Anthraquinone derivatives

Abstract

Anthraquinone derivative represented by the following formula (9-1). In formula (9-1), R1 and R2 are each independently an amino group or a hydroxyl group, and Y1, Y2 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, an alkyl halide 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.

Description

Technology Field

[0001] The present disclosure relates to anthraquinone derivatives. Background Technology

[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 dichromatic dyes for liquid crystal devices and polarizing films is also underway.

[0003] Among organic pigments, there are many anthraquinone derivatives that have an anthraquinone backbone, which have high stability against light, heat, temperature, etc., and excellent fastness. For this reason, among anthraquinone derivatives, many studies are being conducted on compounds that can be used as pigments corresponding to the three primary colors, from the perspective of controlling absorption wavelengths or coloring power, solubility in solvents or resins, and improving dichromaticity. For example, Patent Documents 1 and 2 describe anthraquinone derivatives that can be used as cyanide pigments and have a wavelength of maximum absorption in the wavelength range of 580 nm or more. Prior art literature

[0004] Japanese Patent Publication No. Sho 63-90568 Japanese Patent Publication No. Sho 63-278994 The problem to be solved

[0005] For pigments, good lightfastness is desired, that is, minimal fading due to light. As mentioned above, although there are many compounds among anthraquinone derivatives that possess high fastness, it tends to be difficult to obtain lightfastness in anthraquinone derivatives used as cyanide pigments. Therefore, anthraquinone derivatives that have a wavelength of maximum absorption in the wavelength range of 580 nm or higher and also possess good lightfastness are required. means of solving the problem

[0006] One embodiment of an anthraquinone derivative is represented by the following formula (9-1). In formula (9-1), R 1 and R 2is, each independently, an amino group or a hydroxyl group, and Y 1 , Y 2 and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, an alkyl halide 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.

[0007]

[0008] Another embodiment of the anthraquinone derivative is represented by the following formula (1-1). In formula (1-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group, and also R 1 , R 2 and R 3 At least one of is a hydroxyl group. Y 1 and Y 2 At least one of is an electron-donating group, said electron-donating group is an alkylamino group, an amino group, or a piperidyl group, and Y 1 and Y 2 In the case where only one side is an electron donor, Y 1 and Y 2 The other side 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.

[0009]

[0010] Another embodiment of the anthraquinone derivative is represented by the following formula (1-1). In formula (1-1), R 1 , R 2 and R 3Each is independently an amino group or a hydroxyl group. Y 1 and Y 2 At least one side of is an electron-donating group, said electron-donating group is an acetamide group or a hydroxyl group, and Y 1 and Y 2 In the case where only one side is an electron donor, Y 1 and Y 2 The other side 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.

[0011]

[0012] Another embodiment of the anthraquinone derivative is represented by the following formula (2-1). In formula (2-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group, and also R 1 , R 2 and R 3 At least one of is a hydroxyl group. Y 1 and Y 2 Each is 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, and the electron-withdrawing group is a cyano group or an alkyl halide group.

[0013]

[0014] Another embodiment of the anthraquinone derivative is represented by the following formula (2-1). In formula (2-1), R 1 , R 2 and R3 Each is independently an amino group or a hydroxyl group. Y 1 and Y 2 Each is 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, and said electron-withdrawing group is an aldehyde group, an acetyl group, or a sulfonate group.

[0015]

[0016] Another embodiment of the anthraquinone derivative is represented by the following formula (3-1). In formula (3-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group, and also R 1 , R 2 and R 3 At least one of is a hydroxyl group. Y 1 and Y 2 At least one side of is a cyclohexyl group, and the cyclohexyl group may have a substituent, and Y 1 and Y 2 In the case where only one side is a cyclohexyl group, Y 1 and Y 2 The other side 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.

[0017]

[0018] Another embodiment of an anthraquinone derivative is represented by the following formula (8-1). In formula (8-1), A is a direct bond, oxygen atom, or -NH-, and Y 1 , Y 2 and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, an alkyl halide group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents.

[0019] Specific details for implementing the invention

[0020] Hereinafter, anthraquinone derivatives of the first to ninth embodiments are described. In addition, in each embodiment, an anthraquinone derivative is a compound having a skeleton of 9,10-anthraquinone. In addition, regarding the substitution positions of the anthraquinone skeleton, the 1st, 4th, 5th, and 8th positions are α positions, and the 2nd, 3rd, 6th, and 7th positions are β positions.

[0021] The anthraquinone derivatives of each embodiment are used as pigments. Their use as pigments is not particularly limited. For example, anthraquinone derivatives can be used as pigments for inks for sublimation transfer printing or inkjet printing, toners for laser printers or photocopiers, optical filters such as color filters for liquid crystal displays or color separation filters used in image tubes, and inks for anti-tampering and anti-counterfeiting printing. In addition, anthraquinone derivatives can also be used as dichromatic pigments for guest-host type liquid crystal elements or polarizing films.

[0022] Additionally, the notation "at least one" used in this specification means "one or more" of the desired options. For example, the notation "at least one" used in this specification means "only one option" or "both of the two options" if the number of options is two. For another example, the notation "at least one" used in this specification means "only one option" or "a combination of two or more arbitrary options" if the number of options is three or more.

[0023] (First embodiment)

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

[0025]

[0026] In Equation (1-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group. In formula (1-1), Y 1 and Y 2 At least one side of is an electron donor, and Y 1 and Y 2 In the case where only one side is an electron donor, Y 1 and Y 2 The other side 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. Preferably, the substituent is an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group. Preferably, the cyclic hydrocarbon group is a cyclohexyl group or a phenyl group.

[0027] The electron-donating group is preferably an alkylamino group, an amino group, a piperidyl group, an acetamide group, or a hydroxyl group. The alkyl group of the alkylamino group may have one or two alkyl groups. The number of carbon atoms in the alkyl group of the alkylamino group is preferably 1 to 10. Y 1 and Y 2 In the case where both sides are electron-donating organs, Y 1 and Y 2 They may be the same or different.

[0028] 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 having the alkylamino group may have one or two alkyl groups. The number of carbon atoms in the alkyl group having the alkylamino group is preferably 1 to 10.

[0029] The action of the anthraquinone derivative of the present embodiment is explained. The type of substituent in the anthraquinone backbone affects the absorption wavelength of the anthraquinone derivative. The anthraquinone derivative of the first embodiment has, for four α positions, a substituted or unsubstituted anilino group at the 1st position and an amino group or a hydroxyl group at the 4th, 5th, and 8th positions. Additionally, the anthraquinone derivative has substituents at only two of the four β positions, specifically at the 3rd and 7th positions, and said substituents are substituted or unsubstituted phenyl groups. Anthraquinone derivative having such a structure can be used as a cyanide dye because it has a maximum absorption wavelength in the wavelength range of 600 nm or more.

[0030] In addition, it is believed that one factor in photodegradation of anthraquinone derivatives is that photoreduction occurs in the anthraquinone backbone using resins or the like surrounding the anthraquinone derivative as a hydrogen source. Furthermore, conventional anthraquinone derivatives are known to have a structure in which a functional group, such as a phenyl group, is attached to the β-site via an ether bond. In contrast, in the anthraquinone derivative of the present embodiment, a phenyl group is directly bonded to a carbon of the anthraquinone backbone at the β-site. Due to this structure, the progress of the photoreduction reaction is suppressed, and thus high light resistance is obtained.

[0031] More specifically, it is thought that when a phenyl group is directly bonded to the β-position, compared to when an ether bond exists on the β-position, the molecular structure at the bonding portion on the β-position is difficult to rotate, making it difficult for the structure of the anthraquinone backbone after photoreduction to become a stable structure, and therefore, the progress of the photoreduction reaction is inhibited.

[0032] In addition, regarding the pigment, high coloring power, that is, high absorbance, is desired. Since a higher coloring power allows for a reduction in the amount of pigment incorporated, it is also beneficial from a cost perspective. Regarding the absorbance of anthraquinone derivatives, it has been suggested that absorbance increases as the overlap between the distribution of molecular orbitals in the ground state and the excited state increases. Furthermore, molecular orbitals in the ground state are easily variable by molecular structures such as substituents and tend to be more spread out than those in the excited state. In contrast, the anthraquinone derivative of the first embodiment has a para-substituted phenyl group containing an electron-donating group at least one β-position. Since the substituent on the para position of the phenyl group is an electron-donating group, the spread of the molecular orbitals in the ground state is suppressed, thereby increasing the absorption coefficient, and as a result, the coloring power of the anthraquinone derivative is increased.

[0033] In the anthraquinone derivative of the first embodiment, the R 1 and R 3is a hydroxyl group, and R 2 It is preferable that the group be an amino group. Such a compound is represented by the following formula (1-2).

[0034]

[0035] In Equation (1-2), Y 1 , Y 2 Z and are defined in the same way as in Formula (1-1). Synthesis is easy if it is an anthraquinone derivative represented by Formula (1-2). In addition, if a hydroxyl group is present on the α-position, the photoreduction described above is likely to occur, but according to the anthraquinone derivative of the present embodiment, the photoreduction reaction is suppressed due to the structure in which a phenyl group is directly bonded to the β-position as described above. Therefore, the disadvantages of a structure having a hydroxyl group on the α-position can be overcome, while the advantages of said structure can be enjoyed.

[0036] Additionally, in the anthraquinone derivative of the first embodiment, Y 1 and Y 2 It is preferable that both sides of are electron-donating sites. As a result, since the control power in the direction of increasing the absorption coefficient is enhanced for the molecular orbitals related to the aforementioned photoexcitation, a higher coloring power is obtained. In particular, Y 1 and Y 2 It is preferable that each of the above be an alkylamino group, an amino group, or a piperidyl group. Since these functional groups have high electron-donating properties, high control power is obtained for the molecular orbitals related to the aforementioned photoexcitation. Therefore, higher coloring power is obtained.

[0037] Y 1 and Y 2 Compounds in which each of is an alkylamino group or an amino group are represented by the following formula (1-3). Y 1 and Y 2 Each of the compounds in which the piperidyl group is a piperidyl group is represented by the following formula (1-4).

[0038]

[0039] In Equation (1-3), Z is defined as in Equation (1-1). R 4 and R 5 Each is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0040]

[0041] In Equation (1-4), Z is defined as in Equation (1-1).

[0042] The anthraquinone derivative of the first embodiment can be prepared by introducing each substituent into the anthraquinone backbone, for example, using 1,5-dihydroxy-4,8-dinitroanthraquinone or 1,5-diamino-4,8-dinitroanthraquinone as a starting material. Known methods may be used for introducing the substituents. For example, the desired substituent is introduced by using the reduction of the nitro group, substituent conversion, bromolation of the β-site, and conversion of the bromo group.

[0043] (Second embodiment)

[0044] An anthraquinone derivative of the second embodiment is described. The anthraquinone derivative of the second embodiment is a compound represented by the following formula (2-1).

[0045]

[0046] In Equation (2-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group. Y 1 and Y 2 Each is 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.

[0047] Preferably, the halogen atom is F, Cl, or Br. The alkyl group of the alkylamino group may have one or two alkyl groups. Preferably, the number of carbon atoms in the alkyl group of the alkylamino group is 1 to 10. Preferably, the substituent of the aryl group or cyclohexyl group is an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group. Preferably, the cyclic hydrocarbon group is a cyclohexyl group or a phenyl group.

[0048] 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 derived from a carboxylic acid, an acetyl group, a sulfo group, a nitro group, or an alkyl halide group. The halogen included in the alkyl halide group is preferably F, Cl, or Br. The number of carbon atoms in the alkyl halide group is preferably 1 to 10.

[0049] The anthraquinone derivative of the second embodiment has, for four α positions, a substituted anilino group at the 1st position and an amino or hydroxyl group at the 4th, 5th, and 8th positions. Additionally, the anthraquinone derivative of the second embodiment has two substituted or unsubstituted phenyl groups at the β position. Therefore, the anthraquinone derivative of the second embodiment, like the first embodiment, can be used as a cyanide dye in that it has a wavelength of maximum absorption in the wavelength range of 600 nm or more.

[0050] In addition, in the anthraquinone derivative of the second embodiment, a phenyl group at the β position is directly bonded to a carbon atom constituting the anthraquinone backbone. Due to this structure, as in the first embodiment, the progress of the photoreduction reaction is suppressed, so high light resistance is obtained.

[0051] Additionally, the anthraquinone derivative of the second embodiment has a para-substituted anilino group containing an electron-withdrawing group on the α-position. Because the substituent on the para-position of the anilino group is an electron-withdrawing group, the electron density of the aromatic ring of the anilino group is reduced, and the spreading of molecular orbitals toward the anilino group is suppressed. By this, molecular orbitals related to photoexcitation are controlled to increase the absorption coefficient, and as a result, the coloring power of the anthraquinone derivative is increased.

[0052] In addition, if the anthraquinone derivative has a phenyl group having an electron-donating group as a substituent of the para group on the β-position, as in the first embodiment, the effect of improving coloring power is further enhanced.

[0053] In the anthraquinone derivative of the second embodiment, the R 1 and R 3 is a hydroxyl group, and R 2 It is preferable that the group be an amino group. Such a compound is represented by the following formula (2-2).

[0054]

[0055] In Equation (2-2), Y 1 , Y 2 Z is defined as in Formula (2-1). Synthesis is easy if it is an anthraquinone derivative represented by Formula (2-2). In addition, if a hydroxyl group is present on the α-position, the photoreduction described above is likely to occur, but according to the anthraquinone derivative of the present embodiment, the photoreduction reaction is suppressed due to the structure in which a phenyl group is directly bonded to the β-position as described above. Therefore, the disadvantages of a structure having a hydroxyl group on the α-position can be overcome, while the advantages of said structure can be enjoyed.

[0056] Additionally, the anthraquinone derivative of the second embodiment is preferably a compound represented by the following formula (2-3).

[0057]

[0058] In Equation (2-3), Z is defined as in Equation (2-1). R 4 and R 5 Each is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cyclic hydrocarbon group. Among liquid crystal compounds, there are many compounds having a cyclohexane ring, and phenylcyclohexane-based liquids are also suitably used. If it is an anthraquinone derivative represented by formula (2-3), it can be suitably used as a dichromatic pigment together with the liquid crystal material because it is easy to mix with such liquid crystal materials.

[0059] The anthraquinone derivative of the second embodiment can be prepared by introducing each substituent into the anthraquinone backbone, for example, using 1,5-dihydroxy-4,8-dinitroanthraquinone or 1,5-diamino-4,8-dinitroanthraquinone as a starting material. Known methods may be used for introducing the substituents. For example, the desired substituent is introduced by using the reduction of the nitro group, substituent conversion, bromolation of the β-site, and conversion of the bromo group.

[0060] (Third embodiment)

[0061] An anthraquinone derivative of the third embodiment is described. The anthraquinone derivative of the third embodiment is a compound represented by the following formula (3-1).

[0062]

[0063] In Equation (3-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group. In formula (3-1), Y 1 and Y 2 At least one of the groups is a cyclohexyl group, and the cyclohexyl group may have a substituent. The substituent of the 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.

[0064] Y 1 and Y 2 In the case where only one side is a cyclohexyl group, Y 1 and Y 2 The other side 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 having the alkylamino group may be one or two. The number of carbon atoms in the alkyl group having the alkylamino group is preferably 1 to 10. The substituent having the aryl group is preferably an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group.

[0065] 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 having the alkylamino group may have one or two alkyl groups. The number of carbon atoms in the alkyl group having the alkylamino group is preferably 1 to 10.

[0066] In the anthraquinone derivative of the third embodiment, the substituent at the α-position is the same as in the first embodiment. In addition, the anthraquinone derivative of the third embodiment has two substituted or unsubstituted phenyl groups at the β-position, just as in the first embodiment. Therefore, the anthraquinone derivative of the third embodiment can also be used as a cyanide dye in that it has a wavelength of maximum absorption in the wavelength range of 600 nm or more.

[0067] In addition, in the anthraquinone derivative of the third embodiment, a phenyl group at the β position is directly bonded to a carbon atom constituting the anthraquinone backbone. Due to this structure, as with the first and second embodiments, the progress of the photoreduction reaction is suppressed, so high light resistance is obtained.

