Fluorinated phthalocyanine compound, coloring composition, and inkjet ink

Abstract

The present invention provides a fluorinated phthalocyanine compound represented by formula (1) and an application thereof. (In the formula, M represents a metal atom or an oxide of a metal atom; each of R101, R102, R103, R104, R105, R106, R107 and R108 independently represents a substituted or unsubstituted alkyl group or the like, provided that at least one of the two groups in each of combination A of R101 and R102, combination B of R103 and R104, combination C of R105 and R106, and combination D of R107 and R108 represents a substituted or unsubstituted alkyl group, and it is not possible that all of R101, R102, R103, R104, R105, R106, R107 and R108 are -CH2CH2(OCH2CH2)pR1 or (CqH2q)NR2R3.)

Description

[Technical Field]

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

[0002] Fluorinated phthalocyanine compounds are used in a variety of applications, such as colorants and materials for various optical filters.

[0003] For example, Patent Document 1 describes a fluorinated phthalocyanine compound having a specific structure that is used as a near-infrared absorbing material. Patent Document 2 describes a colored curable composition containing a phthalocyanine compound that is soluble in organic solvents and has a main absorption in a chloroform solvent in the range of 680 nm to 800 nm. Patent Document 3 describes a phthalocyanine compound having a specific structure that is used in a photosensitive resin composition used to form a color filter. Patent Document 4 describes a resin composition for forming a light selective transmission filter that contains a fluorinated phthalocyanine compound having a specific structure.

[0004] Patent document 1: Japanese Patent Application Laid-Open No. 4-345861 Patent Document 2: Japanese Patent Application Laid-Open No. 2013-182214 Patent Document 3: Korean Patent Publication No. 10-2016-0060542 Patent Document 4: Japanese Patent Application Laid-Open No. 2014-6361 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of one embodiment of the present disclosure is to provide a fluorinated phthalocyanine compound that is excellent in light resistance and moisture resistance. Another embodiment of the present disclosure has an object to provide a coloring composition or an inkjet ink containing the fluorinated phthalocyanine compound. [Means for solving the problem]

[0006] The present disclosure encompasses the following aspects. <1> A fluorinated phthalocyanine compound represented by the following formula (1):

[0007] A fluorinated phthalocyanine compound represented by the following formula (1): [ka]

[0008] In formula (1), M represents a metal atom or an oxide of a metal atom, and 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 and R 102 Groups A and R 103 and R 104 Groups B and R 105 and R 106 Set C and R 107 and R 108 At least one of the two groups in each group D represents a substituted or unsubstituted alkyl group, and R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 But all are -CH2CH2(OCH2CH2) p R 1 Or, all-(C q H 2q )NR 2 R 3 It is not. R 1 represents an acyl group or an alkoxy group having 1 to 4 carbon atoms, and R 2 and R 3each independently represents an alkyl group having 1 to 4 carbon atoms; p is an integer of 0 to 5; and q is an integer of 1 to 6.

[0009] <2> In formula (1), R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 each independently represents an unsubstituted alkyl group or an aryl group represented by the following formula (2), provided that R 101 and R 102 Groups A and R 103 and R 104 Groups B and R 105 and R 106 Set C and R 107 and R 108 and at least one of the two groups in each group D represents an unsubstituted alkyl group. <1> Fluorinated phthalocyanine compounds according to claim 1. [ka]

[0010] In formula (2), R 201 , R 202 , R 203 , R 204 , and R 205 each independently represents a hydrogen atom or a monovalent substituent, provided that R 201 , R 202 , R 203 , R 204 , and R 205 At least one of these represents a group represented by the following formula (3): [ka]

[0011] In formula (3), R 301 represents a hydrogen atom or a monovalent substituent, L 3 represents a single bond or a divalent linking group.

[0012] <3> In formula (1), R 101 and R 102 Groups A and R 103 and R 104 Groups B and R 105 and R 106 Set C and R 107 and R 108 In each group D, one of the two groups is an alkyl group having 1 to 2 carbon atoms, and the other group is a substituted or unsubstituted aryl group. <1> Fluorinated phthalocyanine compounds according to claim 1.

