Fluorinated phthalocyanine compound, coloring composition, and inkjet ink

Abstract

A fluorinated phthalocyanine compound represented by formula (1) and the application thereof (In formula (1), M represents a metal atom or an oxide of a metal atom, R101-R108 each independently represent an alkyl group, an aryl group, or a heterocyclic group. Where, at least one of R101-R108 is a group represented by formula (2). In formula (2), R201-R205 each independently represent a hydrogen atom or a monovalent substituent. Where, at least one of R201-R205 is any one group selected from the group consisting of formula (3), formula (4), formula (5), formula (6), and formula (7).).

Description

[Technical field]

[0001] The present disclosure relates to a fluorinated phthalocyanine compound, a coloring composition, and an ink-jet ink. [Background technology]

[0002] Fluorinated phthalocyanine compounds are widely used, for example, as colorants, which are required to have a desired hue and good fastness, such as light resistance.

[0003] For example, JP-A-5-345861 describes a fluorine-containing phthalocyanine compound in which a fluorine atom is directly bonded to a phthalocyanine nucleus, and JP-A-2006-342264 describes a phthalocyanine compound having a polymerizable substituent at the molecular end. Summary of the Invention [Problem to be solved by the invention]

[0004] An object of one embodiment of the present disclosure is to provide a fluorinated phthalocyanine compound that exhibits green color and has excellent light resistance. Another embodiment of the present disclosure has an object to provide a coloring composition or an ink-jet ink containing the above fluorinated phthalocyanine compound. [Means for solving the problem]

[0005] The present disclosure encompasses the following aspects. <1> A fluorinated phthalocyanine compound represented by the following formula (1).

[0006] [ka]

[0007] In formula (1), M represents a metal atom or an oxide of a metal atom, R 101 , R 102 , R103 , R 104 , R 105 , R 106 , R 107 , and R 108 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 At least one of these is a group represented by the following formula (2):

[0008] [ka]

[0009] In formula (2), R 201 , R 202 , R 203 , R 204 , and R 205 Each independently represents a hydrogen atom or a monovalent substituent. 201 , R 202 , R 203 , R 204 , and R 205 At least one of the above is any one group selected from the group consisting of the following formula (3), the following formula (4), the following formula (5), the following formula (6), and the following formula (7).

[0010] [ka]

[0011] In formula (3), R 301 , R 302 , and R 303 each independently represents a hydrogen atom or a monovalent substituent; L 3 represents a single bond, a divalent linking group, or a trivalent linking group; and n represents 1 or 2. In formula (4), R 401 , R 402, R 403 , R 404 , and R 405 each independently represents a hydrogen atom or a monovalent substituent; L 4 represents a single bond or a divalent linking group. In formula (5), L 5 represents a single bond or a divalent linking group, R 501 is a hydrogen atom, a fluoroalkyl group, -CR 502 R 503 R 504 or -CHR 505 OR 506 Represents R 502 , R 503 , R 504 , R 505 , and R 506 each independently represents a substituted or unsubstituted alkyl group; R 505 and R 506 may be bonded to each other to form a ring. In formula (6), L 6 represents a single bond or a divalent linking group. In formula (7), L 7 represents a single bond or a divalent linking group.

[0012] <2> R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 are all groups represented by formula (2). <1> Fluorinated phthalocyanine compound according to claim 1. <3> R in Equation (2) 202 , R 203 , and R 204 any one of the formulas (3), (4), (5), (6), and (7) is any one group selected from the group consisting of formula (3), formula (4), formula (5), formula (6), and formula (7), and R 202 , R 203 , and R 204 The remaining two of these, R 201 , and R 205 are all hydrogen atoms, <1> or <2> Fluorinated phthalocyanine compound according to claim 1. <4> R in Equation (2) 203 is any one group selected from the group consisting of formula (3), formula (4), formula (5), formula (6), and formula (7), and R 201 , R 202 , R 204 , and R 205 are all hydrogen atoms, <1> ~ <3> 1. The fluorinated phthalocyanine compound according to any one of the above items. <5> M is copper, zinc, or oxyvanadium; <1> ~ <4> 1. The fluorinated phthalocyanine compound according to any one of the above items. <6> M is copper or zinc; <1> ~ <5> 1. The fluorinated phthalocyanine compound according to any one of the above items. <7> M is zinc; <1> ~ <6> 1. The fluorinated phthalocyanine compound according to any one of the above items.

[0013] <8> <1> ~ <7> A coloring composition comprising the fluorinated phthalocyanine compound according to any one of the above items. <9> <1> ~ <7> 13. An ink-jet ink comprising the fluorinated phthalocyanine compound according to any one of claims 1 to 12. Effect of the Invention

[0014] According to one embodiment of the present disclosure, there is provided a fluorinated phthalocyanine compound that exhibits green color and has excellent light resistance. According to another embodiment of the present disclosure, there is provided a coloring composition or an ink-jet ink comprising the above fluorinated phthalocyanine compound. [Brief description of the drawings]

[0015] [Figure 1] 1 is an absorption spectrum of a dilute solution of compound (G-1) in ethyl acetate. [Diagram 2] 1 is an absorption spectrum of a dilute solution of compound (G-5) in ethyl acetate. [Diagram 3] 1 is an absorption spectrum of a dilute solution of compound (G-16) in ethyl acetate. [Figure 4]This is a 1H-NMR spectrum of compound (G-1) in deuterated chloroform. [Diagram 5] This is a 1H-NMR spectrum of compound (G-5) in deuterated chloroform. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments. The following embodiments may be modified as appropriate within the scope of the present disclosure.