[0068] Additionally, the anthraquinone derivative of the third embodiment has at least one para-substituted phenyl group on the β-site, and the substituent on the para-site of the phenyl group is a substituted or unsubstituted cyclohexyl group. The substituent on the para-site on the β-site allows for control of molecular orbitals related to photoexcitation, and if the substituent is a cyclohexyl group, absorption in the short-wavelength region shifts to the ultraviolet region. As a result, the blue component in the reflected light increases, so the blue light as a pigment becomes stronger. Having a strong blue light is advantageous for cyanide pigments used in correspondence with the three primary colors. Therefore, the anthraquinone derivative of the third embodiment can be suitably used as a cyanide pigment.

[0069] In the anthraquinone derivative of the third embodiment, the R 1 and R 3 is a hydroxyl group, and R 2 It is preferable that the group be an amino group. Such a compound is represented by the following formula (3-2).

[0070]

[0071] In Equation (3-2), Y 1 , Y 2Z and are defined as in Formula (3-1). Synthesis is easy if it is an anthraquinone derivative represented by Formula (3-2). In addition, if a hydroxyl group is present on the α-position, the photoreduction described above is likely to occur, but according to the anthraquinone derivative of the present embodiment, the photoreduction reaction is suppressed due to the structure in which a phenyl group is directly bonded to the β-position as described above. Therefore, the disadvantages of a structure having a hydroxyl group on the α-position can be overcome, while the advantages of said structure can be enjoyed.

[0072] Additionally, the anthraquinone derivative of the third embodiment is preferably a compound represented by the following formula (3-3).

[0073]

[0074] In Equation (3-3), Z is defined as in Equation (3-1). R 4 and R 5 Each is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cyclic hydrocarbon group. The anthraquinone derivative represented by formula (3-3) has a cyclohexyl group in which the para group substituents on the phenyl groups located on the two β-positions are both substituted or unsubstituted. As a result, a stronger blue light is obtained because a higher effect of suppressing absorption in the short wavelength region is obtained.

[0075] In addition, if the anthraquinone derivative has an anilino group having an electron-withdrawing group as a substituent of the para group on the α-position, as in the second embodiment, the effect of improving coloring power is obtained.

[0076] The anthraquinone derivative of the third embodiment can be prepared by introducing each substituent into the anthraquinone backbone, for example, using 1,5-dihydroxy-4,8-dinitroanthraquinone or 1,5-diamino-4,8-dinitroanthraquinone as a starting material. Known methods may be used for introducing the substituents. For example, the desired substituent is introduced by using the reduction of the nitro group, substituent conversion, bromolation of the β-site, and conversion of the bromo group.

[0077] (Fourth embodiment)

[0078] An anthraquinone derivative of the fourth embodiment is described. The anthraquinone derivative of the fourth embodiment is a compound represented by the following formula (4-1), and is a compound having a total energy difference ΔE before and after the reaction represented by the following reaction formula (4-2) of -16 kcal / mol or more.

[0079]

[0080]

[0081] In Equation (4-1), X is -NH- or a sulfur atom. In Equation (4-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group. In Formula (4-1), A 1 and A 2 Each of these is, independently, directly bonded to an oxygen atom, a sulfur atom, or -NH-. Also, A 1 , A 2 Direct bonding means that at the β-position of an anthraquinone derivative, a substituted or unsubstituted phenyl group is directly bonded to a carbon atom constituting the anthraquinone backbone.

[0082] In Equation (4-1), Y 1 , Y 2Z 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, an alkyl halide 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. Preferably, the substituent is an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group. Preferably, the cyclic hydrocarbon group is a cyclohexyl group or a phenyl group. Preferably, the halogen atom and the halogen atom included in the alkyl halide group are F, Cl, or Br. The alkyl group having the alkylamino group may be one or two. Preferably, the number of carbon atoms in the alkyl group having the alkylamino group is 1 to 10.

[0083] The above reaction scheme (4-2) represents the photoreduction reaction of an anthraquinone derivative represented by the above scheme (4-1). In this reaction, the photoreduction of the anthraquinone derivative P4 occurs using a resin or the like present around the anthraquinone derivative P4 as a hydrogen source, and a hydrogen adduct K4, which is a compound in which hydrogen is added to the anthraquinone backbone, is produced.

[0084] 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).

[0085] The respective energies Ep and Ek of the anthraquinone derivative P4 and the hydrogen adduct K4 can be obtained by quantum chemical calculations using Density Functional Theory (DFT). B3LYP is used for the functionals, and 6-31G(d) is used for the basis functions. These quantum chemical calculations can be performed using general-purpose quantum chemical calculation programs such as Gaussian or GAMESS. Each energy Ep and Ek represents the total energy of the molecule in the optimized structure obtained by the above quantum chemical calculations.

[0086] The action of the anthraquinone derivative of the fourth embodiment is explained. An anthraquinone derivative having a substituent as in formula (4-1) above can be used as a cyanide pigment in that it has a wavelength of maximum absorption in the wavelength range of 580 nm to 830 nm.

[0087] In addition, for the anthraquinone derivative of the fourth embodiment, the total energy difference ΔE is -16 kcal / mol or greater. One factor in the degradation of the anthraquinone derivative by light is the occurrence of the reaction represented by the above reaction scheme (4-2). The greater 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 greater, good light resistance is obtained. Furthermore, to obtain higher light resistance, it is preferable that the total energy difference ΔE be -14 kcal / mol or greater.

[0088] In the fourth embodiment, a first example of a suitable anthraquinone derivative is among the compounds described above represented by formula (4-1), R 1 , R 2 and R 3 These are compounds in which each of them is an amino group. For such compounds, high light resistance is obtained because the total energy difference ΔE becomes larger. Given that it is thought that photoreduction reactions become more likely when an anthraquinone derivative has a hydroxyl group at the α-position, R 1, R 2 and R 3 It is believed that the degradation caused by photoreduction reactions is accurately suppressed because all of them are amino groups.

[0089] In the fourth embodiment, a second example of a suitable anthraquinone derivative is among the compounds described above represented by formula (4-1), R 1 and R 3 This is a hydroxyl group, and R 2 ga is an amino group, and A 1 , A 2 It is a compound in which the β-group is directly bonded. With such a compound, high light resistance is obtained because the total energy difference ΔE becomes larger. In this structure, as described in the first embodiment, it is believed that the degradation caused by the photoreduction reaction is accurately suppressed due to the stereochemical structure of the molecule, as the phenyl group is directly bonded to the β-group.

[0090] In addition, the anthraquinone derivative of the fourth embodiment may be a compound described in the first to third embodiments, provided that the total energy difference ΔE is -16 kcal / mol or more. Among the compounds described in the first to third embodiments, even if it is a compound different from the compound represented by formula (4-1) above, good light resistance is obtained by having a total energy difference ΔE of -16 kcal / mol or more.

[0091] (Fifth embodiment)

[0092] An anthraquinone derivative of the fifth embodiment is 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.

[0093]

[0094] In Equation (5-1), X is -NH- or a sulfur atom. In Equation (5-1), R 1 , R 2 and R 3Each is independently an amino group or a hydroxyl group. In Formula (5-1), A 1 and A 2 Each of these is, independently, directly bonded to an oxygen atom, a sulfur atom, or -NH-. Also, A 1 , A 2 Direct bonding means that at the β-position of an anthraquinone derivative, a substituted or unsubstituted phenyl group is directly bonded to a carbon atom constituting the anthraquinone backbone.

[0095] In Equation (5-1), Y 1 , Y 2 Z 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, an alkyl halide 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. Preferably, the substituent is an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group. Preferably, the cyclic hydrocarbon group is a cyclohexyl group or a phenyl group. Preferably, the halogen atom and the halogen atom included in the alkyl halide group are F, Cl, or Br. The alkyl group having the alkylamino group may be one or two. Preferably, the number of carbon atoms in the alkyl group having the alkylamino group is 1 to 10.

[0096] The above thermogravimetric measurement is performed under conditions of a gas flow rate of 200 mL / min and a temperature rise of 10℃ / min. Air is used as the gas.

[0097] The action of the anthraquinone derivative of the fifth embodiment is explained. An anthraquinone derivative having a substituent as in formula (5-1) above can be used as a cyanide pigment in that it has a wavelength of maximum absorption in the wavelength range of 580 nm to 830 nm.

[0098] In addition, for the anthraquinone derivative of the fifth embodiment, the 10% weight loss temperature in the thermogravimetric measurement is 350°C or higher. When high heat is applied to the anthraquinone derivative, the anthraquinone derivative decomposes to generate radicals, and further reactions such as decomposition proceed through the action of these radicals. Since the factor causing the photodegradation of the anthraquinone derivative is radicals generated from the surroundings or itself, anthraquinone derivatives that are resistant to thermal decomposition—that is, anthraquinone derivatives with a high 10% weight loss temperature—tend to have high light resistance. Good light resistance is obtained when the 10% weight loss temperature is 350°C or higher. Furthermore, to obtain even higher light resistance, it is preferable that the 10% weight loss temperature be 365°C or higher.

[0099] In the fifth embodiment, a first example of a suitable anthraquinone derivative is among the compounds described above represented by formula (5-1), R 2 It is a compound in which the group is an amino group. If it is such a compound, synthesis is easy.

[0100] In the fifth embodiment, a second example of a suitable anthraquinone derivative is among the compounds described above represented by formula (5-1), R 1 and R 3 This is a hydroxyl group, and R 2 It is a compound in which the group is an amino group. If it is such a compound, synthesis is easy.

[0101] In the fifth embodiment, a third example of a suitable anthraquinone derivative is among the compounds described above represented by formula (5-1), R 1 , R 2 and R 3 Each of them is a compound in which an amino group is present. With such compounds, the 10% weight loss temperature is higher, so high light resistance is obtained.

[0102] In the fifth embodiment, the fourth example of a suitable anthraquinone derivative is among the compounds described above represented by formula (5-1), R 2ga is an amino group, and A 1 and A 2 It is a compound in which the bond is a direct bond. With such a compound, the 10% weight loss temperature is higher, so high light resistance is obtained.

[0103] In addition, the anthraquinone derivative of the fifth embodiment may be a compound described in the first to third embodiments, provided that the 10% weight loss temperature is 350°C or higher. Among the compounds described in the first to third embodiments, even if it is a compound different from the compound represented by formula (5-1) above, good light resistance is obtained by having a 10% weight loss temperature of 350°C or higher.

[0104] (Sixth embodiment)

[0105] For pigments, high coloring power, that is, high absorbance, is desired. The coloring power of anthraquinone derivatives varies depending on the type and position of the substituents they possess. Given the wide range of substituents that can be introduced into anthraquinone derivatives, the variation in coloring power among them is significant, and many conventional anthraquinone derivatives contain compounds with low coloring power.

[0106] Higher coloring power allows for a reduction in the amount of pigment incorporated, which is advantageous from a cost perspective. Additionally, regarding anthraquinone derivatives, there are limitations to enhancing color by increasing the amount incorporated due to the high molecular planarity and difficulty in increasing solubility. Therefore, improving coloring power is an important task. The anthraquinone derivative of the 6th embodiment addresses the improvement of coloring power.

[0107] An anthraquinone derivative of the sixth embodiment is 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 3.30D or greater and 5.00D or less.

[0108] The transition dipole moment of an anthraquinone derivative is the electric dipole moment that occurs during electron transition in vacuum regarding 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 chemistry calculations can be performed using general-purpose quantum chemistry calculation programs such as Gaussian or GAMESS.

[0109] Since the molar extinction coefficient is proportional to the square of the transition dipole moment, there is a tendency for higher absorbance to be obtained as the transition dipole moment increases. When the magnitude of the transition dipole moment is 3.30 D or greater, good coloring power is obtained in that sufficient absorbance is obtained.

[0110] In addition, the type or position of the substituents in the anthraquinone derivatives is related to the magnitude of the transition dipole moment, as well as the magnitude of the absorption maximum wavelength. If the magnitude of the transition dipole moment is 3.30 D or greater, both the absorbance and the absorption maximum wavelength are obtained well.

[0111] In addition, if the magnitude of the transition dipole moment is 5.00D or less, the complexity of the arrangement or structure of the substituents is suppressed, making synthesis easier.

[0112] The anthraquinone derivative of the sixth embodiment is preferably a compound represented by the following formula (6-1).

[0113]

[0114] In Equation (6-1), X is -NH- or a sulfur atom. In Equation (6-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group.

[0115] In Equation (6-1), Y 1 , Y 2Z 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, an alkyl halide 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. Preferably, the substituent is an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group. Preferably, the cyclic hydrocarbon group is a cyclohexyl group or a phenyl group. Preferably, the halogen atom and the halogen atom included in the alkyl halide group are F, Cl, or Br. The alkyl group having the alkylamino group may be one or two. Preferably, the number of carbon atoms in the alkyl group having the alkylamino group is 1 to 10.

[0116] If the anthraquinone derivative has a substituent as in the above formula (6-1), the transition dipole moment can be increased, and the wavelength of maximum absorption is also increased. Specifically, the wavelength of maximum absorption is obtained in the wavelength range of 580 nm to 830 nm. Therefore, it can be used as a cyanide pigment with high coloring power. In addition, good lightfastness is obtained because a phenyl group is directly bonded to the β-position.

[0117] Among the compounds represented by the above formula (6-1), a first example of a suitable anthraquinone derivative is R 1 and R 3 This is a hydroxyl group, and R 2 It is a compound in which the group is an amino group. If it is such a compound, synthesis is easy.

[0118] Among the compounds represented by the above formula (6-1), a second example of a suitable anthraquinone derivative is R 2It is a compound in which g is an amino group and X is a sulfur atom. This compound combines a structure in which the amino or hydroxyl group on the α-position and the phenyl group directly bonded to the β-position contribute significantly to the long-wavelength shift of the absorption maximum wavelength, and a structure in which the phenylthio group on the α-position contributes less to the long-wavelength shift of the absorption maximum wavelength. Therefore, while realizing an absorption maximum wavelength of 580 nm or more that is usable as a cyanide pigment, the absorption maximum wavelength is suppressed from becoming too large. Specifically, it is possible to set the absorption maximum wavelength to a range of 580 nm or more and 670 nm or less. As a result, excellent blue light is obtained.

[0119] The anthraquinone derivative of the 6th embodiment may be the anthraquinone derivative of the 1st embodiment. With such a compound, high lightfastness is obtained, and coloring power is increased by the action of a para-substituted phenyl group having an electron-donating group on the β-position.

[0120] The anthraquinone derivative of the 6th embodiment may be the anthraquinone derivative of the 2nd embodiment. With such a compound, high lightfastness is obtained, and the coloring power is increased by the action of the para-substituted aniline group having an electron-withdrawing group at the α position.

[0121] The anthraquinone derivative of the 6th embodiment may be the anthraquinone derivative of the 3rd embodiment. With such a compound, high light resistance is obtained, and a strong blue light is obtained through the action of a para-substituted phenyl group having a cyclohexyl group at the β position.

[0122] (7th embodiment)

[0123] The anthraquinone derivative of the seventh embodiment has the objective of improving coloring power, just like the sixth embodiment.

[0124] An anthraquinone derivative of the seventh embodiment is described. The anthraquinone derivative of the seventh embodiment is a compound represented by the following formula (7-1) and satisfies the conditions described below regarding molecular orbital coefficients.

[0125]

[0126] In Equation (7-1), C 11 , C 12 , C 21 , C 22 Each of is a carbon atom. In Equation (7-1), X is -NH- or a sulfur atom. In Equation (7-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group. In Formula (7-1), A 1 and A 2 Each of these is, independently, directly bonded to an oxygen atom, a sulfur atom, or -NH-. Also, A 1 , A 2 Direct bonding means that at the β-position of an anthraquinone derivative, a substituted or unsubstituted phenyl group is directly bonded to a carbon atom constituting the anthraquinone backbone.