[0013] <4> <1> ~ <3> A coloring composition comprising the fluorinated phthalocyanine compound according to any one of the above items. <5> <1> ~ <3> 10. An ink-jet ink comprising the fluorinated phthalocyanine compound according to any one of claims 1 to 9. [Effects of the Invention]

[0014] According to one embodiment of the present disclosure, a fluorinated phthalocyanine compound having excellent light resistance and moisture resistance is provided. According to another embodiment of the present disclosure, there is provided a coloring composition or inkjet ink containing the fluorinated phthalocyanine compound. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a diagram showing a print pattern used in the evaluation of the examples. DETAILED DESCRIPTION OF THE INVENTION

[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 "to" means a range that includes the numerical values ​​before and after "to" 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. Furthermore, 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 the present disclosure, when referring to the amount of each component in a composition, if there are multiple substances corresponding to each component 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. In the present disclosure, "mass %" and "weight %" are synonymous.

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

[0021] In the present disclosure, the substituent group referred to as "substituent S" means the substituent group shown below. (Substituent S) Examples of the substituent S include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (which may be linear, branched, or cyclic), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a silyl group, a hydroxy group, a nitro group, an amino group, an alkylamino group, an alkoxy group, an aryloxy group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfonyl Examples of the alkyl group include an aryl group, an alkoxycarbonyl group, a heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imido group, a heterocyclic thio group, a phosphoryl group, an acyl group, a carboxy group, and a sulfo group. Each of these groups may further have a substituent.

[0022] As a result of extensive investigations, the present inventors have found a novel fluorophthalocyanine compound having a structure represented by the formula (1) below, which has excellent light resistance and moisture resistance.

[0023] The reason why the fluorinated phthalocyanine compound represented by formula (1) (hereinafter also referred to as the specific fluorinated phthalocyanine compound) has excellent light resistance and moisture resistance is not clear, but it is thought that the specific fluorinated phthalocyanine compound has a fluorinated phthalocyanine skeleton and two groups in each of the groups A, B, C, and D (i.e., R 101 It is presumed that the reason for this is that when at least one of the groups (groups such as fluorinated phthalocyanine compounds) is a substituted or unsubstituted alkyl group, the state of association and aggregation due to intermolecular interactions is appropriately alleviated, while the dissipation of light energy and the affinity for moisture are efficiently reduced. The coloring composition and inkjet ink according to the present disclosure contain a specific fluorinated phthalocyanine compound, and therefore have excellent lightfastness and moisture resistance. Furthermore, the appropriate alleviation of the state of association and aggregation of the specific fluorinated phthalocyanine compound can also contribute to excellent ejection stability when the specific fluorinated phthalocyanine compound is used in an inkjet ink. Therefore, continuous printing can be performed stably by using an inkjet ink containing the specific fluorinated phthalocyanine compound.

[0024] On the other hand, the phthalocyanine compounds described in the above Patent Documents 1 to 4 are inferior to specific fluorinated phthalocyanine compounds in both light resistance and moisture resistance, and inkjet inks using these phthalocyanine compounds also lack ejection stability.

[0025] <Fluorinated phthalocyanine compound represented by formula (1)> The fluorinated phthalocyanine compound represented by formula (1) (specific fluorinated phthalocyanine compound) is a novel fluorinated phthalocyanine compound.

[0026] [ka]

[0027] In formula (1), M represents a metal atom or an oxide of a metal atom, and 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 and R 102 Groups A and R 103 and R 104 Groups B and R 105 and R 106 Set C and R 107 and R 108 and D, at least one of the two groups in each group represents a substituted or unsubstituted alkyl group, and R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 But all are -CH2CH2(OCH2CH2) p R 1 Or, all-(C q H 2q )NR 2 R 3 It is not. R 1 represents an acyl group or an alkoxy group having 1 to 4 carbon atoms; p is an integer of 0 to 5; and q is an integer of 1 to 6.

[0028] The specific fluorinated phthalocyanine compound will be specifically described below.

[0029] In formula (1), M represents a metal atom or an oxide of a metal atom. Examples of the metal atoms include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the oxides of the metal atoms include oxides of the metal atoms listed above, and specific examples include oxytitanium (Ti=O) and oxyvanadium (V=O). 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 lightfastness, M is preferably zinc or copper. Furthermore, from the viewpoint of ease of obtaining raw materials for synthesizing the specific fluorophthalocyanine compound and from the viewpoint of solubility in a solvent when applied to an ink, M is preferably zinc.