[0017] In the present disclosure, a numerical range indicated using "~" means a range including the numerical values ​​described before and after "~" as the lower and upper limits, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0018] In this disclosure, when referring to the amount of each component in a composition, if multiple substances corresponding to each component are present in the composition, it means the total amount of the multiple components present in the composition, unless otherwise specified.

[0019] In the present disclosure, a combination of two or more preferred aspects or embodiments is a more preferred aspect or embodiment.

[0020] In the present disclosure, when a group (atomic group) is represented without specifying whether it is substituted or unsubstituted, it includes both unsubstituted and substituted groups. For example, a "hydrocarbon group" includes not only unsubstituted hydrocarbon groups but also substituted hydrocarbon groups.

[0021] As a result of intensive investigations, the present inventors have found a novel fluorophthalocyanine compound having a structure represented by the formula (1) described below, which exhibits green color and has excellent light resistance. The reason why the fluorinated phthalocyanine compound according to the present disclosure exhibits green color and has excellent light resistance is unclear, but it is believed that this is because a substituent having a specific structure introduced at the molecular end (i.e., any one group selected from the group consisting of formula (3), formula (4), formula (5), formula (6), and formula (7)) effectively acts to dissipate light energy while appropriately relaxing the association and aggregation state of the phthalocyanine.

[0022] In the present disclosure, "green" refers to a hue angle (h°) of 150° to 210°. In other words, the hue angle (h°) of the fluorophthalocyanine compound according to the present disclosure is 150° to 210°, and preferably 160° to 200°. In this disclosure, the hue angle is the L standardized by the CIE (International Commission on Illumination) in 1976 and standardized in JIS Z 8781-5:2013. * a * b * The hue angle is calculated by the formula: hue angle (h°) = tan -1 (a * / b * ) is calculated as follows: The hue angle (h°) in this disclosure is a measured value by the method described in the Examples below. * and b * can be calculated by substituting into the above formula.

[0023] <Fluorinated phthalocyanine compounds> The fluorophthalocyanine compound according to the present disclosure is a compound represented by the following formula (1).

[0024] [ka]

[0025] In formula (1), M represents a metal atom or an oxide of a metal atom, R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R107 , and R 108 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 At least one of these is a group represented by the following formula (2):

[0026] [ka]

[0027] In formula (2), R 201 , R 202 , R 203 , R 204 , and R 205 Each independently represents a hydrogen atom or a monovalent substituent. 201 , R 202 , R 203 , R 204 , and R 205 At least one of the above is any one group selected from the group consisting of the following formula (3), the following formula (4), the following formula (5), the following formula (6), and the following formula (7). Hereinafter, a group selected from the group consisting of formula (3), formula (4), formula (5), formula (6), and formula (7) is also referred to as a "specific substituent".

[0028] [ka]

[0029] In formula (3), R 301 , R 302 , and R 303 each independently represents a hydrogen atom or a monovalent substituent; L 3 represents a single bond, a divalent linking group, or a trivalent linking group; and n represents 1 or 2. In formula (4), R 401 , R 402 , R403 , R 404 , and R 405 each independently represents a hydrogen atom or a monovalent substituent; L 4 represents a single bond or a divalent linking group. In formula (5), L 5 represents a single bond or a divalent linking group, R 501 is a hydrogen atom, a fluoroalkyl group, -CR 502 R 503 R 504 or -CHR 505 OR 506 Represents R 502 , R 503 , R 504 , R 505 , and R 506 each independently represents a substituted or unsubstituted alkyl group; R 505 and R 506 may be bonded to each other to form a ring. In formula (6), L 6 represents a single bond or a divalent linking group. In formula (7), L 7 represents a single bond or a divalent linking group.

[0030] The structure of the fluorinated phthalocyanine compound represented by formula (1) will be specifically described below.

[0031] In the formula (1), M represents a metal atom or an oxide of a metal atom. Examples of the metal atom include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. The oxides of the above metal atoms include oxides of the metal atoms exemplified above, and specific examples thereof include oxytitanium (Ti=O), oxyvanadium (V=O), and the like. M is preferably copper, zinc, cobalt, nickel, iron, oxytitanium, or oxyvanadium, and more preferably copper, zinc, or oxyvanadium. In particular, from the viewpoint of improving light fastness, M is preferably zinc or copper. Furthermore, from the viewpoint of exhibiting a green color with a hue angle of 150° to 210°, from the viewpoint of ease of obtaining raw materials for synthesizing the fluorophthalocyanine compound represented by formula (1), and from the viewpoint of solubility in a solvent when applied to an ink, M is preferably zinc.