[0127] In Equation (7-1), Y 1 , Y 2Z 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, an alkyl halide 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. Preferably, the substituent is an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group. Preferably, the cyclic hydrocarbon group is a cyclohexyl group or a phenyl group. Preferably, the halogen atom and the halogen atom included in the alkyl halide group are F, Cl, or Br. The alkyl group having the alkylamino group may be one or two. Preferably, the number of carbon atoms in the alkyl group having the alkylamino group is 1 to 10.

[0128] In the anthraquinone derivative of the seventh embodiment, regarding the molecular orbital coefficient of the Highest Occupied Molecular Orbital (HOMO) obtainable by quantum chemical calculation using Density Functional Theory (DFT), C 11 , C 12 , C 21 , C 22 The average Mv of the square root of the sum of squares of the coefficients corresponding to each orbital on a carbon atom is between 0.03 and 0.2. B3LYP is used for the functional, and 6-31G(d) is used for the basis functions.

[0129] That is, C 11 The square root of the sum of the squares of the molecular orbital coefficients for is M 11 and, C 12 The square root of the sum of the squares of the molecular orbital coefficients for is M 12 and, C 21 The square root of the sum of the squares of the molecular orbital coefficients for is M 21 and, C 22 The square root of the sum of the squares of the molecular orbital coefficients for is M22 It is said that. At this time, M 11 , M 12 , M 21 , M 22 The average value is the mean Mv.

[0130] The above quantum chemistry calculation can be performed using a general-purpose quantum chemistry calculation program such as Gaussian or GAMESS.

[0131] The action of the anthraquinone derivative of the seventh embodiment is explained. An anthraquinone derivative having a substituent as in formula (7-1) above can be used as a cyanide pigment in that it has a wavelength of maximum absorption in the wavelength range of 580 nm to 830 nm.

[0132] Generally, the electron transition exhibiting an absorption maximum is the electron transition from HOMO to LUMO (Lowest Unoccupied Molecular Orbital). It is believed that higher absorbance is obtained when the overlap between the molecular orbitals of HOMO and LUMO is greater, as this increases the probability of electron transition. As a result of repeated investigations by the inventors, a trend of spreading between the molecular orbitals of HOMO and LUMO in anthraquinone derivatives was discovered.

[0133] That is, regarding the LUMO molecular orbitals of anthraquinone derivatives, the influence of the type or arrangement of substituents is small, and the LUMO molecular orbitals tend to gather around the anthraquinone backbone. On the other hand, the HOMO molecular orbitals vary significantly depending on the type or arrangement of substituents. Among these, in the structure represented by the above formula (7-1), the HOMO molecular orbitals tend to spread toward the α-position to which an anilino group or phenylthio group is attached, that is, toward the substituent containing X.

[0134] Therefore, it is thought that if the molecular orbital of the HOMO is configured to spread toward the substituent at the β position, that is, spread over the benzene ring containing the substituent at the β position, the excessive spreading of the molecular orbital of the HOMO toward the α position is suppressed, and it spreads well in balance around the anthraquinone backbone, and the overlap between the molecular orbitals of the HOMO and LUMO increases.

[0135] The dispersion of the HOMO molecular orbital onto the benzene ring at the β-position can be indicated by the coefficient of the orbital on the carbon atom contained in the benzene ring. That is, the larger the average Mv, the more the molecular orbital is dispersed onto the benzene ring at the β-position. If the average Mv is 0.03 or higher, the overlap between the HOMO and LUMO molecular orbitals becomes large enough to obtain good absorbance at the wavelength of maximum absorption, and high coloring power is obtained. On the other hand, if the average Mv is 0.2 or lower, the complexity of the arrangement of substituents or the structure is suppressed, making the synthesis of anthraquinone derivatives easier. Furthermore, the reduction of the overlap between the HOMO and LUMO molecular orbitals caused by the HOMO molecular orbital spreading too much toward the substituent at the β-position is also suppressed.

[0136] In the seventh embodiment, a first example of a suitable anthraquinone derivative is among the compounds described above represented by formula (7-1), R 1 and R 3 This is a hydroxyl group, and R 2 It is a compound in which the group is an amino group. If it is such a compound, synthesis is easy.

[0137] In the seventh embodiment, a second example of a suitable anthraquinone derivative is among the compounds described above represented by formula (7-1), R 1 and R 3 This is a hydroxyl group, and R 2 ga is an amino group, and A 1 and A 2 It is an anthraquinone derivative with direct bonding. With such a compound, in addition to being easy to synthesize, light resistance is also enhanced. Furthermore, the average Mv can be significantly increased.

[0138] In addition, the anthraquinone derivative of the seventh embodiment may be a compound described in the first to third embodiments, provided that the average Mv is 0.03 or higher and 0.2 or lower. Among the compounds described in the first to third embodiments, even if it is a compound different from the compound represented by formula (7-1) above, good coloring power is obtained by having an average Mv of 0.03 or higher and 0.2 or lower.

[0139] In an anthraquinone derivative, to increase the average Mv within the range of 0.03 or more and 0.2 or less, it is preferable that a substituted or unsubstituted phenyl group is directly bonded to the β-position. Similarly, to increase the average Mv within the above range, it is preferable that the anthraquinone derivative has a para-substituted phenyl group on the β-position, and that the substituent on the para-position of the phenyl group is an electron-donating group. That is, if it is an anthraquinone derivative of the first embodiment, good coloring power is obtained. Similarly, to increase the average Mv within the above range, it is preferable that the anthraquinone derivative has a para-substituted anilino group on the α-position, and that the substituent on the para-position of the anilino group is an electron-withdrawing group. That is, if it is an anthraquinone derivative of the second embodiment, good coloring power is obtained.

[0140] (8th embodiment)

[0141] The anthraquinone derivative of the eighth embodiment, like the first embodiment, has the task of improving light resistance.

[0142] The anthraquinone derivative of the eighth embodiment is a compound represented by the following formula (8-1).

[0143]

[0144] In formula (8-1), A is a direct bond, an oxygen atom, or -NH-. Also, A being a direct bond indicates that a substituted or unsubstituted phenyl group at the β-position of the anthraquinone derivative is directly bonded to a carbon atom constituting the anthraquinone backbone.

[0145] In Equation (8-1), Y 1 , Y 2 Z 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, an alkyl halide group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents. Preferably, the substituent is an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group. Preferably, the cyclic hydrocarbon group is a cyclohexyl group or a phenyl group. Preferably, the halogen atom and the halogen atom included in the alkyl halide group are F, Cl, or Br. The alkyl group having the alkylamino group may be one or two. Preferably, the number of carbon atoms in the alkyl group having the alkylamino group is 1 to 10.

[0146] The type of substituent in the anthraquinone backbone affects the absorption wavelength of the anthraquinone derivative. The anthraquinone derivative of the present embodiment has one substituted or unsubstituted anilino group and three amino groups on the α-site. Anthraquinone derivatives having this structure can be used as cyanide dyes because they have a maximum absorption wavelength in the wavelength range of 600 nm or more.

[0147] One factor in photodegradation of anthraquinone derivatives is thought to be photoreduction occurring in the anthraquinone backbone using resins or the like surrounding the anthraquinone derivative as a hydrogen source. If an anthraquinone derivative has a hydroxyl group at the α-position, such photoreduction is likely to occur. In addition, changes in the chemical structure caused by the generation of radicals from the hydroxyl group also lead to photodegradation. In contrast, since the anthraquinone derivative of the present embodiment does not have a hydroxyl group at the α-position, the occurrence of photodegradation caused by the hydroxyl group is suppressed. Therefore, high light resistance is obtained with the anthraquinone derivative of the present embodiment.

[0148] In the anthraquinone derivative of the present embodiment, it is preferable that A is an oxygen atom or a direct bond. A compound in which A is an oxygen atom is represented by the following formula (8-2), and a compound in which A is a direct bond is represented by the following formula (8-3).

[0149]

[0150] In Equation (8-2), Y 1 , Y 2 and Z are defined as in Equation (8-1). If they are an anthraquinone derivative represented by Equation (8-2), solubility in solvents or resins can be increased.

[0151]

[0152] In Equation (8-3), Y 1 , Y 2Z and Z are defined as in Equation (8-1). In the anthraquinone derivative represented by Equation (8-3), a substituted or unsubstituted phenyl group is directly bonded to the β-site. This structure further enhances light resistance. Specifically, when a phenyl group is directly bonded to the β-site, compared to the case where the β-site is an ether bond or a secondary amine, the molecular structure at the bonding portion of the β-site is difficult to rotate, so the structure of the anthraquinone backbone after photoreduction is difficult to become a stable structure, and therefore, it is thought that the progress of the photoreduction reaction is inhibited.

[0153] The anthraquinone derivative of the present embodiment can be prepared by introducing each substituent into the anthraquinone backbone, for example, using 1,5-diaminoanthraquinone as a starting material. Known methods may be used for introducing the substituents. For example, the desired substituent is introduced through nitration of the α-site or bromolation of the β-site.

[0154] In addition, the compound represented by the formula (8-1), which is an anthraquinone derivative of the eighth embodiment, may be an anthraquinone derivative of the first to seventh embodiments.

[0155] (Ninth embodiment)

[0156] The anthraquinone derivative of the ninth embodiment, like the first embodiment, has the improvement of light resistance as its primary objective.

[0157] In addition, among cyanide pigments, the color of compounds with an absorption maximum wavelength close to 700 nm becomes blue-green due to an increase in the green component. On the other hand, a strong blue light is desired for cyanide pigments used as pigments corresponding to the three primary colors. The anthraquinone derivative of the ninth embodiment has the enhancement of blue light as a second objective.

[0158] The anthraquinone derivative of the ninth embodiment is a compound represented by the following formula (9-1).

[0159]

[0160] In Equation (9-1), R 1 and R 2 is, independently, an amino group or a hydroxyl group. Y 1 , Y 2 and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, an alkyl halide 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. Preferably, the substituent is an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group. Preferably, the cyclic hydrocarbon group is a cyclohexyl group or a phenyl group.

[0161] Preferably, the halogen atom and the halogen atom included in the alkyl halide group are F, Cl, or Br. The alkyl group having the alkylamino group may be one or two. Preferably, the number of carbon atoms in the alkyl group having the alkylamino group is 1 to 10.

[0162] The action of the anthraquinone derivative of the present embodiment is explained. It is believed that one factor in photodegradation of anthraquinone derivatives is that photoreduction occurs in the anthraquinone backbone using resins or the like surrounding the anthraquinone derivative as a hydrogen source. Furthermore, conventional anthraquinone derivatives are known to have a structure in which a functional group, such as a phenyl group, is attached to the β-site via an ether bond. In contrast, in the anthraquinone derivative of the present embodiment, a substituted or unsubstituted phenyl group at the β-site is directly bonded to a carbon of the anthraquinone backbone. Due to this structure, the progress of the photoreduction reaction is suppressed, thereby obtaining high light resistance.

[0163] More specifically, it is thought that when a phenyl group is directly bonded to the β-position, compared to when an ether bond exists on the β-position, the molecular structure at the bonding portion on the β-position is difficult to rotate, making it difficult for the structure of the anthraquinone backbone after photoreduction to become a stable structure, and therefore, the progress of the photoreduction reaction is inhibited.

[0164] In addition, the type of substituent in the anthraquinone backbone affects the absorption wavelength of the anthraquinone derivative. Regarding the substituent on the α-position, substituents with high electron-donating properties, such as amino groups, hydroxyl groups, and aniline groups, cause the absorption maximum wavelength to shift toward the longer wavelength side. Furthermore, a structure in which a substituted or unsubstituted phenyl group is directly bonded to the β-position also causes the absorption maximum wavelength to shift toward the longer wavelength side.

[0165] For conventional cyanide-based pigments, anthraquinone derivatives, a structure is known in which one of the substituents on the α-position is an anilino group and the other three are amino or hydroxyl groups. In such compounds, if a structure in which a phenyl group is directly bonded to the β-position is adopted to improve lightfastness, the wavelength of maximum absorption shifts toward longer wavelengths, and it is difficult to avoid an increase in the green component of the color exhibited by the compound.

[0166] In contrast, the anthraquinone derivative of the present embodiment has a substituted or unsubstituted phenylthio group on the α-site. Since the phenylthio group has a smaller electron-donating capacity than amino groups, hydroxyl groups, or anilino groups, the introduction of a phenylthio group on the α-site suppresses the shift of the absorption maximum wavelength toward the long wavelength side, even if a phenyl group is directly bonded to the β-site compared to the conventional structure.

[0167] As such, the anthraquinone derivative of the present embodiment combines a structure that contributes significantly to the long-wavelength shift of the absorption maximum wavelength, such as an amino or hydroxyl group on the α-position and a phenyl group directly bonded to the β-position, with a structure that contributes less to the long-wavelength shift of the absorption maximum wavelength, such as a phenylthio group on the α-position. Therefore, while realizing an absorption maximum wavelength of 580 nm or more that is usable as a cyanide pigment, the absorption maximum wavelength is suppressed from becoming too large. Specifically, it is possible to set the absorption maximum wavelength to a range of 580 nm or more and 670 nm or less, thereby obtaining excellent blue light. Furthermore, since excellent blue light is obtained while having a structure in which a phenyl group is directly bonded to the β-position, it is possible to achieve both lightfastness and blue light.

[0168] In the anthraquinone derivative of the present embodiment, the R 1 and R 2 It is preferable that the group be a hydroxyl group. Such a compound is represented by the following formula (9-2).

[0169]

[0170] In Equation (9-2), Y 1 , Y 2 Z is defined as in Formula (9-1). Synthesis is easy if it is an anthraquinone derivative represented by Formula (9-2). In addition, if a hydroxyl group is present on the α-position, the aforementioned photoreduction is likely to occur, but according to the anthraquinone derivative of the present embodiment, the photoreduction reaction is suppressed due to the structure in which a phenyl group is directly bonded to the β-position as described above. Therefore, the disadvantages of a structure having a hydroxyl group on the α-position can be overcome, while the advantages of said structure can be enjoyed.

[0171] The anthraquinone derivative of the present embodiment can be prepared by introducing each substituent into the anthraquinone backbone, for example, using 1,5-dihydroxy-4,8-dinitroanthraquinone or 1,5-diamino-4,8-dinitroanthraquinone as a starting material. Known methods may be used for introducing the substituents. For example, the desired substituent is introduced by using the reduction of the nitro group, substituent conversion, bromolation of the β-site, and bromo group conversion.

[0172] In addition, the compound represented by the formula (9-1), which is an anthraquinone derivative of the ninth embodiment, may be an anthraquinone derivative of the fourth to seventh embodiments.

[0173] [Example]

[0174] The anthraquinone derivatives described above will be explained using specific examples. Additionally, the weight parts of each material described below indicate the ratio of the relative weights of each material mixed together.

[0175] [First Embodiment: Test Example Corresponding to the First Embodiment]

[0176] (Test Examples 1-1 to 1-13)

[0177] Synthesis of Precursor A1

[0178] 1,5-dihydroxy-4,8-dinitroanthraquinone (5.0 parts by weight) and N,N-dimethylformamide (100 parts by weight) were added to a two-necked flask. To this, N-bromosuccinimide (5.9 parts by weight) was added at room temperature and stirred for 1 hour at room temperature. 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. Subsequently, the precipitated solid was recovered by suction filtration, and the recovered material was vacuum dried overnight at 60°C to obtain precursor A1 as a yellow solid. Precursor A1 is a compound represented by the following formula (1-a).

[0179]

[0180] Synthesis of Precursor A2

[0181] Precursor A1 (1.0 parts by weight) and N-methyl-2-pyrrolidone (20 parts by weight) were added to a two-necked flask. 4-heptylaniline (0.8 parts by weight) was added to this, 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 cooled to room temperature. Then, ethyl acetate (30 parts by weight) and water (10 parts by weight) were added, and the mixture was vigorously stirred at room temperature. Since insoluble matter was generated at this stage, it was removed by Celite filtration. After separating the two layers, the organic layer was sequentially washed with distilled water, a 5% aqueous hydrochloric acid solution, and saturated saline solution. Subsequently, anhydrous magnesium sulfate was added, and the mixture was dried. Then, the drying agent was filtered and separated, and 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 deep blue solid. Precursor A2 is a compound represented by the following formula (1-b).

[0182]

[0183] Synthesis of Precursor A3

[0184] In the synthesis process of the above precursor A2, the 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).

