Fluorinated phthalocyanine compound, coloring composition, and ink for inkjet

Abstract

Fluorinated phthalocyanine compounds represented by the following formula (1) and applications thereof (in formula (1), M represents a metal atom or an oxide of a metal atom, R 101 ~R 108 each independently represents an alkyl group, an aryl group, or a heterocyclic group. Among them, at least one of R 101 ~R 108 is a group represented by formula (2). In formula (2), R 201 ~R 205 each independently represents a hydrogen atom or a monovalent substituent. Among them, at least one of R 201 ~R 205 is a group selected from any one of formula (3), formula (4), formula (5), formula (6), and formula (7).

Description

Technical Field

[0001] This invention relates to a fluorinated phthalocyanine compound, a coloring composition, and an ink for inkjet printing. Background Technology

[0002] Fluorinated phthalocyanine compounds are widely used as colorants, for example. As colorants, requirements include, for example, a desired hue and good fastness, such as lightfastness.

[0003] For example, Japanese Patent Application Publication No. 5-345861 discloses a fluorinated phthalocyanine compound in which fluorine atoms are directly bonded to the phthalocyanine core. Furthermore, Japanese Patent Application Publication No. 2006-342264 discloses a phthalocyanine compound with polymerizable substituents at the molecule's ends. Summary of the Invention

[0004] The technical problem to be solved by the invention

[0005] One embodiment of the present invention aims to provide a green fluorinated phthalocyanine compound with excellent lightfastness.

[0006] Another objective of this invention is to provide a coloring composition or inkjet ink comprising the above-mentioned fluorinated phthalocyanine compound.

[0007] means for solving technical problems

[0008] The present invention includes the following methods.

[0009] <1> A fluorinated phthalocyanine compound, represented by the following formula (1).

[0010] [Chemical Formula 1]

[0011]

[0012] 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 of these groups independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Wherein, R... 101 R 102 R 103 R 104 R 105 R 106 R 107 and R 108At least one of them is a group represented by the following formula (2).

[0013] [Chemical Formula 2]

[0014]

[0015] In equation (2), R 201 R 202 R 203 R 204 and R 205 Each can independently represent a hydrogen atom or a monovalent substituent. Where R... 201 R 202 R 203 R 204 and R 205 At least one of them is a group selected from any one of the following formulas (3), (4), (5), (6) and (7).

[0016] [Chemical Formula 3]

[0017]

[0018] *-L 6 -OH (6)

[0019] *-L 7 -NH2 (7)

[0020] In equation (3), R 301 R 302 and R 303 Each can be independently represented by a hydrogen atom or a monovalent substituent, L 3 This indicates a single bond, a divalent linker, or a trivalent linker, where n represents 1 or 2.

[0021] In equation (4), R 401 R 402 R 403 R 404 and R 405 Each can be independently represented by a hydrogen atom or a monovalent substituent, L 4 This indicates a single bond or a divalent linker.

[0022] In equation (5), L 5 R represents a linker base that is either a single bond or divalent. 501 Indicates hydrogen atom, fluoroalkyl group, -CR 502 R 503 R 504 、or -CHR 505 OR 506 R 502 R 503 R 504R 505 and R 506 Each alkyl group can be independently represented as either substituted or unsubstituted, R 505 With R 506 They can bond together to form a ring.

[0023] In equation (6), L 6 Indicates a linker base that is either a single bond or divalent.

[0024] In equation (7), L 7 This indicates a single bond or a divalent linker.

[0025] <2> according to <1> The fluorinated phthalocyanine compound, wherein,

[0026] R 101 R 102 R 103 R 104 R 105 R 106 R 107 and R 108 All are groups represented by formula (2).

[0027] <3> according to <1> or <2> The fluorinated phthalocyanine compound, wherein,

[0028] R in equation (2) 202 R 203 and R 204 Any one of them is selected from any one of formulas (3), (4), (5), (6) and (7), R 202 R 203 and R 204 The remaining two, R 201 and R 205 It consists entirely of hydrogen atoms.

[0029] <4> according to <1> to <3> In any one of the fluorinated phthalocyanine compounds, wherein,

[0030] R in equation (2) 203 R is any group selected from formula (3), formula (4), formula (5), formula (6) and formula (7). 201 R 202 R 204 and R 205 It consists entirely of hydrogen atoms.

[0031] <5> according to <1> to <4> The fluorinated phthalocyanine compound described in any one of the following statements, wherein M is copper, zinc, or vanadium oxychloride.

[0032] <6> according to <1> to <5> The fluorinated phthalocyanine compound described in any one of the following statements, wherein M is copper or zinc.

[0033] <7> according to <1> to <6> The fluorinated phthalocyanine compound described in any one of the following statements, wherein M is zinc.

[0034] <8> A coloring composition comprising <1> to <7> The fluorinated phthalocyanine compound mentioned in any one of the following.

[0035] <9> An inkjet ink comprising <1> to <7> The fluorinated phthalocyanine compound mentioned in any one of the following.

[0036] Invention Effects

[0037] According to one embodiment of the present invention, a fluorinated phthalocyanine compound that is green and has excellent lightfastness is provided.

[0038] According to another embodiment of the present invention, a coloring composition or inkjet ink comprising the above-mentioned fluorinated phthalocyanine compound is provided. Attached Figure Description

[0039] Figure 1 It is the absorption spectrum of a dilute ethyl acetate solution of compound (G-1).

[0040] Figure 2 This is the absorption spectrum of a dilute ethyl acetate solution of compound (G-5).

[0041] Figure 3 This is the absorption spectrum of a dilute ethyl acetate solution of compound (G-16).

