electron-donating group is preferably an alkylamino group, an amino group, a piperidyl group, an acetamido group, or a hydroxyl group. 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. When both Y 1 and Y 2 are electron-donating groups, Y 1 and Y 2 may be the same as or different from each other.

[0048] In formula (1-1), Z is 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, an amino group, or an alkylamino group. The halogen atom is 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.

[0049] The action of the anthraquinone derivative of this embodiment will be described. The type of substituent in the anthraquinone skeleton affects the absorption wavelength of the anthraquinone derivative. The anthraquinone derivative of the first embodiment has a substituted or unsubstituted anilino group at the 1-position for the four α-positions, and an amino group or a hydroxyl group at the 4, 5, and 8-positions. Further, among the four β-positions of the anthraquinone derivative, only two of the 3- and 7-positions have substituents, and the substituents are substituted or unsubstituted phenyl groups. 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.

[0050] Also, 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. As a conventional anthraquinone derivative, a structure in which a functional group such as a phenyl group is bonded by an ether bond at the β-position is known. On the other hand, in the anthraquinone derivative of this embodiment, a phenyl group 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.

[0051] Specifically, when a phenyl group is directly bonded at the β-position, the molecular structure is difficult to rotate at the bonding portion at the β-position compared to the case where an ether bond exists at the β-position. Therefore, the structure after photoreduction of the anthraquinone skeleton is unlikely to become a stable structure, and for this reason, it is considered that the progress of the photoreduction reaction is suppressed.

[0052] In addition, for dyes, it is desirable that the coloring power be high, that is, the absorbance be high. The higher the coloring power, the more the amount of the dye can be reduced, which is beneficial from the viewpoint of cost. Regarding the absorbance of anthraquinone derivatives, it has been suggested that the larger the overlap of the molecular orbital distributions between the ground state and the excited state, the higher the absorbance. And the molecular orbital of the ground state is likely to vary depending on the molecular structure such as substituents and tends to be broader than that of the excited state. On the other hand, the anthraquinone derivative of the first embodiment has a para-substituted phenyl group containing an electron-donating group at at least one β-position. Since the substituent at the para-position in the phenyl group is an electron-donating group, the spread of the molecular orbital of the ground state is suppressed, so that the extinction coefficient is increased. As a result, the coloring power of the anthraquinone derivative is increased.

[0053] In the anthraquinone derivative of the first embodiment, the above R 1 and R 3 are hydroxyl groups, and R 2 is preferably an amino group. Such a compound is represented by the following formula (1-2).

[0054]

Chemical formula

[0055] In formula (1-2), Y 1 , Y 2 , and Z are defined in the same manner as in formula (1-1). If it is an anthraquinone derivative represented by formula (1-2), the synthesis is easy. Further, when a hydroxyl group is present at the α-position, the above-described photoreduction is likely to occur. However, according to the anthraquinone derivative of the present 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 disadvantages of the structure having a hydroxyl group at the α-position, the advantages of the structure can be enjoyed.

[0056] Furthermore, in the anthraquinone derivative of the first embodiment, Y 1 and Y 2It is preferable that both are electron-donating groups. Thereby, regarding the molecular orbitals related to the above-mentioned photoexcitation, the control power in the direction of increasing the extinction coefficient is enhanced, so that higher coloring power can be obtained. In particular, Y 1 and Y 2 Each of them is preferably an alkylamino group, an amino group, or a piperidyl group. Since these functional groups have high electron-donating properties, a high control power can be obtained for the molecular orbitals related to the above-mentioned photoexcitation. Therefore, higher coloring power can be obtained.

[0057] Y 1 and Y 2 Compounds in which each of them is an alkylamino group or an amino group are represented by the following formula (1-3). Y 1 and Y 2 Compounds in which each of them is a piperidyl group are represented by the following formula (1-4).

[0058]

Chemical formula

[0059] In formula (1-3), Z is defined in the same manner as in formula (1-1). R 4 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0060]

Chemical formula

[0061] In formula (1-4), Z is defined in the same manner as in formula (1-1). The anthraquinone derivative of the first 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, the desired substituent is introduced by utilizing the reduction of a nitro group, substituent conversion, bromination at the β-position, and conversion of the bromo group.

[0062] (Second Embodiment) The anthraquinone derivative of the second embodiment will be described. The anthraquinone derivative of the second embodiment is a compound represented by the following formula (2-1).

[0063] [Chemical Formula]

[0064] In formula (2-1), R 1 , R 2 , and R 3 are each independently an amino group or a hydroxyl group. Y 1 and Y 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, a cyano group, a nitro group, a halogen atom, an amino group, an alkylamino group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have a substituent.

[0065] The halogen atom is preferably F, Cl, or Br. The alkyl group of the alkylamino group may have one or two alkyl groups. The alkyl group of the alkylamino group preferably has 1 to 10 carbon atoms. The substituent of the aryl group or cyclohexyl group 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.

[0066] In formula (2-1), Z is an electron-withdrawing group. The electron-withdrawing group is preferably a cyano group, an aldehyde group, an ester group, an acetyl group, a sulfo group, a nitro group, or a halogenated alkyl group. The halogen contained in the halogenated alkyl group is preferably F, Cl, or Br. The number of carbon atoms of the halogenated alkyl group preferably ranges from 1 to 10.

[0067] The anthraquinone derivative of the second embodiment has a substituted anilino group at the 1-position and an amino group or a hydroxyl group at the 4, 5, and 8-positions for the four α-positions. Also, the anthraquinone derivative of the second embodiment has two substituted or unsubstituted phenyl groups at the β-position. Therefore, similar to the first embodiment, since the anthraquinone derivative of the second embodiment also has an absorption maximum wavelength in the wavelength range of 600 nm or more, it can be used as a cyan-based dye.

[0068] Also, in the anthraquinone derivative of the second embodiment, at the β-position, the phenyl group is directly bonded to the carbon atom constituting the anthraquinone skeleton. Due to such a structure, similar to the first embodiment, the progress of the photoreduction reaction is suppressed, and thus high light resistance can be obtained.

[0069] Furthermore, the anthraquinone derivative of the second embodiment has a para-substituted anilino group containing an electron-withdrawing group at the α-position. Since the substituent at the para-position in the anilino group is an electron-withdrawing group, the electron density of the aromatic ring of the anilino group decreases, and the spread of the molecular orbital toward the anilino group can be suppressed. Also by this, the molecular orbital related to photoexcitation is controlled to increase the extinction coefficient, and as a result, the coloring power of the anthraquinone derivative is increased.

[0070] Note that when the anthraquinone derivative has a phenyl group having an electron-donating group as a para-substituent at the β-position, similar to the first embodiment, the effect of improving the coloring power is further enhanced.

[0071] In the anthraquinone derivative of the second embodiment, the above R 1 and R 3is a hydroxyl group, and R 2 is preferably an amino group. Such a compound is represented by the following formula (2-2).

[0072]

Chemical formula

[0073] In formula (2-2), Y 1 , Y 2 , and Z are defined in the same manner as in formula (2-1). If it is an anthraquinone derivative represented by formula (2-2), the synthesis is easy. Further, when a hydroxyl group is present at the α-position, the above-described photoreduction is likely to occur. However, according to the anthraquinone derivative of the present 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 disadvantages of the structure having a hydroxyl group at the α-position, the advantages of the structure can be enjoyed.

[0074] Furthermore, the anthraquinone derivative of the second embodiment is preferably a compound represented by the following formula (2-3).

[0075]

Chemical formula

[0076] In formula (2-3), Z is defined in the same manner as in formula (2-1). R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cyclic hydrocarbon group. Many liquid crystal compounds have a cyclohexane ring, and phenylcyclohexane-based liquid crystals are also preferably used. If it is an anthraquinone derivative represented by formula (2-3), it can be easily mixed with such a liquid crystal material, and thus can be preferably used as a dichroic dye together with the liquid crystal material.

[0077] The anthraquinone derivative of the second 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.

[0078] (Third Embodiment) The anthraquinone derivative of the third embodiment will be described. The anthraquinone derivative of the third embodiment is a compound represented by the following formula (3-1).

[0079] [Chemical formula]

[0080] In formula (3-1), R 1 , R 2 , and R 3 are each independently an amino group or a hydroxyl group. In formula (3-1), at least one of Y 1 and Y 2 is a cyclohexyl group, and the cyclohexyl group may have a substituent. The substituent that the cyclohexyl group has 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.

[0081] Y 1 and Y 2 When only one of them is a cyclohexyl group, Y 1 and Y 2The other is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, a cyano group, a nitro group, a halogen atom, an amino group, or an alkylamino group, and the aryl group may have a substituent. The halogen atom is preferably F, Cl, or Br. The alkyl group of the alkylamino group may be one or two. The number of carbon atoms of the alkyl group of the alkylamino group is preferably 1 to 10. The substituent of the aryl group is preferably an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group.

[0082] In formula (3-1), Z is 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, an amino group, or an alkylamino group. The halogen atom is preferably F, Cl, or Br. The alkyl group of the alkylamino group may be one or two. The number of carbon atoms of the alkyl group of the alkylamino group is preferably 1 to 10.

[0083] In the anthraquinone derivative of the third embodiment, the substituent at the α-position is the same as that in the first embodiment. Also, the anthraquinone derivative of the third embodiment has two phenyl groups, which may be substituted or unsubstituted, at the β-position in the same manner as in the first embodiment. Therefore, since the anthraquinone derivative of the third embodiment also has an absorption maximum wavelength in the wavelength range of 600 nm or more, it can be used as a cyan-based dye.

[0084] Also, in the anthraquinone derivative of the third embodiment, at the β-position, the phenyl group is directly bonded to the carbon atom constituting the anthraquinone skeleton. Due to such a structure, the progress of the photoreduction reaction is suppressed as in the first and second embodiments, and high light resistance can be obtained.

[0085] Furthermore, the anthraquinone derivative of the third embodiment has a para-substituted phenyl group at at least one β-position, and the substituent at the para-position in the phenyl group is a substituted or unsubstituted cyclohexyl group. The substituent at the para-position at the β-position enables control of the molecular orbitals involved in photoexcitation. When the substituent is a cyclohexyl group, the absorption in the short-wavelength region shifts to the ultraviolet region. As a result, the blue component increases in the reflected light, making the blue color of the dye stronger. Having a strong blue color is beneficial for cyan dyes used corresponding to the three primary colors of light. Therefore, the anthraquinone derivative of the third embodiment can be suitably used as a cyan dye.

[0086] In the anthraquinone derivative of the third embodiment, the above R 1 and R 3 are hydroxyl groups, and R 2 is preferably an amino group. Such a compound is represented by the following formula (3-2).

[0087]

Chemical formula

[0088] In formula (3-2), Y 1 , Y 2 , and Z are defined in the same manner as in formula (3-1). For an anthraquinone derivative represented by formula (3-2), synthesis is easy. Also, when a hydroxyl group is present at the α-position, the above-described 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 disadvantages of the structure having a hydroxyl group at the α-position, the advantages of this structure can be enjoyed.

[0089] Furthermore, the anthraquinone derivative of the third embodiment is preferably a compound represented by the following formula (3-3).

[0090]

Chemical formula

[0091] In formula (3-3), Z is defined in the same manner as in formula (3-1). R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cyclic hydrocarbon group. In the anthraquinone derivative represented by formula (3-3), the substituents at the para positions in the two phenyl groups located at the β positions are both substituted or unsubstituted cyclohexyl groups. As a result, the effect of suppressing absorption in the short wavelength region is obtained more highly, and thus a stronger blue color is obtained. In addition, when the anthraquinone derivative has an anilino group having an electron-withdrawing group as a para substituent at the α position, in the same manner as in the second embodiment, the effect of improving the coloring power can be obtained.

[0092] The anthraquinone derivative of the third 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. A known method may be used for introducing the substituent. For example, a desired substituent is introduced by utilizing reduction of a nitro group, substituent conversion, bromination with respect to the β position, and conversion of a bromo group.

[0093] (Fourth Embodiment) The anthraquinone derivative of the fourth embodiment will be described. The anthraquinone derivative of the fourth embodiment is a compound represented by the following formula (4-1), and is a compound in which the total energy difference ΔE before and after the reaction represented by the following reaction formula (4-2) is -16 kcal / mol or more.

[0094] [Chemical formula]

[0095] [Chemical formula]

[0096] In formula (4-1), X is -NH- or a sulfur atom. In formula (4-1), R 1 , R 2 , and R 3 are each independently an amino group or a hydroxyl group. In formula (4-1), A 1 , and A 2 are each independently a direct bond, an oxygen atom, a sulfur atom, or -NH-. Note that when A 1 , A 2 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.