[0185]

[0186] <Synthesis of the pigment of Test Example 1-1>

[0187] 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 tetracyclophenylphosphine palladium (0.06 parts by weight) as a catalyst were added to a branch flask equipped with a dimrose condenser and subjected to nitrogen purification, and the mixture was 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, pure water was added, and extraction with ethyl acetate was performed. Sodium sulfate was added to the obtained organic layer, and after drying, 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).

[0188]

[0189] <Synthesis of the pigment of Test Example 1-2>

[0190] In the synthesis process of the pigment of Test Example 1-1 above, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-dibutylaminophenylboronic acid, and the anthraquinone derivative of Test Example 1-2 was obtained. The anthraquinone derivative of Test Example 1-2 is a compound represented by the following formula (P1-2).

[0191]

[0192] <Synthesis of the pigments of Test Example 1-3>

[0193] In the synthesis process of the pigment of Test Example 1-1 above, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-monobutylaminophenylboronic acid, and the anthraquinone derivative of Test Example 1-3 was obtained. The anthraquinone derivative of Test Example 1-3 is a compound represented by the following formula (P1-3).

[0194]

[0195] <Synthesis of Pigments in Test Example 1-4>

[0196] In the synthesis process of the pigment of 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, thereby obtaining the anthraquinone derivative of Test Example 1-4. The anthraquinone derivative of Test Example 1-4 is a compound represented by the following formula (P1-4).

[0197]

[0198] <Synthesis of Pigments in Test Example 1-5>

[0199] In the synthesis process of the pigment of Test Example 1-1 above, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to (4-piperisin-1-yl)phenylboronic acid, and the 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).

[0200]

[0201] <Synthesis of Pigments in Test Example 1-6>

[0202] In the synthesis process of the pigment of 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 the 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).

[0203]

[0204] <Synthesis of the pigment of Test Example 1-7>

[0205] In the synthesis process of the pigment of Test Example 1-1 above, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-acetamidephenylboronic 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).

[0206]

[0207] <Synthesis of Pigments in Test Example 1-8>

[0208] In the synthesis process of the pigment of Test Example 1-1 above, 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).

[0209]

[0210] <Synthesis of the pigment of Test Example 1-9>

[0211] In the synthesis process of the pigment of Test Example 1-1 above, precursor A2 was changed to precursor A3, and 1.2 equivalents of 4-monobutylaminophenylboronic 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-heptylphenylboronic acid were additionally added, and heating and stirring were performed at 80°C for 2 hours or more. After that, extraction and purification were performed in the same manner as the synthesis process of the pigment of Test Example 1-1 above to obtain the anthraquinone derivative of Test Example 1-9. The anthraquinone derivative of Test Example 1-9 is a compound represented by the following formula (P1-9).

[0212]

[0213] <Synthesis of Pigments in Test Example 1-10>

[0214] In the synthesis process of the pigment of Test Example 1-1 above, the synthesis was carried out in the same manner except that 4-dimethylaminophenylboronic acid was changed to 4-heptyloxyphenylboronic acid, and the 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).

[0215]

[0216] <Synthesis of the pigment of Test Example 1-11>

[0217] In the synthesis process of the pigment of 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-heptyloxyphenylboronic acid, thereby obtaining the anthraquinone derivative of Test Example 1-11. The anthraquinone derivative of Test Example 1-11 is a compound represented by the following formula (P1-11).

[0218]

[0219] <Synthesis of Pigments in Test Example 1-12>

[0220] 4-heptyloxyphenol (8.65 parts by weight) and N-methyl-2-pyrrolidone (100 parts by weight) were placed in a two-necked flask. Sodium hydride (55%, 1.7 parts by weight) was slowly added in five divided portions and stirred for 3 hours in an oil bath at 60°C. Precursor A3 (5.00 parts by weight) was added to this solution and heated and stirred for 24 hours in an oil bath at 130°C. 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 sequentially washed with distilled water and saturated saline solution, after which anhydrous magnesium sulfate was added and the mixture was dried. Then, the drying agent was filtered and separated, and 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).

[0221]

[0222] <Synthesis of the pigment of Test Example 1-13>

[0223] In the synthesis process of the pigment of Test Example 1-12 above, the synthesis was carried out in the same manner except that 4-heptyloxyphenol (8.65 parts by weight) was changed to 4-butylaminophenol (6.86 parts by weight) and precursor A3 was changed to precursor A2, thereby obtaining 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).

[0224]

[0225] (Test Example 1-14, Test Example 1-15)

[0226] Synthesis of Precursor B1

[0227] 1,5-diaminoanthraquinone (5.0 parts by weight), N,N-dimethylformamide (397 parts by weight), and pyridine (10.3 parts by weight) were added to a two-necked flask and nitrogen purging was performed. The solution was sufficiently cooled in an ice bath, and acetyl chloride (19.8 parts by weight) was added dropwise over 45 minutes while ice cooling. Afterward, the solution was stirred for 10 minutes while ice cooling, and then stirred at room temperature for 24 hours. The precipitate was recovered by suction filtration, and the recovered product was washed with diethyl ether and dried to obtain a brown crude product. Subsequently, the crude product (5.5 parts by weight) and ethyl acetate (54 parts by weight) were added to a branched flask, heated to the reflux temperature, and suspension washing was performed for 30 minutes. Afterwards, the recovered material by suction filtration was washed with diethyl ether and 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).

[0228]

[0229] Synthesis of Precursor B2

[0230] Concentrated sulfuric acid (48 parts by weight) was added to a four-necked flask equipped with a thermometer and a mechanical stirrer, and potassium nitrate (6.0 parts by weight) was additionally added and completely dissolved. The mixture was then cooled until the internal temperature of the four-necked flask reached 0°C. To this solution, precursor B1 (3.0 parts by weight) was added in six portions of 0.5 parts by weight each, ensuring that the internal temperature of the four-necked flask did not exceed 5°C. Shortly after the addition of precursor B1, a light brown precipitate formed. Subsequently, the mixture was stirred for 6 hours while the internal temperature of the four-necked flask was maintained between 0°C and 5°C, 1Stirring was stopped because the disappearance of the substrate was confirmed by H-NMR measurement (solvent: DMSO-d6). This solution was added in small amounts to pure water cooled to 0°C to 5°C, the precipitate was recovered by suction filtration, and the recovered 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 recovered by filtration was dried under reduced pressure at 60°C to obtain precursor B2 as a turbid yellow powder. Precursor B2 is a compound represented by the following formula (1-e).

[0231]

[0232] Synthesis of Precursor B3

[0233] Pure water (5.5 parts by weight) was placed in a 2-neck flask, and additionally, concentrated sulfuric acid (40 parts by weight) was slowly added while ice cooling. Then, precursor B2 (2.2 parts by weight) was added while ice cooling. After stirring this solution at 95°C for 2 hours, it was added to pure water (200 parts by weight) while ice cooling. Afterward, the precipitate was recovered by suction filtration, and the recovered 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).

[0234]

[0235] Synthesis of Precursor B4

[0236] Precursor B3 (1.6 parts by weight) and N-bromosuccinimide (1.9 parts by weight) were placed in a two-necked flask and nitrogen purging was performed. To this, nitrogen-bubbled N,N-dimethylformamide (30 parts by weight) was added and stirred at room temperature for 20 hours. This reaction solution was injected into methanol (200 parts by weight) and stirred at room temperature for 15 minutes. Afterward, the precipitate was recovered by suction filtration, and the recovered 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).

[0237]

[0238] Synthesis of Precursor B5

[0239] Nitrogen purging was performed on a branch flask equipped with a dimrose condenser. To this, toluene (5 parts by weight), water (2.5 parts by weight), precursor B4 (0.30 parts by weight), (4-piperidine-1-yl)phenylboronic acid (0.28 parts by weight), potassium carbonate (0.21 parts by weight), and tetracyclostriphenylphosphine palladium (0.06 parts by weight) were added, and the mixture was heated and stirred at 80°C for at least 2 hours. After confirming the completion of the reaction by thin-layer chromatography, the mixture was returned to room temperature, pure water was added, and extraction with ethyl acetate was performed. Sodium sulfate was added to the obtained organic layer, and after drying, the solvent was removed under reduced pressure using an evaporator. The resulting 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).

[0240]

[0241] Synthesis of Precursor B6

[0242] Precursor B5 (0.20 parts by weight) was placed in a 2-neck flask and nitrogen purging was performed. To this, nitrobenzene (4.8 parts by weight) and 4-heptylaniline (0.52 parts 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 remove nitrobenzene by distillation, thereby obtaining a residue. Methanol was injected into this residue, and the precipitated powder was recovered by suction filtration to obtain precursor B6. Precursor B6 is a compound represented by the following formula (1-i).

[0243]

[0244] Synthesis of Precursor B7

[0245] In the synthesis process of the above precursor B5, the synthesis was carried out in the same manner except that (4-piperidin-1-yl)phenylboronic acid was changed to 4-heptyloxyphenylboronic acid, and precursor B7 was obtained. Precursor B7 is a compound represented by the following formula (1-j).

[0246]

[0247] Synthesis of Precursor B8

[0248] In the synthesis process of the above precursor B6, the synthesis was carried out in the same manner except that precursor B5 was changed to precursor B7, thereby obtaining precursor B8. Precursor B8 is a compound represented by the following formula (1-k).

[0249]

[0250] <Synthesis of the pigment of Test Example 1-14>

[0251] Precursor B6 (0.20 parts by weight) was placed in a 2-neck flask and nitrogen purging was performed. Then, 2-propanol (3.1 parts by weight) was added, the mixture was heated to 80°C, sodium borohydride (0.22 parts by weight) was additionally added, and the mixture was stirred for 27 hours. The reaction solution was poured into cold water, and the precipitated powder was recovered by suction filtration and 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).

[0252]

[0253] <Synthesis of Pigments in Test Example 1-15>

[0254] In the synthesis process of the pigment of Test Example 1-14 above, 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).

[0255]

[0256] (Evaluation Method)

[0257] <Preparation of Evaluation Specimens>

[0258] A pigment-containing composition was prepared by using an anthraquinone derivative of each test example and mixing the following materials.

[0259] · Mixture of pentaerythritol tetraacrylate and isoboronyl acrylate (70 mass% of pentaerythritol tetraacrylate, 30 mass% of isoboronyl acrylate): 45 parts by weight

[0260] · Photopolymerization initiator (Omnirad TPO, IGM Resins BV): 4.5 parts by weight

[0261] · Anthraquinone derivative: 1 part by weight

[0262] · Methyl ethyl ketone: 50 parts by weight

[0263] As a transparent substrate, a polyethylene terephthalate film with a thickness of 60 μm was used, a pigment-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. After that, the coating film was cured by irradiating it with ultraviolet light at an irradiation dose of 150 mJ / cm² using an ultraviolet irradiation device (manufactured by Fusion UV Systems Japan, light source H bulb). An evaluation test specimen was prepared by adjusting the thickness so that the film thickness after curing was 8.0 μm.

[0264] <Evaluation of Absorption Wavelength and Coloring Power>

[0265] For each test example, the ultraviolet-visible absorption spectrum was measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi Seisakusho) for the evaluation specimen, and the absorption maximum wavelength λmax and the absorbance at the corresponding wavelength were determined.

[0266] In evaluating the coloring power, based on Test Example 1-10, which corresponds to a conventional anthraquinone derivative, if the absorbance is greater than Test Example 1-10, it is rated as "Good" ("G"), and if the absorbance is less than or equal to Test Example 1-10, it is rated as "Bad" ("B").

[0267] <Evaluation of Lightfastness>

[0268] For each test example, a light resistance test was performed on the evaluation specimen using a xenon weather meter tester (X75, manufactured by Suga Shikenki). In the light resistance test, a UV-cut adhesive film that absorbs light of 395 nm or less was attached to the front surface of the evaluation specimen, and the evaluation specimen was placed for 120 hours under conditions of xenon lamp illuminance of 60 W / cm² (300 nm to 400 nm), temperature of 45°C, and humidity of 50% RH.

[0269] For each evaluation specimen before and after the light tolerance test, absorbance measurements were performed using an automatic spectrophotometer (U-4100, manufactured by Hitachi Seisakusho), and the absorbance at the wavelength exhibiting maximum absorbance in the visible light region was determined. Then, the rate of change in absorbance ΔAbs between before and after the light tolerance test was calculated. That is, when the measured value before the light tolerance test is denoted as absorbance Abs1 and the measured value after the light tolerance test as absorbance Abs2, ΔAbs(%) = {(Abs1 - Abs2) / Abs1} × 100.

[0270] In evaluating lightfastness, when ΔAbs is 2% or less, it is designated as "Excellent" (E); when ΔAbs exceeds 2% and is 10% or less, it is designated as "Good" (G); and when ΔAbs exceeds 10%, it is designated as "Bad" (B).

[0271] Measurement of the two-color ratio

[0272] 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 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 device. The cell has a structure in which two glass plates with transparent electrodes attached and homogeneously aligned are positioned opposite each other so that the alignment surfaces are antiparallel. The alignment treatment was performed by applying a polyimide resin to the transparent electrodes, curing the resin, and then performing a rubbing treatment. The thickness of the cell is 10 μm.

[0273] 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 of absorbance A / / to absorbance A⊥ (A / / / A⊥) was calculated as a two-color ratio.

[0274] (Evaluation Results)

[0275] 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 rate of change in absorbance ΔAbs, the evaluation results of the lightfastness, and the two-color ratio for Test Examples 1-1 to 1-15. The structure of the anthraquinone derivative of each test example is represented by the following formula (I), and R, A, and Y in Table 1 1 , Y 2 , Z are R, A, and Y in the following equation (I). 1 , Y 2 Corresponds to , Z.

[0276]

[0277]

[0278] As shown in Table 1, the anthraquinone derivatives of each test example have a wavelength of maximum absorption in the wavelength range of 600 nm or higher. Therefore, the anthraquinone derivatives of each test example exhibit a blue color and can be used as cyanide dyes.

[0279] In addition, in Test Examples 1-1 to 1-11, 1-14, and 1-15, where a substituted phenyl group is directly bonded to the β-position, very high light resistance is obtained compared to Test Examples 1-12 and 1-13, where the β-position is ether-bonded.

[0280] Additionally, in Test Examples 1-1 to 1-9 and 1-14, where the substituent of the para group of the phenyl group directly bonded at at least one β-position is an electron donor, the absorbance is higher compared to Test Examples 1-10, 1-11, and 1-15, where the substituent is not an electron donor, and good coloring power is obtained. Furthermore, in Test Examples 1-1 to 1-9 and 1-14, high absorbance is also obtained for Test Examples 1-12 and 1-13, where the β-position is ether-bonded.

[0281] In addition, when comparing Test Examples 1-3 and 1-9, a higher absorbance is obtained when both of the two β-position phenyl groups have electron-donating substituents compared to when only one of the substituents is an electron-donating substituent. Also, referring to Test Examples 1-1 to 1-8, it was confirmed that when the electron-donating substituent is an alkylamino group, a piperidyl group, or an amino group, the effect of improving absorbance is higher than when the electron-donating substituent is an acetamide group or a hydroxyl group.

[0282] In addition, good color ratios were obtained in all test examples, and it was confirmed that a high color ratio of 10.0 or higher was obtained, especially when there are two hydroxyl groups on the α-site.

[0283] [Second Embodiment: Test Example Corresponding to the Second Embodiment]

[0284] In the second embodiment, synthesis was performed using precursors A1, A2, and A3, similar to those in the first embodiment.

[0285] (Test Example 2-1)

[0286] Synthesis of Precursor C1

[0287] Precursor A1 (1.0 parts by weight) and p-aminobenzonitrile (2.42 parts by weight) were placed in a two-necked flask, and nitrogen purging was performed. Nitrobenzene (24 parts by weight) was added to this, 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 vacuum drying at 70°C. By injecting methanol into the resulting residue and recovering the precipitated powder by suction filtration, precursor C1 was obtained as a purple powder. Precursor C1 is a compound represented by the following formula (2-a).