[0042] Figure 4 It is compound (G-1) in deuterated chloroform 1 H-NMR spectrum.

[0043] Figure 5 It is compound (G-5) in deuterated chloroform 1 H-NMR spectrum. Detailed Implementation

[0044] The embodiments of the present invention will now be described in detail. The present invention is not limited to any of the following embodiments. The following embodiments may also be appropriately modified within the scope of the objectives of the present invention.

[0045] In this invention, the numerical range indicated by "~" refers to the range encompassed by using the values ​​before and after "~" as the lower and upper limits, respectively. In the numerical ranges described in stages in this invention, the upper or lower limit value described within a certain numerical range can be replaced with the upper or lower limit value of other numerical ranges described in stages. Furthermore, the upper or lower limit value described within a certain numerical range in this invention can also be replaced with the values ​​shown in the embodiments.

[0046] In this invention, when referring to the amount of each component in a composition, if there are multiple substances corresponding to each component in the composition, unless otherwise specified, it refers to the total amount of the multiple components present in the composition.

[0047] In this invention, a combination of two or more preferred modes or forms is a more preferred mode or form.

[0048] Regarding the designation of groups (atomic groups) in this invention, designations that do not specify substituted and unsubstituted groups include groups without substituents as well as groups with substituents. For example, "hydrocarbon group" includes not only unsubstituted hydrocarbon groups but also substituted hydrocarbon groups.

[0049] As a result of in-depth research, the inventors discovered a novel fluorinated phthalocyanine compound with a structure represented by the formula (1) described later, which is green in color and has excellent light resistance.

[0050] The reason why the fluorinated phthalocyanine compounds involved in this invention are green and have excellent light resistance is not yet clear, but it can be considered that the substituents with specific structures introduced to the end of the molecule (i.e., any one of the groups selected from formula (3), formula (4), formula (5), formula (6) and formula (7)) effectively dissipate light energy while appropriately mitigating the associated aggregation state of phthalocyanine.

[0051] In this invention, "green" refers to a hue angle (h°) of 150° to 210°. That is, the hue angle (h°) of the fluorinated phthalocyanine compound involved in this invention is 150° to 210°, preferably 160° to 200°.

[0052] In this invention, the hue angle is based on the standard established by the CIE (International Commission on Illumination) in 1976 and standardized by JIS Z8781-5:2013. * a * b * Color system. Hue angle formula: Hue angle (h°) = tan -1 (a * / b * ) to calculate.

[0053] The hue angle (h°) in this invention is determined by the method described in the embodiments below, α. * and b * Substitute into the above formula to find the answer.

[0054] <Fluorocyanine compounds>

[0055] The fluorinated phthalocyanine compounds involved in this invention are compounds represented by the following formula (1).

[0056] [Chemical Formula 4]

[0057]

[0058] 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 of these groups independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Wherein, R... 101 R 102 R 103 R 104 R 105 R 106 R 107 and R 108 At least one of them is a group represented by the following formula (2).

[0059] [Chemical Formula 5]

[0060]

[0061] In equation (2), R 201 R 202 R 203 R 204 and R 205 Each can independently represent a hydrogen atom or a monovalent substituent. Where R... 201 R 202 R 203 R 204 and R 205 At least one of them is a group selected from any one of the following formulas (3), (4), (5), (6) and (7). Hereinafter, the group selected from formulas (3), (4), (5), (6) and (7) will also be referred to as a "specific substituent".

[0062] [Chemical Formula 6]

[0063]

[0064] *-L 6 -OH (6)

[0065] *-L 7 -NH2 (7)

[0066] In equation (3), R 301 R 302 and R303 Each can be independently represented by a hydrogen atom or a monovalent substituent, L 3 This indicates a single bond, a divalent linker, or a trivalent linker, where n represents 1 or 2.

[0067] In equation (4), R 401 R 402 R 403 R 404 and R 405 Each can be independently represented by a hydrogen atom or a monovalent substituent, L 4 This indicates a single bond or a divalent linker.

[0068] In equation (5), L 5 R represents a linker base that is either a single bond or divalent. 501 Indicates hydrogen atom, fluoroalkyl group, -CR 502 R 503 R 504 、or -CHR 505 OR 506 R 502 R 503 R 504 R 505 and R 506 Each alkyl group can be independently represented as either substituted or unsubstituted, R 505 With R 506 They can bond together to form a ring.

[0069] In equation (6), L 6 Indicates a linker base that is either a single bond or divalent.

[0070] In equation (7), L 7 This indicates a single bond or a divalent linker.

[0071] The structure of the fluorinated phthalocyanine compound represented by formula (1) will be described in detail below.

[0072] In equation (1), M represents a metal atom or an oxide of a metal atom.

[0073] Examples of metal atoms mentioned above include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin.

[0074] As oxides of the aforementioned metal atoms, examples include oxides of various metal atoms listed above, such as titanium oxide (Ti=O) and vanadium oxide (V=O).

[0075] M is preferably copper, zinc, cobalt, nickel, iron, titanium oxide, or vanadium oxide, and more preferably copper, zinc, or vanadium oxide. In particular, from the viewpoint of improving lightfastness, 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 readily obtaining raw materials for synthesizing the fluorinated phthalocyanine compound represented by formula (1), and from the viewpoint of solubility relative to the solvent when applied to ink, M is preferably zinc.

[0076] In equation (1), R 101 R 102 R 103 R 104 R 105 R 106 R 107 and R 108 Each of these groups independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Wherein, R... 101 R 102 R 103 R 104 R 105 R 106 R 107 and R 108 At least one of them is a group represented by formula (2).