[0097] In formula (4-1), 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. 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.

[0098] The above reaction formula (4-2) shows the photoreduction reaction of the anthraquinone derivative represented by the above formula (4-1). In this reaction, using a resin or the like existing around the anthraquinone derivative P4 as a hydrogen source, photoreduction of the anthraquinone derivative P4 occurs, and a hydrogen adduct K4, which is a compound in which hydrogen is added to the anthraquinone skeleton, is generated.

[0099] The total energy difference ΔE is the value obtained by subtracting the total energy Ep of the anthraquinone derivative P4 from the total energy Ek of the hydrogen adduct K4 (ΔE = Ek - Ep). The energies Ep and Ek of the anthraquinone derivative P4 and the hydrogen adduct K4, respectively, are determined by quantum chemical calculations using the density functional theory (DFT). The B3LYP functional is used for the functional, and the 6-31G(d) basis function is used. 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.

[0100] The action of the anthraquinone derivative of the fourth embodiment will be described. Since the anthraquinone derivative having a substituent as shown in the above formula (4-1) has an absorption maximum wavelength in the wavelength range of 580 nm or more and 830 nm or less, it can be used as a cyan-based dye.

[0101] In the anthraquinone derivative of the fourth embodiment, the total energy difference ΔE is -16 kcal / mol or more. One cause of the deterioration of the anthraquinone derivative by light is that the reaction shown in the above reaction formula (4-2) 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. Further, in order to obtain higher light resistance, the total energy difference ΔE is preferably -14 kcal / mol or more.

[0102] In the fourth embodiment, a first example of a suitable anthraquinone derivative is among the above-described compounds represented by the above formula (4-1), where R 1 , R 2 , and R 3 are each an amino group. With such a compound, the total energy difference ΔE becomes larger, so high light resistance can be obtained. Since it is considered that the photoreduction reaction is likely to occur when the anthraquinone derivative has a hydroxyl group at the α-position, R 1 , R2 and R 3 Since all of them are amino groups, it is considered that deterioration due to photoreduction reaction can be accurately suppressed.

[0103] In the fourth embodiment, a second example of a suitable anthraquinone derivative is among the above-described compounds represented by the above formula (4-1), where R 1 and R 3 are hydroxyl groups, R 2 is an amino group, and A 1 , A 2 is a direct bond. For such a compound, since the total energy difference ΔE becomes larger, high light resistance can be obtained. In such a structure, as described in the first embodiment, due to the direct bonding of a phenyl group at the β-position, it is considered that deterioration due to photoreduction reaction can be accurately suppressed due to the three-dimensional structure of the molecule.

[0104] In addition, for the anthraquinone derivative of the fourth embodiment, if the total energy difference ΔE is -16 kcal / mol or more, it may be a compound described in the first to third embodiments. Among the compounds described in the first to third embodiments, even if it is a compound different from the compound represented by the above formula (4-1), good light resistance can be obtained due to the total energy difference ΔE being -16 kcal / mol or more.

[0105] (Fifth Embodiment) The anthraquinone derivative of the fifth embodiment will be described. The anthraquinone derivative of the fifth embodiment is a compound represented by the following formula (5-1), and is a compound having a 10% weight loss temperature in thermogravimetric measurement of 350 °C or higher.

[0106] [Chemical formula]

[0107] In formula (5-1), X is -NH- or a sulfur atom. In formula (5-1), R 1 , R 2 , and R 3is, independently of each other, an amino group or a hydroxyl group. In formula (5-1), A 1 , and each of A 2 is, independently of each other, a direct bond, an oxygen atom, a sulfur atom, or -NH-. Note that when A 1 , A 2 is a direct bond, it means that a substituted or unsubstituted phenyl group is directly bonded to a carbon atom constituting the anthraquinone skeleton at the β-position of the anthraquinone derivative.

[0108] In formula (5-1), Y 1 , Y 2 , and Z are, independently of each other, 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. 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.

[0109] The above thermogravimetric measurement is carried out under the conditions of a gas flow rate of 200 mL / min and a temperature increase rate of 10 °C / min. Air is used as the gas. The action of the anthraquinone derivative of the fifth embodiment will be described. Since the anthraquinone derivative having a substituent as in the above formula (5-1) has an absorption maximum wavelength in the wavelength range of 580 nm or more and 830 nm or less, it can be used as a cyan-based dye.

[0110] In the anthraquinone derivative of the fifth embodiment, the 10% weight loss temperature in the above thermogravimetric measurement is 350°C or higher. When high heat is applied to the anthraquinone derivative, the anthraquinone derivative decomposes to generate radicals, and reactions such as further decomposition proceed due to the action of these radicals. Since radicals generated from the surroundings or the anthraquinone derivative itself also contribute to the photo-degradation of the anthraquinone derivative, an anthraquinone derivative that is less likely 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. Further, in order to obtain higher light resistance, it is preferable that the 10% weight loss temperature is 365°C or higher.

[0111] In the fifth embodiment, the first example of a suitable anthraquinone derivative is a compound in which R among the above-described compounds represented by the above formula (5-1) 2 is an amino group. Such a compound is easy to synthesize.

[0112] In the fifth embodiment, the second example of a suitable anthraquinone derivative is a compound in which R and R among the above-described compounds represented by the above formula (5-1) 1 and R 3 are hydroxyl groups, and R 2 is an amino group. Such a compound is easy to synthesize.

[0113] In the fifth embodiment, the third example of a suitable anthraquinone derivative is a compound in which each of R, R, and R among the above-described compounds represented by the above formula (5-1) 1 , R 2 , and, R 3 is an amino group. Such a compound has a higher 10% weight loss temperature, so high light resistance can be obtained.

[0114] In the fifth embodiment, the fourth example of a suitable anthraquinone derivative is a compound in which R among the above-described compounds represented by the above formula (5-1) 2 is an amino group, and A 1 and A 2It is a compound with a direct bond. For such a compound, since the 10% weight loss temperature is higher, high light resistance can be obtained.

[0115] In addition, for the anthraquinone derivative of the fifth embodiment, if the 10% weight loss temperature is 350°C or higher, it may be a compound described in the first to third embodiments. Among the compounds described in the first to third embodiments, even if it is a compound different from the compound represented by the above formula (5-1), good light resistance can be obtained by the 10% weight loss temperature being 350°C or higher.

[0116] (Sixth Embodiment) For a pigment, it is desired to have high coloring power, that is, high absorbance. The coloring power of an anthraquinone derivative varies depending on the type and position of the substituents the anthraquinone derivative has. Since there are many choices of substituents that can be introduced into the anthraquinone derivative, the difference in coloring power in the anthraquinone derivative is large, and among conventional anthraquinone derivatives, there are also many compounds with low coloring power.

[0117] The higher the coloring power, the more the blending amount of the pigment can be reduced, which is beneficial from the perspective of cost. Furthermore, in the anthraquinone derivative, since the planarity of the molecule is high and it is difficult to enhance solubility, there is also a limit to increasing the blending amount to strengthen the color. Therefore, improving the coloring power is an important issue. The anthraquinone derivative of the sixth embodiment aims to improve the coloring power.

[0118] The anthraquinone derivative of the sixth embodiment will be described. In the anthraquinone derivative of the sixth embodiment, 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.

[0119] The transition dipole moment of an anthraquinone derivative is the dipole moment generated during 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 performed using general quantum chemical calculation programs such as Gaussian and GAMESS.

[0120] Since the molar extinction coefficient is proportional to the square of the transition dipole moment, the larger the transition dipole moment, the higher the absorbance tends to be. 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.

[0121] 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.

[0122] Also, 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. The anthraquinone derivative of the sixth embodiment is preferably a compound represented by the following formula (6-1).

[0123]

Chemical formula

[0124] In formula (6-1), X is -NH- or a sulfur atom. In formula (6-1), R 1 , R 2 , and R 3 are each independently an amino group or a hydroxyl group.

[0125] In formula (6-1), 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. 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 from 1 to 10.

[0126] For an anthraquinone derivative having a substituent as represented by the above formula (6-1), the transition dipole moment can be increased and the absorption maximum wavelength can also be increased. Specifically, an absorption maximum wavelength can be obtained in a wavelength range of 580 nm or more and 830 nm or less. Therefore, it can be used as a cyan-based dye having high coloring power. Further, since a phenyl group is directly bonded to the β-position, good light resistance can also be obtained.

[0127] Among the compounds represented by the above formula (6-1), the first example of a preferred anthraquinone derivative is R 1 and R 3 are hydroxyl groups, and R 2 is an amino group. Such a compound is easy to synthesize.

[0128] Among the compounds represented by the above formula (6-1), the second example of a preferred anthraquinone derivative is R 2is an amino group and X is a sulfur atom. Such compounds have a structure with a large contribution to the bathochromic shift of the absorption maximum wavelength, namely, an amino group or a hydroxyl group at the α-position and a phenyl group directly bonded at the β-position, and a structure with a small contribution to the bathochromic shift of the absorption maximum wavelength, namely, 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. As a result, an excellent blue color can be obtained.

[0129] The anthraquinone derivative of the sixth embodiment may be the anthraquinone derivative of the first embodiment. With such a compound, high light resistance can be obtained, and the coloring power is enhanced by the action of the para-substituted phenyl group having an electron-donating group at the β-position.

[0130] The anthraquinone derivative of the sixth embodiment may be the anthraquinone derivative of the second embodiment. With such a compound, high light resistance can be obtained, and the coloring power is enhanced by the action of the para-substituted anilino group having an electron-withdrawing group at the α-position.

[0131] The anthraquinone derivative of the sixth embodiment may be the anthraquinone derivative of the third embodiment. With such a compound, high light resistance can be obtained, and a strong blue color is obtained by the action of the para-substituted phenyl group having a cyclohexyl group at the β-position.

[0132] (Seventh Embodiment) Similar to the sixth embodiment, the anthraquinone derivative of the seventh embodiment aims to improve the coloring power.

[0133] The anthraquinone derivative of the seventh embodiment will be described. The anthraquinone derivative of the seventh embodiment is a compound represented by the following formula (7-1) and satisfies the conditions to be described later regarding the molecular orbital coefficient.

[0134] [Chemistry]

[0135] In formula (7-1), C 11 , C 12 , C 21 , C 22 each represents a carbon atom. In formula (7-1), X represents -NH- or a sulfur atom. In formula (7-1), R 1 , R 2 , and R 3 are each independently an amino group or a hydroxyl group. In formula (7-1), A 1 , and A 2 each independently represents a direct bond, an oxygen atom, a sulfur atom, or -NH-. Note that when A 1 , A 2 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.

[0136] In formula (7-1), 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. 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.

[0137] In the anthraquinone derivative of the seventh embodiment, regarding the molecular orbital coefficient of the highest occupied molecular orbital (HOMO) obtained by quantum chemical calculation using the density functional theory (DFT), C 11 、C 12 、C 21 、C 22 The average Mv of 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.

[0138] 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. At this time, M 11 、M 12 、M 21 、M 22 The average value of is the average Mv.

[0139] The above quantum chemical calculation can be executed using general-purpose quantum chemical calculation programs such as Gaussian and GAMESS.

[0140] The action of the anthraquinone derivative of the seventh embodiment will be described. Since the anthraquinone derivative having a substituent as in the above formula (7-1) has an absorption maximum wavelength in the wavelength range of 580 nm or more and 830 nm or less, it can be used as a cyan-based dye.

[0141] Generally, the electronic transition showing an absorption maximum is the electronic transition from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). It is considered that a higher absorbance can be obtained because the probability of electronic transition increases when the overlap of the molecular orbitals of HOMO and LUMO is larger. As a result of repeated studies by the inventors, a tendency of the spread of the molecular orbitals of HOMO and LUMO in anthraquinone derivatives was found.

[0142] That is, with respect to the molecular orbital of the LUMO of the anthraquinone derivative, the influence of the type and arrangement of substituents is small, and the molecular orbital of the 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 (7-1), the molecular orbital of HOMO tends to spread toward the α-position to which the anilino group or phenylthio group is bonded, that is, toward the substituent containing X.

[0143] 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 becomes large.

[0144] The fact that the molecular orbital of HOMO spreads on 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 on 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 molecular orbital of HOMO from spreading too much toward the substituent at the β-position and the overlap of the molecular orbitals of HOMO and LUMO from becoming small.