[0288]

[0289] Synthesis of Precursor C2

[0290] In a two-necked flask, precursor C1 (1.0 parts 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 parts by weight), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.147 parts by weight) were added, and nitrogen purification was performed. To this, toluene (71 parts by weight), ethanol (7.2 parts by weight), and pure water (4.5 parts by weight) were added, and the mixture was stirred for 2 hours in an oil bath at 80°C. The reaction solution was cooled to room temperature, separated into dichloromethane and pure water, and the organic layer was dried with sodium sulfate. Then, sodium sulfate was filtered and the remaining solution was concentrated and purified by silica gel column chromatography (developing solvent: dichloromethane / hexane = 1 / 1) to obtain a crude product. By column purifying this crude product, precursor C2 was obtained as a purple powder. The yield of precursor C2 was 11%. Precursor C2 is a compound represented by the following formula (2-b).

[0291]

[0292] <Synthesis of the pigment of Test Example 2-1>

[0293] In a two-necked flask, precursor C2 (1 part by weight), iron (0.325 parts by weight), and ammonium chloride (0.311 parts by weight) were placed, and nitrogen purging was performed. To this, toluene (27.9 parts by weight), ethanol (8.38 parts by weight), and pure water (5.31 parts by weight) were added, and the mixture was heated and stirred for 1 hour in an oil bath at 70°C. The reaction solution was cooled to room temperature, and after filtering out insoluble components with Celite, it was separated into dichloromethane and pure water. The mixture was washed with pure water and saturated saline solution, and the organic layer was dried with sodium sulfate. The sodium sulfate was filtered and separated, and the remaining solution was concentrated and 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).

[0294]

[0295] (Test Example 2-2)

[0296] Synthesis of Precursor C3

[0297] In the synthesis process of the above precursor C1, the 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).

[0298]

[0299] Synthesis of Precursor C4

[0300] In the synthesis process of the above precursor C2, the synthesis was carried out in the same manner except that precursor C1 was changed to precursor C3, thereby obtaining precursor C4. Precursor C4 is a compound represented by the following formula (2-d).

[0301]

[0302] <Synthesis of the pigment of Test Example 2-2>

[0303] In the synthesis process of the pigment of Test Example 2-1 above, the synthesis was carried out in the same manner except that precursor C2 was changed to precursor C4, and the 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).

[0304]

[0305] (Test Example 2-3)

[0306] <Synthesis of the pigment of Test Example 2-3>

[0307] In the synthesis process of the above 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, thereby obtaining precursor C5. Then, in the synthesis process of the pigment of Test Example 2-1, the synthesis was carried out in the same manner except that precursor C2 was changed to precursor C5, thereby obtaining the anthraquinone derivative of Test Example 2-3. The anthraquinone derivative of Test Example 2-3 is a compound represented by the following formula (P2-3).

[0308]

[0309] (Test Example 2-4)

[0310] <Synthesis of the pigment of Test Example 2-4>

[0311] In the synthesis process of the above 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, thereby obtaining precursor C6. Then, in the synthesis process of the pigment of Test Example 2-1, the synthesis was carried out in the same manner except that precursor C2 was changed to precursor C6, thereby obtaining the anthraquinone derivative of Test Example 2-4. The anthraquinone derivative of Test Example 2-4 is a compound represented by the following formula (P2-4).

[0312]

[0313] (Test Example 2-5)

[0314] <Synthesis of the pigment of Test Example 2-5>

[0315] In the synthesis process of the above precursor C2, the synthesis was carried out in the same manner except that (4-pentyloxy)phenylboronic acid was changed to 4-(dimethylamino)phenylboronic acid, thereby obtaining precursor C7. Then, in the synthesis process of the pigment of Test Example 2-1, the synthesis was carried out in the same manner except that precursor C2 was changed to precursor C7, thereby obtaining 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).

[0316]

[0317] (Test Example 2-6)

[0318] The pigment of Test Example 1-10 of the first embodiment was 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).

[0319]

[0320] (Test Example 2-7)

[0321] The pigment of Test Example 1-11 of the first embodiment was 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).

[0322]

[0323] (Test Example 2-8)

[0324] <Synthesis of the pigment of Test Example 2-8>

[0325] In the synthesis process of the pigment 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-(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).

[0326]

[0327] (Test Example 2-9)

[0328] <Synthesis of the pigment of Test Example 2-9>

[0329] In the synthesis process of the pigment 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 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).

[0330]

[0331] (Test Example 2-10)

[0332] The pigment of Test Example 1-12 of the first embodiment was 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).

[0333]

[0334] (Test Example 2-11)

[0335] Synthesis of Precursor C8

[0336] In the synthesis process of the pigment of Test Example 1-12 of the first embodiment, the 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).

[0337]

[0338] <Synthesis of the pigment of Test Example 2-11>

[0339] In the synthesis process of the pigment of Test Example 2-1 above, the 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).

[0340]

[0341] (Evaluation Method)

[0342] For the anthraquinone derivatives of Test Examples 2-1 to 2-11, evaluation specimens were prepared in the same manner as in the first example, and the absorption wavelength, coloring power, lightfastness, and color ratio were evaluated. In addition, regarding the evaluation of coloring power, Test Example 2-6, which corresponds to a conventional anthraquinone derivative, was used as a standard. If the absorbance was greater than that of Test Example 2-6, it was rated as "Good" ("G"), and if the absorbance was less than or equal to that of Test Example 2-6, it was rated as "Bad" ("B").

[0343] (Evaluation Results)

[0344] Table 2 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 rate of change in absorbance ΔAbs, the evaluation results of the lightfastness, and the two-color ratio for Test Examples 2-1 to 2-11. The structure of the anthraquinone derivative of each test example is represented by the following formula (I), and R, A, and Y in Table 2 1 , Y 2 , Z are R, A, and Y in the following equation (I). 1 , Y 2 Corresponds to , Z.

[0345]

[0346]

[0347] As shown in Table 2, the anthraquinone derivatives of each test example have a wavelength of maximum absorption in the wavelength range of 600 nm or higher. Therefore, the anthraquinone derivatives of each test example exhibit a blue color and can be used as cyanide dyes.

[0348] In addition, in Test Examples 2-1 to 2-9, where a substituted phenyl group is directly bonded to the β-position, very high light resistance is obtained compared to Test Examples 2-10 and 2-11, where the β-position is ether-bonded.

[0349] Additionally, in the structure in which a substituted phenyl group is directly bonded to the β-position, Test Examples 2-1 to 2-5, in which the substituent of the para-position of the anilino group on the α-position is an electron-withdrawing group, have higher absorbance and good coloring power compared to Test Examples 2-6 to 2-9, in which the substituent is not an electron-withdrawing group. Furthermore, in Test Examples 2-1 to 2-5, high absorbance is also obtained for Test Examples 2-10 and 2-11, in which the β-position is ether-bonded.

[0350] In addition, referring to Test Examples 2-1 to 2-5, it was confirmed that in Test Example 2-5, in addition to the electron-withdrawing group of the para group on the α group, the phenyl group on the β group has an electron-donating group as a substituent of the para group, a particularly high absorbance was obtained compared to other Test Examples that do not have such an electron-donating group.

[0351] In addition, it was confirmed that a good two-color ratio was obtained in all test examples.

[0352] [Third Embodiment: Test Example Corresponding to the Third Embodiment]

[0353] In the third embodiment, synthesis was performed using precursors A1 to A3 and B1 to B4, similar to those in the first embodiment.

[0354] (Test Example 3-1)

[0355] The pigment of Test Example 2-8 of the second embodiment was 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).

[0356]

[0357] (Test Example 3-2)

[0358] <Synthesis of the pigment of Test Example 3-2>

[0359] In the synthesis process of the pigment 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).

[0360]

[0361] (Test Example 3-3)

[0362] <Synthesis of the pigment of Test Example 3-3>

[0363] In the synthesis process of the pigment 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).

[0364]

[0365] (Test Example 3-4)

[0366] <Synthesis of the pigment of Test Example 3-4>

[0367] In the synthesis process of the pigment 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).

[0368]

[0369] (Test Example 3-5)

[0370] The pigment of Test Example 2-9 of the second embodiment was 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).

[0371]

[0372] (Test Example 3-6)

[0373] <Synthesis of the pigment of Test Example 3-6>

[0374] In the synthesis process of the pigment 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 additionally added, and heating and stirring were performed at 80°C for 2 hours or more. After that, extraction and purification were performed in the same manner as the synthesis process of the pigment 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).

[0375]

[0376] (Test Example 3-7)

[0377] <Synthesis of the pigment of Test Example 3-7>

[0378] In the synthesis process of the pigment of Test Example 1-1 of the first embodiment, 1.2 equivalents of 4-monobutylaminophenylboronic 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 additionally added, and heating and stirring were performed at 80°C for 2 hours or more. After that, extraction and purification were performed in the same manner as the synthesis process of the pigment of 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).

[0379]

[0380] (Test Example 3-8)

[0381] The pigment of Test Examples 1-10 of the first embodiment was the anthraquinone derivative of Test Examples 3-8. The anthraquinone derivative of Test Examples 3-8 is a compound represented by the following formula (P3-8).

[0382]

[0383] (Test Example 3-9)

[0384] The pigment of Test Example 1-11 of the first embodiment was 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).

[0385]

[0386] (Test Example 3-10)

[0387] The pigment of Test Example 1-3 of the first embodiment was 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).

[0388]

[0389] (Test Example 3-11)

[0390] <Synthesis of the pigment of Test Example 3-11>

[0391] In the synthesis process of Test Examples 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, thereby obtaining the anthraquinone derivative of Test Examples 3-11. The anthraquinone derivative of Test Examples 3-11 is a compound represented by the following formula (P3-11).

[0392]

[0393] (Test Example 3-12)

[0394] Synthesis of Precursor B9

[0395] 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 to obtain precursor B9. Precursor B9 is a compound represented by the following formula (3-a).

[0396]

[0397] Synthesis of Precursor B10

[0398] 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).

[0399]

[0400] <Synthesis of the pigment of Test Example 3-12>

[0401] In the synthesis process of the pigment 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 B10, and the anthraquinone derivative of Test Examples 3-12 was obtained. The anthraquinone derivative of Test Examples 3-12 is a compound represented by the following formula (P3-12).

[0402]

[0403] (Test Example 3-13)

[0404] The pigment of Test Example 1-15 of the first embodiment was 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).

[0405]

[0406] (Evaluation Method)

[0407] For the anthraquinone derivatives of Test Examples 3-1 to 3-13, evaluation test specimens were prepared in the same manner as in the first example, and the absorption wavelength, lightfastness, and color ratio were evaluated.

[0408] In addition, as a measure of negative absorption, the total sum of absorbances in the short wavelength region from 380 nm to 480 nm was calculated using the spectrum obtained after normalizing the ultraviolet-visible absorption spectrum so that the absorbance at the maximum absorption wavelength becomes 1.0. The total sum of absorbances is an integral value corresponding to the area of ​​the range from 380 nm to 480 nm in the spectrum after normalization. In addition, absorption in the short wavelength region from 380 nm to 480 nm is defined as negative absorption.

[0409] (Evaluation Results)

[0410] Table 3 shows the structure of the anthraquinone derivative, the absorption maximum wavelength λmax, the degree of negative absorption, the rate of change in absorbance ΔAbs, the evaluation results of lightfastness, and the dichromatic ratio for Test Examples 3-1 to 3-13. The structure of the anthraquinone derivative of each test example is represented by the following formula (I), and R, A, and Y in Table 3 1 , Y 2 , Z are R, A, and Y in the following equation (I). 1 , Y 2 Corresponds to , Z.

[0411]

[0412]

[0413] As shown in Table 3, the anthraquinone derivatives of each test example have a wavelength of maximum absorption in the wavelength range of 600 nm or more. Therefore, the anthraquinone derivatives of each test example exhibit a blue color and can be used as cyanide pigments.

[0414] In addition, in Test Examples 3-1 to 3-10, 3-12, and 3-13, where a substituted phenyl group is directly bonded to the β-position, very high light resistance is obtained compared to Test Example 3-11, where the β-position is ether-bonded.

[0415] In addition, when comparing Test Examples 3-1 to 3-4 with Test Examples 3-8 and 3-10, it was confirmed that the degree of side absorption can be reduced by having the substituent on the para group of the phenyl group on the β-position be a substituted or unsubstituted cyclohexyl group. Similarly, by comparing Test Example 3-5 with Test Example 3-9 and Test Example 3-12 with Test Example 3-13, it was confirmed that the degree of side absorption is reduced when the substituent on the para group of the β-position is a cyclohexyl group. Thus, it can be said that if the substituent on the para group of the β-position is a cyclohexyl group, an excellent blue color with reduced yellowness can be obtained in anthraquinone derivatives.

[0416] In addition, 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 on the para group of the β group is present, an effect of inhibiting the degree of side absorption is obtained. Furthermore, by comparing Test Example 3-1 with Test Examples 3-6 and 3-7, it was confirmed that when both substituents on the para group of the β group are cyclohexyl groups, the effect of inhibiting the degree of side absorption is higher compared to the case where only one is a cyclohexyl group.

[0417] In addition, good dichromatic ratios were obtained in all test examples, and it was confirmed that a high dichromatic ratio was obtained, especially when there were two hydroxyl groups on the α-site.

[0418] [Fourth Embodiment: Test Example Corresponding to the Fourth Embodiment]

[0419] In the fourth embodiment, synthesis was performed using the same precursor as in the first to third embodiments.

[0420] (Test Example 4-1)

[0421] Synthesis of Precursor B11

[0422] 4-heptyloxyphenol (0.45 parts by weight) and potassium carbonate (0.30 parts by weight) were placed in a 2-neck flask and nitrogen purging was performed. Dehydrated N-methyl-2-pyrrolidone (20 parts by weight) was added to this, and the mixture was stirred at 120°C for 3 hours. Precursor B4 (0.50 parts by weight) was added to this solution, and the mixture was stirred at 80°C for 7 hours. The reaction solution was returned to room temperature, and water / dichloromethane was added to separate the liquids. The organic layer obtained by separation was dried with sodium sulfate and then concentrated using an evaporator. Purification was performed by silica gel column chromatography (developing solvent: hexane / dichloromethane = 1 / 4, with 1 mass% of triethylamine added), and the recovered material 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).

[0423]

[0424] Synthesis of Precursor B12

[0425] Precursor B11 (0.20 parts by weight) was placed in a two-necked flask and nitrogen purging was performed. To this, nitrobenzene (4.8 parts by weight) and 4-heptylaniline (0.52 parts 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 the nitrobenzene, thereby obtaining a residue. Methanol was injected into this residue, and the precipitated powder was recovered by suction filtration to obtain precursor B12 as a purple powder. Precursor B12 is a compound represented by the following formula (4-b).

[0426]

[0427] <Synthesis of the pigment of Test Example 4-1>

[0428] In the synthesis process of the pigment of Test Example 1-14 of the first embodiment, the synthesis was carried out in the same manner except that precursor B6 was changed to precursor B12, and the anthraquinone derivative of Test Example 4-1 was obtained. The anthraquinone derivative of Test Example 4-1 is a compound represented by the following formula (P4-1).

[0429]

[0430] (Test Example 4-2)

[0431] The pigment of Test Example 1-10 of the first embodiment was 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).

[0432]

[0433] (Test Example 4-3)

[0434] The pigment of Test Example 2-8 of the second embodiment was 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).

[0435]

[0436] (Test Example 4-4)

[0437] The pigment of Test Example 1-11 of the first embodiment was the anthraquinone derivative of Test Example 4-4. The anthraquinone derivative of Test Example 4-4 is a compound represented by the following formula (P4-4).

[0438]

[0439] (Test Example 4-5)

[0440] <Synthesis of Pigments in Test Example 4-5>

[0441] In the synthesis process of the pigment 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-pentyloxybiphenylboronic acid were additionally added, and heating and stirring were performed at 80°C for 2 hours or more. After that, extraction and purification were performed in the same manner as the synthesis process of the pigment 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).

[0442]

[0443] (Test Example 4-6)

[0444] The pigment of Test Example 3-6 of the third embodiment was the anthraquinone derivative of Test Example 4-6. The anthraquinone derivative of Test Example 4-6 is a compound represented by the following formula (P4-6).