[0077] The substituted or unsubstituted alkyl group described above is preferably an alkyl group with a total carbon number of 1 to 18, and more preferably an alkyl group with a total carbon number of 1 to 12. There are no particular limitations on the substituents having the substituted alkyl group; for example, substituent S described later can be cited. Here, when the alkyl group has a substituent containing a carbon atom, the total carbon number of the alkyl group refers to the total number of carbon atoms including the carbon atoms of its substituents.

[0078] The aryl group, whether substituted or unsubstituted, is preferably an aryl group with a total carbon number of 6 to 18, more preferably an aryl group with a total carbon number of 6 to 14, and particularly preferably a group represented by formula (2). There are no particular limitations on the substituents present in the substituted aryl group; for example, substituent S described later can be cited, wherein a specific substituent is preferred. Here, when the aryl group has substituents containing carbon atoms, the total carbon number of the aryl group refers to the total number of carbon atoms including the carbon atoms of its substituents.

[0079] As the aforementioned substituted or unsubstituted heterocyclic group, the heteroatom is preferably a heterocyclic group containing nitrogen atoms, oxygen atoms, sulfur atoms, etc., with a total carbon number of 2 to 12, more preferably a heterocyclic group with a total carbon number of 3 to 8. There are no particular limitations on the substituents present in the substituted heterocyclic group; for example, substituent S described later can be cited. Here, when the heterocyclic group has substituents containing carbon atoms, the total carbon number of the heterocyclic group refers to the total number of carbon atoms including the carbon atoms of the substituents.

[0080] In formula (1), considering the viewpoints of easy synthesis, presenting a green with a hue angle of 150° to 210°, and improving lightfastness, R 101 and R 102 At least one of them, R 103 and R 104 At least one of them, R 105 and R 106 At least one of them and R 107 and R 108 At least one of the four or more groups is preferably represented by formula (2). From the viewpoint of presenting a green with a hue angle of 150° to 210° and from the viewpoint of further improving lightfastness, R 101 R 102 R 103 R 104 R 105 R 106 R 107 and R 108 Preferably, all groups are represented by formula (2).

[0081] In equation (2), R 201 R 202 R 203 R 204 and R 205 Each can independently represent a hydrogen atom or a monovalent substituent. Where R... 201 R 202 R 203 R 204 and R 205 At least one of them is a group selected from formula (3), formula (4), formula (5), formula (6) and formula (7) (i.e., a specific substituent).

[0082] There are no particular limitations on the monovalent substituents mentioned above, and examples include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, amino groups, alkylamino groups, alkoxy groups, aryloxy groups, amide groups, arylamino groups, urea groups, aminosulfonylamino groups, alkylthio groups, arylthio groups, alkoxycarbonylamino groups, sulfonylamino groups, carbamoyl groups, aminosulfonyl groups, sulfonyl groups, alkoxycarbonyl groups, heterocyclic thio groups, azo groups, acyloxy groups, carbamoyloxy groups, silanoxy groups, aryloxycarbonyl groups, aryloxycarbonylamino groups, imide groups, heterocyclic thio groups, phosphoryl groups, acyl groups, carboxyl groups, or sulfonyl groups. These groups may further have substituents. Furthermore, in this invention, these monovalent substituents are referred to as "substituent S", and monovalent substituents other than the specific substituents are referred to as "substituent T".

[0083] As a substituent with a 1 valence, a specific substituent is preferred.

[0084] In formula (2), the number of substitutions of a specific substituent is not particularly limited, but from the viewpoints of ease of synthesis, the presentation of a green with a hue angle of 150° to 210°, and improved lightfastness, 1 is preferred. That is, from the viewpoints of ease of synthesis, the presentation of a green with a hue angle of 150° to 210°, and improved lightfastness, R in formula (2) is... 201 R 202 R 203 R 204 and R 205 If any one of them is a specific substituent, R 201 R 202 R 203 R 204 and R 205 The remaining four preferred atoms are each independently a hydrogen atom or the aforementioned substituent T.

[0085] Furthermore, from the viewpoint of exhibiting a green hue angle of 150° to 210° and from the viewpoint of improving lightfastness, the substitution of specific substituents is preferably meta- or para-position, and from the viewpoint of readily obtaining raw materials for synthesizing the fluorinated phthalocyanine compound represented by formula (1), para-position is more preferred. That is, R in formula (2) 202 R 203 and R 204 If any one of them is a specific substituent, R 202 R 203 and R 204 The remaining two, R 201 and R 205 Preferably, each is an independent hydrogen atom or one of the above substituents T, R. 203 For specific substituents, R 201 R 202 R 204 and R 205More preferably, each is independently a hydrogen atom or the aforementioned substituent T.

[0086] In equation (2), considering the viewpoint of presenting green with a hue angle of 150° to 210°, R 201 and R 205 Hydrogen atoms are preferred.

[0087] Furthermore, in equation (2), considering both the presentation of green with a hue angle of 150° to 210° and the further improvement of lightfastness, R 202 R 203 and R 204 If any one of them is a specific substituent, R 202 R 203 and R 204 The remaining two, R 201 and R 205 Ideally, all atoms should be hydrogen atoms, R 203 For specific substituents, R 201 R 202 R 204 and R 205 More preferably, it consists entirely of hydrogen atoms.

[0088] In equation (1), there are multiple specific substituents that can be the same or different from each other. From the point of view of easy synthesis, it is preferred that they are the same.

[0089] Furthermore, in formula (1), there are multiple groups represented by formula (2) that can be the same or different from each other. From the point of view of easy synthesis, it is preferred that they are the same.