[0145] In the seventh embodiment, the first example of a suitable anthraquinone derivative is among the above-described compounds represented by the above formula (7-1), where R 1 and R 3 are hydroxyl groups, and R 2 is an amino group. Such a compound is easy to synthesize.

[0146] In the seventh embodiment, the second example of a suitable anthraquinone derivative is among the above-described compounds represented by the above formula (7-1), where R 1 and R 3 are hydroxyl groups, R 2 is an amino group, and A 1 and A 2 are direct bonds. Such a compound is easy to synthesize, and in addition, its light resistance can be enhanced. Also, the average Mv can be increased.

[0147] Note that for the anthraquinone derivative of the seventh embodiment, if the average Mv is 0.03 or more and 0.2 or less, it may be a compound described in the first to third embodiments. Among the compounds described in the first to third embodiments, even if it is a compound different from the compound represented by the above formula (7-1), a good coloring power can be obtained by having an average Mv of 0.03 or more and 0.2 or less.

[0148] In an anthraquinone derivative, in order to increase the average Mv within the range of 0.03 or more and 0.2 or less, it is preferable that a phenyl group which may be substituted at the β-position is directly bonded. Similarly, in order to increase the average Mv within the above range, it is preferable that the anthraquinone derivative has a para-substituted phenyl group at the β-position and the substituent at the para-position of the phenyl group is an electron-donating group. That is, for the anthraquinone derivative of the first embodiment, a good coloring power can be obtained. Similarly, in order to increase the average Mv within the above range, it is preferable that the anthraquinone derivative has a para-substituted anilino group at the α-position and the substituent at the para-position of the anilino group is an electron-withdrawing group. That is, for the anthraquinone derivative of the second embodiment, a good coloring power can be obtained.

[0149] [Example] The above anthraquinone derivatives will be described using specific 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.

[0150] 〔First Example: Test Example Corresponding to the First Embodiment〕 (Test Examples 1-1 to 1-13) <Synthesis of Precursor A1> 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. Here, 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. Then, the precipitated solid was collected by suction filtration, and the recovered product was vacuum dried at 60 °C overnight to obtain Precursor A1 as a yellow solid. Precursor A1 is a compound represented by the following formula (1-a).

[0151] [Chemical formula]

[0152] <Synthesis of Precursor A2> Into a two-necked eggplant flask, precursor A1 (1.0 part by weight) and N-methyl-2-pyrrolidone (20 parts by weight) were added. To this, 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, and 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 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), and the obtained solid was vacuum dried to obtain precursor A2 as a dark blue solid. Precursor A2 is a compound represented by the following formula (1-b).

[0153]

Chemical formula

[0154] <Synthesis of Precursor A3> In the synthesis step of the above precursor A2, synthesis was carried out in the same manner except that 4-heptylaniline was changed to 4-heptyloxyaniline to obtain precursor A3. Precursor A3 is a compound represented by the following formula (1-c).

[0155]

Chemical formula

[0156] <Synthesis of the Dye in Test Example 1-1> A nascent flask equipped with a Jim-Roth cooler and subjected to nitrogen replacement was charged with toluene (5 parts by weight), water (2.5 parts by weight), precursor A2 (0.30 parts by weight, 1 equivalent), 4-dimethylaminophenylboronic acid (0.28 parts by weight, 2.4 equivalents), potassium carbonate (0.21 parts by weight) as a base, and tetrakis(triphenylphosphine)palladium (0.06 parts by weight) as a catalyst, and heated and stirred 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, then 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 Test Example 1-1. The anthraquinone derivative of Test Example 1-1 is a compound represented by the following formula (P1-1).

[0157] [Chemical formula]

[0158] [Synthesis of the dye of Test Example 1-2] In the synthesis step of the dye of Test Example 1-1 above, synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-dibutylaminophenylboronic acid to obtain the anthraquinone derivative of Test Example 1-2. The anthraquinone derivative of Test Example 1-2 is a compound represented by the following formula (P1-2).

[0159] [Chemical formula]

[0160] [Synthesis of the dye of Test Example 1-3] In the synthesis step of the dye of Test Example 1-1 above, synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-monobutylaminophenylboronic acid to obtain the anthraquinone derivative of Test Example 1-3. The anthraquinone derivative of Test Example 1-3 is a compound represented by the following formula (P1-3).

[0161]

Chem.

[0162] <Synthesis of the Dyes in Test Examples 1-4> In the synthesis process of the dye in Test Example 1-1 above, the synthesis was carried out in the same manner except that precursor A2 was changed to precursor A3 and 4-dimethylaminophenylboronic acid was changed to 4-monobutylaminophenylboronic acid, and an anthraquinone derivative of Test Example 1-4 was obtained. The anthraquinone derivative of Test Example 1-4 is a compound represented by the following formula (P1-4).

[0163]

Chem.

[0164] <Synthesis of the Dye in Test Example 1-5> In the synthesis process of the dye in Test Example 1-1 above, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to (4-piperidin-1-yl)phenylboronic acid, and an anthraquinone derivative of Test Example 1-5 was obtained. The anthraquinone derivative of Test Example 1-5 is a compound represented by the following formula (P1-5).

[0165]

Chem.

[0166] <Synthesis of the Dye in Test Example 1-6> In the synthesis process of the dye in Test Example 1-1 above, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-aminophenylboronic acid, and an anthraquinone derivative of Test Example 1-6 was obtained. The anthraquinone derivative of Test Example 1-6 is a compound represented by the following formula (P1-6).

[0167]

Chem.

[0168] <Synthesis of the Dyes in Test Examples 1-7> In the synthesis process of the dye in Test Example 1-1, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-acetamidophenylboronic acid, and the anthraquinone derivative of Test Example 1-7 was obtained. The anthraquinone derivative of Test Example 1-7 is a compound represented by the following formula (P1-7).

[0169]

Chemical formula

[0170] <Synthesis of the Dye in Test Example 1-8> In the synthesis process of the dye in Test Example 1-1, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-hydroxyphenylboronic acid, and the anthraquinone derivative of Test Example 1-8 was obtained. The anthraquinone derivative of Test Example 1-8 is a compound represented by the following formula (P1-8).

[0171]

Chemical formula

[0172] <Synthesis of the Dye in Test Example 1-9> In the synthesis process of the dye in Test Example 1-1, precursor A2 was changed to precursor A3, and in addition to replacing 4-dimethylaminophenylboronic acid, 1.2 equivalents of 4-monobutylaminophenylboronic acid was added, and the reaction solution was stirred at 80 °C for 1 hour. Then, 1.2 equivalents of 4-heptylphenylboronic 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 process of the dye in Test Example 1-1, and the anthraquinone derivative of Test Example 1-9 was obtained. The anthraquinone derivative of Test Example 1-9 is a compound represented by the following formula (P1-9).

[0173]

Chemical formula

[0174] <Synthesis of the Dyes in Test Examples 1 - 10> In the synthesis process of the dye in Test Example 1 - 1, synthesis was carried out in the same manner except that 4 - dimethylaminophenylboronic acid was changed to 4 - heptyloxyphenylboronic acid, and an anthraquinone derivative of Test Example 1 - 10 was obtained. The anthraquinone derivative of Test Example 1 - 10 is a compound represented by the following formula (P1 - 10).

[0175]

Chemical formula

[0176] <Synthesis of the Dye in Test Example 1 - 11> In the synthesis process of the dye in Test Example 1 - 1, synthesis was carried out in the same manner except that precursor A2 was changed to precursor A3 and 4 - dimethylaminophenylboronic acid was changed to 4 - heptyloxyphenylboronic acid, and an anthraquinone derivative of Test Example 1 - 11 was obtained. The anthraquinone derivative of Test Example 1 - 11 is a compound represented by the following formula (P1 - 11).

[0177]

Chemical formula

[0178] <Synthesis of the Dye in Test Example 1 - 12> Into a two-necked round-bottom flask, 4-heptyloxyphenol (8.65 parts by weight) and N-methyl-2-pyrrolidone (100 parts by weight) were added. Sodium hydride (55%, 1.7 parts by weight) was gently added in 5 portions, and the mixture was stirred in an oil bath at 60 °C for 3 hours. Precursor A3 (5.00 parts by weight) was added to this solution, and the mixture was heated and stirred in an oil bath at 130 °C for 24 hours. After confirming the completion of the reaction by thin-layer chromatography, the reaction solution was returned to room temperature, ethyl acetate and distilled water were added, and the mixture was vigorously stirred at room temperature. After separating the two layers, the organic layer was successively washed with distilled water and saturated brine, 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 = 1 / 1 to 1 / 2), and the obtained solid was washed with ethanol and vacuum dried at 60 °C to obtain the anthraquinone derivative of Test Example 1-12. The anthraquinone derivative of Test Example 1-12 is a compound represented by the following formula (P1-12).

[0179] [Chemical formula]

[0180] <Synthesis of the dye of Test Example 1-13> In the synthesis process of the dye of Test Example 1-12 above, 4-heptyloxyphenol (8.65 parts by weight) was changed to 4-butylaminophenol (6.86 parts by weight), and the synthesis was carried out in the same manner except that precursor A3 was changed to precursor A2 to obtain the anthraquinone derivative of Test Example 1-13. The anthraquinone derivative of Test Example 1-13 is a compound represented by the following formula (P1-13).

[0181] [Chemical formula]

[0182] (Test Example 1-14, Test Example 1-15) <Synthesis of Precursor B1> 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 carried out. 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 being ice-cooled. Thereafter, the solution was stirred for 10 minutes while being ice-cooled and then stirred at room temperature for 24 hours. Then, the precipitate was collected by suction filtration, and the recovered product was washed with diethyl ether and dried to obtain a brown crude product. Thereafter, the crude product (5.5 parts by weight) and ethyl acetate (54 parts by weight) were placed in an eggplant flask, heated to the reflux temperature, and subjected to suspension washing for 30 minutes. Then, the recovered product by suction filtration was washed with diethyl ether and then dried under reduced pressure at 60 °C to obtain precursor B1 as a brown powder. Precursor B1 is a compound represented by the following formula (1-d).

[0183] [Chemical formula]

[0184] [Synthesis of Precursor B2] Concentrated sulfuric acid (48 parts by weight) was placed in a four-necked flask equipped with a thermometer and a mechanical stirrer, and potassium nitrate (6.0 parts by weight) was further added and completely dissolved, and the flask was cooled until the internal temperature reached 0 °C. Precursor B1 (3.0 parts by weight) was added to this solution in six portions of 0.5 parts by weight each while keeping the internal temperature of the four-necked flask from exceeding 5 °C. After the addition of precursor B1, a light brown precipitate formed after a while. Thereafter, when the solution was stirred at an internal temperature of 0 °C to 5 °C for 6 hours, 1Stirring was stopped because disappearance of the substrate was confirmed by 1H-NMR measurement (solvent: DMSO-d6). 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. 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 allowing this solution to cool naturally to room temperature, the precipitate collected by filtration was dried under reduced pressure at 60 °C to obtain precursor B2 as a dull yellow powder. Precursor B2 is a compound represented by the following formula (1-e).

[0185]

Chemical formula

[0186] <Synthesis of Precursor B3> 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 while ice-cooling. Precursor B2 (2.2 parts by weight) was added thereto while ice-cooling. This solution was stirred at 95 °C for 2 hours and then added to pure water (200 parts by weight) while ice-cooling. Thereafter, the precipitate was collected by suction filtration, and the collected product was dried under reduced pressure at 60 °C to obtain precursor B3 as a red powder. Precursor B3 is a compound represented by the following formula (1-f).

[0187]

Chemical formula

[0188] <Synthesis of Precursor B4> Precursor B3 (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 stirred at room temperature for 15 minutes. Thereafter, the precipitate was collected by suction filtration, and the collected product was dried under reduced pressure at 60 °C to obtain precursor B4 as a reddish brown powder. Precursor B4 is a compound represented by the following formula (1-g).

[0189]

Chem.

[0190] <Synthesis of Precursor B5> 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 B4 (0.30 part by weight), (4-piperidin-1-yl)phenylboronic acid (0.28 part by weight), potassium carbonate (0.21 part by weight), and tetrakis(triphenylphosphine)palladium (0.06 part 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 B5. Precursor B5 is a compound represented by the following formula (1-h).

[0191]

Chem.

[0192] <Synthesis of Precursor B6> Precursor B5 (0.20 part by weight) was placed in a two-necked flask and purged with nitrogen. To this, nitrobenzene (4.8 parts by weight) and 4-heptylaniline (0.52 part by weight) were added, 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 B6. Precursor B6 is a compound represented by the following formula (1-i).

[0193]

Chem.