[0032] In formula (1), R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 At least one of these is a group represented by formula (2). The substituted or unsubstituted alkyl group is preferably an alkyl group having a total of 1 to 18 carbon atoms, more preferably an alkyl group having a total of 1 to 12 carbon atoms. The substituent on the substituted alkyl group is not particularly limited, and examples thereof include the substituent S described below. Here, the total carbon number of the alkyl group means the total number of carbon atoms including the carbon number of the substituent when the alkyl group has a substituent containing a carbon atom. The substituted or unsubstituted aryl group is preferably an aryl group having a total of 6 to 18 carbon atoms, more preferably an aryl group having a total of 6 to 14 carbon atoms, and particularly preferably a group represented by formula (2). The substituent of the substituted aryl group is not particularly limited, and examples thereof include the substituent S described below, among which specific substituents are preferred. Here, the total number of carbon atoms of the aryl group means the total number of carbon atoms including the number of carbon atoms of the substituent when the aryl group has a substituent containing a carbon atom. The above-mentioned substituted or unsubstituted heterocyclic group is preferably a heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom, etc. as a heteroatom and having a total of 2 to 12 carbon atoms, more preferably a heterocyclic group containing a total of 3 to 8 carbon atoms. The substituent that the substituted heterocyclic group has is not particularly limited, and examples thereof include the substituent S described below. Here, the total number of carbon atoms in the heterocyclic group means the total number of carbon atoms including the number of carbon atoms of the substituent when the heterocyclic group has a substituent containing a carbon atom.

[0033] In the formula (1), from the viewpoints of ease of synthesis, of exhibiting a green color with a hue angle of 150° to 210°, and of improving light fastness, 101 and R 102 At least one of R 103 and R 104 At least one of R 105 and R 106 At least one of and R 107 and R 108 and R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 It is preferable that all of the above are groups represented by formula (2).

[0034] In formula (2), R 201 , R 202 , R 203 , R204 , and R 205 Each independently represents a hydrogen atom or a monovalent substituent. 201 , R 202 , R 203 , R 204 , and R 205 At least one of these is any one group (i.e., a specific substituent) selected from the group consisting of formula (3), formula (4), formula (5), formula (6), and formula (7). The monovalent substituent is not particularly limited, and examples thereof include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxy groups, nitro groups, amino groups, alkylamino groups, alkoxy groups, aryloxy groups, acylamino groups, arylamino groups, ureido groups, sulfamoylamino groups, alkylthio groups, arylthio groups, alkoxycarbonylamino groups, sulfonamide groups, carbamoyl groups, sulfamoyl groups, sulfonyl groups, alkoxycarbonyl groups, heterocyclic oxy groups, azo groups, acyloxy groups, carbamoyloxy groups, silyloxy groups, aryloxycarbonyl groups, aryloxycarbonylamino groups, imido groups, heterocyclic thio groups, phosphoryl groups, acyl groups, carboxy groups, and sulfo groups. Each of these groups may further have a substituent. In the present disclosure, these monovalent substituents are referred to as "substituent S", and monovalent substituents other than the specific substituents are referred to as "substituent T". As the monovalent substituent, specific substituents are preferred.

[0035] In formula (2), the number of substitutions of the specific substituent is not particularly limited, but from the viewpoints of ease of synthesis, of exhibiting a green color with a hue angle of 150° to 210°, and of improving light fastness, it is preferably 1. That is, from the viewpoints of ease of synthesis, of exhibiting a green color with a hue angle of 150° to 210°, and of improving light fastness, R 201 , R 202 , R 203 , R 204 , and R 205 Any one of the following is a specific substituent: R 201 , R 202 , R 203 , R204 , and R 205 The remaining four of these are preferably each independently a hydrogen atom or the above-mentioned substituent T. In addition, the substitution position of the specific substituent is preferably the meta position or the para position from the viewpoint of exhibiting a green color with a hue angle of 150° to 210° and improving light resistance, and more preferably the para position from the viewpoint of easy availability of raw materials for synthesizing the fluorinated phthalocyanine compound represented by formula (1). 202 , R 203 , and R 204 Any one of the following is a specific substituent: R 202 , R 203 , and R 204 The remaining two of these, R 201 , and R 205 are each independently preferably a hydrogen atom or the above-mentioned substituent T, and R 203 is a specific substituent, and R 201 , R 202 , R 204 , and R 205 are each independently a hydrogen atom or the above-mentioned substituent T.

[0036] In formula (2), from the viewpoint of presenting green with a hue angle of 150° to 210°, R 201 and R 205 is preferably a hydrogen atom. In addition, in terms of formula (2), from the viewpoint of presenting a green color with a hue angle of 150° to 210° and from the viewpoint of further improving light fastness, R 202 , R 203 , and R 204 Any one of the following is a specific substituent: R 202 , R 203 , and R 204 The remaining two of these, R 201 , and R 205 are preferably all hydrogen atoms, 203 is a specific substituent, and R 201 , R 202 , R 204 , and R 205 It is more preferable that all of are hydrogen atoms.

[0037] In formula (1), a plurality of specific substituents may be the same or different from each other, but from the viewpoint of ease of synthesis, it is preferable that they are the same. In addition, in formula (1), a plurality of groups represented by formula (2) may be the same or different from each other, but from the viewpoint of ease of synthesis, it is preferable that they are the same.