[0090] The group represented by formula (3) has a carbon-carbon double bond at the end.

[0091] In equation (3), R 301 R 302 and R 303 Each can be independently represented by a hydrogen atom or a monovalent substituent, L 3 This indicates a single bond, a divalent linker, or a trivalent linker, where n represents 1 or 2.

[0092] As a substituent with the above-mentioned 1 valence, the above-mentioned substituent S can be cited.

[0093] Furthermore, as examples of the aforementioned divalent linking bases, -O-, -S-, -C(=O)-, and -CR- can be used. A R B -、-C(=S)-、-NR CA divalent linker is a combination of one or more divalent groups, such as -SO-, -SO2-, residues obtained by removing two hydrogen atoms from a hydrocarbon ring (e.g., 1,4-phenylene, cyclohexane-1,4-diyl, etc.), and residues obtained by removing two hydrogen atoms from a heterocycle (e.g., thiophene-2,5-diyl, pyridine-2,5-diyl, etc.). Here, R... A R B and R C Each group can independently represent a hydrogen atom or a monovalent substituent. These groups may also have substituents such as substituent S. In addition, in this invention, these divalent linking groups are referred to as "linking groups R".

[0094] Here, R A R B and R C Preferably, each is a hydrogen atom or a substituent S independently, and more preferably, each is a hydrogen atom, an alkyl group or a specific substituent independently.

[0095] Furthermore, examples of trivalent linkers include trivalent hydrocarbon groups such as methine or trivalent groups with -N<, as well as trivalent linkers formed by combinations of such trivalent groups and the linker R described above.

[0096] In equation (3), from the perspective of presenting green with a hue angle of 150° to 210° and from the perspective of improving lightfastness, R 301 R 302 and R 303 Preferably, each hydrogen atom or alkyl group is represented independently; more preferably, all of them are hydrogen atoms.

[0097] In equation (3), from the perspective of presenting a green with a hue angle of 150° to 210° and from the perspective of improving lightfastness, L 3 Preferably, it is a divalent or trivalent linker, more preferably a divalent or trivalent linker composed of a combination of -C(=O)- and -O-, -NH-, or -N<.

[0098] The group represented by formula (4) has a phenoxy carbonyl group.

[0099] In equation (4), R 401 R 402 R 403 R 404 and R 405 Each can be independently represented by a hydrogen atom or a monovalent substituent, L 4 This indicates a single bond or a divalent linker.

[0100] As a substituent with the above-mentioned 1 valence, the above-mentioned substituent S can be cited.

[0101] Furthermore, the aforementioned linker R can be cited as an example of a dual-valent linker.

[0102] In equation (4), from the perspective of presenting a green with a hue angle of 150° to 210° and from the perspective of improving lightfastness, R 401 R 402 R 403 R 404 and R 405 All are hydrogen atoms, or R 401 R 402 R 404 and R 405 All are hydrogen atoms, preferably R 403 Substituents with a valence of 1 (e.g., substituent S).

[0103] In equation (4), from the perspective of presenting a green with a hue angle of 150° to 210° and from the perspective of improving lightfastness, L 4 Single bonds are preferred.

[0104] In equation (5), L 5 This indicates a single bond or a divalent linker.

[0105] As a divalent linker, the linker R mentioned above can be cited.

[0106] In equation (5), from the perspective of presenting a green with a hue angle of 150° to 210° and from the perspective of improving lightfastness, L 5 Single bonds are preferred.

[0107] In equation (5), R 501 Indicates hydrogen atom, fluoroalkyl group, -CR 502 R 503 R 504 、or -CHR 505 OR 506 R 502 R 503 R 504 R 505 and R 506 Each alkyl group can be independently represented as either substituted or unsubstituted, R 505 With R 506 They can bond together to form a ring. Here, fluoroalkyl means an alkyl group substituted with at least one fluorine atom. Substituents such as substituent S can be cited as examples of substituents in the above-mentioned substituted alkyl groups.

[0108] In equation (5), considering both the presentation of green with a hue angle of 150° to 210° and the improvement of lightfastness, R 501 Hydrogen atoms are preferred.

[0109] The group represented by formula (6) has a hydroxyl group at the end.

[0110] In equation (6), L 6 This indicates a single bond or a divalent linker.

[0111] As a divalent linker, the linker R mentioned above can be cited.

[0112] In equation (6), from the perspective of presenting a green with a hue angle of 150° to 210° and from the perspective of improving lightfastness, L 6 Preferably, it is a divalent linker, more preferably a linker consisting of -C(=O)-, -O-, or -CR. A R B -and-NR C A divalent linker consisting of one or more of each of -C(=O)-, -O-, -NH-, and -CH2- is further preferably a divalent linker consisting of one or more of each of -C(=O)-, -O-, -NH-, and -CH2-. Here, R A R B and R C Each of the substituents, representing a hydrogen atom or a monovalent substituent, is represented independently, preferably in the manner described above as R. A R B and R C same.

[0113] The group represented by formula (7) has an unsubstituted amino group at the end.

[0114] In equation (7), L 7 This indicates a single bond or a divalent linker.

[0115] As a divalent linker, the linker R mentioned above can be cited.

[0116] In equation (7), from the perspective of presenting a green with a hue angle of 150° to 210° and from the perspective of improving lightfastness, L 7 Preferably, it is a divalent linker, more preferably a linker consisting of -C(=O)-, -O-, or -CR. A R B -and-NR C A divalent linker consisting of one or more of each of -C(=O)-, -O-, -NH-, and -CH2- is further preferably a divalent linker consisting of one or more of each of -C(=O)-, -O-, -NH-, and -CH2-. Here, R A R B and R C Each of the substituents, representing a hydrogen atom or a monovalent substituent, is represented independently, preferably in the manner described above as R. A R B and R C same.