[0194] <Synthesis of Precursor B7> In the synthesis step of the precursor B5, synthesis was carried out in the same manner except that (4-piperidin-1-yl)phenylboronic acid was changed to 4-heptyloxyphenylboronic acid to obtain precursor B7. Precursor B7 is a compound represented by the following formula (1-j).

[0195]

Chemical formula

[0196] <Synthesis of Precursor B8> In the synthesis step of the precursor B6, synthesis was carried out in the same manner except that precursor B5 was changed to precursor B7 to obtain precursor B8. Precursor B8 is a compound represented by the following formula (1-k).

[0197]

Chemical formula

[0198] <Synthesis of the Dyes in Test Example 1-14> Precursor B6 (0.20 part by weight) was placed in a two-necked flask and purged with nitrogen. After adding 2-propanol (3.1 parts by weight) thereto, the mixture was heated to 80 °C, and further sodium borohydride (0.22 part by weight) was added and stirred for 27 hours. The reaction solution was poured into cold water, and the precipitated powder was collected by suction filtration and then purified by column chromatography to obtain the anthraquinone derivative of Test Example 1-14. The anthraquinone derivative of Test Example 1-14 is a compound represented by the following formula (P1-14).

[0199]

Chemical formula

[0200] <Synthesis of the Dye in Test Example 1-15> In the synthesis process of the dyes in Test Examples 1-14, the synthesis was carried out in the same manner except that precursor B6 was changed to precursor B8, and the anthraquinone derivative of Test Example 1-15 was obtained. The anthraquinone derivative of Test Example 1-15 is a compound represented by the following formula (P1-15).

[0201] [Chemical formula]

[0202] (Evaluation method) [Preparation of test pieces for evaluation] Using the anthraquinone derivatives of each test example, 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

[0203] 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, and a test piece for evaluation was prepared.

[0204] [Evaluation of absorption wavelength and coloring power] Regarding the test pieces for evaluation of each test example, an ultraviolet-visible absorption spectrum was measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the maximum absorption wavelength λmax and the absorbance at that wavelength were determined.

[0205] In the evaluation of coloring power, based on Test Examples 1-10 corresponding to conventional anthraquinone derivatives, when the absorbance was greater than that of Test Examples 1-10, it was rated as good "○", and when the absorbance was less than or equal to that of Test Examples 1-10, it was rated as poor "×".

[0206] <Evaluation of lightfastness> For the test pieces for evaluation of each test example, a xenon weather meter tester (X75, manufactured by Suga Test Instruments Co., Ltd.) was used to conduct a lightfastness test. In the lightfastness 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), 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.

[0207] For each test piece for evaluation before and after the lightfastness test, absorbance measurement was performed using an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the absorbance at the wavelength showing the maximum absorbance in the visible light region was determined. Then, the absorbance change rate ΔAbs before and after the lightfastness test was calculated. That is, when the measured value before the lightfastness test is the absorbance Abs1 and the measured value after the lightfastness test is the absorbance Abs2, ΔAbs (%) = {(Abs1 - Abs2) / Abs1} × 100.

[0208] In the evaluation of lightfastness, when ΔAbs was 2% or less, it was rated as particularly good "◎", when ΔAbs exceeded 2% and was 10% or less, it was rated as good "○", and when ΔAbs exceeded 10%, it was rated as poor "×".

[0209] <Measurement of dichroic ratio> For each test example, an anthraquinone derivative was mixed with a cyanocyclohexylbenzene-based liquid crystal (ZLI-1840, manufactured by Merck) at a ratio of 1.0% by mass to prepare a liquid crystal composition. Subsequently, the liquid crystal composition was injected into a cell to fabricate a guest-host type liquid crystal element. The cell had a structure in which two glass plates with transparent electrodes, which were subjected to homogeneous alignment treatment, were opposed to each other such that the alignment treatment surfaces were anti-parallel. The alignment treatment was performed by applying a polyimide resin to the transparent electrode, curing the resin, and then performing a rubbing treatment. The thickness of the cell was 10 μm.

[0210] The above liquid crystal element was placed in the optical path of a spectrophotometer, and the absorbance A / / when linearly polarized light parallel to the rubbing direction was applied to the liquid crystal element and the absorbance A⊥ when linearly polarized light perpendicular to the rubbing direction was applied to the liquid crystal element were measured. Then, the ratio (A / / / A⊥) of the absorbance A / / to the absorbance A⊥ was calculated as the dichroic ratio.

[0211] (Evaluation Results) Table 1 shows the structure of the anthraquinone derivative, the absorption maximum wavelength λmax, the absorbance at the absorption maximum wavelength λmax, the evaluation results of the coloring power, the absorbance change rate ΔAbs, the evaluation results of the light resistance, and the dichroic ratio for Test Examples 1-1 to 1-15. The structure of the anthraquinone derivative in each test example is represented by the following formula (I), and R, A, Y 1 ,Y 2 ,Z in Table 1 corresponds to R, A, Y 1 ,Y 2 ,Z in the following formula (I).

[0212] [Chemical formula]

[0213] [Table 1]

[0214] As shown in Table 1, the anthraquinone derivatives of each test example have an absorption maximum wavelength in the wavelength range of 600 nm or more. Therefore, the anthraquinone derivatives of each test example exhibit blue color and can be used as cyan dyes.

[0215] And in Test Examples 1-1 to 1-11, 1-14, 1-15 in which a substituted phenyl group is directly bonded to the β-position, extremely high light resistance is obtained as compared with Test Examples 1-12, 1-13 in which the β-position has an ether bond.

[0216] Furthermore, in Test Examples 1-1 to 1-9, 1-14 in which the substituent at the para-position of the directly bonded phenyl group is an electron-donating group at at least one β-position, the absorbance is higher than that in Test Examples 1-10, 1-11, 1-15 in which the substituent is not an electron-donating group, and good coloring power is obtained. Also, in Test Examples 1-1 to 1-9, 1-14, high absorbance is obtained even with respect to Test Examples 1-12, 1-13 in which the β-position has an ether bond.

[0217] Also, when comparing Test Example 1-3 and Test Example 1-9, higher absorbance is obtained when both of the phenyl groups at the two β-positions have an electron-donating group as a substituent than when only one of the substituents is an electron-donating group. Also, referring to Test Examples 1-1 to 1-8, it was confirmed that when the electron-donating group is an alkylamino group, a piperidyl group, or an amino group, the effect of improving the absorbance is higher than when the electron-donating group is an acetamide group or a hydroxyl group. Also, good dichroic ratios are obtained in all of the test examples. In particular, it was confirmed that when having two hydroxyl groups at the α-position, a high dichroic ratio of 10.0 or more is obtained.

[0218] [Second Example: Test Examples Corresponding to the Second Embodiment] In the second example, synthesis was carried out using the same precursors A1, A2, A3 as in the first example.

[0219] (Test Example 2-1) ><Synthesis of Precursor C1> Into a two-necked eggplant flask, precursor A1 (1.0 part by weight) and p-aminobenzonitrile (2.42 parts by weight) were placed, and nitrogen substitution was carried out. Nitrobenzene (24 parts by weight) was added thereto, and the mixture was heated and stirred in an oil bath at 190 °C for 5 hours. After cooling the reaction solution to room temperature, the solvent was removed by drying under reduced pressure at 70 °C. Methanol was poured into the obtained residue, and the precipitated powder was collected by suction filtration to obtain precursor C1 as a purple powder. Precursor C1 is a compound represented by the following formula (2-a).

[0220]

Chemical formula

[0221] <Synthesis of Precursor C2> Into a two-necked eggplant flask, precursor C1 (1.0 part by weight), (4-pentyloxy)phenylboronic acid (1.18 parts by weight), cesium carbonate (1.74 parts by weight), [1,1'-bis(diphenylphosphinoferrocene)]dichloropalladium(II) (0.131 part by weight), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.147 part by weight) were placed, and nitrogen substitution was carried out. Toluene (71 parts by weight), ethanol (7.2 parts by weight), and pure water (4.5 parts by weight) were added thereto, and the mixture was stirred in an oil bath at 80 °C for 2 hours. The reaction solution was cooled to room temperature, separated with dichloromethane and pure water, and the organic layer was dried over sodium sulfate. Then, sodium sulfate was filtered off, the remaining solution was concentrated, and purified by silica gel column chromatography (developing solvent: dichloromethane / hexane = 1 / 1) to obtain a crude product. The crude product was purified by column chromatography to obtain precursor C2 as a purple powder. The yield of precursor C2 was 11%. Precursor C2 is a compound represented by the following formula (2-b).

[0222]

Chemical formula

[0223] <Synthesis of the Dye in Test Example 2-1> Into a two-necked round-bottom flask, precursor C2 (1 part by weight), iron powder (0.325 part by weight), and ammonium chloride (0.311 part by weight) were added, and nitrogen substitution was performed. Toluene (27.9 parts by weight), ethanol (8.38 parts by weight), and pure water (5.31 parts by weight) were added thereto, and the mixture was heated and stirred in an oil bath at 70 °C for 1 hour. The reaction solution was cooled to room temperature, and the insoluble components were filtered off with celite. Then, the solution was separated with dichloromethane and pure water, washed with pure water and saturated brine, and the organic layer was dried over sodium sulfate. The sodium sulfate was filtered off, and the remaining solution was concentrated and then purified by silica gel column chromatography (developing solvent: dichloromethane / hexane = 2 / 1 to 1 / 1) to obtain the anthraquinone derivative of Test Example 2-1 as a purple powder. The anthraquinone derivative of Test Example 2-1 is a compound represented by the following formula (P2-1).

[0224] [Chemical formula]

[0225] (Test Example 2-2) [Synthesis of Precursor C3] In the synthesis step of the above precursor C1, synthesis was carried out in the same manner except that p-aminobenzonitrile (2.42 parts by weight) was changed to p-aminobenzotrifluoride (3.3 parts by weight) to obtain precursor C3. Precursor C3 is a compound represented by the following formula (2-c).

[0226] [Chemical formula]

[0227] [Synthesis of Precursor C4] In the synthesis step of the above precursor C2, synthesis was carried out in the same manner except that precursor C1 was changed to precursor C3 to obtain precursor C4. Precursor C4 is a compound represented by the following formula (2-d).

[0228] [Chemical formula]

[0229] <Synthesis of the Dye in Test Example 2-2> In the synthesis process of the dye in Test Example 2-1, the synthesis was carried out in the same manner except that precursor C2 was changed to precursor C4, and an anthraquinone derivative of Test Example 2-2 was obtained. The anthraquinone derivative of Test Example 2-2 is a compound represented by the following formula (P2-2).

[0230]

Chemical formula

[0231] (Test Example 2-3) <Synthesis of the Dye in Test Example 2-3> In the synthesis process of precursor C2, the synthesis was carried out in the same manner except that (4-pentyloxy)phenylboronic acid was changed to 4-(trans-4-pentylcyclohexyl)phenylboronic acid to obtain precursor C5. Then, in the synthesis process of the dye in Test Example 2-1, the synthesis was carried out in the same manner except that precursor C2 was changed to precursor C5, and an anthraquinone derivative of Test Example 2-3 was obtained. The anthraquinone derivative of Test Example 2-3 is a compound represented by the following formula (P2-3).

[0232]

Chemical formula

[0233] (Test Example 2-4) <Synthesis of the Dye in Test Example 2-4> In the synthesis process of precursor C2, the synthesis was carried out in the same manner except that precursor C1 was changed to precursor C3 and (4-pentyloxy)phenylboronic acid was changed to 4-(trans-4-pentylcyclohexyl)phenylboronic acid to obtain precursor C6. Then, in the synthesis process of the dye in Test Example 2-1, the synthesis was carried out in the same manner except that precursor C2 was changed to precursor C6, and an anthraquinone derivative of Test Example 2-4 was obtained. The anthraquinone derivative of Test Example 2-4 is a compound represented by the following formula (P2-4).

[0234]

Chem.

[0235] (Test Example 2-5) <Synthesis of the Dye of Test Example 2-5> In the synthesis process of the above precursor C2, synthesis was carried out in the same manner except that (4-pentyloxy)phenylboronic acid was changed to 4-(dimethylamino)phenylboronic acid to obtain precursor C7. Then, in the synthesis process of the dye of Test Example 2-1, synthesis was carried out in the same manner except that precursor C2 was changed to precursor C7 to obtain the anthraquinone derivative of Test Example 2-5. The anthraquinone derivative of Test Example 2-5 is a compound represented by the following formula (P2-5).

[0236]

Chem.