[0445]

[0446] (Test Example 4-7)

[0447] The pigment of Test Example 2-9 of the second embodiment was the anthraquinone derivative of Test Example 4-7. The anthraquinone derivative of Test Example 4-7 is a compound represented by the following formula (P4-7).

[0448]

[0449] (Test Example 4-8)

[0450] The pigment of Test Example 2-3 of the second embodiment was 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).

[0451]

[0452] (Test Example 4-9)

[0453] The pigment of Test Example 3-7 of the third embodiment was 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).

[0454]

[0455] (Test Examples 4-10 to 4-12)

[0456] Synthesis of Precursor D1

[0457] 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 to a two-necked flask, and the mixture was heated and stirred at 80°C for at least 2 hours. After confirming the completion of the reaction by thin-layer chromatography, the reaction solution was returned to room temperature, pure water was added, and extraction with ethyl acetate was performed. Sodium sulfate was added to the obtained organic layer, and after drying, 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).

[0458]

[0459] Synthesis of Precursor D2

[0460] In the synthesis process of the above precursor D1, the 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).

[0461]

[0462] Synthesis of Precursor D3

[0463] In the synthesis process of the above precursor D1, the 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).

[0464]

[0465] <Synthesis of Pigments in Test Example 4-10>

[0466] Precursor D1 (1.0 parts by weight) was placed in a two-necked flask, and after purging the system with nitrogen, tetrahydrofuran (18.0 parts by weight) was added. Subsequently, using a separate flask, a solution was 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. This solution was added to the solution containing precursor D1 in the two-necked flask and heated and stirred at 50°C. After confirming the completion of the reaction by thin-layer chromatography, the reaction solution was cooled to room temperature. Then, dilute hydrochloric acid (a mixture of 35% hydrochloric acid (20.0 parts by weight) and pure water (80.0 parts by weight)) was added, and the precipitated solid was recovered by filtration. The recovered solid (1.0 parts by weight) and zinc powder (0.5 parts by weight) were placed in a two-necked flask, and the system was purged with nitrogen. Here, dichloromethane (200.0 parts by weight) and acetic acid (18.0 parts by weight) were added and stirred at room temperature. After confirming the completion of the reaction by thin-layer chromatography, the reaction mixture was filtered, pure water was added to the filtrate, and the mixture was extracted with dichloromethane. Sodium sulfate was added to the obtained organic layer, and after drying, the solvent was removed under reduced pressure using an evaporator. The resulting 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 deep blue solid. The anthraquinone derivative of Test Example 4-10 is a compound represented by the following formula (P4-10).

[0467]

[0468] <Synthesis of the pigment of Test Example 4-11>

[0469] In the synthesis process of the pigment of Test Example 4-10 above, the synthesis was carried out in the same manner except that precursor D1 was changed to precursor D2, and the anthraquinone derivative of Test Example 4-11 was obtained. The anthraquinone derivative of Test Example 4-11 is a compound represented by the following formula (P4-11).

[0470]

[0471] <Synthesis of the pigment of Test Example 4-12>

[0472] In the synthesis process of the pigment of Test Example 4-10 above, the synthesis was carried out in the same manner except that precursor D1 was changed to 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).

[0473]

[0474] (Test Example 4-13)

[0475] <Synthesis of the pigment of Test Example 4-13>

[0476] 4-heptyloxyphenol (0.36 parts by weight) and potassium carbonate (0.24 parts by weight) were placed in a 2-neck flask and nitrogen was applied. Dehydrated N-methyl-2-pyrrolidone (10 parts by weight) was added and stirred at 120°C for 3 hours. Then, precursor A2 (0.50 parts by weight) was added and stirred at 120°C for 7 hours. The reaction solution was returned to room temperature, water / dichloromethane was added, and the mixture was separated. The obtained organic layer was dried with sodium sulfate and concentrated in an evaporator. Then, purification was performed by silica gel column chromatography, and the anthraquinone derivative of Test Example 4-13 was obtained as a blue powder by drying under reduced pressure at 60°C. The anthraquinone derivative of Test Example 4-13 is a compound represented by the following formula (P4-13).

[0477]

[0478] (Test Example 4-14)

[0479] <Synthesis of the pigment of Test Example 4-14>

[0480] In the synthesis process of the pigment of Test Example 4-13 above, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylphenol, and the 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).

[0481]

[0482] (Test Example 4-15)

[0483] <Synthesis of Pigments in Test Example 4-15>

[0484] In the synthesis process of the pigment of Test Example 4-13 above, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylcyclohexylphenol, and the 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). In addition, the anthraquinone derivative of Test Example 4-15 is the same compound as the anthraquinone derivative of Test Example 3-11.

[0485]

[0486] (Evaluation Method)

[0487] <Evaluation of Absorption Wavelength and Lightfastness>

[0488] For the anthraquinone derivatives of Test Examples 4-1 to 4-15, evaluation test specimens were prepared in the same manner as in the first example, and the absorption wavelength and light resistance were evaluated.

[0489] <Calculation of Total Energy Difference ΔE>

[0490] For the anthraquinone derivatives of Test Examples 4-1 to 4-15, the total energy difference ΔE before and after the reaction represented by the reaction scheme (4-2) described above was calculated. The calculation of the total energy difference ΔE was performed using the quantum chemistry calculation program GAMESS, with the functional being B3LYP and the basis function being 6-31G(d), in the following order.

[0491] (1) For each anthraquinone derivative of the test example, structural optimization was performed by SCF calculation, and the total energy Ep of the molecule in the optimized structure was obtained.

[0492] (2) The structure in which hydrogen is added to the anthraquinone backbone of the anthraquinone derivative after structural optimization was used as the initial structure of the hydrogen adduct, and the structure of the hydrogen adduct was optimized by SCF calculation. Then, for the hydrogen adduct, the total energy Ek of the molecule in the optimized structure was obtained.

[0493] Hydrogen adducts 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 thought that the most stable structure, which is the structure with the most stable energy, is likely to be formed. Therefore, the most stable structure was adopted as the stereostructure of the hydrogen adduct. The most stable structure was searched by performing a Relaxed Scan calculation that rotates the dihedral angle at the location where the substituent at the β-position is attached.

[0494] (3) The total energy difference ΔE was calculated using the formula ΔE=Ek-Ep.

[0495] (Evaluation Results)

[0496] Table 4 shows the structure of the anthraquinone derivative, absorption maximum wavelength λmax, total energy difference ΔE, absorbance change rate ΔAbs, and lightfastness evaluation results for Test Examples 4-1 to 4-15. The structure of the anthraquinone derivative of each test example is represented by the following formula (II), and R, A, X, and Y in Table 4 1 , Y 2 , Z are R, A, X, and Y in the following equation (II). 1 , Y 2 Corresponds to , Z.

[0497]

[0498]

[0499] As shown in Table 4, the anthraquinone derivatives of each test example can be used as cyanide pigments in that they have a wavelength of maximum absorption in the wavelength range of 580 nm or higher.

[0500] In addition, high light resistance is obtained in Test Examples 4-1 to 4-12, where the total energy difference ΔE is -16 kcal / mol or higher. 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 of Table 4, it is suggested that if the structure does not have a hydroxyl group on the α-site, or if the structure has a substituent directly bonded to the β-site, the total energy difference ΔE increases and high light resistance is obtained.

[0501] [Fifth Embodiment: Test Example Corresponding to the Fifth Embodiment]

[0502] In the fifth embodiment, synthesis was performed using the same precursor as in the first to fourth embodiments.

[0503] (Test Example 5-1)

[0504] The pigment of Test Example 1-10 of the first embodiment was 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).

[0505]

[0506] (Test Example 5-2)

[0507] The pigment of Test Example 1-11 of the first embodiment was 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).

[0508]

[0509] (Test Example 5-3)

[0510] <Synthesis of the pigment of Test Example 5-3>

[0511] In the synthesis process of the pigment of Test Example 1-1 of the first embodiment, precursor A2 was changed to precursor A3, and 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-(trans-4-pentylcyclohexyl)phenylboronic acid were additionally added, and heating and stirring were performed at 80°C for 2 hours or more. After that, extraction and purification were performed in the same manner as the synthesis process of the pigment of 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).

[0512]

[0513] (Test Example 5-4)

[0514] The pigment of Test Example 1-2 of the first embodiment was 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).

[0515]

[0516] (Test Example 5-5)

[0517] <Synthesis of the pigment of Test Example 5-5>

[0518] In the synthesis process of the pigment of Test Examples 4-10 of the 4th 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, and the anthraquinone derivative of Test Example 5-5 was obtained. The anthraquinone derivative of Test Example 5-5 is a compound represented by the following formula (P5-5).

[0519]

[0520] (Test Example 5-6)

[0521] The pigment of Test Example 4-11 of the 4th Example was 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).

[0522]

[0523] (Test Example 5-7)

[0524] <Synthesis of the pigment of Test Example 5-7>

[0525] In the synthesis process of the pigment of Test Examples 4-10 of the 4th embodiment, the synthesis was carried out in the same manner except that 4-methoxybenzenethiol was changed to 4-heptyloxybenzenethiol, and the anthraquinone derivative of Test Examples 5-7 was obtained. The anthraquinone derivative of Test Examples 5-7 is a compound represented by the following formula (P5-7).

[0526]

[0527] (Test Example 5-8)

[0528] <Synthesis of Pigments in Test Example 5-8>

[0529] In the synthesis process of the pigment of Test Examples 4-10 of the 4th 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, thereby obtaining the anthraquinone derivative of Test Examples 5-8. The anthraquinone derivative of Test Examples 5-8 is a compound represented by the following formula (P5-8).

[0530]

[0531] (Test Example 5-9)

[0532] Synthesis of Precursor B13

[0533] 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, thereby obtaining precursor B13. Precursor B13 is a compound represented by the following formula (5-a).

[0534]

[0535] <Synthesis of the pigment of Test Example 5-9>

[0536] In the synthesis process of the pigment 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 B13 and 4-dimethylaminophenylboronic acid was changed to 4-heptyloxyphenylboronic acid, thereby obtaining the anthraquinone derivative of Test Example 5-9. The anthraquinone derivative of Test Example 5-9 is a compound represented by the following formula (P5-9). In addition, the anthraquinone derivative of Test Example 5-9 is the same compound as the anthraquinone derivative of Test Example 1-15.

[0537]

[0538] (Test Example 5-10)

[0539] The pigment of Test Example 4-1 of the 4th Example was the anthraquinone derivative of Test Example 5-10. The anthraquinone derivative of Test Example 5-10 is a compound represented by the following formula (P5-10).

[0540]

[0541] (Test Example 5-11)

[0542] The pigment of Test Example 4-13 of the 4th Example was the anthraquinone derivative of Test Example 5-11. The anthraquinone derivative of Test Example 5-11 is a compound represented by the following formula (P5-11).

[0543]

[0544] (Test Example 5-12)

[0545] The pigment of Test Example 4-14 of the 4th Example was 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).

[0546]

[0547] (Evaluation Method)

[0548] <Evaluation of Absorption Wavelength and Lightfastness>

[0549] For the anthraquinone derivatives of Test Examples 5-1 to 5-12, evaluation test specimens were prepared in the same manner as in the first example, and the absorption wavelength and light resistance were evaluated.

[0550] Thermogravimetric measurement

[0551] For the anthraquinone derivatives of Test Examples 5-1 to 5-12, weight measurements were performed by increasing the temperature from 30°C to 550°C using a differential thermal simultaneous thermogravimetric measurement device (STA7200RV, manufactured by Hitachi High-Tech Science) under conditions of gas flow rate: 200 mL / min and temperature increase: 10°C min. Air was used as the gas. Based on the weight at the start of the temperature increase, the 10% weight loss temperature was determined.

[0552] (Evaluation Results)

[0553] Table 5 shows the evaluation results for the structure of the anthraquinone derivative, absorption maximum wavelength λmax, 10% weight loss temperature, absorbance change rate ΔAbs, and 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, and Y in Table 5 1 , Y 2 , Z are R, A, X, and Y in the following equation (II). 1 , Y 2 Corresponds to , Z.

[0554]

[0555]

[0556] As shown in Table 5, the anthraquinone derivatives of each test example can be used as cyanide pigments in that they have a wavelength of maximum absorption in the wavelength range of 580 nm or higher.

[0557] In addition, 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 5-11 and 5-12, where the 10% weight loss temperature is less than 350°C, light resistance is low.

[0558] From the results in Table 5, it is suggested that structures lacking a hydroxyl group on the α-position, or structures with a substituent directly bonded to the β-position, result in a higher 10% weight loss temperature and higher light resistance. Furthermore, it was confirmed that structures where X is a -NH- atom tend to exhibit higher 10% weight loss temperatures and light resistance compared to structures where X is a sulfur atom. In addition, Y 1 , Y 2 It was confirmed that if the electron donor group is an alkylamino group, the 10% weight loss temperature and light resistance tend to decrease.

[0559] [6th Embodiment: Test Example Corresponding to the 6th Embodiment]

[0560] In the 6th embodiment, synthesis was performed using the same precursor as in the 1st to 5th embodiments.

[0561] (Test Example 6-1)

[0562] The pigment of Test Example 1-11 of the first embodiment was 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).

[0563]

[0564] (Test Example 6-2)

[0565] The pigment of Test Example 2-8 of the second embodiment was 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).

[0566]

[0567] (Test Example 6-3)

[0568] The pigment of Test Example 1-3 of the first embodiment was 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).

[0569]

[0570] (Test Example 6-4)

[0571] The pigment of Test Example 1-2 of the first embodiment was 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).

[0572]

[0573] (Test Example 6-5)

[0574] <Synthesis of the pigment of Test Example 6-5>

[0575] In the synthesis process of the pigment of Test Example 1-1 of the first embodiment, 1.2 equivalents of 4-(trans-4-pentylcyclohexyl)phenylboronic 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-pentyloxybiphenylboronic acid were additionally added, and heating and stirring were performed at 80°C for 2 hours or more. After that, extraction and purification were performed in the same manner as the synthesis process of the pigment of Test Example 1-1, 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).

[0576]

[0577] (Test Example 6-6)

[0578] <Synthesis of the pigment of Test Example 6-6>

[0579] In the synthesis process of the pigment of Test Example 1-1 of the first embodiment, 1.2 equivalents of 4-(trans-4-pentylcyclohexyl)phenylboronic 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-monobutylaminophenylboronic acid were additionally added, and the mixture was heated and stirred at 80°C for at least 2 hours. After that, extraction and purification were performed in the same manner as the synthesis process of the pigment of Test Example 1-1, 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).

[0580]

[0581] (Test Example 6-7)

[0582] The pigment of Test Example 5-5 of the 5th Example was 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).

[0583]

[0584] (Test Example 6-8)

[0585] The pigment of Test Example 4-12 of the 4th Example was 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).

[0586]

[0587] (Test Example 6-9)

[0588] The pigment of Test Example 5-7 of the 5th Example was the anthraquinone derivative of Test Example 6-9. The anthraquinone derivative of Test Example 6-9 is a compound represented by the following formula (P6-9).

[0589]

[0590] (Test Example 6-10)

[0591] Synthesis of Precursor B14

[0592] In the synthesis process of precursor A2 of the first embodiment, precursor A1 was changed to precursor B4, and 4-heptylaniline was changed to 4-heptyloxyaniline, except that the synthesis was carried out in the same manner to obtain precursor B14. Precursor B14 is a compound represented by the following formula (6-a).

[0593]

[0594] <Synthesis of Pigments in Test Examples 6-10>

[0595] In the synthesis process of the pigment 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, thereby obtaining 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).

[0596]

[0597] (Test Example 6-11)

[0598] <Synthesis of the pigment of Test Example 6-11>

[0599] In the synthesis process of the pigment of Test Example 4-13 of the 4th 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).

[0600]

[0601] (Test Example 6-12)

[0602] Synthesis of Precursor D4

[0603] In the synthesis process of precursor B11 of the fourth example, 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).

[0604]

[0605] <Synthesis of Pigments in Test Example 6-12>

[0606] In the synthesis process of the pigment of Test Examples 4-10 of the 4th 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 Examples 6-12 was obtained. The anthraquinone derivative of Test Examples 6-12 is a compound represented by the following formula (P6-12).