[0117] From the viewpoint of solubility in solvents when applied to ink, a group represented by formula (3) or formula (5) is preferred as a specific substituent. Furthermore, from the viewpoint of readily available raw materials for synthesizing the fluorinated phthalocyanine compound represented by formula (1) and ease of synthesis, a group represented by formula (3), formula (4), or formula (5) is preferred as a specific substituent. Moreover, from the viewpoint of reducing penetration during printing on printing substrates such as cellulose-based ordinary paper and photographic paper composed of inorganic porous materials when applied to ink, a group represented by formula (6) or formula (7) is preferred as a specific substituent.

[0118] From the viewpoint of presenting a green color with a hue angle of 150° to 210° and from the viewpoint of improving lightfastness, the number of specific substituents in the fluorinated phthalocyanine compound represented by formula (1) is preferably 1 to 12, more preferably 4 to 10, and even more preferably 8.

[0119] The fluorinated phthalocyanine compounds involved in this invention preferably have a maximum absorption wavelength 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.

[0120] The molar absorptivity of the fluorinated phthalocyanine compound involved in this invention at the maximum absorption wavelength is preferably 100,000 L / (mol·cm) or more, and more preferably 120,000 L / (mol·cm) or more.

[0121] The aforementioned maximum absorption wavelength and molar absorptivity are the maximum absorption wavelength and molar absorptivity in the absorption spectrum of the fluorinated phthalocyanine compound in solution, determined using a spectrophotometer. Specific determination methods are described below. For example, using ethyl acetate, chloroform, or dimethylformamide as solvents, prepare 1×10⁻⁶... -6 For the obtained solution, a spectrophotometer (e.g., SHIMADZU CORPORATION UV-3100) was used to determine the concentration of M using a quartz cuvette with a path length of 10 mm.

[0122] The following are specific examples of fluorinated phthalocyanine compounds involved in this invention [(G-1) to (G-17)]. However, the fluorinated phthalocyanine compounds involved in this invention are not limited to the following specific examples.

[0123] [Chemical Formula 7]

[0124]

[0125] [Chemical Formula 8]

[0126]

[0127] [Chemical Formula 9]

[0128]

[0129] [Chemical Formula 10]

[0130]

[0131] [Chemical Formula 11]

[0132]

[0133] [Chemical Formula 12]

[0134]

[0135] [Chemical Formula 13]

[0136]

[0137] [Chemical Formula 14]

[0138]

[0139] [Chemical Formula 15]

[0140]

[0141] [Synthesis Method]

[0142] There are no particular limitations on the method for manufacturing the fluorinated phthalocyanine compounds involved in this invention. For example, they can be manufactured using known methods or by referring to known methods. For example, they can be synthesized according to the methods described in Japanese Patent Application Publication No. 2005-298491, etc.

[0143] Specifically, for example, the fluorinated phthalocyanine compounds involved in this invention can be manufactured by reacting 3,6-difluorophthalonitrile having various substituents at the 4 and 5 positions with metal salts such as copper acetate and zinc iodide in solvents such as diethylene glycol and benzonitrile at a temperature of 80°C to 200°C.

[0144] [use]

[0145] Since the fluorinated phthalocyanine compounds involved in this invention are green, they are suitable for use as colorants or pigments.

[0146] Furthermore, since the fluorinated phthalocyanine compound involved in this invention is green, it is suitable for use as a coloring composition containing the fluorinated phthalocyanine compound involved in this invention, or as an inkjet ink containing the fluorinated phthalocyanine compound involved in this invention.

[0147] <Coloring Composition>

[0148] There are no particular limitations on the coloring compositions involved in this invention, as long as they contain the fluorinated phthalocyanine compounds involved in this invention.

[0149] The properties of the coloring composition involved in this invention are particularly limited; for example, at 25°C, it can be liquid, solid, or semi-solid.

[0150] Furthermore, the components included in the coloring composition according to the present invention, other than the fluorinated phthalocyanine compounds according to the present invention (hereinafter also referred to as other components), may be appropriately determined according to the intended use of the coloring composition.

[0151] Examples of uses for the coloring compositions involved in this invention include various inks, coatings, dyes, coloring resins, masterbatches, and coloring resin particles.

[0152] Other components included in the coloring composition of the present invention may include solvents, resins, colorants other than the fluorinated phthalocyanine compounds involved in the present invention, release agents, antioxidants, surfactants, preservatives, and various other additives.

[0153] The content of the fluorinated phthalocyanine compound involved in the present invention in the coloring composition may be appropriately determined according to the intended use of the coloring composition.

[0154] Inkjet ink

[0155] There are no particular limitations on the inkjet inks involved in this invention, as long as they contain the fluorinated phthalocyanine compounds involved in this invention. For example, inkjet inks involved in this invention can be those in which the fluorinated phthalocyanine compounds involved in this invention are dissolved and / or dispersed in an oleophilic or aqueous medium.

[0156] In the inkjet inks of this invention, in addition to the fluorinated phthalocyanine compounds and oleophilic or aqueous media involved in this invention, as needed, colorants, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, mildew inhibitors, pH adjusters, surface tension adjusters, defoamers, viscosity adjusters, dispersants, dispersion stabilizers, rust inhibitors, chelating agents, and other known additives are included.