[0030] At least one of the two groups in each of the groups A, B, C, and D, i.e., R 101 and R 102 and at least one of R 103 and R 104 and at least one of R 105 and R 106 At least one of and R 107 and R 108 At least one of the four groups, ie, the groups 1 and 2, is a substituted or unsubstituted alkyl group.

[0031] In formula (1), one of the two groups in each of Groups A, B, C, and D may be a substituted or unsubstituted alkyl group and the other may be a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, or both of the two groups may be substituted or unsubstituted alkyl groups. From the viewpoint of further improving light fastness and moisture fastness, it is preferable that one of the two groups in each of Groups A, B, C, and D is a substituted or unsubstituted alkyl group and the other is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and it is more preferable that one is an unsubstituted alkyl group and the other is a substituted aryl group.

[0032] In formula (1), two groups in each of groups A, B, C, and D (i.e., R 101 and R 102 , R 103 and R 104 , R 105 and R 106 , and R 107 and R 108 The same applies hereinafter.) may be the same combination of groups in each set, or may be a different combination of groups in each set. From the viewpoint of ease of synthesis, it is preferable that the two groups in each of sets A, B, C, and D are the same combination of groups in each set.

[0033] R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , or R 108 represents a substituted or unsubstituted alkyl group, the alkyl chain in the alkyl group may be any of a linear chain, a branched chain, and a cyclic chain, but from the viewpoint of further improving light fastness and moisture fastness, the alkyl chain is preferably a linear chain.

[0034] R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107, or R 108 The substituted or unsubstituted alkyl group represented by 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, still more preferably an alkyl group having a total of 1 to 8 carbon atoms, and particularly preferably an alkyl group having a total of 1 or 2 carbon atoms. The alkyl group also includes a cycloalkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a decyl group, a dodecyl group, and a stearyl group.

[0035] R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , or R 108 When represents a substituted or unsubstituted alkyl group, from the viewpoint of further improving light resistance and moisture resistance, it is preferably an unsubstituted alkyl group, more preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, and even more preferably an unsubstituted alkyl group having 1 or 2 carbon atoms (i.e., a methyl group or an ethyl group).

[0036] R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , or R 108is a substituted alkyl group, examples of the substituent on the alkyl group include a substituent selected from the substituents S. From the viewpoint of easy availability of raw materials, a halogen atom, an alkoxy group, an amino group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkylamino group, an aryloxy group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclicoxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imido group, a heterocyclicthio group, a phosphoryl group, an acyl group, a carboxy group, or a sulfo group is preferred. More preferred are an alkyl group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclicoxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imido group, a heterocyclicthio group, a phosphoryl group, an acyl group, a carboxy group, or a sulfo group; still more preferred are an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, an acyloxy group, a carbamoyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, or an acyl group; and particularly preferred is a halogen atom.

[0037] R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , or R 108The substituted or unsubstituted aryl group represented by is not particularly limited, and may be a single ring or a condensed ring, and may be an aryl group having a total of 6 to 18 carbon atoms, or an aryl group having a total of 6 to 14 carbon atoms.

[0038] R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , or R 108 The substituted or unsubstituted aryl group represented by the following formula (2) is particularly preferably an aryl group represented by the following formula (2):

[0039] [ka]

[0040] In formula (2), R 201 , R 202 , R 203 , R 204 , and R 205 each independently represents a hydrogen atom or a monovalent substituent.

[0041] R 201 , R 202 , R 203 , R 204 , and R 205 As for the In some embodiments, and R 201 , R 202 , R 203 , R 204 , and R 205 In view of light resistance and moisture resistance, one or two of R 201 , R 202 , R 203 , R 204 , and R 205 It is more preferable that one or two of R 201 , R 203 or R 205 is a monovalent substituent, and R 201 or R205 and R 203 and are monovalent substituents, and R 203 An embodiment in which only is a monovalent substituent is particularly preferred.

[0042] R 201 , R 202 , R 203 , R 204 , or R 205 The monovalent substituent represented by is not particularly limited and includes, for example, a substituent selected from the substituents S, and is preferably a halogen atom, a linear or branched alkyl group, a cyano group, an alkoxy group, an amino group, an alkoxycarbonyl group, a carboxy group, or an acyl group, and more preferably a group represented by the following formula (3):

[0043] [ka]

[0044] In formula (3), R 301 represents a hydrogen atom or a monovalent substituent, L 3 represents a single bond or a divalent linking group.

