Phthalocyanine pigment, phthalocyanine compound, coloring composition, method for producing phthalocyanine pigment, and method for producing coloring composition

Abstract

Provided is a phthalocyanine pigment represented by general formula (1), the pigment having at least one diffraction peak at 3°≤2θ≤7° in the powder X-ray diffraction spectrum.

Description

Phthalocyanine pigment, phthalocyanine compound, colored composition, method for producing phthalocyanine pigment, and method for producing colored composition

[0001] The present disclosure relates to a phthalocyanine pigment, a phthalocyanine compound, a colored composition, a method for producing a phthalocyanine pigment, and a method for producing a colored composition.

[0002] Conventionally, coloring compositions contain various pigments, dyes, etc. For example, JP 2016-141792 A discloses a coloring composition containing C.I. Pigment Green 58 (hereinafter also referred to as "PG58") having a true density of 2.985 to 3.005 as a pigment. In addition, WO 2020 / 171139 discloses a coloring composition containing a dye instead of a pigment for the purpose of improving brightness.

[0003] Pigments contained in coloring compositions are required to have various properties depending on their intended use. For example, in recent years, they are required to be able to suppress color changes caused by prolonged exposure to sunlight or the like (hereinafter also referred to as "lightfastness"). Furthermore, from the viewpoint of forming good images or the like, pigments are required to be able to suppress aggregation over time (hereinafter also referred to as "aggregation suppression"). Pigments with excellent aggregation suppression properties can improve the ejection stability when used in inkjet printing, for example, and as a result, can suppress the occurrence of blurring or the like in images formed by inkjet printing.

[0004] An object of one embodiment of the present disclosure is to provide a phthalocyanine pigment, a phthalocyanine compound, and a colored composition that are excellent in light fastness and aggregation inhibition properties.An object of another embodiment of the present disclosure is to provide a method for producing a phthalocyanine pigment, and a method for producing a colored composition that are excellent in light fastness and aggregation inhibition properties.

[0005] The present disclosure includes the following aspects: <1> A phthalocyanine pigment having at least one diffraction peak at 3°≦2θ≦7° in a powder X-ray diffraction spectrum, and represented by the following general formula (1):

[0006]

[0007] In formula (1), M represents zinc or copper; 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 the above is a group represented by the following formula (2):

[0008]

[0009] In formula (2), R ２０１ , R ２０２ , R ２０３ , R ２０４ , and R ２０５ each independently represents a hydrogen atom, an alkyl group, a phenoxycarbonyl group, or an alkoxy group; R ２０１ , R ２０２ , R ２０３ , R ２０４ , and R ２０５ At least one of R is an alkyl group, a phenoxycarbonyl group, or an alkoxy group, and * represents a linking point with an oxygen atom. ２０１ , R ２０２ , R ２０４ , and R ２０５ is a hydrogen atom, and R ２０３ <4> The phthalocyanine pigment according to the above <2>, wherein in formula (2), R represents an alkyl group, a phenoxycarbonyl group, or an alkoxy group. ２０１ , R ２０２ , R ２０４ , and R ２０５ is a hydrogen atom, and R２０３ represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, or a propyloxy group. <5> The phthalocyanine pigment according to any one of <1> to <4> above, which has a solubility in acetone at 25°C of less than 0.005 mass%. <6> A phthalocyanine compound represented by the following general formula (3):

[0010]

[0011] In formula (3), M represents zinc or copper; ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ , R ３０６ , R ３０７ , and R ３０８ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ , R ３０６ , R ３０７ , and R ３０８ At least one of these is an aryl group represented by the following formula (4).

[0012]

[0013] In formula (4), R ４０１ , R ４０２ , R ４０４ , and R ４０５ is a hydrogen atom, and R ４０３represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, or a propyloxy group, and * represents a linkage with an oxygen atom. <7> A colored composition comprising at least one of the phthalocyanine pigment according to any one of <1> to <5> above and the phthalocyanine compound according to <6> above. <8> The colored composition according to <7> above, which contains a solvent having a boiling point at 1013.2 hPa of less than 160°C. <9> The colored composition according to <8> above, which contains at least one solvent selected from the group consisting of alcohols, ketones, carboxylic acid esters, and ethers. <10> The colored composition according to <7> or <8> above, which contains a carboxylic acid ester. <11> The colored composition according to any one of <7> to <10> above, which does not contain an amide solvent, or which contains an amide solvent, and the content of the amide solvent relative to the total mass of the colored composition is 10 mass% or less. <12> The colored composition according to any one of <7> to <11> above, which contains a dispersant. <13> The colored composition according to <12> above, wherein the dispersant is a polymer dispersant having a weight-average molecular weight of 1,000 to 100,000. <14> The colored composition according to any one of <7> to <13> above, which is an ink-jet ink. <15> A method for producing a phthalocyanine pigment, comprising a mixing step of mixing a phthalonitrile compound represented by any one of the following general formulas (5) to (8), a metal salt of at least one of zinc and copper, and a solvent, wherein in the mixing step, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used is 2.0 times or less, on a mass basis:

[0014]

[0015] In formulas (5) to (8), R １０１ , R １０２ , R １０３ , R １０４ , R １０５ , R １０６ , R １０７ , and R １０８each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. <16> A method for producing a colored composition, comprising a mixing step of mixing at least one of the phthalocyanine pigment according to <1> above and the phthalocyanine compound according to <6> above with a solvent. <17> A method for producing a colored composition according to <16> above, wherein in the mixing step, at least one of the phthalocyanine pigment and the phthalocyanine compound is dispersed in the solvent.