[0607]

[0608] (Test Example 6-13)

[0609] <Synthesis of the pigment of Test Example 6-13>

[0610] In the synthesis process of the pigment of Test Examples 4-13 of the 4th 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 Examples 6-13 was obtained. The anthraquinone derivative of Test Examples 6-13 is a compound represented by the following formula (P6-13). In addition, the anthraquinone derivative of Test Examples 6-13 is the same compound as the anthraquinone derivative of Test Examples 1-13.

[0611]

[0612] (Evaluation Method)

[0613] <Evaluation of Absorption Wavelength and Coloring Power>

[0614] For the anthraquinone derivatives of Test Examples 6-1 to 6-13, evaluation test specimens were prepared in the same manner as in the first example.

[0615] For each test specimen for evaluation in each test example, the ultraviolet-visible absorption spectrum was measured using an automatic spectrophotometer (U-4100, manufactured by Hitachi Seisakusho). Then, for wavelengths in the measurement range from 360 nm to 800 nm, the absorption maximum wavelength λmax and the absorbance at the corresponding wavelength were determined.

[0616] In evaluating the coloring power, a case where the absorbance is 0.40 or higher was called Good “G”, and a case where the absorbance is less than 0.40 was called Bad “B”.

[0617] Calculation of Transition Dipole Moment

[0618] For the anthraquinone derivatives of Test Examples 6-1 to 6-13, the transition dipole moments were calculated using the time-dependent density functional method. Specifically, the transition dipole moments of each anthraquinone derivative in vacuum were calculated using the quantum chemistry computation program GAMESS, with B3LYP as the functional and 6-31G(d) as the basis function. The transition dipole moment is a vector containing x, y, and z components. The value obtained by raising the sum of the squares of each component to the power of 1 / 2 is the magnitude of the transition dipole moment μ(μ=(x 2 +y 2 +z 2 ) 1 / 2 He said.

[0619] (Evaluation Results)

[0620] Table 6 shows the evaluation results for the structure of the anthraquinone derivative, each component of the transition dipole moment and the magnitude of the transition dipole moment μ, the absorption maximum wavelength λmax, absorbance, and coloring power for Test Examples 6-1 to 6-13. The structure of the anthraquinone derivative of each test example is represented by the following formula (II), and R, A, X, and Y in Table 6 1 , Y 2 , Z are R, A, X, and Y in the following equation (II). 1 , Y 2 Corresponds to , Z.

[0621]

[0622]

[0623] As shown in Table 6, in Test Examples 6-1 to 6-10, where the magnitude of the transition dipole moment μ is 3.30D or greater, higher absorbance is obtained compared to Test Examples 6-11 to 6-13, where the magnitude of the transition dipole moment μ is less than 3.30D, and thus the coloring power is good. In addition, the anthraquinone derivatives of Test Examples 6-1 to 6-10 tend to have high absorption maximum wavelengths and have absorption maximum wavelengths in the wavelength range of 580 nm or higher, so they can be used as cyanide-based pigments.

[0624] From the results in Table 6, it is suggested that the transition dipole moment increases at the point where a substituent is directly bonded to the β site. In addition, among Test Examples 6-1 to 6-10, Y 1 , Y 2 It was confirmed that if the group is an electron-donating group such as an alkylamino group, the transition dipole moment increases and a high absorbance is obtained.

[0625] [7th Embodiment: Test Example Corresponding to the 7th Embodiment]

[0626] In the 7th embodiment, synthesis was performed using the same precursor as in the 1st to 6th embodiments.

[0627] (Test Example 7-1)

[0628] The pigment of Test Example 1-11 of the first embodiment was the anthraquinone derivative of Test Example 7-1. The anthraquinone derivative of Test Example 7-1 is a compound represented by the following formula (P7-1).

[0629]

[0630] (Test Example 7-2)

[0631] The pigment of Test Example 2-8 of the second embodiment was the anthraquinone derivative of Test Example 7-2. The anthraquinone derivative of Test Example 7-2 is a compound represented by the following formula (P7-2).

[0632]

[0633] (Test Example 7-3)

[0634] The pigment of Test Example 1-3 of the first embodiment was the anthraquinone derivative of Test Example 7-3. The anthraquinone derivative of Test Example 7-3 is a compound represented by the following formula (P7-3).

[0635]

[0636] (Test Example 7-4)

[0637] The pigment of Test Example 1-2 of the first embodiment was the anthraquinone derivative of Test Example 7-4. The anthraquinone derivative of Test Example 7-4 is a compound represented by the following formula (P7-4).

[0638]

[0639] (Test Example 7-5)

[0640] Synthesis of Precursor A4

[0641] In the synthesis process of precursor A2 of the first embodiment, the 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).

[0642]

[0643] <Synthesis of the pigment of Test Example 7-5>

[0644] In the synthesis process of the pigment 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 A4 and 4-dimethylaminophenylboronic acid was changed to 4-heptyloxyphenylboronic acid, thereby obtaining 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).

[0645]

[0646] (Test Example 7-6)

[0647] <Synthesis of the pigment of Test Example 7-6>

[0648] In the synthesis process of the pigment 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 A4 and 4-dimethylaminophenylboronic acid was changed to 4-pentylcyclohexylphenylboronic acid, thereby obtaining 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). In addition, the anthraquinone derivative of Test Example 7-6 is the same compound as the anthraquinone derivative of Test Example 2-3.

[0649]

[0650] (Test Example 7-7)

[0651] The pigment of Test Example 5-5 of the 5th Example was 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).

[0652]

[0653] (Test Example 7-8)

[0654] The pigment of Test Example 5-7 of the 5th Example was 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).

[0655]

[0656] (Test Example 7-9)

[0657] <Synthesis of the pigment of Test Example 7-9>

[0658] In the synthesis process of the pigment of Test Examples 4-10 of the 4th embodiment, the synthesis was carried out in the same manner except that precursor D1 was changed to precursor D3 and 4-methoxybenzenethiol was changed to 4-heptyloxybenzenethiol, thereby obtaining the anthraquinone derivative of Test Examples 7-9. The anthraquinone derivative of Test Examples 7-9 is a compound represented by the following formula (P7-9).

[0659]

[0660] (Test Example 7-10)

[0661] <Synthesis of Pigments in Test Examples 7-10>

[0662] In the synthesis process of the pigment of Test Examples 4-13 of the 4th embodiment, the synthesis was carried out in the same manner except that precursor A2 was changed to precursor A3, and the anthraquinone derivative of Test Examples 7-10 was obtained. The anthraquinone derivative of Test Examples 7-10 is a compound represented by the following formula (P7-10). In addition, the anthraquinone derivative of Test Examples 7-10 is the same compound as the anthraquinone derivative of Test Examples 1-12.

[0663]

[0664] (Test Example 7-11)

[0665] The pigment of Test Examples 6-11 of the 6th Example was the anthraquinone derivative of Test Examples 7-11. The anthraquinone derivative of Test Examples 7-11 is a compound represented by the following formula (P7-11).

[0666]

[0667] (Test Example 7-12)

[0668] The pigment of Test Examples 6-12 of the 6th Example was the anthraquinone derivative of Test Examples 7-12. The anthraquinone derivative of Test Examples 7-12 is a compound represented by the following formula (P7-12).

[0669]

[0670] (Test Example 7-13)

[0671] Synthesis of Precursor D5

[0672] In the synthesis process of precursor B11 of the fourth example, precursor B4 was changed to precursor A1, and 4-heptyloxyphenol was changed to 4-pentylcyclohexylphenol; otherwise, the synthesis was carried out in the same manner to obtain precursor D5. Precursor D5 is a compound represented by the following formula (7-b).

[0673]

[0674] <Synthesis of Pigments in Test Example 7-13>

[0675] In the synthesis process of the pigment of Test Examples 4-10 of the 4th embodiment, the synthesis was carried out in the same manner except that precursor D1 was changed to precursor D5 and 4-methoxybenzenethiol was changed to 4-heptyloxybenzenethiol, and the anthraquinone derivative of Test Examples 7-13 was obtained. The anthraquinone derivative of Test Examples 7-13 is a compound represented by the following formula (P7-13).

[0676]

[0677] (Evaluation Method)

[0678] <Evaluation of Absorption Wavelength and Coloring Power>

[0679] For the anthraquinone derivatives of Test Examples 7-1 to 7-13, evaluation test specimens were prepared in the same manner as in the first example. Then, in the same manner as in the sixth example, the absorption maximum wavelength λmax and the absorbance at the said wavelength were determined, and the coloring power was evaluated.

[0680] Calculation of Molecular Orbital Coefficients

[0681] For the anthraquinone derivatives of Test Examples 7-1 to 7-13, molecular orbital coefficients were calculated using the density functional method. Specifically, using the quantum chemistry computation program GAMESS, structural optimization was performed on the anthraquinone derivatives with B3LYP as the functional and 6-31G(d) as the basis function, and molecular orbital coefficients in the optimized structure were obtained. C in Equation (7-1) above 11 , C 12 , C 21 , C 22 For each carbon atom, the square root M of the sum of the squares of the coefficients corresponding to the orbitals on the carbon atom 11 , M 12 , M 21 , M 22 Calculate and M 11 , M 12 , M 21 , M 22 The average Mv was calculated. Under the conditions of this calculation, 15 orbitals are assigned to the carbon atom, and molecular orbital coefficients are calculated for each orbital.

[0682] (Evaluation Results)

[0683] Table 7 shows the evaluation results for 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, and Y in Table 7 1 , Y 2 , Z are R, A, X, and Y in the following equation (II). 1 , Y 2 Corresponds to , Z.

[0684]

[0685]

[0686] As shown in Table 7, Test Examples 7-1 to 7-9, in which the average Mv is 0.03 or higher, have a higher absorbance and better coloring power compared to Test Examples 7-10 to 7-13, in which the average Mv is less than 0.03. In addition, the anthraquinone derivatives of Test Examples 7-1 to 7-9 can be used as cyanide pigments because they have a wavelength of maximum absorption in the wavelength range of 580 nm or higher.

[0687] From the results in Table 7, it is suggested that the average Mv increases when a substituent is directly bonded to the β site. Furthermore, from the comparison between Test Example 7-1 and Test Example 7-5, and 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 for high absorbance to be obtained. In addition, from Test Examples 7-3, 7-4, and 7-9, Y 1 , Y 2 It was confirmed that if the group is an electron-donating group such as an alkylamino group, the average Mv increases and a high absorbance is obtained.

[0688] [Eighth Embodiment: Test Example Corresponding to the Eighth Embodiment]

[0689] In the 8th embodiment, synthesis was performed using the same precursor as in the 1st to 7th embodiments.

[0690] (Test Example 8-1)

[0691] The pigment of Test Example 4-1 of the 4th Example was the anthraquinone derivative of Test Example 8-1. The anthraquinone derivative of Test Example 8-1 is a compound represented by the following formula (P8-1).

[0692]

[0693] (Test Example 8-2)

[0694] Synthesis of Precursor B15

[0695] In the synthesis process of precursor B11 of the fourth example, the synthesis was carried out in the same manner except that 4-heptyloxyphenol was changed to 4-heptylphenol, and precursor B15 was obtained. Precursor B15 is a compound represented by the following formula (8-a).

[0696]

[0697] Synthesis of Precursor B16

[0698] In the synthesis process of precursor B12 of the fourth example, the synthesis was carried out in the same manner except that precursor B11 was changed to precursor B15, and precursor B16 was obtained. Precursor B16 is a compound represented by the following formula (8-b).

[0699]

[0700] <Synthesis of the pigment of Test Example 8-2>

[0701] In the synthesis process of the pigment of Test Example 1-14 of the first embodiment, the synthesis was carried out in the same manner except that precursor B6 was changed to precursor B16, and the anthraquinone derivative of Test Example 8-2 was obtained. The anthraquinone derivative of Test Example 8-2 is a compound represented by the following formula (P8-2).

[0702]

[0703] (Test Example 8-3)

[0704] Synthesis of Precursor B17

[0705] In the synthesis process of precursor B12 of the fourth example, the synthesis was carried out in the same manner except that 4-heptylaniline was changed to N,N-dimethyl-1,4-phenylenediamine to obtain precursor B17. Precursor B17 is a compound represented by the following formula (8-c).

[0706]

[0707] <Synthesis of the pigment of Test Example 8-3>

[0708] In the synthesis process of the pigment of Test Example 1-14 of the first embodiment, the synthesis was carried out in the same manner except that precursor B6 was changed to precursor B17, and the anthraquinone derivative of Test Example 8-3 was obtained. The anthraquinone derivative of Test Example 8-3 is a compound represented by the following formula (P8-3).

[0709]

[0710] (Test Example 8-4)

[0711] Synthesis of Precursor B18

[0712] In the synthesis process of precursor B12 of the fourth example, the synthesis was carried out in the same manner except that 4-heptylaniline was changed to 4-aminobenzonitrile, and precursor B18 was obtained. Precursor B18 is a compound represented by the following formula (8-d).

[0713]

[0714] <Synthesis of the pigment of Test Example 8-4>

[0715] In the synthesis process of the pigment of Test Example 1-14 of the first embodiment, the synthesis was carried out in the same manner except that precursor B6 was changed to precursor B18, and the anthraquinone derivative of Test Example 8-4 was obtained. The anthraquinone derivative of Test Example 8-4 is a compound represented by the following formula (P8-4).

[0716]

[0717] (Test Example 8-5)

[0718] The pigment of Test Example 1-15 of the first embodiment was the anthraquinone derivative of Test Example 8-5. The anthraquinone derivative of Test Example 8-5 is a compound represented by the following formula (P8-5).

[0719]

[0720] (Test Example 8-6)

[0721] The pigment of Test Example 3-12 of the third embodiment was the anthraquinone derivative of Test Example 8-6. The anthraquinone derivative of Test Example 8-6 is a compound represented by the following formula (P8-6).

[0722]

[0723] (Test Example 8-7)

[0724] The pigment of Test Example 1-14 of the first embodiment was the anthraquinone derivative of Test Example 8-7. The anthraquinone derivative of Test Example 8-7 is a compound represented by the following formula (P8-7).

[0725]

[0726] (Test Example 8-8)

[0727] Synthesis of Precursor B19

[0728] Precursor B4 (0.20 parts by weight), 4-heptyloxyaniline (1.2 parts by weight), and copper powder (0.053 parts by weight) were placed in a 2-neck flask and nitrogen purging was performed. N-methyl-2-pyrrolidone (3.0 parts by weight) was added to this, and the mixture was stirred at 180°C for 10 hours. The reaction solution was extracted with pure water / dichloromethane, and the resulting organic layer was dried with sodium sulfate, filtered, and then concentrated in an evaporator. Then, precursor B19 was obtained by purification using silica gel column chromatography (developing solvent: hexane / ethyl acetate = 8 / 1). Precursor B19 is a compound represented by the following formula (8-e).

[0729]

[0730] Synthesis of Precursor B20

[0731] In the synthesis process of precursor B12 of the fourth example, the synthesis was carried out in the same manner except that precursor B11 was changed to precursor B19, and precursor B20 was obtained. Precursor B20 is a compound represented by the following formula (8-f).

[0732]

[0733] <Synthesis of the pigment of Test Example 8-8>

[0734] In the synthesis process of the pigment 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 B20, and the anthraquinone derivative of Test Example 8-8 was obtained. The anthraquinone derivative of Test Example 8-8 is a compound represented by the following formula (P8-8).

[0735]

[0736] (Test Example 8-9)

[0737] The pigment of Test Example 4-13 of the 4th Example was the anthraquinone derivative of Test Example 8-9. The anthraquinone derivative of Test Example 8-9 is a compound represented by the following formula (P8-9).

[0738]

[0739] (Test Example 8-10)

[0740] The pigment of Test Example 2-8 of the second embodiment was the anthraquinone derivative of Test Example 8-10. The anthraquinone derivative of Test Example 8-10 is a compound represented by the following formula (P8-10).