[0237] (Test Example 2-6) The dye of Test Example 1-10 of the first embodiment was used as the anthraquinone derivative of Test Example 2-6. The anthraquinone derivative of Test Example 2-6 is a compound represented by the following formula (P2-6).

[0238]

Chem.

[0239] (Test Example 2-7) The dye of Test Example 1-11 of the first embodiment was used as the anthraquinone derivative of Test Example 2-7. The anthraquinone derivative of Test Example 2-7 is a compound represented by the following formula (P2-7).

[0240]

Chem.

[0241] (Test Example 2-8) <Synthesis of the Dye of Test Example 2-8> In the synthesis process of the dye in Test Example 1-1 of the first embodiment, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-(trans-4-pentylcyclohexyl)phenylboronic acid, and the anthraquinone derivative of Test Example 2-8 was obtained. The anthraquinone derivative of Test Example 2-8 is a compound represented by the following formula (P2-8).

[0242] [Chemical formula]

[0243] (Test Example 2-9) (Synthesis of the dye of Test Example 2-9) In the synthesis process of the dye in Test Example 1-1 of the first embodiment, the synthesis was carried out in the same manner except that precursor A2 was changed to precursor A3 and 4-dimethylaminophenylboronic acid was changed to 4-(trans-4-pentylcyclohexyl)phenylboronic acid, and the anthraquinone derivative of Test Example 2-9 was obtained. The anthraquinone derivative of Test Example 2-9 is a compound represented by the following formula (P2-9).

[0244] [Chemical formula]

[0245] (Test Example 2-10) The dye of Test Example 1-12 of the first embodiment was used as the anthraquinone derivative of Test Example 2-10. The anthraquinone derivative of Test Example 2-10 is a compound represented by the following formula (P2-10).

[0246] [Chemical formula]

[0247] (Test Example 2-11) (Synthesis of precursor C8) In the synthesis process of the dyes in Test Examples 1-12 of the first embodiment, synthesis was carried out in the same manner except that precursor A3 was changed to precursor C1, and precursor C8 was obtained. Precursor C8 is a compound represented by the following formula (2-e).

[0248] [Chemical formula]

[0249] [Synthesis of the dye in Test Example 2-11] In the synthesis process of the dye in Test Example 2-1 above, synthesis was carried out in the same manner except that precursor C2 was changed to precursor C8, and the anthraquinone derivative of Test Example 2-11 was obtained. The anthraquinone derivative of Test Example 2-11 is a compound represented by the following formula (P2-11).

[0250] [Chemical formula]

[0251] (Evaluation method) For the anthraquinone derivatives of Test Examples 2-1 to 2-11, test pieces for evaluation were prepared in the same manner as in the first embodiment, and evaluation of the absorption wavelength, coloring power, light resistance, and dichroic ratio was carried out. In the evaluation of the coloring power, based on Test Example 2-6 corresponding to the conventional anthraquinone derivative, when the absorbance was greater than that of Test Example 2-6, it was rated as good "○", and when the absorbance was less than or equal to that of Test Example 2-6, it was rated as poor "×".

[0252] (Evaluation results) Table 2 shows, for Test Examples 2-1 to 2-11, the structure of the anthraquinone derivative, the maximum absorption wavelength λmax, the absorbance at the maximum absorption wavelength λmax, the evaluation result of the coloring power, the absorbance change rate ΔAbs, the evaluation result of the light resistance, and the dichroic ratio. The structure of the anthraquinone derivative of each test example is represented by the following formula (I), and R, A, Y 1 , Y 2 , Z in the following formula (I) are R, A, Y 1 , Y 2 , Z in the following formula (I) corresponding to.

[0253]

Chem.

[0254]

Table 2

[0255] As shown in Table 2, the anthraquinone derivatives of each test example have an absorption maximum wavelength in the wavelength range of 600 nm or more. Therefore, the anthraquinone derivatives of each test example exhibit blue color and can be used as cyan dyes.

[0256] And in Test Examples 2-1 to 2-9 in which a substituted phenyl group is directly bonded to the β-position, extremely high light resistance is obtained as compared with Test Examples 2-10 and 2-11 in which the β-position is an ether bond.

[0257] Furthermore, in the structure in which a substituted phenyl group is directly bonded to the β-position, in Test Examples 2-1 to 2-5 in which the substituent at the para-position of the anilino group at the α-position is an electron-withdrawing group, the absorbance is higher than that in Test Examples 2-6 to 2-9 in which the substituent is not an electron-withdrawing group, and good coloring power is obtained. Also, in Test Examples 2-1 to 2-5, high absorbance is obtained even with respect to Test Examples 2-10 and 2-11 in which the β-position is an ether bond.

[0258] Also, referring to Test Examples 2-1 to 2-5, it was confirmed that in Test Example 2-5 in which, in addition to the electron-withdrawing group at the para-position of the α-position, the phenyl group at the β-position has an electron-donating group as the substituent at the para-position, particularly high absorbance is obtained as compared with other test examples not having such an electron-donating group. Also, it was confirmed that good dichroic ratios are obtained in all test examples.

[0259] 〔Third Example: Test Examples Corresponding to the Third Embodiment〕 In the third example, synthesis was carried out using the same precursors A1 to A3, B1 to B4 as in the first example.

[0260] (Test Example 3-1) The dye of Test Example 2-8 of the second embodiment was used as the anthraquinone derivative of Test Example 3-1. The anthraquinone derivative of Test Example 3-1 is a compound represented by the following formula (P3-1).

[0261]

Chemical formula

[0262] (Test Example 3-2) <Synthesis of the dye of Test Example 3-2> In the synthesis process of the dye of Test Example 1-1 of the first embodiment, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-ethylcyclohexylphenylboronic acid, and the anthraquinone derivative of Test Example 3-2 was obtained. The anthraquinone derivative of Test Example 3-2 is a compound represented by the following formula (P3-2).

[0263]

Chemical formula

[0264] (Test Example 3-3) <Synthesis of the dye of Test Example 3-3> In the synthesis process of the dye of Test Example 1-1 of the first embodiment, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-methylcyclohexylphenylboronic acid, and the anthraquinone derivative of Test Example 3-3 was obtained. The anthraquinone derivative of Test Example 3-3 is a compound represented by the following formula (P3-3).

[0265]

Chemical formula

[0266] (Test Example 3-4) <Synthesis of the dye of Test Example 3-4> In the synthesis process of the dye of Test Example 1-1 of the first embodiment, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to cyclohexylphenylboronic acid, and the anthraquinone derivative of Test Example 3-4 was obtained. The anthraquinone derivative of Test Example 3-4 is a compound represented by the following formula (P3-4).

[0267] [Chemical formula]

[0268] (Test Example 3-5) The dye of Test Example 2-9 of the second embodiment was used as the anthraquinone derivative of Test Example 3-5. The anthraquinone derivative of Test Example 3-5 is a compound represented by the following formula (P3-5).

[0269] [Chemical formula]

[0270] (Test Example 3-6) <Synthesis of the dye of Test Example 3-6> In the synthesis process of the dye of Test Example 1-1 of the first embodiment, 1.2 equivalents of 4-heptyloxyphenylboronic acid were added instead of 4-dimethylaminophenylboronic acid, and the reaction solution was stirred at 80 °C for 1 hour. Then, 1.2 equivalents of 4-pentylcyclohexylphenylboronic acid were 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 process of the dye of Test Example 1-1 to obtain the anthraquinone derivative of Test Example 3-6. The anthraquinone derivative of Test Example 3-6 is a compound represented by the following formula (P3-6).

[0271] [Chemical formula]

[0272] (Test Example 3-7) <Synthesis of the dye of Test Example 3-7> In the synthesis process of the dye in Test Example 1-1 of the first embodiment, instead of 4-dimethylaminophenylboronic acid, 1.2 equivalents of 4-monobutylaminophenylboronic acid was added, and the reaction solution was stirred at 80°C for 1 hour. Then, 1.2 equivalents of 4-pentylcyclohexylphenylboronic acid was added, and heating and stirring were carried out at 80°C for 2 hours or more. Thereafter, extraction and purification were performed in the same manner as in the synthesis process of the dye in Test Example 1-1 to obtain the anthraquinone derivative of Test Example 3-7. The anthraquinone derivative of Test Example 3-7 is a compound represented by the following formula (P3-7).

[0273] [Chemical formula]

[0274] (Test Example 3-8) The dye of Test Example 1-10 of the first embodiment was used as the anthraquinone derivative of Test Example 3-8. The anthraquinone derivative of Test Example 3-8 is a compound represented by the following formula (P3-8).

[0275] [Chemical formula]

[0276] (Test Example 3-9) The dye of Test Example 1-11 of the first embodiment was used as the anthraquinone derivative of Test Example 3-9. The anthraquinone derivative of Test Example 3-9 is a compound represented by the following formula (P3-9).

[0277] [Chemical formula]

[0278] (Test Example 3-10) The dye of Test Example 1-3 of the first embodiment was used as the anthraquinone derivative of Test Example 3-10. The anthraquinone derivative of Test Example 3-10 is a compound represented by the following formula (P3-10).

[0279] [Chemical formula]

[0280] (Test Example 3-11) (Synthesis of the Dye of Test Example 3-11) In the synthesis process of Test Example 1-12 of the first embodiment, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylcyclohexylphenol and precursor A3 was changed to precursor A2, and the anthraquinone derivative of Test Example 3-11 was obtained. The anthraquinone derivative of Test Example 3-11 is a compound represented by the following formula (P3-11).

[0281] [Chemical Formula]

[0282] (Test Example 3-12) (Synthesis of Precursor B9) In the synthesis process of precursor B5 of the first embodiment, the synthesis was carried out in the same manner except that (4-piperidin-1-yl)phenylboronic acid was changed to (4-pentylcyclohexyl)phenylboronic acid, and precursor B9 was obtained. Precursor B9 is a compound represented by the following formula (3-a).

[0283] [Chemical Formula]

[0284] (Synthesis of Precursor B10) In the synthesis process of precursor B6 of the first embodiment, the synthesis was carried out in the same manner except that precursor B5 was changed to precursor B9, and precursor B10 was obtained. Precursor B10 is a compound represented by the following formula (3-b).

[0285] [Chemical Formula]

[0286] (Synthesis of the Dye of Test Example 3-12) In the synthesis process of the dyes in Test Examples 1-14 of the first embodiment, the synthesis was carried out in the same manner except that the precursor B6 was changed to the precursor B10, and the anthraquinone derivatives of Test Examples 3-12 were obtained. The anthraquinone derivative of Test Example 3-12 is a compound represented by the following formula (P3-12).

[0287] [Chemical formula]

[0288] (Test Example 3-13) The dye of Test Example 1-15 of the first embodiment was used as the anthraquinone derivative of Test Example 3-13. The anthraquinone derivative of Test Example 3-13 is a compound represented by the following formula (P3-13).

[0289] [Chemical formula]

[0290] (Evaluation method) For the anthraquinone derivatives of Test Examples 3-1 to 3-13, test pieces for evaluation were prepared in the same manner as in the first embodiment, and the absorption wavelength, light resistance, and dichroic ratio were evaluated.

[0291] In addition, as the degree of side absorption, after normalizing the absorbance at the maximum absorption wavelength in the ultraviolet-visible absorption spectrum to 1.0, the sum of the absorbances in the short wavelength region of 380 nm or more and 480 nm or less was obtained using the obtained spectrum. The sum of the absorbances is an integral value corresponding to the area in the range of 380 nm or more and 480 nm or less in the spectrum after the above normalization. Note that the absorption in the short wavelength region of 380 nm or more and 480 nm or less is defined as side absorption.

[0292] (Evaluation results) Table 3 shows the structure of the anthraquinone derivative, the absorption maximum wavelength λmax, the degree of secondary absorption, the absorbance change rate ΔAbs, the evaluation results of light resistance, and the dichroic ratio for Test Examples 3-1 to 3-13. The structure of the anthraquinone derivative in each test example is represented by the following formula (I), and R, A, Y 1 , Y 2 , Z in the following formula (I) are R, A, Y 1 , Y 2 , Z corresponding to them.

[0293]

Chemical formula

[0294]

Table 3

[0295] As shown in Table 3, the anthraquinone derivative of each test example has an absorption maximum wavelength in the wavelength range of 600 nm or more. Therefore, the anthraquinone derivative of each test example exhibits blue color and can be used as a cyan-based dye.

[0296] And in Test Examples 3-1 to 3-10, 3-12, 3-13 where a substituted phenyl group is directly bonded at the β-position, extremely high light resistance is obtained compared to Test Example 3-11 where the β-position has an ether bond.