[0045] In formula (3), L 3 Examples of the divalent linking group represented by the formula: A R B -, -C(=S)-, -NR C Examples of divalent linking groups include divalent groups consisting of one or a combination of two or more of -, -SO-, -SO2-, 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.). In the present disclosure, these divalent linking groups are referred to as "linking group R". Here, R A , R B , and R C R each independently represents a hydrogen atom or a monovalent substituent. A , R B , and R CThe monovalent substituent in may have a substituent such as the substituent S. where R A , R B , and R C are each independently preferably a hydrogen atom or a substituent S, and more preferably are each independently a hydrogen atom or an alkyl group.

[0046] In formula (3), from the viewpoint of improving light resistance, L 3 is preferably a single bond.

[0047] In formula (3), R 301 The monovalent substituent represented by is not particularly limited and includes, for example, a substituent selected from the substituent S. An alkyl group or an aryl group is preferable, a linear or branched alkyl group having 1 to 18 carbon atoms or a phenyl group is more preferable, an alkyl group having 1 to 6 carbon atoms is still more preferable, and an alkyl group having 1 to 2 carbon atoms (a methyl group or an ethyl group) is particularly preferable.

[0048] R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , or R 108 The substituted or unsubstituted heterocyclic group represented by the formula (I) is preferably a heterocyclic group having a total of 2 to 12 carbon atoms, more preferably a heterocyclic group having a total of 3 to 8 carbon atoms. Examples of heteroatoms include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0049] The heterocyclic group may be a saturated or unsaturated ring, and is preferably a heteroaromatic ring. The number of ring members in the heterocyclic group is preferably 5 or 6, and more preferably 6.

[0050] The substituent that the substituted heterocyclic group has is not particularly limited, and examples thereof include the substituent S. Preferred examples of the substituent that the substituted heterocyclic group has include the group represented by the above formula (3).

[0051] One of the preferred embodiments of the specific fluorinated phthalocyanine compound is a compound represented by the formula (1), wherein R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 are each independently an unsubstituted alkyl group or an aryl group represented by the above formula (2). 201 , R 202 , R 203 , R 204 , and R 205 At least one of these represents a group represented by the above formula (3).

[0052] Another preferred embodiment of the specific fluorinated phthalocyanine compound is a compound represented by the formula (1), wherein R 101 and R 102 Groups A and R 103 and R 104 Groups B and R 105 and R 106 Set C and R 107 and R 108 In this embodiment, one of the two groups in each of the groups D is an alkyl group having 1 to 2 carbon atoms, and the other is a substituted or unsubstituted aryl group.

[0053] The maximum absorption wavelength of the specific fluorophthalocyanine compound 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.

[0054] The molar absorption coefficient at the maximum absorption wavelength of a specific fluorophthalocyanine compound is 100.0 It is preferable that the viscosity is 100,000 L / (mol·cm) or more, and more preferably 120,000 L / (mol·cm) or more.

[0055] The 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: 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 (for example, UV-3100 manufactured by Shimadzu Corporation) in a quartz cell with an optical path length of 10 mm.

[0056] Specific examples of the specific fluorinated phthalocyanine compound are shown below, but the specific fluorinated phthalocyanine compound is not limited to these specific examples. In the following, Me represents a methyl group, and Et represents an ethyl group.

[0057] [ka]

[0058] [ka]

[0059] The compound (G-2) is a mixture of isomers (G-2-1) to (G-2-4) shown in Table 1 below. [Table 1]

[0060] The compounds exemplified below, such as compound (G-3) and subsequent compounds, also include mixtures of isomers, similar to compound (G-2) above.

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [Synthesis method] The method for producing the specific fluorinated phthalocyanine compound is not particularly limited, and the compound may be produced by, for example, referring to a known method. For example, the compound may be synthesized in accordance with the method described in Japanese Patent No. 6054649. Specifically, the specific fluorinated phthalocyanine compound may be produced by heating and stirring difluorophthalonitrile having optional substituents at the 4- and 5-positions and an inorganic compound in an organic solvent.