[0157] The inkjet ink involved in this invention can be an ink that is cured by irradiation with active energy rays. When the ink is cured by irradiation with active energy rays, in addition to the fluorinated phthalocyanine compounds involved in this invention and the oleophilic or aqueous media, it may also contain curing components (e.g., polymerizable compounds, polymerization initiators, epoxy compounds, curing agents, etc.), colorants other than the fluorinated phthalocyanine compounds involved in this invention, and known additives, etc.

[0158] The content of the fluorinated phthalocyanine compound involved in this invention in the inkjet ink of this invention can be appropriately determined according to the type of ink. The content of the fluorinated phthalocyanine compound involved in this invention is preferably 0.5% to 8% by mass, more preferably 3% to 6% by mass, relative to the total mass of the inkjet ink of this invention.

[0159] Example

[0160] The present invention will now be described in detail through embodiments. However, the present invention is not limited to the following embodiments.

[0161] The compounds (G-1) to (G-14) and (G-16) shown below are the same as (G-1) to (G-14) and (G-16) in the specific examples of the fluorinated phthalocyanine compounds involved in the present invention described above.

[0162] <Synthetic Example 1: Synthesis of Compound (G-1)>

[0163] In a 50 mL flask, add 388 mg of zinc iodide, 2.11 g of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile, and 4 mL of benzonitrile. Under a nitrogen atmosphere, react at 150 °C for 3 hours, 160 °C for 3 hours, and 170 °C for 2 hours. Cool the flask to room temperature (25 °C), and reprecipitate with 60 mL of methanol. Filter and collect the precipitated crystals.

[0164] The obtained crystals were purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1 / 1, v / v) to obtain compound (G-1). The yield was 0.44 g, or 17%. MALDI (Matrix-Assisted Laser Desorption / Ionization)-TOF MS (Time-of-Flight Mass Analysis): 2132 ([M+1]) + ).

[0165] The maximum absorption wavelength of compound (G-1) in dilute ethyl acetate solution is 664 nm.

[0166] Figure 1 The absorption spectrum of a dilute ethyl acetate solution of compound (G-1) is shown. Furthermore, Figure 4 The image shows the compound (G-1) in deuterated chloroform. 1 H-NMR spectrum.

[0167] <Synthetic Example 2: Synthesis of Compound (G-2)>

[0168] The 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile in Synthetic Example 1 was changed to 2.43 g of 3,6-difluoro-4,5-bis[4-(diallylaminocarbonyl)phenoxy]phthalonitrile, and compound (G-2) was obtained by the same method. MALDI-TOF MS: 2242 ([M+1]) + ).

[0169] The maximum absorption wavelength of the absorption spectrum of compound (G-2) in a dilute ethyl acetate solution is 664 nm.

[0170] <Synthetic Example 3: Synthesis of Compound (G-3)>

[0171] The 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile: 2.11 g in Synthetic Example 1 was changed to 3,6-difluoro-4,5-bis[4-(allylaminocarbonyl)phenoxy]phthalonitrile: 2.10 g, and the compound (G-3) was obtained by the same method. MALDI-TOF MS: 2122 ([M+1) + ).

[0172] The maximum absorption wavelength of the absorption spectrum of compound (G-3) in a dilute ethyl acetate solution is 664 nm.

[0173] <Synthetic Example 4: Synthesis of Compound (G-4)>

[0174] Compound (G-10), synthesized by the method described in Synthetic Example 10 (described later), was dissolved in 10 mL of N-methylpyrrolidone, and the mixture was cooled to 0°C. Methacrylic anhydride, 0.6 g, was added, and the mixture was reacted at room temperature for 30 minutes, then at 45°C for 60 minutes. The reaction mixture was poured into water, extracted with ethyl acetate, and purified by silica gel column chromatography (developing solvent: ethyl acetate) to obtain compound (G-4). MALDI-TOF MS: 2705 ([M+1]). + ).

[0175] The maximum absorption wavelength of the absorption spectrum of compound (G-4) in a dilute ethyl acetate solution is 664 nm.

[0176] <Synthetic Example 5: Synthesis of Compound (G-5)>

[0177] The amount of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile in Synthetic Example 1 was changed to 2.40 g of 3,6-difluoro-4,5-bis[4-(phenoxycarbonyl)phenoxy]phthalonitrile, and compound (G-5) was obtained by the same method. MALDI-TOF MS: 2417 ([M+1) + ).

[0178] The maximum absorption wavelength of the absorption spectrum of compound (G-5) in a dilute ethyl acetate solution is 664 nm.

[0179] Figure 2 The absorption spectrum of a dilute ethyl acetate solution of compound (G-5) is shown. Furthermore, Figure 5 The image shows the compound (G-5) in deuterated chloroform. 1 H-NMR spectrum.

[0180] <Synthetic Example 6: Synthesis of Compound (G-6)>

[0181] The amount of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile in Synthetic Example 1 was changed to 2.52 g of 3,6-difluoro-4,5-bis[4-((4-methylphenoxy)carbonyl)phenoxy]phthalonitrile, and compound (G-6) was obtained by the same method. MALDI-TOFMS: 2530 ([M+1]) + ).

[0182] The maximum absorption wavelength of the absorption spectrum of compound (G-6) in a dilute ethyl acetate solution is 664 nm.

[0183] <Synthetic Example 7: Synthesis of Compound (G-7)>

[0184] The amount of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile in Synthetic Example 1 was changed to 3,6-difluoro-4,5-bis[4-((4-chlorophenoxy)carbonyl)phenoxy]phthalonitrile: 3.19 g, and the compound (G-7) was obtained by the same method. MALDI-TOFMS: 2689 ([M+1) + ).