[0038] The group represented by formula (3) has a carbon-carbon double bond at its terminal. In formula (3), R 301 , R 302 , and R 303 each independently represents a hydrogen atom or a monovalent substituent; L 3 represents a single bond, a divalent linking group, or a trivalent linking group; and n represents 1 or 2. The monovalent substituent includes the above-mentioned substituent S. The divalent linking group includes, for example, -O-, -S-, -C(=O)-, -CR A R B -, -C(=S)-, -NR C -, -SO-, -SO 2 Examples of the divalent linking group include one or a combination of two or more of the divalent groups R -, a residue obtained by removing two hydrogen atoms from a hydrocarbon ring (e.g., 1,4-phenylene, cyclohexane-1,4-diyl, etc.), and a residue obtained by removing two hydrogen atoms from a heterocycle (e.g., thiophene-2,5-diyl, pyridine-2,5-diyl, etc.). A , R B , and R C Each of independently represents a hydrogen atom or a monovalent substituent. Each of these groups may further have a substituent such as the substituent S. In the present disclosure, these divalent linking groups are referred to as "linking group R". Here, R A , R B , and R C is preferably each independently a hydrogen atom or a substituent S, and more preferably each independently a hydrogen atom, an alkyl group, or a specific substituent. Further, examples of the trivalent linking group include trivalent hydrocarbon groups such as methine groups, trivalent groups of -N<, and trivalent linking groups formed by combining these trivalent groups with the above-mentioned linking group R.

[0039] In formula (3), from the viewpoint of presenting a green color with a hue angle of 150° to 210° and improving light fastness, R 301 , R 302 , and R 303 are preferably each independently a hydrogen atom or an alkyl group, and more preferably all are a hydrogen atom. In formula (3), from the viewpoint of presenting a green color with a hue angle of 150° to 210° and improving light fastness, L 3 is preferably a divalent or trivalent linking group, and more preferably a divalent or trivalent linking group formed from a combination of -C(=O)- and -O-, -NH-, or -N<.

[0040] The group represented by formula (4) has a phenoxycarbonyl group. In formula (4), R 401 , R 402 , R 403 , R 404 , and R 405 each independently represents a hydrogen atom or a monovalent substituent; L 4 represents a single bond or a divalent linking group. The monovalent substituent includes the above-mentioned substituent S. Moreover, examples of the divalent linking group include the linking group R described above.

[0041] In formula (4), from the viewpoint of presenting a green color with a hue angle of 150° to 210° and from the viewpoint of improving light fastness, R 401 , R 402 , R 403 , R 404 , and R 405 are all hydrogen atoms or R 401 , R 402 , R 404 , and R 405 are all hydrogen atoms, and R 403is preferably a monovalent substituent (eg, the substituent S). In formula (4), from the viewpoint of presenting a green color with a hue angle of 150° to 210° and improving light fastness, L 4 is preferably a single bond.

[0042] In formula (5), L 5 represents a single bond or a divalent linking group. The divalent linking group includes the linking group R described above. In formula (5), from the viewpoint of presenting a green color having a hue angle of 150° to 210° and improving light fastness, L 5 is preferably a single bond. In formula (5), R 501 is a hydrogen atom, a fluoroalkyl group, -CR 502 R 503 R 504 or -CHR 505 OR 506 Represents R 502 , R 503 , R 504 , R 505 , and R 506 each independently represents a substituted or unsubstituted alkyl group; R 505 and R 506 may be bonded to each other to form a ring. Here, the fluoroalkyl group represents an alkyl group substituted with at least one fluorine atom. Examples of the substituents on the substituted alkyl group include the substituent S. In formula (5), from the viewpoint of presenting a green color with a hue angle of 150° to 210° and from the viewpoint of improving light fastness, R 501 is preferably a hydrogen atom.

[0043] The group represented by formula (6) has a hydroxy group at its terminal. In formula (6), L 6 represents a single bond or a divalent linking group. The divalent linking group includes the linking group R described above. In formula (6), from the viewpoint of exhibiting a green color with a hue angle of 150° to 210° and improving light fastness, L 6is preferably a divalent linking group, such as -C(=O)-, -O-, -CR A R B - and -NR C More preferably, it is a divalent linking group consisting of one or more combinations of -C(=O)-, -O-, -NH-, and -CH 2 It is more preferable that R is a divalent linking group consisting of one or more combinations of R A , R B , and R C Each independently represents a hydrogen atom or a monovalent substituent, and a preferred embodiment is the above-mentioned R A , R B , and R C is the same as:

[0044] The group represented by formula (7) has an unsubstituted amino group at the terminal. In formula (7), L 7 represents a single bond or a divalent linking group. The divalent linking group includes the linking group R described above. In formula (7), from the viewpoint of presenting a green color having a hue angle of 150° to 210° and improving light fastness, L 7 is preferably a divalent linking group, such as -C(=O)-, -O-, -CR A R B - and -NR C More preferably, it is a divalent linking group consisting of one or more combinations of -C(=O)-, -O-, -NH-, and -CH 2 It is more preferable that R is a divalent linking group consisting of one or more combinations of R A , R B , and R C Each independently represents a hydrogen atom or a monovalent substituent, and a preferred embodiment is the above-mentioned R A , R B , and R C is the same as:

[0045] As the specific substituent, from the viewpoint of solubility in a solvent when applied to an ink, a group represented by formula (3) or formula (5) is preferred. As the specific substituent, from the viewpoint of ease of obtaining raw materials for synthesizing the fluorophthalocyanine compound represented by formula (1) and from the viewpoint of ease of synthesis, a group represented by formula (3), formula (4), or formula (5) is preferred. Furthermore, as the specific substituent, from the viewpoint of reducing printing bleeding on printing substrates such as cellulose-based plain paper and inorganic porous photo paper when applied to an ink, a group represented by formula (6) or formula (7) is preferred. The number of specific substituents in the fluorophthalocyanine compound represented by formula (1) is preferably 1 to 12, more preferably 4 to 10, and even more preferably 8, from the viewpoint of exhibiting a green color with a hue angle of 150° to 210° and improving light fastness.