[0068] [Application] The specific fluorophthalocyanine compound can be suitably used as a colorant. Furthermore, since the specific fluorinated phthalocyanine compound exhibits a hue (specifically, cyan to green), it can be suitably used as a coloring composition containing the specific fluorinated phthalocyanine compound or as an inkjet ink containing the fluorinated phthalocyanine compound according to the present disclosure.

[0069] <Coloring composition> The coloring composition according to the present disclosure is not particularly limited as long as it contains a specific fluorinated phthalocyanine compound.

[0070] The colored composition according to the present disclosure contains the specific fluorophthalocyanine compound, and therefore has excellent light fastness and moisture resistance.

[0071] The coloring composition according to the present disclosure is not particularly limited in its state, and may be, for example, liquid, solid, or semi-solid at 25°C.

[0072] Components other than the specific fluorinated phthalocyanine compound (hereinafter also referred to as other components) contained in the colored composition according to the present disclosure may be determined appropriately depending on the application of the colored composition.

[0073] Examples of uses of the colored composition according to the present disclosure include various inks, paints, dyes, colored resins, color masterbatches, and colored resin pellets.

[0074] 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 specific fluorinated phthalocyanine compound, a release agent, an antioxidant, a surfactant, and a preservative.

[0075] The content of the specific fluorinated phthalocyanine compound in the colored composition according to the present disclosure may be determined appropriately depending on the application of the colored composition.

[0076] <Inkjet ink> The inkjet ink according to the present disclosure is not particularly limited as long as it contains the specific fluorinated phthalocyanine compound. For example, the inkjet ink according to the present disclosure may be an ink in which the specific fluorinated phthalocyanine compound is dissolved and / or dispersed in an oleophilic medium or an aqueous medium.

[0077] The inkjet ink according to the present disclosure contains the specific fluorinated phthalocyanine compound, and therefore has excellent light resistance and moisture resistance, as well as excellent ejection stability.

[0078] The inkjet ink according to the present disclosure contains, in addition to the specific fluorinated phthalocyanine compound 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 (humectant), an anti-fading agent, an emulsion stabilizer, a penetration enhancer, 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.

[0079] 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, it preferably contains, in addition to the specific fluorinated phthalocyanine compound and an oleophilic medium or an aqueous medium, a curable component (for example, 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, known additives, etc.

[0080] The content of the fluorinated phthalocyanine compound according to the present disclosure in the inkjet ink according to the present disclosure may be determined appropriately depending on the type of ink. For example, the content of the fluorinated phthalocyanine compound according to the present disclosure is preferably 0.5% by mass to 8% by mass, and more preferably 3% by mass to 6% by mass, relative to the total mass of the inkjet ink according to the present disclosure. [Example]

[0081] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to the following examples.

[0082] The compounds (G-1) to (G-6) shown below are the same as the compounds (G-1) to (G-6) given as specific examples of the above-mentioned specific fluorinated phthalocyanine compound, respectively.

[0083] <Synthesis Example 1: Synthesis of Compound (G-1)> [ka]

[0084] <<Synthesis of Intermediate (G-1b)>> A three-neck flask was charged with 100 g of compound G-1a and 400 mL of acetone, cooled to an internal temperature of -11°C, and stirred. A solution prepared by stirring 133 g of octanol, 1,000 mL of tetrahydrofuran, and 116 g of potassium t-butoxide was added dropwise to the flask at an internal temperature of -10°C to -7°C and stirred. The temperature was then gradually returned to room temperature (25°C, the same applies below) and stirred for an additional 6 hours. To the resulting reaction solution, 1,000 mL of toluene was added, and the solution was concentrated to approximately one-third of its original volume. The resulting residue was separated by adding 500 mL of water and 500 mL of saturated saline. The toluene solution layer was then washed three times with 500 mL of water and 500 mL of saturated saline. The toluene solution layer was then dried over anhydrous sodium sulfate and concentrated. The resulting residue was purified by silica gel column chromatography to obtain 191 g of the desired intermediate (G-1b) (yield 91%).

[0085] <<Synthesis of Compound (G-1)>> A three-neck flask was charged with 42.1 g of intermediate G-1b, 9.6 g of zinc iodide, and 80 mL of benzonitrile (PhCN), and the mixture was heated and stirred for 5 hours at an internal temperature of 165° C. The resulting reaction solution was concentrated, and the resulting residue was purified by silica gel column chromatography to obtain 37.5 g of the target compound (G-1) (yield 87%). MALDI (Matrix-Assisted Laser Desorption / Ionization)-TOF MS (Time-of-Flight Mass Spectrometry): 1746 ([M+1] + ).