[0297] Furthermore, when comparing Test Examples 3-1 to 3-4 with Test Examples 3-8, 3-10, it was confirmed that the substituent at the para-position of the phenyl group at the β-position being a substituted or unsubstituted cyclohexyl group can reduce the degree of secondary absorption. Similarly, by comparing Test Example 3-5 with Test Example 3-9 and comparing Test Example 3-12 with Test Example 3-13, it was also confirmed that the degree of secondary absorption becomes smaller when the substituent at the para-position of the β-position is a cyclohexyl group. Thus, it can be said that if the substituent at the para-position of the β-position is a cyclohexyl group, excellent blue color with reduced yellowness can be obtained in the anthraquinone derivative.

[0298] Also, by comparing Test Example 3-6 with Test Example 3-8 and Test Example 3-7 with Test Example 3-10, it was confirmed that even if only one of the cyclohexyl groups at the para position of the β-position is present, the effect of suppressing the degree of side absorption can be obtained. And when comparing Test Example 3-1 with Test Example 3-6 and 3-7, it was confirmed that when both of the substituents at the para position of the β-position are cyclohexyl groups, the effect of suppressing the degree of side absorption is higher than when only one is a cyclohexyl group. Also, in each test example, a good dichroic ratio was obtained. In particular, it was confirmed that a high dichroic ratio can be obtained when there are two hydroxyl groups at the α-position.

[0299] [Fourth Embodiment: Test Examples Corresponding to the Fourth Embodiment] In the fourth embodiment, synthesis was carried out using the same precursors as in the first to third embodiments.

[0300] (Test Example 4-1) >[Synthesis of Precursor B11] Into a two-necked flask, 4-heptyloxyphenol (0.45 parts by weight) and potassium carbonate (0.30 parts by weight) were placed and 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. To this solution, Precursor B4 (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 performed. 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 B11 as a red powder. Precursor B11 is a compound represented by the following formula (4-a).

[0301] [Chemical Formula]

[0302] >[Synthesis of Precursor B12] Precursor B11 (0.20 parts by weight) was placed in a two-necked flask and purged with nitrogen. 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 a residue was obtained. Methanol was poured into this residue, and the precipitated powder was collected by suction filtration to obtain precursor B12 as a purple powder. Precursor B12 is a compound represented by the following formula (4-b).

[0303] [Chemical formula]

[0304] [Synthesis of the dye of Test Example 4-1] In the synthesis step of the dyes of Test Examples 1-14 of the first embodiment, the synthesis was carried out in the same manner except that precursor B6 was changed to precursor B12 to obtain the anthraquinone derivative of Test Example 4-1. The anthraquinone derivative of Test Example 4-1 is a compound represented by the following formula (P4-1).

[0305] [Chemical formula]

[0306] (Test Example 4-2) The dyes of Test Examples 1-10 of the first embodiment were used as the anthraquinone derivative of Test Example 4-2. The anthraquinone derivative of Test Example 4-2 is a compound represented by the following formula (P4-2).

[0307] [Chemical formula]

[0308] (Test Example 4-3) The dyes of Test Examples 2-8 of the second embodiment were used as the anthraquinone derivative of Test Example 4-3. The anthraquinone derivative of Test Example 4-3 is a compound represented by the following formula (P4-3).

[0309] [Chemical formula]

[0310] (Test Example 4-4) The dyes of Test Examples 1-11 of the first embodiment were used as the anthraquinone derivatives of Test Example 4-4. The anthraquinone derivative of Test Example 4-4 is a compound represented by the following formula (P4-4).

[0311] [Chemical formula]

[0312] (Test Example 4-5) <Synthesis of the dye of Test Example 4-5> In the synthesis step of the dye of Test Example 1-1 of the first embodiment, 1.2 equivalents of 4-heptyloxyphenylboronic acid was added instead of 4-dimethylaminophenylboronic acid, and the reaction solution was stirred at 80 °C for 1 hour. Then, 1.2 equivalents of 4-pentyloxybiphenylboronic acid was added, and heating and stirring were performed at 80 °C for 2 hours or more. Thereafter, extraction and purification were performed in the same manner as in the synthesis step of the dye of Test Example 1-1 to obtain the anthraquinone derivative of Test Example 4-5. The anthraquinone derivative of Test Example 4-5 is a compound represented by the following formula (P4-5).

[0313] [Chemical formula]

[0314] (Test Example 4-6) The dyes of Test Example 3-6 of the third embodiment were used as the anthraquinone derivatives of Test Example 4-6. The anthraquinone derivative of Test Example 4-6 is a compound represented by the following formula (P4-6).

[0315] [Chemical formula]

[0316] (Test Example 4-7) The dye of Test Example 2-9 of the second embodiment was used as the anthraquinone derivative of Test Examples 4-7. The anthraquinone derivative of Test Examples 4-7 is a compound represented by the following formula (P4-7).

[0317] [Chemical formula]

[0318] (Test Example 4-8) The dye of Test Example 2-3 of the second embodiment was used as the anthraquinone derivative of Test Example 4-8. The anthraquinone derivative of Test Example 4-8 is a compound represented by the following formula (P4-8).

[0319] [Chemical formula]

[0320] (Test Example 4-9) The dye of Test Example 3-7 of the third embodiment was used as the anthraquinone derivative of Test Example 4-9. The anthraquinone derivative of Test Example 4-9 is a compound represented by the following formula (P4-9).

[0321] [Chemical formula]

[0322] (Test Examples 4-10 to 4-12) [Synthesis of Precursor D1] To a two-necked round-bottom flask, toluene (100 parts by weight), ethanol (20 parts by weight), water (10 parts by weight), precursor A1 (1 part by weight), 4-pentylcyclohexylphenylboronic acid (1.2 parts by weight), triethylamine (0.62 parts by weight), and tris(dibenzylideneacetone)dipalladium (0.2 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 reaction solution was returned to room temperature, then 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 solid was purified by column chromatography (developing solvent: hexane / dichloromethane = 1 / 1 to 2 / 3) to obtain precursor D1 as a dark red solid. Precursor D1 is a compound represented by the following formula (4-c).

[0323]

Chemical formula

[0324] <Synthesis of Precursor D2> In the synthesis step of the above precursor D1, synthesis was carried out in the same manner except that 4-pentylcyclohexylphenylboronic acid was changed to 4-heptyloxyphenylboronic acid to obtain precursor D2. Precursor D2 is a compound represented by the following formula (4-d).

[0325]

Chemical formula

[0326] <Synthesis of Precursor D3> In the synthesis step of the above precursor D1, synthesis was carried out in the same manner except that 4-pentylcyclohexylphenylboronic acid was changed to 4-monobutylaminophenylboronic acid to obtain precursor D3. Precursor D3 is a compound represented by the following formula (4-e).

[0327]

Chemical formula

[0328] <Synthesis of the Dye of Test Example 4-10> Into a two-necked eggplant flask, precursor D1 (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 prepared by mixing 4-methoxybenzenethiol (3.3 parts by weight) and pyridine (1.6 parts by weight) and stirring at room temperature for 30 minutes was prepared. This solution was added to the solution containing precursor D1 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 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 Test Example 4-10 as a dark blue solid. The anthraquinone derivative of Test Example 4-10 is a compound represented by the following formula (P4-10).

[0329]

Chemical formula

[0330] <Synthesis of the Dye of Test Example 4-11> In the synthesis step of the dye of Test Example 4-10 described above, synthesis was carried out in the same manner except that precursor D1 was changed to precursor D2 to obtain the anthraquinone derivative of Test Example 4-11. The anthraquinone derivative of Test Example 4-11 is a compound represented by the following formula (P4-11).

[0331]

Chemical formula

[0332] <Synthesis of the Dye of Test Example 4-12> In the synthesis process of the dye of Test Example 4-10, the synthesis was carried out in the same manner except that the precursor D1 was changed to the precursor D3, and the anthraquinone derivative of Test Example 4-12 was obtained. The anthraquinone derivative of Test Example 4-12 is a compound represented by the following formula (P4-12).

[0333]

Chemical formula

[0334] (Test Example 4-13) <Synthesis of the Dye of Test Example 4-13> Into a two-necked flask, 4-heptyloxyphenol (0.36 parts by weight) and potassium carbonate (0.24 parts by weight) were added, 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. Herein, the precursor A2 (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 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 was performed at 60 °C to obtain the anthraquinone derivative of Test Example 4-13 as a blue powder. The anthraquinone derivative of Test Example 4-13 is a compound represented by the following formula (P4-13).

[0335]

Chemical formula

[0336] (Test Example 4-14) <Synthesis of the Dye of Test Example 4-14> In the synthesis process of the dyes in Test Examples 4-13, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylphenol, and an anthraquinone derivative of Test Example 4-14 was obtained. The anthraquinone derivative of Test Example 4-14 is a compound represented by the following formula (P4-14).

[0337]

Chemical formula

[0338] (Test Example 4-15) <Synthesis of the Dye in Test Example 4-15> In the synthesis process of the dyes in Test Example 4-13, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylcyclohexylphenol, and an anthraquinone derivative of Test Example 4-15 was obtained. The anthraquinone derivative of Test Example 4-15 is a compound represented by the following formula (P4-15). Note that the anthraquinone derivative of Test Example 4-15 is the same compound as the anthraquinone derivative of Test Example 3-11.

[0339]

Chemical formula

[0340] (Evaluation Method) <Evaluation of Absorption Wavelength and Lightfastness> For the anthraquinone derivatives of Test Examples 4-1 to 4-15, test pieces for evaluation were prepared in the same manner as in the First Example, and the absorption wavelength and lightfastness were evaluated.

[0341] <Calculation of Total Energy Difference ΔE> For the anthraquinone derivatives of Test Examples 4-1 to 4-15, the total energy difference ΔE before and after the reaction shown by the above reaction formula (4-2) was calculated. The calculation of the total energy difference ΔE was carried out using the quantum chemistry calculation program GAMESS with the functional B3LYP and the basis function 6-31G(d) according to the following procedure.

[0342] (1) For the anthraquinone derivatives in each test example, 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.

[0343] 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 highly 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 by the formula ΔE = Ek - Ep.

[0344] (Evaluation Results) Table 4 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 Test Examples 4-1 to 4-15. The structures of the anthraquinone derivatives in each test example are represented by the following formula (II), and R, A, X, Y 1 , Y 2 , Z in Table 4 correspond to R, A, X, Y 1 , Y 2 , Z in the following formula (II).

[0345]

Chemical Formula

[0346]

Table 4

[0347] As shown in Table 4, since the anthraquinone derivatives of each test example have an absorption maximum wavelength in the wavelength range of 580 nm or more, they can be used as cyan dyes. And in Test Examples 4-1 to 4-12 where the total energy difference ΔE is -16 kcal / mol or more, high light resistance is obtained. On the other hand, in Test Examples 4-13 to 4-15 where the total energy difference ΔE is less than -16 kcal / mol, the light resistance is low. From the results in Table 4, it is suggested that when the structure does not have a hydroxyl group at the α-position or the substituent is directly bonded at the β-position, the total energy difference ΔE becomes large and high light resistance can be obtained.

[0348] 〔Fifth Embodiment: Test Examples Corresponding to the Fifth Embodiment〕 In the fifth embodiment, synthesis was carried out using the same precursors as in the first to fourth embodiments.

[0349] (Test Example 5-1) The dye of Test Example 1-10 of the first embodiment was used as the anthraquinone derivative of Test Example 5-1. The anthraquinone derivative of Test Example 5-1 is a compound represented by the following formula (P5-1).

[0350]

Chemical formula

[0351] (Test Example 5-2) The dye of Test Example 1-11 of the first embodiment was used as the anthraquinone derivative of Test Example 5-2. The anthraquinone derivative of Test Example 5-2 is a compound represented by the following formula (P5-2).

[0352]

Chemical formula

[0353] (Test Example 5-3) <Synthesis of the Dye of Test Example 5-3> In the synthesis process of the dye in Test Example 1-1 of the first embodiment, precursor A2 was changed to precursor A3, and instead of 4-dimethylaminophenylboronic acid, 1.2 equivalents of 4-heptyloxyphenylboronic acid were added, and the reaction solution was stirred at 80 °C for 1 hour. Then, 1.2 equivalents of 4-(trans-4-pentylcyclohexyl)phenylboronic acid were 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 process of the dye in Test Example 1-1 to obtain the anthraquinone derivative of Test Example 5-3. The anthraquinone derivative of Test Example 5-3 is a compound represented by the following formula (P5-3).