[0046] The maximum absorption wavelength of the fluorophthalocyanine compound according to the present disclosure is preferably in the wavelength range of 630 nm to 690 nm, more preferably in the wavelength range of 640 nm to 680 nm, and even more preferably in the wavelength range of 650 nm to 670 nm. The molar absorption coefficient at the maximum absorption wavelength of the fluorophthalocyanine compound according to the present disclosure is preferably 100,000 L / (mol·cm) or more, and more preferably 120,000 L / (mol·cm) or more. The above maximum absorption wavelength and molar absorption coefficient are those in the absorption spectrum of a solution of a fluorophthalocyanine compound, and are measured using a spectrophotometer. The specific measurement method is as follows. That is, for example, ethyl acetate, chloroform, or dimethylformamide is used as a solvent, and 1×10 -6 A solution having a concentration of M is prepared, and the resulting solution is measured using a spectrophotometer (eg, Shimadzu UV-3100) in a quartz cell with an optical path length of 10 mm.

[0047] Specific examples of the fluorinated phthalocyanine compound according to the present disclosure [(G-1) to (G-17)] are shown below. Note that the fluorinated phthalocyanine compound according to the present disclosure is not limited to the following specific examples.

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [Synthesis method] The method for producing the fluorinated phthalocyanine compound according to the present disclosure is not particularly limited, and the compound may be produced by a known method or by reference to a known method. For example, the compound may be synthesized in accordance with the method described in JP-A-2005-298491. Specifically, for example, 3,6-difluorophthalonitrile having various substituents at the 4- and 5-positions, which can be synthesized by a method known in the literature, is reacted with a metal salt such as copper acetate or zinc iodide in a solvent such as diethylene glycol or benzonitrile at a temperature of 80° C. to 200° C. to produce the fluorinated phthalocyanine compound according to the present disclosure.

[0058] [Application] The fluorophthalocyanine compound according to the present disclosure exhibits a green color and can therefore be suitably used as a colorant or dye. In addition, since the fluorinated phthalocyanine compound according to the present disclosure exhibits a green color, it can be suitably used as a coloring composition containing the fluorinated phthalocyanine compound according to the present disclosure or an inkjet ink containing the fluorinated phthalocyanine compound according to the present disclosure.

[0059] <Coloring composition> The coloring composition according to the present disclosure is not particularly limited as long as it contains the fluorinated phthalocyanine compound according to the present disclosure. The coloring composition according to the present disclosure is not particularly limited in terms of its state, and may be, for example, liquid, solid, or semi-solid at 25°C. In addition, components other than the fluorinated phthalocyanine compound according to the present disclosure that are contained in the colored composition according to the present disclosure (hereinafter, also referred to as other components) may be appropriately determined depending on the application of the colored composition. Examples of applications of the colored composition according to the present disclosure include various inks, paints, dyes, colored resins, color masterbatches, and colored resin pellets.

[0060] Examples of other components contained in the colored composition according to the present disclosure include various additives such as a solvent, a resin, a colorant other than the fluorinated phthalocyanine compound according to the present disclosure, a release agent, an antioxidant, a surfactant, and a preservative. The content of the fluorinated phthalocyanine compound according to the present disclosure in the colored composition according to the present disclosure may be appropriately determined depending on the application of the colored composition.

[0061] <Inkjet ink> The inkjet ink according to the present disclosure is not particularly limited as long as it contains the fluorinated phthalocyanine compound according to the present disclosure. For example, the inkjet ink according to the present disclosure may be an ink in which the fluorinated phthalocyanine compound according to the present disclosure is dissolved and / or dispersed in an oleophilic medium or an aqueous medium. The inkjet ink according to the present disclosure contains, in addition to the fluorinated phthalocyanine compound according to the present disclosure and the lipophilic medium or aqueous medium, known additives such as a colorant other than the fluorinated phthalocyanine compound according to the present disclosure, an anti-drying agent (wetting agent), an anti-fading agent, an emulsion stabilizer, a penetration promoter, an ultraviolet absorber, an antiseptic, an anti-fungal agent, a pH adjuster, a surface tension adjuster, an antifoaming agent, a viscosity adjuster, a dispersant, a dispersion stabilizer, an anti-rust agent, and a chelating agent, as necessary.

[0062] The inkjet ink according to the present disclosure may be an ink that is cured by irradiation with active energy rays. When the ink is cured by irradiation with active energy rays, the ink contains a fluorinated phthalocyanine compound according to the present disclosure and an oleophilic medium or an aqueous medium, as well as a curable component (e.g., a polymerizable compound, a polymerization initiator, an epoxy compound, a curing agent, etc.), a colorant other than the fluorinated phthalocyanine compound according to the present disclosure, a known additive, etc.