[0086] <Synthesis Example 2: Synthesis of Compound (G-2)> [ka]

[0087] <<Synthesis of Intermediate (G-2b)>> A three-neck flask was charged with 100 g of compound (G-2a), 750 mL of ethanol, and 100 mL of tetrahydrofuran, and the mixture was dissolved. An ethanol solution of 33.0 g of potassium hydroxide was added dropwise over 40 minutes at an internal temperature of -7°C to -3°C, followed by stirring for 30 minutes. After concentrating the mixture, the resulting residue was extracted three times with ethyl acetate. The combined extracts were dried over anhydrous sodium sulfate and concentrated. The resulting residue was purified by silica gel column chromatography to obtain 109 g of the desired intermediate G-2b (yield 96%).

[0088] <<Synthesis of Intermediate (G-2c)>> A three-neck flask was charged with 90.5 g of intermediate G-2b, 26.0 g of potassium fluoride, and 450 mL of acetone, and the mixture was stirred at room temperature to dissolve. The mixture was then cooled, and a solution of 67.1 g of ethyl 4-hydroxybenzoate in 270 mL of acetone was added dropwise at an internal temperature of -11 to -9°C. The mixture was then gradually returned to room temperature while stirring continued for 7 hours. Insoluble matter in the reaction mixture was filtered off, and the filtrate was concentrated. The resulting residue was purified by silica gel column chromatography to obtain 137 g of the desired intermediate G-2c (yield 92%).

[0089] <<Synthesis of Compound (G-2)>> 37.2 g of intermediate G-2c, 9.6 g of zinc iodide, and 70 mL of benzonitrile were placed in a three-neck flask and heated with stirring for 5 hours at an internal temperature of 165° C. The reaction solution was concentrated, and the resulting residue was purified by silica gel column chromatography to obtain 34.2 g of the target compound (G-2) (yield 88%). MALDI-TOF MS: 1553 ([M+1] + ).

[0090] <Synthesis Example 3: Synthesis of Compound (G-3)> Compound (G-3) was synthesized in the same manner as in the synthesis of compound (G-2), except that ethanol was replaced with methanol in the synthesis of intermediate (G-2b). MALDI-TOF MS: 1497 ([M+1] + ).

[0091] <Synthesis Example 4: Synthesis of Compound (G-4)> Compound (G-4) was synthesized in the same manner as in the synthesis of compound (G-2), except that in the synthesis of intermediate (G-2b), ethanol was replaced with methanol, and in the synthesis of intermediate (G-2c), ethyl 4-hydroxybenzoate was replaced with phenyl 4-hydroxybenzoate. MALDI-TOF MS: 1689 ([M+1] + ).

[0092] <Synthesis Example 5: Synthesis of Compound (G-5)> Compound (G-5) was synthesized in the same manner as in the synthesis of compound (G-2), except that ethanol was replaced with octanol in the synthesis of intermediate (G-2b). MALDI-TOF MS: 1890 ([M+1] + ).

[0093] <Synthesis Example 6: Synthesis of Compound (G-6)> Compound (G-6) was synthesized in the same manner as in the synthesis of compound (G-2), except that ethanol was replaced with octanol in the synthesis of intermediate (G-2b), and ethyl 4-hydroxybenzoate was replaced with phenol in the synthesis of intermediate (G-2c). MALDI-TOF MS: 1602 ([M+1] + ).

[0094] <Preparation of Inkjet Ink (1)> 7.5 g of compound (G-1), 7.04 g of dioctyl sodium sulfosuccinate, 4.22 g of tri(m-toluyl)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, and an oil-in-water solution was obtained. A droplet-shaped coarse particle dispersion was prepared. Next, this coarse particle dispersion was passed through a Microfluidizer (manufactured by Microfluidex Inc.) five times at a pressure of 60 MPa to micronize it. The resulting emulsion was then desolvated using 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.

[0095] <Preparation of Inkjet Inks (2) to (6)> Inkjet inks (2) to (6) were obtained in the same manner as in the preparation of inkjet ink (1), except that compound (G-1) was replaced with one of compounds (G-2) to (G-6).