[0185] The maximum absorption wavelength of the absorption spectrum of compound (G-7) in a dilute ethyl acetate solution is 664 nm.

[0186] <Synthetic Example 8: Synthesis of Compound (G-8)>

[0187] The amount of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile in Synthetic Example 1 was changed to 2.77 g of 3,6-difluoro-4,5-bis[4-((4-nitrophenoxy)carbonyl)phenoxy]phthalonitrile, and compound (G-8) was obtained by the same method. MALDI-TOFMS: 2777 ([M+1) + ).

[0188] The maximum absorption wavelength of the absorption spectrum of compound (G-8) in a dilute ethyl acetate solution is 665 nm.

[0189] <Synthetic Example 9: Synthesis of Compound (G-9)>

[0190] The 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile in Synthetic Example 1 was changed to 1.77 g of 3,6-difluoro-4,5-bis(4-carboxyphenoxy)phthalonitrile, and compound (G-9) was obtained by the same method. MALDI-TOF MS: 1809 ([M+1]) + ).

[0191] The maximum absorption wavelength of the absorption spectrum of compound (G-9) in a dilute ethyl acetate solution is 663 nm.

[0192] <Synthetic Example 10: Synthesis of Compound (G-10)>

[0193] The amount of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile in Synthetic Example 1 was changed to 2.14 g of 3,6-difluoro-4,5-bis[4-((2-hydroxyethyloxy)carbonyl)phenoxy]phthalonitrile, and compound (G-10) was obtained by the same method. MALDI-TOF MS: 2161 ([M+1]) + ).

[0194] The maximum absorption wavelength of the absorption spectrum of compound (G-10) in a dilute ethyl acetate solution is 664 nm.

[0195] <Synthetic Example 11: Synthesis of Compound (G-11)>

[0196] The amount of 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile in Synthetic Example 1 was changed to 2.13 g of 3,6-difluoro-4,5-bis[4-((2-aminoethyl)oxycarbonyl)phenoxy]phthalonitrile, and compound (G-11) was obtained by the same method. MALDI-TOF MS: 2153 ([M+1) +).

[0197] The maximum absorption wavelength of the absorption spectrum of compound (G-11) in dilute ethyl acetate solution is 664 nm.

[0198] <Synthetic Example 12: Synthesis of Compound (G-12)>

[0199] The 3,6-difluoro-4,5-bis[4-(allyloxycarbonyl)phenoxy]phthalonitrile in Synthetic Example 1 was changed to 2.11 g of 3,6-difluoro-4,5-bis[3-(allylaminocarbonyl)phenoxy]phthalonitrile, and compound (G-12) was obtained by the same method, except that. MALDI-TOFMS: 2122([M+1) + ).

[0200] The maximum absorption wavelength of the absorption spectrum of compound (G-12) in a dilute ethyl acetate solution is 668 nm.

[0201] <Synthetic Example 13: Synthesis of Compound (G-13)>

[0202] In Synthesis Example 1, zinc iodide (388 mg) was replaced with anhydrous copper acetate (112 mg), and benzonitrile was replaced with ethylene glycol as the solvent. All other things being equal, compound (G-13) was obtained. MALDI-TOF MS: 2128 ([M+1]) + ).

[0203] The maximum absorption wavelength of the absorption spectrum of compound (G-13) in a dilute ethyl acetate solution is 639 nm.

[0204] <Synthetic Example 14: Synthesis of Compound (G-14)>

[0205] In Synthesis Example 1, zinc iodide (388 mg) was replaced with vanadium trichloride (58 mg), and the solvent benzonitrile was replaced with diethylene glycol monobutyl ether. All other things being equal, compound (G-14) was obtained in the same manner. MALDI-TOF MS: 2132 ([M+1] + ).

[0206] The maximum absorption wavelength of the absorption spectrum of compound (G-14) in a dilute ethyl acetate solution is 679 nm.

[0207] <Synthetic Example 15: Synthesis of Compound (G-16)>

[0208] The 3,6-difluoro-4,5-bis[4-(oxycarbonyl)phenoxy]phthalonitrile: 2.11 g in Synthesis Example 1 was replaced with 3,6-difluoro-4,5-bis[4-((2,2,2,-trifluoroethyl)oxycarbonyl)phenoxy]phthalonitrile: 2.45 g, and the compound (G-16) was obtained by the same method. MALDI-TOF MS: 2465 ([M+1) + ).

[0209] The maximum absorption wavelength of the absorption spectrum of compound (G-16) in a dilute ethyl acetate solution is 664 nm.

[0210] Figure 3 The absorption spectrum of a dilute ethyl acetate solution of compound (G-16) is shown in the figure.

[0211] <Preparation of Inkjet Ink (1)>

[0212] 7.5 g of compound (G-1), 7.04 g of sodium dioctyl sulfosuccinate, 4.22 g of tris(m-formyl)phosphine oxide, 5.63 g of tris(tert-octyl)phosphine oxide, and 50 mL of ethyl acetate were mixed and dissolved at 70 °C. While stirring with a magnetic stirrer, 500 mL of deionized water was added to the solution to prepare an oil droplet-type coarse dispersion in water. Then, the coarse dispersion was micronized by passing it through a microfluidic generator (manufactured by MICROFLUIDEX INC.) five times at a pressure of 60 MPa. Furthermore, the supported emulsion was desolvated using a rotary evaporator until the odor of ethyl acetate disappeared. To prepare an ink, 140 g of diethylene glycol, 50 g of glycerol, 7 g of SURFYNOL 465 (Air Products & Chemicals), and 900 mL of deionized water were added to the thus obtained microemulsion of compound (G-1).