[0063] The content of the fluorinated phthalocyanine compound according to the present disclosure in the inkjet ink according to the present disclosure may be appropriately determined depending on the type of ink. The content of the fluorinated phthalocyanine compound according to the present disclosure is, for example, preferably 0.5% by mass to 8% by mass, more preferably 3% by mass to 6% by mass, based on the total mass of the inkjet ink according to the present disclosure. EXAMPLES

[0064] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to the following examples. Compounds (G-1) to (G-14), and (G-16) shown below are the same as compounds (G-1) to (G-14), and (G-16), respectively, in the specific examples of the fluorinated phthalocyanine compound according to the present disclosure described above.

[0065] <Synthesis Example 1: Synthesis of compound (G-1)> 388 mg of zinc iodide, 2.11 g of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile, and 4 mL of benzonitrile were placed in a 50 mL recovery flask, and the mixture was reacted under a nitrogen atmosphere at 150°C for 3 hours, 160°C for 3 hours, and 170°C for 2 hours. The contents of the recovery flask were cooled to room temperature (25°C), and reprecipitation was carried out with 60 mL of methanol, and the precipitated crystals were collected by filtration. The obtained crystals were purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1 / 1, v / v) to obtain compound (G-1). The yield was 0.44 g, and the yield was 17%. MALDI (matrix-assisted laser desorption / ionization)-TOF MS (time-of-flight mass spectrometry): 2132 ([M+1] + ). The maximum absorption wavelength in the absorption spectrum of compound (G-1) in a dilute solution of ethyl acetate was 664 nm. Fig. 1 shows the absorption spectrum of a dilute solution of compound (G-1) in ethyl acetate, and Fig. 4 shows the 1H-NMR spectrum of compound (G-1) in deuterated chloroform.

[0066] <Synthesis Example 2: Synthesis of compound (G-2)> Compound (G-2) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy)phthalonitrile was replaced with 2.43 g of 3,6-difluoro-4,5-bis[4-(diallylaminocarbonyl)phenoxy]phthalonitrile. MALDI-TOF MS: 2242 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-2) in a dilute solution of ethyl acetate was 664 nm.

[0067] <Synthesis Example 3: Synthesis of compound (G-3)> Compound (G-3) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile was replaced with 2.10 g of 3,6-difluoro-4,5-bis[4-(allylaminocarbonyl)phenoxy]phthalonitrile. MALDI-TOF MS: 2122 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-3) in a dilute solution of ethyl acetate was 664 nm.

[0068] <Synthesis Example 4: Synthesis of compound (G-4)> 1.0 g of compound (G-10) synthesized by the method described in Synthesis Example 10 below was dissolved in 10 mL of N-methylpyrrolidone and cooled to 0°C. 0.6 g of methacrylic anhydride was added and reacted at room temperature for 30 minutes and at 45°C for 60 minutes. The reaction solution was poured into water and extracted with ethyl acetate, and then purified by silica gel column chromatography (eluent: ethyl acetate) to obtain compound (G-4). MALDI-TOF MS: 2705 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-4) in a dilute solution of ethyl acetate was 664 nm.

[0069] <Synthesis Example 5: Synthesis of compound (G-5)> Compound (G-5) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile was replaced with 2.40 g of 3,6-difluoro-4,5-bis[4-(phenoxycarbonyl)phenoxy]phthalonitrile. MALDI-TOF MS: 2417 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-5) in a dilute solution of ethyl acetate was 664 nm. Fig. 2 shows the absorption spectrum of a dilute solution of compound (G-5) in ethyl acetate, and Fig. 5 shows the 1H-NMR spectrum of compound (G-5) in deuterated chloroform.

[0070] <Synthesis Example 6: Synthesis of compound (G-6)> Compound (G-6) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-((4-methylphenoxy)carbonyl)phenoxy]phthalonitrile was used instead of 2.52 g. MALDI-TOF MS: 2530 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-6) in a dilute solution of ethyl acetate was 664 nm.

[0071] <Synthesis Example 7: Synthesis of compound (G-7)> Compound (G-7) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy)phthalonitrile was replaced with 3.19 g of 3,6-difluoro-4,5-bis[4-((4-chlorophenoxy)carbonyl)phenoxy]phthalonitrile. MALDI-TOF MS: 2689 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-7) in a dilute solution of ethyl acetate was 664 nm.

[0072] <Synthesis Example 8: Synthesis of compound (G-8)> Compound (G-8) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-((4-nitrophenoxy)carbonyl)phenoxy]phthalonitrile was used instead of 2.77 g. MALDI-TOF MS: 2777 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-8) in a dilute solution of ethyl acetate was 665 nm.

[0073] <Synthesis Example 9: Synthesis of compound (G-9)> Compound (G-9) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy)phthalonitrile was replaced with 1.77 g of 3,6-difluoro-4,5-bis[4-carboxyphenoxy)phthalonitrile. MALDI-TOF MS: 1809 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-9) in a dilute solution of ethyl acetate was 663 nm.