[0096] <Preparation of Inkjet Inks (A), (B), (C), and (D)> Inkjet inks (A), (B), (C) and (D) were obtained in the same manner as in the preparation of inkjet ink (1), except that compound (G-1) was replaced with any of the following comparative compounds (A), (B), (C) and (D).

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] (evaluation) 1. Lightfastness evaluation Using the inkjet inks (1) to (6) and (A) to (D), 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 resulting print samples were used to evaluate lightfastness as follows.

[0102] The resulting 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 with xenon light, was measured using a reflection densitometer (X-Rite, trade name: X-Rite i1Pro) after irradiation with xenon light. Since the reflection density of the solid image before irradiation with xenon light was 1.0, the compound residual rate (%) before and after irradiation with xenon light was calculated using the following formula. The higher the compound residual 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) × 100

[0103] 2. Bleeding evaluation Using inkjet inks (1) to (6) and (A) to (D), four squares were printed on white art paper to obtain the print pattern shown in Figure 1, to obtain a print sample. In the print sample, the width of the white gap between each square was 1 mm. The resulting print samples were stored for 72 hours under conditions of 25°C and 90% RH. After storage, the print samples were visually observed for an increase in color density (i.e., bleeding) in the gaps in the white background, and evaluated by comparing them with the gaps in the white background immediately after printing. The evaluation criteria are as follows: A good bleeding evaluation means that the specific fluorophthalocyanine compound has excellent moisture resistance. (Evaluation criteria) A: No bleeding. B: There is slight bleeding. C: There is bleeding. D: There is a lot of bleeding.

[0104] <Evaluation of ejection stability (continuous printing)> Using the inkjet inks (1) to (6) and (A) to (D), continuous printing was performed on 100 sheets of A4 paper using an inkjet printer (manufactured by Fujifilm Corporation, product name: Material Printer DMP-2850), and the print quality of the printed matter was visually evaluated according to the following evaluation criteria. (Evaluation criteria) A: There was no distortion in the print from start to finish. B: A small number of prints were found to have print defects. C: Printouts with printing distortion were generated. D: A large amount of printouts with poor printing were produced.

[0105] The evaluation results are shown in Table 2 below.

[0106] [Table 2]

[0107] As is clear from Table 2, all of the specific fluorinated phthalocyanine compounds (that is, the fluorinated phthalocyanine compounds represented by formula (1)) are excellent in light resistance and in suppressing bleeding (humidity resistance). It is also apparent that the inkjet ink using the specific fluorinated phthalocyanine compound is excellent in ejection stability (continuous printing property). On the other hand, it is found that the comparative compounds (A) to (D) have low and inferior light resistance compared to the specific fluorophthalocyanine compound. It is also found that the inkjet inks using the comparative compounds (A) to (D) are inferior in ejection stability (continuous printing ability).

[0108] The disclosure of Japanese Patent Application No. 2022-003363, filed on January 12, 2022, is incorporated herein by reference in its entirety. In addition, 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 zinc, 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 or a substituted or unsubstituted aryl group. １０１ and R １０２ Groups A and R １０３ and R １０４ Groups B and R １０５ and R １０６ Set C and R １０７ and R １０８ and D, one of the two groups in each group represents an unsubstituted alkyl group, and the two groups in each group are not both unsubstituted alkyl groups.

2. In formula (1), 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 each independently represents an unsubstituted alkyl group or an aryl 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 these represents a group represented by the following formula (3): 【Transformation 3】 In formula (3), R ３０１ represents a hydrogen atom or a monovalent substituent; L ３ represents a single bond or a divalent linking group.

3. In formula (1), R １０１ and R １０２ Groups A and R １０３ and R １０４ Groups B and R １０５ and R １０６ Sets C and R １０７ and R １０８ 2. The fluorinated phthalocyanine compound according to claim 1, wherein, of the two groups in each group D, one group represents an unsubstituted alkyl group having 1 to 2 carbon atoms, and the other group represents a substituted or unsubstituted aryl group.

4. A coloring composition comprising the fluorophthalocyanine compound according to any one of claims 1 to 3.

5. An inkjet ink comprising the fluorinated phthalocyanine compound according to any one of claims 1 to 3.

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