[0213] <Production of Inkjet Ink (2)~(14)>

[0214] Instead of compound (G-1), any one of compounds (G-2) to (G-14) was used, and inkjet inks (2) to (14) were obtained in the same manner as the preparation of inkjet ink (1).

[0215] <Preparation of Inkjet Ink (A)~(B)>

[0216] Instead of compound (G-1), comparative compound (A) or comparative compound (B) described below were used, and inkjet inks (A) to (B) were obtained in the same manner as the preparation of inkjet ink (1).

[0217] [Chemical Formula 16]

[0218]

[0219] (Preparation and evaluation of printed samples)

[0220] Using each of the inkjet inks (1) to (14) and (A) to (B), a solid image with a reflectance 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, trade name: Material Printer DMP-2850) to obtain a printed sample.

[0221] Using the obtained printed samples, the following evaluations were conducted: lightfastness, hue angle measurement, visual color confirmation, and maximum color concentration measurement. The results are shown in Table 1.

[0222] <Lightfastness Evaluation>

[0223] The obtained print samples were irradiated with a xenon lamp (85,000 lux) for 7 days using a thermometer (Atlas, Ci65). The reflectance of solid images with a reflectance of 1.0 before irradiation was measured using a reflectance meter (X-Rite ilPro). Since the reflectance of the solid image before xenon lamp irradiation was 1.0, the compound retention rate (%) after xenon lamp irradiation was calculated using the following formula. A higher compound retention rate (%) indicates better lightfastness of the fluorinated phthalocyanine compounds contained in the print sample.

[0224] Compound retention rate (%) = (Reflectance concentration of the solid image after xenon lamp irradiation) / (Reflectance concentration of the solid image before xenon lamp irradiation = 1.0) × 100

[0225] <Calculation of Hue Angle>

[0226] The hue angle in the solid image of the printed sample with a reflectance density of 1.0 was calculated as follows: First, the color value L of the solid image of the printed sample with a reflectance density of 1.0 was measured using a reflectance density meter (X-Rite, trade name: X-Rite ilPro) under conditions of a viewing angle of 2 degrees and a C light source. * a * b * The obtained a * and b * Substitution formula: Hue angle (h°) = tan -1 (a * / b * ), calculate the hue angle in a solid image of a printed sample with a reflectance concentration of 1.0.

[0227] <Color>

[0228] The color of the solid image with a reflectance concentration of 1.0 obtained from the printed sample was visually confirmed.

[0229] Maximum color density

[0230] The reflectance density in the solid image of the obtained printed sample with maximum color density was measured using a reflectance density meter (X-Rite, trade name: X-Rite ilPro) under conditions of 2-degree viewing angle and C light source.

[0231] [Table 1]

[0232]

[0233] As can be seen from Table 1, the fluorinated phthalocyanine compounds involved in this invention (i.e., fluorinated phthalocyanine compounds represented by formula (1)) have a hue angle in the range of 150° to 210°, exhibit green color, and also have excellent lightfastness.

[0234] Furthermore, it is known that images with the highest color density can be obtained by using the fluorinated phthalocyanine compounds involved in this invention (i.e., fluorinated phthalocyanine compounds represented by formula (1)).

[0235] It can be seen that the comparative compound (A) used in Comparative Example 1 is green, but its lightfastness is poor compared with that of the examples.

[0236] The comparative compound (B) used in Comparative Example 2 has excellent lightfastness, but it is not green and appears cyan instead of green when the hue angle is outside the range of 150° to 210°.

[0237] The entire disclosure of Japanese Patent Application No. 2021-188790, filed on November 19, 2021, is incorporated herein by reference. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as each document, patent application, and technical standard specifically and individually described and referenced by reference.

Claims

1. A fluorinated phthalocyanine compound, represented by the following formula (1), 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 All are groups represented by the following formula (2), R in equation (2) 202 R 203 and R 204 R is any one of the groups selected from formulas (3), (4), (5), (6), and (7). 202 R 203 and R 204 The remaining two, R 201 and R 205 All are hydrogen atoms. In equation (3), R 301 R 302 and R 303 Each can be used independently to represent a hydrogen atom or an alkyl group, L 3 This represents a divalent or trivalent linker group consisting of combinations of -C(=O)- and -O-, -NH-, or -N<, where n represents 1 or 2. In equation (4), R 401 R 402 R 403 R 404 and R 405 Each of the following can be independently represented: hydrogen atom, halogen atom, alkyl group, or nitro group. 4 Indicates a single key. In equation (5), L 5 Indicates a single bond, R 501 Represents a hydrogen atom. In equation (6), L 6 It represents -C(=O)-O-CH2-CH2-, In equation (7), L 7 It represents -C(=O)-NH-CH2-CH2-.

2. The fluorinated phthalocyanine compound according to claim 1, wherein, R in equation (2) 203 R is selected from any one of the groups in formula (3), formula (4), formula (5), formula (6) and formula (7). 201 R 202 R 204 and R 205 It consists entirely of hydrogen atoms.

3. The fluorinated phthalocyanine compound according to claim 1 or 2, wherein, M can be copper, zinc, or vanadium oxide.

4. The fluorinated phthalocyanine compound according to claim 3, wherein, M represents copper or zinc.

5. The fluorinated phthalocyanine compound according to claim 4, wherein, M stands for zinc.

6. A coloring composition comprising the fluorinated phthalocyanine compound according to any one of claims 1 to 5.

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

Images