[0074] <Synthesis Example 10: Synthesis of compound (G-10)> Compound (G-10) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy)phthalonitrile was replaced with 2.14 g of 3,6-difluoro-4,5-bis[4-((2-hydroxyethyloxy)carbonyl)phenoxy]phthalonitrile. MALDI-TOF MS: 2161 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-10) in a dilute solution of ethyl acetate was 664 nm.

[0075] <Synthesis Example 11: Synthesis of compound (G-11)> Compound (G-11) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy)phthalonitrile was replaced with 2.13 g of 3,6-difluoro-4,5-bis[4-((2-aminoethoxy)oxycarbonyl)phenoxy]phthalonitrile. MALDI-TOF MS: 2153 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-11) in a dilute solution of ethyl acetate was 664 nm.

[0076] <Synthesis Example 12: Synthesis of compound (G-12)> Compound (G-12) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile was used instead of 2.11 g of 3,6-difluoro-4,5-bis[3-(allylaminocarbonyl)phenoxy]phthalonitrile. MALDI-TOF MS: 2122 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-12) in a dilute solution of ethyl acetate was 668 nm.

[0077] <Synthesis Example 13: Synthesis of compound (G-13)> Compound (G-13) was obtained in the same manner as in Synthesis Example 1, except that 388 mg of zinc iodide was replaced with 112 mg of copper acetate (anhydrous) and benzonitrile as the solvent was replaced with ethylene glycol. MALDI-TOF MS: 2128 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-13) in a dilute solution of ethyl acetate was 639 nm.

[0078] <Synthesis Example 14: Synthesis of compound (G-14)> Compound (G-14) was obtained in the same manner as in Synthesis Example 1, except that the amount of zinc iodide: 388 mg was changed to vanadium trichloride: 58 mg, and the solvent benzonitrile was changed to diethylene glycol or butyl ether. MALDI-TOF MS: 2132 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-14) in a dilute solution of ethyl acetate was 679 nm.

[0079] <Synthesis Example 15: Synthesis of compound (G-16)> Compound (G-16) was obtained in the same manner as in Synthesis Example 1, except that 2.11 g of 3,6-difluoro-4,5-bis[4-(oxycarbonyl)phenoxy)phthalonitrile was used instead of 2.45 g of 3,6-difluoro-4,5-bis[4-((2,2,2,-trifluoroethyl)oxycarbonyl)phenoxy]phthalonitrile. MALDI-TOF MS: 2465 ([M+1] + ). The maximum absorption wavelength of the absorption spectrum of compound (G-16) in a dilute solution of ethyl acetate was 664 nm. FIG. 3 shows the absorption spectrum of a dilute solution of compound (G-16) in ethyl acetate.

[0080] <Preparation of Inkjet Ink (1)> 7.5 g of compound (G-1), 7.04 g of sodium dioctyl sulfosuccinate, 4.22 g of tri(m-tolyl)phosphine oxide, 5.63 g of tri(tert-octyl)phosphine oxide, and 50 mL of ethyl acetate were mixed and dissolved at 70°C. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to prepare a coarse-grained dispersion of oil-in-water type. Next, this coarse-grained dispersion was passed through a microfluidizer (manufactured by MICROFLUIDEX INC.) five times at a pressure of 60 MPa to perform microparticulation. Furthermore, the resulting emulsion was desolvated with a rotary evaporator until the odor of ethyl acetate disappeared. To the fine emulsion of compound (G-1) thus obtained, 140 g of diethylene glycol, 50 g of glycerin, 7 g of SURFYNOL 465 (Air Products & Chemicals), and 900 ml of deionized water were added to prepare an ink.

[0081] <Preparation of Inkjet Inks (2) to (14)> Inkjet inks (2) to (14) were obtained in the same manner as in the preparation of inkjet ink (1), except that compound (G-1) was replaced with any of compounds (G-2) to (G-14).

[0082] <Preparation of Inkjet Inks (A) and (B)> Inkjet inks (A) to (B) were obtained in the same manner as in the preparation of inkjet ink (1), except that the following comparative compound (A) or the following comparative compound (B) was used instead of compound (G-1).

[0083] [ka]

[0084] (Preparation and evaluation of print samples) Using each of the inkjet inks (1) to (14) and (A) to (B), a solid image with a reflection density of 1.0 and a solid image with the maximum color density were printed on art paper using an inkjet printer (manufactured by FUJIFILM Corporation, product name: Material Printer DMP-2850) to obtain print samples. The obtained print samples were used to evaluate lightfastness, measure hue angle, visually confirm color, and measure maximum color density as follows. The results are shown in Table 1.

[0085] <Light resistance evaluation> The obtained print sample was irradiated with xenon light (85,000 lux) for 7 days using a weather meter (Atlas, Ci65), and the reflection density of the solid image, which had a reflection density of 1.0 before irradiation, after irradiation with xenon light was measured using a reflection densitometer (X-Rite, product name: X-Rite i1Pro). Since the reflection density of the solid image before irradiation with xenon light was 1.0, the compound remaining rate (%) before and after irradiation with xenon light was calculated from the following formula. The higher the compound remaining rate (%), the better the light resistance of the fluorophthalocyanine compound contained in the print sample. Compound remaining rate (%) = (reflection density of solid image after irradiation with xenon light) / (reflection density of solid image before irradiation with xenon light = 1.0) x 100

[0086] <Calculating the hue angle> The hue angle of the solid image of the obtained print sample with a reflection density of 1.0 was calculated as follows. First, the color value L of the solid image of the print sample with a reflection density of 1.0 was measured using a reflection densitometer (manufactured by X-Rite, product name: X-Rite i1Pro) under the conditions of a viewing angle of 2 degrees and a C light source. * a * b * The obtained a * and b * The formula: Hue angle (h°) = tan -1 (a * / b * ) to calculate the hue angle of a solid image with a reflection density of 1.0 of the print sample.