[0741]

[0742] (Test Example 8-11)

[0743] <Synthesis of Pigments in Test Examples 8-11>

[0744] In the synthesis process of the pigment 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-piperidyl-1-yl)phenylboronic acid, and the anthraquinone derivative of Test Example 8-11 was obtained. The anthraquinone derivative of Test Example 8-11 is a compound represented by the following formula (P8-11).

[0745]

[0746] (Test Example 8-12)

[0747] <Synthesis of Pigments in Test Examples 8-12>

[0748] In the synthesis process of the above precursor B19, the synthesis was carried out in the same manner except that precursor B4 was changed to precursor A2, and the anthraquinone derivative of Test Examples 8-12 was obtained. The anthraquinone derivative of Test Examples 8-12 is a compound represented by the following formula (P8-12).

[0749]

[0750] (Evaluation Method)

[0751] For the anthraquinone derivatives of Test Examples 8-1 to 8-12, evaluation test specimens were prepared in the same manner as in the first example, and the absorption maximum wavelength λmax was determined. In addition, in the same manner as in the first example, a lightfastness test was performed on the evaluation test specimens, and the rate of change in absorbance ΔAbs before and after the lightfastness test was calculated. In evaluating lightfastness, a case where ΔAbs was 2% or less was designated as "Good" (G), and a case where ΔAbs exceeded 2% was designated as "Bad" (B).

[0752] (Evaluation Results)

[0753] Table 8 shows the evaluation results of the structure of the anthraquinone derivative, the absorption maximum wavelength λmax, the rate of change in absorbance ΔAbs, and light resistance for Test Examples 8-1 to 8-12. The structure of the anthraquinone derivative of each test example is represented by the following formula (I), and R, A, and Y in Table 8 1 , Y 2 , Z are R, A, and Y in the following equation (I). 1 , Y 2 Corresponds to , Z.

[0754]

[0755]

[0756] As shown in Table 8, the anthraquinone derivatives of Test Examples 8-1 to 8-8 have a wavelength of maximum absorption in the wavelength range of 600 nm or more. Therefore, the anthraquinone derivatives of Test Examples 8-1 to 8-8 exhibit a blue color and can be used as cyanide pigments. In addition, high lightfastness is obtained in Test Examples 8-1 to 8-8.

[0757] The anthraquinone derivatives of Test Examples 8-9 to 8-12 have a hydroxyl group on the α-position. In Test Examples 8-9 and 8-12, where the β-position is an ether bond or a secondary amine, the absorption change rate ΔAbs is 25% or more, and the light resistance is very low. In Test Examples 8-10 and 8-11, where a substituted phenyl group is directly bonded to the β-position, the light resistance is significantly improved compared to Test Examples 8-9 and 8-12.

[0758] In addition, in Test Examples 8-1 to 8-8, which do not have a hydroxyl group on the α-position, higher light resistance than in Test Examples 8-10 and 8-11 is obtained regardless of whether the β-position is directly bonded. Therefore, it is suggested that in the anthraquinone derivatives of Test Examples 8-1 to 8-8, high light resistance is obtained due to the structure in which the substituent on the α-position is an amino group or an anilino group.

[0759] [9th Embodiment: Test Example Corresponding to the 9th Embodiment]

[0760] In the ninth embodiment, synthesis was performed using the same precursor as in the first to eighth embodiments.

[0761] Synthesis of Precursor D6

[0762] In the synthesis process of precursor D1 of the 4th test example, precursor D6 was obtained by performing the synthesis in the same manner except that 4-pentylcyclohexylphenylboronic acid was changed to 4-heptyloxyphenylboronic acid and precursor A1 was changed to precursor B4. Precursor D6 is a compound represented by the following formula (9-a). Also, precursor D6 is the same compound as precursor B7.

[0763]

[0764] Synthesis of Precursor D7

[0765] In the synthesis process of precursor D1 of the 4th test example, the synthesis was carried out in the same manner except that 4-pentylcyclohexylphenylboronic acid was changed to 4-(dimethylamino)phenylboronic acid, and precursor D7 was obtained. Precursor D7 is a compound represented by the following formula (9-b).

[0766]

[0767] Synthesis of Precursor D8

[0768] In the synthesis process of precursor D1 of the 4th test example, instead of adding 1.2 parts by weight of 4-pentylcyclohexylphenylboronic acid, 0.7 parts by weight of 4-pentylcyclohexylphenylboronic acid was added and the reaction solution was stirred for 1 hour, after which 0.5 parts by weight of 4-monobutylaminophenylboronic acid was additionally added and heated and stirred at 80°C for 2 hours or more. After that, extraction and purification were performed in the same manner as the synthesis process of precursor D1 to obtain precursor D8. Precursor D8 is a compound represented by the following formula (9-c).

[0769]

[0770] (Test Example 9-1)

[0771] <Synthesis of the pigment of Test Example 9-1>

[0772] In the synthesis process of the pigment of Test Example 4-10 of the 4th 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-heptylbenzenethiol, thereby obtaining the anthraquinone derivative of Test Example 9-1. The anthraquinone derivative of Test Example 9-1 is a compound represented by the following formula (P9-1).

[0773]

[0774] (Test Example 9-2)

[0775] The pigment of Test Example 5-5 of the 5th Example was the anthraquinone derivative of Test Example 9-2. The anthraquinone derivative of Test Example 9-2 is a compound represented by the following formula (P9-2).

[0776]

[0777] (Test Example 9-3)

[0778] The pigment of Test Example 4-11 of the 4th Example was the anthraquinone derivative of Test Example 9-3. The anthraquinone derivative of Test Example 9-3 is a compound represented by the following formula (P9-3).

[0779]

[0780] (Test Example 9-4)

[0781] The pigment of Test Example 5-8 of the 5th Example was the anthraquinone derivative of Test Example 9-4. The anthraquinone derivative of Test Example 9-4 is a compound represented by the following formula (P9-4).

[0782]

[0783] (Test Example 9-5)

[0784] <Synthesis of the pigment of Test Example 9-5>

[0785] In the synthesis process of the pigment of Test Examples 4-10 of the 4th embodiment, the synthesis was carried out in the same manner except that precursor D1 was changed to precursor D6 and 4-methoxybenzenethiol was changed to 4-heptylbenzenethiol, thereby obtaining the anthraquinone derivative of Test Example 9-5. The anthraquinone derivative of Test Example 9-5 is a compound represented by the following formula (P9-5).

[0786]

[0787] (Test Example 9-6)

[0788] The pigment of Test Example 5-7 of the 5th Example was the anthraquinone derivative of Test Example 9-6. The anthraquinone derivative of Test Example 9-6 is a compound represented by the following formula (P9-6).

[0789]

[0790] (Test Example 9-7)

[0791] <Synthesis of the pigment of Test Example 9-7>

[0792] In the synthesis process of the pigment of Test Examples 4-10 of the 4th embodiment, the synthesis was carried out in the same manner except that precursor D1 was changed to precursor D7 and 4-methoxybenzenethiol was changed to 4-heptyloxybenzenethiol, thereby obtaining the anthraquinone derivative of Test Example 9-7. The anthraquinone derivative of Test Example 9-7 is a compound represented by the following formula (P9-7).

[0793]

[0794] (Test Example 9-8)

[0795] <Synthesis of the pigment of Test Example 9-8>

[0796] In the synthesis process of the pigment of Test Examples 4-10 of the 4th embodiment, the synthesis was carried out in the same manner except that precursor D1 was changed to precursor D7 and 4-methoxybenzenethiol was changed to 4-cyanobenzenethiol, thereby obtaining the anthraquinone derivative of Test Examples 9-8. The anthraquinone derivative of Test Examples 9-8 is a compound represented by the following formula (P9-8).

[0797]

[0798] (Test Example 9-9)

[0799] The pigment of Test Example 7-9 of the 7th Example was the anthraquinone derivative of Test Example 9-9. The anthraquinone derivative of Test Example 9-9 is a compound represented by the following formula (P9-9).

[0800]

[0801] (Test Example 9-10)

[0802] <Synthesis of Pigments in Test Examples 9-10>

[0803] In the synthesis process of the pigments of Test Examples 4-10 of the 4th embodiment, the synthesis was carried out in the same manner except that precursor D1 was changed to precursor D8 and 4-methoxybenzenethiol was changed to 4-heptyloxybenzenethiol, thereby obtaining the anthraquinone derivatives of Test Examples 9-10. The anthraquinone derivatives of Test Examples 9-10 are compounds represented by the following formula (P9-10).

[0804]

[0805] (Test Example 9-11)

[0806] <Synthesis of Pigments in Test Examples 9-11>

[0807] In the synthesis process of the pigment 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-heptyloxyphenylboronic acid, and the anthraquinone derivative of Test Example 9-11 was obtained. The anthraquinone derivative of Test Example 9-11 is a compound represented by the following formula (P9-11).

[0808]

[0809] (Test Example 9-12)

[0810] The pigment of Test Examples 6-12 of the 6th Example was the anthraquinone derivative of Test Examples 9-12. The anthraquinone derivative of Test Examples 9-12 is a compound represented by the following formula (P9-12).

[0811]

[0812] (Evaluation Method)

[0813] For the anthraquinone derivatives of Test Examples 9-1 to 9-12, evaluation test specimens were prepared in the same manner as in the first example, and the absorption maximum wavelength λmax was determined.

[0814] In evaluating the absorption wavelength, when the maximum absorption wavelength λmax is 580 nm or more and 670 nm or less, the blue light is called "Good" (G), and when the maximum absorption wavelength λmax is less than 580 nm or exceeds 670 nm, the blue light is called "Bad" (B).

[0815] In addition, as in the first embodiment, a light resistance test was performed on the evaluation test specimen, and the light resistance was evaluated.

[0816] (Evaluation Results)

[0817] Table 9 shows the structure of the anthraquinone derivative, the absorption maximum wavelength λmax, the evaluation results of the absorption wavelength, the rate of change in absorbance ΔAbs, and the evaluation results of light resistance for Test Examples 9-1 to 9-10. The structure of the anthraquinone derivative of each test example is represented by the following formula (III), and R and Y in Table 9 1 , Y 2 , Z are R and Y in the following equation (III). 1 , Y 2 Corresponds to , Z.

[0818]

[0819]

[0820] Table 10 shows the structure of the anthraquinone derivative, the absorption maximum wavelength λmax, the evaluation results of the absorption wavelength, the rate of change in absorbance ΔAbs, and the evaluation results of light resistance for Test Examples 9-11 and 9-12. The structure of the anthraquinone derivative of each test example is represented by the following formula (II), and R, A, X, and Y in Table 10 1 , Y 2 , Z are R, A, X, and Y in the following equation (II). 1 , Y 2 Corresponds to , Z.

[0821]

[0822]

[0823] As shown in Tables 9 and 10, good light resistance was obtained in Test Examples 9-1 to 9-11, where a substituted phenyl group was directly bonded to the β-site of the anthraquinone backbone, whereas in Test Example 9-12, where the β-site was ether-bonded, the light resistance was very poor. Therefore, it was confirmed that light resistance is improved due to the structure in which a substituted phenyl group is directly bonded to the β-site.

[0824] In addition, in Test Examples 9-1 to 9-10, in which a substituted phenyl group is directly bonded to the β-site and a substituted phenylthio group is also formed on the α-site, the maximum absorption wavelength λmax is obtained in the range of 580 nm or more and 670 nm or less. On the other hand, in Test Example 9-11, in which a substituted phenyl group is directly bonded to the β-site and a substituted anilino group is also formed on the α-site, the maximum absorption wavelength λmax exceeds 680 nm, and in Test Example 9-12, in which the β-site is ether-bonded and a substituted phenylthio group is also formed on the α-site, the maximum absorption wavelength λmax is 570 nm or less.

[0825] Accordingly, it was confirmed that by combining a direct bonding structure of a substituted phenyl group at the β-position, which contributes significantly to the long-wavelength shift of the absorption maximum wavelength λmax, with a substituted phenylthio group at the α-position, which contributes less to the long-wavelength shift, an absorption maximum wavelength λmax is obtained within a suitable range, and compatibility with light resistance and blue light is possible.

Claims

Claim 1 An anthraquinone derivative represented by the following formula (9-1). In Equation (9-1), R 1 and R 2 is, each independently, an amino group or a hydroxyl group, and Y 1 , Y 2 and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, an alkyl halide 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. Claim 2 An anthraquinone derivative of claim 1, represented by the following formula (9-2). In Equation (9-2), Y 1 , Y 2 and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, an alkyl halide 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. Claim 3 An anthraquinone derivative represented by the following formula (1-1). In Equation (1-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group, and also R 1 , R 2 and R 3 At least one of is a hydroxyl group. Y 1 and Y 2 At least one of is an electron-donating group, said electron-donating group is an alkylamino group, an amino group, or a piperidyl group, and Y 1 and Y 2 In the case where only one side is an electron donor, Y 1 and Y 2 The other side 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. Claim 4 An anthraquinone derivative represented by the following formula (1-1). In Equation (1-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group. Y 1 and Y 2 At least one side of is an electron-donating group, said electron-donating group is an acetamide group or a hydroxyl group, and Y 1 and Y 2 In the case where only one side is an electron donor, Y 1 and Y 2 The other side 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. Claim 5 In paragraph 3 or 4, in the above formula (1-1), R 1 and R 3 Each of these is a hydroxyl group, and R 2 is an amino group, anthraquinone derivative. Claim 6 An anthraquinone derivative represented by the following formula (2-1). In Equation (2-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group, and also R 1 , R 2 and R 3 At least one of is a hydroxyl group. Y 1 and Y 2 Each is 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, and the electron-withdrawing group is a cyano group or an alkyl halide group. Claim 7 An anthraquinone derivative represented by the following formula (2-1). In Equation (2-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group. Y 1 and Y 2 Each is 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, and said electron-withdrawing group is an aldehyde group, an acetyl group, or a sulfonate group. Claim 8 In claim 6 or 7, in the above formula (2-1), R 1 and R 3 Each of these is a hydroxyl group, and R 2 is an amino group, anthraquinone derivative. Claim 9 In paragraph 8, an anthraquinone derivative represented by the following formula (2-3). In Equation (2-3), R 4 and R 5 Each is independently a hydrogen atom, a carbon-1 to carbon-10 alkyl group, or a cyclic hydrocarbon group, and Z is the electron-withdrawing group. Claim 10 An anthraquinone derivative represented by the following formula (3-1). In Equation (3-1), R 1 , R 2 and R 3 Each is independently an amino group or a hydroxyl group, and also R 1 , R 2 and R 3 At least one of is a hydroxyl group. Y 1 and Y 2 At least one side of is a cyclohexyl group, and the cyclohexyl group may have a substituent, and Y 1 and Y 2 In the case where only one side is a cyclohexyl group, Y 1 and Y 2 The other side 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. Claim 11 In item 10, an anthraquinone derivative represented by the following formula (3-2). In Equation (3-2), Y 1 and Y 2 At least one side of is a cyclohexyl group, and the cyclohexyl group may have a substituent, and Y 1 and Y 2 In the case where only one side is a cyclohexyl group, Y 1 and Y 2 The other side 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. Claim 12 In paragraph 11, an anthraquinone derivative represented by the following formula (3-3). In Equation (3-3), R 4 and R 5 Each is independently a hydrogen atom, a C1 to C10 alkyl group, or a cyclic hydrocarbon group, and Z is a hydrogen atom, a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a cyano group, a nitro group, a halogen atom, an amino group, or an alkylamino group. Claim 13 An anthraquinone derivative represented by the following formula (8-1). In Equation (8-1), A is a directly bonded oxygen atom, or -NH-, and Y 1 , Y 2 and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, an alkyl halide group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents. Claim 14 In paragraph 13, an anthraquinone derivative represented by the following formula (8-2). In Equation (8-2), Y 1 , Y 2 and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, an alkyl halide group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents. Claim 15 In paragraph 13, an anthraquinone derivative represented by the following formula (8-3). In Equation (8-3), Y 1 , Y 2 and Z are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, a halogen atom, an alkyl halide group having 1 to 10 carbon atoms, an amino group, an alkylamino group, an aryl group, a piperidyl group, or a cyclohexyl group, and the aryl group and the cyclohexyl group may have substituents.

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