[0354] [Chemical formula]

[0355] (Test Example 5-4) The dye of Test Example 1-2 of the first embodiment was used as the anthraquinone derivative of Test Example 5-4. The anthraquinone derivative of Test Example 5-4 is a compound represented by the following formula (P5-4).

[0356] [Chemical formula]

[0357] (Test Example 5-5) ><Synthesis of the dye of Test Example 5-5> In the synthesis process of the dye in Test Example 4-10 of the fourth embodiment, the synthesis was carried out in the same manner except that precursor D1 was changed to precursor D2 and 4-methoxybenzenethiol was changed to 4-heptyloxybenzenethiol to obtain the anthraquinone derivative of Test Example 5-5. The anthraquinone derivative of Test Example 5-5 is a compound represented by the following formula (P5-5).

[0358] [Chemical formula]

[0359] (Test Example 5-6) The dye of Test Example 4-11 of the fourth embodiment was used as the anthraquinone derivative of Test Example 5-6. The anthraquinone derivative of Test Example 5-6 is a compound represented by the following formula (P5-6).

[0360]

Chemical formula

[0361] (Test Example 5-7) <Synthesis of the dye of Test Example 5-7> In the synthesis step of the dye of Test Example 4-10 of the fourth embodiment, the synthesis was carried out in the same manner except that 4-methoxybenzenethiol was changed to 4-heptyloxybenzenethiol to obtain the anthraquinone derivative of Test Example 5-7. The anthraquinone derivative of Test Example 5-7 is a compound represented by the following formula (P5-7).

[0362]

Chemical formula

[0363] (Test Example 5-8) <Synthesis of the dye of Test Example 5-8> In the synthesis step of the dye of Test Example 4-10 of the fourth embodiment, the synthesis was carried out in the same manner except that precursor D1 was changed to precursor D2 and 4-methoxybenzenethiol was changed to 4-cyanobenzenethiol to obtain the anthraquinone derivative of Test Example 5-8. The anthraquinone derivative of Test Example 5-8 is a compound represented by the following formula (P5-8).

[0364]

Chemical formula

[0365] (Test Example 5-9) <Synthesis of Precursor B13> In the synthesis step of precursor A2 of the first embodiment, synthesis was carried out in the same manner except that precursor A1 was changed to precursor B4 to obtain precursor B13. Precursor B13 is a compound represented by the following formula (5-a).

[0366]

Chemical formula

[0367] <Synthesis of the dye in Test Example 5-9> In the synthesis step of the dye in Test Example 1-1 of the first embodiment, synthesis was carried out in the same manner except that precursor A2 was changed to precursor B13 and 4-dimethylaminophenylboronic acid was changed to 4-heptyloxyphenylboronic acid to obtain the anthraquinone derivative in Test Example 5-9. The anthraquinone derivative in Test Example 5-9 is a compound represented by the following formula (P5-9). Note that the anthraquinone derivative in Test Example 5-9 is the same compound as the anthraquinone derivative in Test Example 1-15.

[0368]

Chemical formula

[0369] (Test Example 5-10) The dye in Test Example 4-1 of the fourth embodiment was used as the anthraquinone derivative in Test Example 5-10. The anthraquinone derivative in Test Example 5-10 is a compound represented by the following formula (P5-10).

[0370]

Chemical formula

[0371] (Test Example 5-11) The dye in Test Example 4-13 of the fourth embodiment was used as the anthraquinone derivative in Test Example 5-11. The anthraquinone derivative in Test Example 5-11 is a compound represented by the following formula (P5-11).

[0372]

Chemical formula

[0373] (Test Example 5-12) The dye of Test Example 4-14 of the fourth embodiment was used as the anthraquinone derivative of Test Example 5-12. The anthraquinone derivative of Test Example 5-12 is a compound represented by the following formula (P5-12).

[0374] [Chemical formula]

[0375] (Evaluation Method) (Evaluation of Absorption Wavelength and Light Resistance) For the anthraquinone derivatives of Test Examples 5-1 to 5-12, test specimens for evaluation were prepared in the same manner as in the first embodiment, and the absorption wavelength and light resistance were evaluated.

[0376] (Thermogravimetric Measurement) For the anthraquinone derivatives of Test Examples 5-1 to 5-12, using a differential thermal thermogravimetric simultaneous measurement device (STA7200RV, manufactured by Hitachi High-Tech Science), with 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.

[0377] (Evaluation Results) Table 5 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 Test Examples 5-1 to 5-12. The structure of the anthraquinone derivative of each test example is represented by the following formula (II), and R, A, X, Y 1 , Y 2 , Z in the following formula (II) are the R, A, X, Y 1 , Y 2 , Z corresponding to those in the following formula (II).

[0378] [Chemical formula]

[0379]

Table 5

[0380] As shown in Table 5, since the anthraquinone derivatives in each test example have an absorption maximum wavelength in the wavelength range of 580 nm or more, they can be used as cyan dyes. And in Test Examples 5-1 to 5-10 where the 10% weight loss temperature is 350 °C or higher, high light resistance is obtained. On the other hand, in Test Examples 5-111 and 5-12 where the 10% weight loss temperature is less than 350 °C, the light resistance is low.

[0381] From the results in Table 5, it is suggested that when the structure has no hydroxyl group at the α-position or the substituent is directly bonded at the β-position, the 10% weight loss temperature becomes high and high light resistance is obtained. Also, it was confirmed that the structure with -NH- has a higher tendency of 10% weight loss temperature and light resistance than the structure where X is a sulfur atom. Also, Y 1 , Y 2 When it is an electron-donating group such as an alkylamino group, it was confirmed that the 10% weight loss temperature and light resistance tend to decrease.

[0382] 〔Sixth Example: Test Examples Corresponding to the Sixth Embodiment〕 In the sixth example, synthesis was carried out using the same precursors as in the first to fifth examples.

[0383] (Test Example 6-1) The dye of Test Example 1-11 in the first example was used as the anthraquinone derivative of Test Example 6-1. The anthraquinone derivative of Test Example 6-1 is a compound represented by the following formula (P6-1).

[0384]

Chemical formula

[0385] (Test Example 6-2) The dye of Test Example 2-8 of the second embodiment was used as the anthraquinone derivative of Test Example 6-2. The anthraquinone derivative of Test Example 6-2 is a compound represented by the following formula (P6-2).

[0386] [Chemical formula]

[0387] (Test Example 6-3) The dye of Test Example 1-3 of the first embodiment was used as the anthraquinone derivative of Test Example 6-3. The anthraquinone derivative of Test Example 6-3 is a compound represented by the following formula (P6-3).

[0388] [Chemical formula]

[0389] (Test Example 6-4) The dye of Test Example 1-2 of the first embodiment was used as the anthraquinone derivative of Test Example 6-4. The anthraquinone derivative of Test Example 6-4 is a compound represented by the following formula (P6-4).

[0390] [Chemical formula]

[0391] (Test Example 6-5) (Synthesis of the dye of Test Example 6-5) In the synthesis step of the dye of Test Example 1-1 of the first embodiment, 1.2 equivalents of 4-(trans-4-pentylcyclohexyl)phenylboronic acid was added instead of 4-dimethylaminophenylboronic acid, and the reaction solution was stirred at 80 °C for 1 hour. Then, 1.2 equivalents of 4-pentyloxybiphenylboronic 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 dye of Test Example 1-1 above to obtain the anthraquinone derivative of Test Example 6-5. The anthraquinone derivative of Test Example 6-5 is a compound represented by the following formula (P6-5).

[0392] [Chemical formula]

[0393] (Test Example 6-6) <Synthesis of the Dye in Test Example 6-6> In the synthesis process of the dye in Test Example 1-1 of the first embodiment, instead of 4-dimethylaminophenylboronic acid, 1.2 equivalents of 4-(trans-4-pentylcyclohexyl)phenylboronic acid was added, and the reaction solution was stirred at 80 °C for 1 hour. Then, 1.2 equivalents of 4-monobutylaminophenylboronic acid was added, and heating and stirring were performed at 80 °C for 2 hours or more. Thereafter, extraction and purification were carried out in the same manner as in the synthesis process of the dye in Test Example 1-1 above to obtain the anthraquinone derivative of Test Example 6-6. The anthraquinone derivative of Test Example 6-6 is a compound represented by the following formula (P6-6).

[0394] [Chemical formula]

[0395] (Test Example 6-7) The dye in Test Example 5-5 of the fifth embodiment was used as the anthraquinone derivative of Test Example 6-7. The anthraquinone derivative of Test Example 6-7 is a compound represented by the following formula (P6-7).

[0396] [Chemical formula]

[0397] (Test Example 6-8) The dye in Test Example 4-12 of the fourth embodiment was used as the anthraquinone derivative of Test Example 6-8. The anthraquinone derivative of Test Example 6-8 is a compound represented by the following formula (P6-8).

[0398] [Chemical formula]

[0399] (Test Examples 6 - 9) The dyes of Test Examples 5 - 7 of the fifth embodiment were used as the anthraquinone derivatives of Test Examples 6 - 9. The anthraquinone derivatives of Test Examples 6 - 9 are compounds represented by the following formula (P6 - 9).

[0400]

Chemical formula

[0401] (Test Examples 6 - 10) (Synthesis of Precursor B14) In the synthesis process of Precursor A2 of the first embodiment, the synthesis was carried out in the same manner except that Precursor A1 was changed to Precursor B4 and 4 - heptylaniline was changed to 4 - heptyloxyaniline, to obtain Precursor B14. Precursor B14 is a compound represented by the following formula (6 - a).

[0402]

Chemical formula

[0403] (Synthesis of the Dye of Test Example 6 - 10) In the synthesis process of the dye of Test Example 1 - 1 of the first embodiment, the synthesis was carried out in the same manner except that Precursor A2 was changed to Precursor B14 and 4 - dimethylaminophenylboronic acid was changed to 4 - heptyloxyphenylboronic acid, to obtain the anthraquinone derivative of Test Example 6 - 10. The anthraquinone derivative of Test Example 6 - 10 is a compound represented by the following formula (P6 - 10).

[0404]

Chemical formula

[0405] (Test Examples 6 - 11) (Synthesis of the Dye of Test Example 6 - 11) In the synthesis process of the dye in Test Example 4-13 of the fourth embodiment, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-(trans-4-pentylcyclohexyl)phenol, and the anthraquinone derivative of Test Example 6-11 was obtained. The anthraquinone derivative of Test Example 6-11 is a compound represented by the following formula (P6-11).

[0406]

Chemical formula

[0407] (Test Example 6-12) <Synthesis of Precursor D4> In the synthesis process of Precursor B11 of the fourth embodiment, the synthesis was carried out in the same manner except that Precursor B4 was changed to Precursor A1, and Precursor D4 was obtained. Precursor D4 is a compound represented by the following formula (6-b).

[0408]

Chemical formula

[0409] <Synthesis of the Dye in Test Example 6-12> In the synthesis process of the dye in Test Example 4-10 of the fourth embodiment, the synthesis was carried out in the same manner except that Precursor D1 was changed to Precursor D4 and 4-methoxybenzenethiol was changed to 4-heptyloxybenzenethiol, and the anthraquinone derivative of Test Example 6-12 was obtained. The anthraquinone derivative of Test Example 6-12 is a compound represented by the following formula (P6-12).

[0410]

Chemical formula

[0411] (Test Example 6-13) <Synthesis of the Dye in Test Example 6-13> In the synthesis process of the dye in Test Example 4-13 of the fourth embodiment, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-monobutylaminophenol, and the anthraquinone derivative of Test Example 6-13 was obtained. The anthraquinone derivative of Test Example 6-13 is a compound represented by the following formula (P6-13). The anthraquinone derivative of Test Example 6-13 is the same compound as the anthraquinone derivative of Test Example 1-13.

[0412] [Chemical formula]

[0413] (Evaluation method) <Evaluation of absorption wavelength and coloring power> For the anthraquinone derivatives of Test Examples 6-1 to 6-13, test pieces for evaluation were prepared in the same manner as in the first embodiment.

[0414] For the test pieces for evaluation of each test example, an ultraviolet-visible absorption spectrum was measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.). Then, for the 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 "×".