[0087] <Color> The color of a solid image having a reflection density of 1.0 of the obtained print sample was visually confirmed.

[0088] <Maximum color density> The reflection density of a solid image having the maximum color density of the obtained print sample was measured using a reflection densitometer (manufactured by X-Rite, trade name: X-Rite i1Pro) under conditions of a viewing angle of 2 degrees and C light source.

[0089] [Table 1]

[0090] As is clear from Table 1, the fluorinated phthalocyanine compound according to the present disclosure (i.e., the fluorinated phthalocyanine compound represented by formula (1)) has a hue angle in the range of 150° to 210°, exhibits a green color, and further has excellent light resistance. It is also apparent that by using the fluorophthalocyanine compound according to the present disclosure (that is, the fluorophthalocyanine compound represented by formula (1)), an image with a high maximum color density can be obtained. It is clear that the comparative compound (A) used in Comparative Example 1 exhibits green color, but is inferior in light resistance to the examples. The comparative compound (B) used in Comparative Example 2 was excellent in light fastness, but had a hue angle outside the range of 150° to 210° and exhibited a cyan color instead of green.

[0091] The disclosure of Japanese Patent Application No. 2021-188790, filed on November 19, 2021, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A fluorinated phthalocyanine compound represented by the following formula (1): 【Chemistry 1】 In formula (1), M represents a metal atom or an oxide of a metal atom; １０１ , R １０２ , R １０３ , R １０４ , R １０５ , R １０６ , R １０７ , and R １０８ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. １０１ , R １０２ , R １０３ , R １０４ , R １０５ , R １０６ , R １０７ , and R １０８ At least one of these is a group represented by the following formula (2). 【Chemistry 2】 In formula (2), R ２０１ , R ２０２ , R ２０３ , R ２０４ , and R ２０５ Each independently represents a hydrogen atom or a monovalent substituent. ２０１ , R ２０２ , R ２０３ , R ２０４ , and R ２０５ At least one of the above is any one group selected from the group consisting of the following formula (3), the following formula (4), the following formula (5), the following formula (6), and the following formula (7). 【Chemistry 3】 In formula (3), R ３０１ , R ３０２ , and R ３０３ each independently represents a hydrogen atom or a monovalent substituent; L ３ represents a single bond, a divalent linking group, or a trivalent linking group; n represents 1 or 2. In formula (4), R ４０１ , R ４０２ , R ４０３ , R ４０４ , and R ４０５ each independently represents a hydrogen atom or a monovalent substituent; L ４ represents a single bond or a divalent linking group. In formula (5), L ５ represents a single bond or a divalent linking group; R ５０１ represents a hydrogen atom, a fluoroalkyl group, -CR ５０２ R ５０３ R ５０４ or -CHR ５０５ OR ５０６ Represents R ５０２ , R ５０３ , R ５０４ , R ５０５ , and R ５０６ each independently represents a substituted or unsubstituted alkyl group; R ５０５ and R ５０６ may be bonded to each other to form a ring. In formula (6), L ６ represents a single bond or a divalent linking group. In formula (7), L ７ represents a single bond or a divalent linking group.

2. R １０１ , R １０２ , R １０３ , R １０４ , R １０５ , R １０６ , R １０７ , and R １０８ The fluorinated phthalocyanine compound according to claim 1 , wherein all of the above are groups represented by formula (2).

3. R in formula (2) ２０２ , R ２０３ , and R ２０４ any one of the formulas (3), (4), (5), (6), and (7) is any one group selected from the group consisting of formula (3), formula (4), formula (5), formula (6), and formula (7), R ２０２ , R ２０３ , and R ２０４ The remaining two of them, R ２０１ , and R ２０５ The fluorinated phthalocyanine compound according to claim 1 , wherein all of are hydrogen atoms.

4. R in formula (2) ２０３ is any one group selected from the group consisting of formula (3), formula (4), formula (5), formula (6), and formula (7), and R ２０１ , R ２０２ , R ２０４ , and R ２０５ The fluorinated phthalocyanine compound according to claim 3 , wherein all of are hydrogen atoms.

5. 2. The fluorinated phthalocyanine compound according to claim 1, wherein M is copper, zinc, or oxyvanadium.

6. The fluorinated phthalocyanine compound according to claim 5 , wherein M is copper or zinc.

7. 7. The fluorinated phthalocyanine compound according to claim 6, wherein M is zinc.

8. A coloring composition comprising the fluorinated phthalocyanine compound according to any one of claims 1 to 7.

9. An ink-jet ink comprising the fluorinated phthalocyanine compound according to any one of claims 1 to 7.

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