[0415] <Calculation of transition dipole moment> For the anthraquinone derivatives of Test Examples 6-1 to 6-13, 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 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 )

[0416] (Evaluation result) Table 6 shows the evaluation results of 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 coloring power for Test Examples 6-1 to 6-13. The structure of the anthraquinone derivative in each test example is 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 corresponding to

[0417]

Chemical formula

[0418]

Table 6

[0419] As shown in Table 6, in Test Examples 6-1 to 6-10 where the magnitude μ of the transition dipole moment is 3.30 D or more, higher absorbance is obtained and the coloring power is good compared to Test Examples 6-11 to 6-13 where the magnitude μ of the transition dipole moment is less than 3.30 D. Further, the anthraquinone derivatives of Test Examples 6-1 to 6-10 tend to have a high absorption maximum wavelength and have an absorption maximum wavelength in the wavelength range of 580 nm or more, and thus can be used as cyan dyes.

[0420] 1 , Y 2 When, Y

[0421] [Example 7: Test Example Corresponding to the Seventh Embodiment] In the seventh embodiment, synthesis was carried out using the same precursors as in the first to sixth embodiments.

[0422] (Test Example 7-1) The dyes of Test Examples 1-11 of the first embodiment were used as the anthraquinone derivatives of Test Example 7-1. The anthraquinone derivative of Test Example 7-1 is a compound represented by the following formula (P7-1).

[0423] [Chemical formula]

[0424] (Test Example 7-2) The dyes of Test Examples 2-8 of the second embodiment were used as the anthraquinone derivatives of Test Example 7-2. The anthraquinone derivative of Test Example 7-2 is a compound represented by the following formula (P7-2).

[0425] [Chemical formula]

[0426] (Test Example 7-3) The dyes of Test Examples 1-3 of the first embodiment were used as the anthraquinone derivatives of Test Example 7-3. The anthraquinone derivative of Test Example 7-3 is a compound represented by the following formula (P7-3).

[0427] [Chemical formula]

[0428] (Test Example 7-4) The dyes of Test Examples 1-2 of the first embodiment were used as the anthraquinone derivatives of Test Example 7-4. The anthraquinone derivative of Test Example 7-4 is a compound represented by the following formula (P7-4).

[0429] [Chemical formula]

[0430] (Test Example 7-5) <Synthesis of Precursor A4> In the synthesis process of precursor A2 in the first embodiment, synthesis was carried out in the same manner except that 4-heptylaniline was changed to 4-cyanoaniline to obtain precursor A4. Precursor A4 is a compound represented by the following formula (7-a).

[0431]

Chemical formula

[0432] <Synthesis of the Dye in Test Example 7-5> In the synthesis process of the dye in Test Example 1-1 of the first embodiment, synthesis was carried out in the same manner except that precursor A2 was changed to precursor A4 and 4-dimethylaminophenylboronic acid was changed to 4-heptyloxyphenylboronic acid to obtain the anthraquinone derivative of Test Example 7-5. The anthraquinone derivative of Test Example 7-5 is a compound represented by the following formula (P7-5).

[0433]

Chemical formula

[0434] (Test Example 7-6) <Synthesis of the Dye in Test Example 7-6> In the synthesis process of the dye in Test Example 1-1 of the first embodiment, synthesis was carried out in the same manner except that precursor A2 was changed to precursor A4 and 4-dimethylaminophenylboronic acid was changed to 4-pentylcyclohexylphenylboronic acid to obtain the anthraquinone derivative of Test Example 7-6. The anthraquinone derivative of Test Example 7-6 is a compound represented by the following formula (P7-6). Note that the anthraquinone derivative of Test Example 7-6 is the same compound as the anthraquinone derivative of Test Example 2-3.

[0435]

Chemical formula

[0436] (Test Example 7-7) The dye of Test Example 5-5 of the fifth embodiment was used as the anthraquinone derivative of Test Example 7-7. The anthraquinone derivative of Test Example 7-7 is a compound represented by the following formula (P7-7).

[0437]

Chemical formula

[0438] (Test Example 7-8) The dye of Test Example 5-7 of the fifth embodiment was used as the anthraquinone derivative of Test Example 7-8. The anthraquinone derivative of Test Example 7-8 is a compound represented by the following formula (P7-8).

[0439]

Chemical formula

[0440] (Test Example 7-9) (Synthesis of the dye of Test Example 7-9) In the synthesis process of the dye of Test Example 4-10 of the fourth embodiment, the precursor D1 was changed to the precursor D3, and 4-methoxybenzenethiol was changed to 4-heptyloxybenzenethiol, and the synthesis was carried out in the same manner to obtain the anthraquinone derivative of Test Example 7-9. The anthraquinone derivative of Test Example 7-9 is a compound represented by the following formula (P7-9).

[0441]

Chemical formula

[0442] (Test Example 7-10) (Synthesis of the dye of Test Example 7-10) In the synthesis process of the dye of Test Example 4-13 of the fourth embodiment, the synthesis was carried out in the same manner except that the precursor A2 was changed to the precursor A3, and the anthraquinone derivative of Test Example 7-10 was obtained. The anthraquinone derivative of Test Example 7-10 is a compound represented by the following formula (P7-10). The anthraquinone derivative of Test Example 7-10 is the same compound as the anthraquinone derivative of Test Example 1-12.

[0443]

Chemical formula

[0444] (Test Example 7-11) The dye of Test Example 6-11 of the sixth embodiment was used as the anthraquinone derivative of Test Example 7-11. The anthraquinone derivative of Test Example 7-11 is a compound represented by the following formula (P7-11).

[0445]

Chemical formula

[0446] (Test Example 7-12) The dye of Test Example 6-12 of the sixth embodiment was used as the anthraquinone derivative of Test Example 7-12. The anthraquinone derivative of Test Example 7-12 is a compound represented by the following formula (P7-12).

[0447]

Chemical formula

[0448] (Test Example 7-13) <Synthesis of Precursor D5> In the synthesis process of the precursor B11 of the fourth embodiment, the synthesis was carried out in the same manner except that the precursor B4 was changed to the precursor A1 and 4-heptyloxyphenol was changed to 4-pentylcyclohexylphenol, and the precursor D5 was obtained. The precursor D5 is a compound represented by the following formula (7-b).

[0449] [Chemical formula]

[0450] <Synthesis of the Dye of Test Example 7-13> In the synthesis process of the dye of Test Example 4-10 of the fourth embodiment, the precursor D1 was changed to the precursor D5, and 4-methoxybenzenethiol was changed to 4-heptyloxybenzenethiol, and the synthesis was carried out in the same manner to obtain the anthraquinone derivative of Test Example 7-13. The anthraquinone derivative of Test Example 7-13 is a compound represented by the following formula (P7-13).

[0451] [Chemical formula]

[0452] (Evaluation Method) (Evaluation of Absorption Wavelength and Color Strength) For the anthraquinone derivatives of Test Examples 7-1 to 7-13, 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 sixth embodiment, and the color strength was evaluated.

[0453] (Calculation of Molecular Orbital Coefficient) For the anthraquinone derivatives of Test Examples 7-1 to 7-13, 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 to obtain the molecular orbital coefficients at the optimized structure. For each carbon atom 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 the carbon atom M 11 , M 12 , M 21 , M 22 was calculated 、 M 11 , M 12 , M 21 , M22 The average Mv was determined. Under these calculation conditions, 15 orbits are assigned to carbon atoms, and the molecular orbital coefficients are calculated for each orbit.

[0454] (Evaluation results) Table 7 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 Test Examples 7-1 to 7-13. The structure of the anthraquinone derivative of each test example is represented by the following formula (II), and R, A, X, Y 1 , Y 2 , Z in Table 7 are R, A, X, Y in the following formula (II) 1 , Y 2 , Z in the following formula (II).

[0455]

Chemical formula

[0456]

Table 7

[0457] As shown in Table 7, in Test Examples 7-1 to 7-9 where the average Mv is 0.03 or more, higher absorbance is obtained compared to Test Examples 7-10 to 7-13 where the average Mv is less than 0.03, and the coloring power is good. In addition, since the anthraquinone derivatives of Test Examples 7-1 to 7-9 have an absorption maximum wavelength in the wavelength range of 580 nm or more, they can be used as cyan dyes.

[0458] From the results of Table 7, it is suggested that the direct bonding of a substituent at the β-position increases the average Mv. Also, from the comparison between Test Example 7-1 and Test Example 7-5, and the comparison between Test Example 7-2 and Test Example 7-6, it was confirmed that when Z is an electron-withdrawing group such as a cyano group, the average Mv increases and a tendency to obtain high absorbance is observed. Also, from Test Examples 7-3, 7-4, 7-9, Y 1 , Y 2When it is an electron-donating group such as an alkylamino group, it was confirmed that the average Mv increases and a high absorbance tends to be obtained.

Claims

1. An anthraquinone derivative represented by the following formula (1-1). 【Chemical 1】 In formula (1-1), R １ , R ２ , and R ３ are each independently an amino group or a hydroxyl group. At least one of Y １ and Y ２ is an electron-donating group. When only one of Y １ and Y ２ is an electron-donating group, the other of Y １ and Y ２ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents. Z is 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, an amino group, or an alkylamino group.

2. The anthraquinone derivative according to Claim 1, represented by the following formula (1-2). 【Chemical Formula 2】 In formula (1-2), Y １ and Y ２ at least one of which is an electron-donating group. When only one of Y １ and Y ２ is an electron-donating group, the other of Y １ and Y ２ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents. Z is 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, an amino group, or an alkylamino group.

3. The electron-donating group is an alkylamino group, an amino group, a piperidyl group, an acetamide group, or a hydroxyl group The anthraquinone derivative according to Claim 1 or 2.

4. In the formula (1-2), Y １ and Y ２ are each independently an alkylamino group, an amino group, or a piperidyl group The anthraquinone derivative according to Claim 2.

5. An anthraquinone derivative represented by the following formula (2-1). [Chemical Formula 3] In formula (2-1), R １ , R ２ , and R ３ are each independently an amino group or a hydroxyl group. Y １ and Y ２ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, a cyano group, a nitro group, a halogen atom, an amino group, an alkylamino group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have a substituent. Z is an electron-withdrawing group.

6. The anthraquinone derivative according to Claim 5, represented by the following formula (2-2). 【Chemical Formula 4】 In formula (2-2), Y １ and Y ２ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, a cyano group, a nitro group, a halogen atom, an amino group, an alkylamino group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have a substituent. Z is an electron-withdrawing group.

7. The anthraquinone derivative according to Claim 6, represented by the following formula (2-3). [Chemical Formula 5] In formula (2-3), R ４ and R ５ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cyclic hydrocarbon group, and Z is an electron-withdrawing group.

8. The electron-withdrawing group is a cyano group, an aldehyde group, an ester group, an acetyl group, a sulfo group, a nitro group, or a halogenated alkyl group The anthraquinone derivative according to any one of Claims 5 to 7.

9. An anthraquinone derivative represented by the following formula (3-1). 【Chemical Formula 6】 In formula (3-1), R １ , R ２ , and R ３ are each independently an amino group or a hydroxyl group. At least one of Y １ and Y ２ is a cyclohexyl group, and the cyclohexyl group may have a substituent. When only one of Y １ and Y ２ is a cyclohexyl group, the other of Y １ and Y ２ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, a cyano group, a nitro group, a halogen atom, an amino group, or an alkylamino group, and the aryl group may have a substituent. Z is 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, an amino group, or an alkylamino group.

10. The anthraquinone derivative according to Claim 9, represented by the following formula (3-2). 【Chemical Formula 7】 In formula (3-2), Y １ and Y ２ at least one of which is a cyclohexyl group, and the cyclohexyl group may have a substituent. When only one of Y １ and Y ２ is a cyclohexyl group, the other of Y １ and Y ２ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, a cyano group, a nitro group, a halogen atom, an amino group, or an alkylamino group, and the aryl group may have a substituent. Z is 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, an amino group, or an alkylamino group.

11. The anthraquinone derivative according to Claim 10, represented by the following formula (3-3). 【Chemical 8】 In formula (3-3), R ４ and R ５ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cyclic hydrocarbon group, and Z is 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, an amino group, or an alkylamino group.

12. The anthraquinone derivative according to any one of Claims 1, 5, and 9, wherein the compound on the left side in the following reaction formula (4-2) 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 (4-2), determined by the density functional method, is -16 kcal / mol or more. 【Chemical Formula 9】

13. The anthraquinone derivative according to any one of Claims 1, 5, and 9, wherein the 10% weight loss temperature is 350°C or higher.

14. The anthraquinone derivative according to any one of Claims 1, 5, and 9, 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.

15. The anthraquinone derivative according to any one of Claims 1, 5, and 9, The following formula (7-1) represents the anthraquinone derivative. Regarding the molecular orbital coefficients of the highest occupied molecular orbital of the anthraquinone derivative obtained by the density functional method, for 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 carbon atom is determined 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 10】

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