[0016] According to one embodiment of the present disclosure, it is possible to provide a phthalocyanine pigment, a phthalocyanine compound, and a colored composition that are excellent in light fastness and aggregation inhibition properties. According to another embodiment of the present disclosure, it is possible to provide a method for producing a phthalocyanine pigment and a colored composition that are excellent in light fastness and aggregation inhibition properties.

[0017] FIG. 1 is an X-ray diffraction spectrum obtained by subjecting the pigment G-1 produced in Example 1 to powder X-ray diffraction.

[0018] Hereinafter, an embodiment of the present invention will be described. These descriptions and examples are intended to illustrate the embodiments and do not limit the scope of the invention. In this disclosure, the use of "to" to indicate a numerical range means that the numerical values ​​before and after it are included as the upper and lower limits. In numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with the value shown in the examples.

[0019] In this disclosure, "pigment" refers to a compound having a solubility in acetone at 25°C of less than 0.01% by mass. The solubility is preferably less than 0.005% by mass. In this disclosure, "dye" refers to a compound having a solubility in acetone at 25°C of 0.01% by mass or more. Here, pigments and dyes have different crystallinity, and this crystallinity changes the degree of interaction between the compounds, resulting in changes in solubility in the solvent. In other words, even if two compounds have the same structure, one can be classified as a pigment and the other as a dye based on the difference in crystallinity. In this disclosure, powder X-ray diffraction spectroscopy is used as one method for evaluating this crystallinity.

[0020] Each component may contain multiple corresponding substances. When referring to the amount of each component in a composition, if multiple substances corresponding to each component are present in the composition, the total amount of those multiple substances present in the composition is meant unless otherwise specified. In this disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. In this disclosure, "(meth)acrylic" refers to acrylic and methacrylic. In this disclosure, a combination of two or more preferred aspects is a more preferred aspect. In this disclosure, when embodiments are described with reference to drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings.

[0021] [Phthalocyanine Pigment] The phthalocyanine pigment of the present disclosure has at least one diffraction peak at 3°≦2θ≦7° in a powder X-ray diffraction spectrum, and is represented by the following general formula (1). In formula (1), M represents zinc or copper, preferably zinc; 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.

[0022] The phthalocyanine pigment of the present disclosure has excellent lightfastness and aggregation-suppressing properties. The reason for this effect is not clear, but is presumed to be as follows. The phthalocyanine pigment of the present disclosure has at least one diffraction peak at 3°≦2θ≦7° in its powder X-ray diffraction spectrum. This indicates that the pigment contains a crystalline state with a large lattice plane spacing d, and it is presumed that the proportion of phthalocyanine rings exhibiting strong association per unit area is small. Therefore, it is presumed that the influence of π-π interactions between phthalocyanine rings is reduced when pigment particles approach each other, thereby reducing the tendency for the pigment particles to aggregate. Furthermore, the phthalocyanine pigment of the present disclosure has a smaller particle surface area than dyes, making it less susceptible to attack by active oxygen and the like, and therefore is presumed to have excellent lightfastness.

[0023] The phthalocyanine pigment of the present disclosure has at least one diffraction peak at 3°≦2θ≦7° in its powder X-ray diffraction spectrum, but may have two or more diffraction peaks. The diffraction peak of the phthalocyanine pigment of the present disclosure can be adjusted by adjusting the ratio of the amount of solvent used to the amount of phthalonitrile compound used in the production of the phthalocyanine pigment. The diffraction peak can also be adjusted by, for example, changing the type of phthalonitrile compound used.

[0024] In the present disclosure, diffraction peaks are observed as follows. X-ray diffraction is performed using the phthalocyanine pigment powder of the present disclosure under the following conditions, and the number of diffraction peaks at diffraction angles 2θ of 3° to 7° is confirmed. A known device can be used as the measurement device. Examples of X-ray devices that can be used include the smartlab manufactured by Rigaku Corporation, the D8 Discover and Malvern manufactured by Bruker, and the Empyrean manufactured by Panalytical. When the maximum peak intensity in the obtained X-ray diffraction spectrum (diffraction angle 2θ = 2° to 60°) is designated as Z, a peak having an intensity of 1 / 4Z or more is recognized as a diffraction peak. (Measurement conditions) Radiation source: Cu Diffraction angle 2θ: 2° to 60° θ step: 0.01°

[0025] From the viewpoint of aggregation suppression, the phthalocyanine pigment of the present disclosure preferably has at least one diffraction peak within the range of 3.8°≦2θ≦6° in a powder X-ray diffraction spectrum.

[0026] In formula (1), R １０１ , R １０２ , R １０３ , R １０４ , R １０５ , R １０６ , R １０７ , and R １０８each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 9-anthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a 5-naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 1-acenaphthyl group, a 2-fluorenyl group, a 9-fluorenyl group, a 3-perylenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2, Examples include a 3-xylyl group, a 2,5-xylyl group, a mesityl group, a p-cumenyl group, a p-dodecylphenyl group, a p-cyclohexylphenyl group, a 4-biphenyl group, an o-fluorophenyl group, a m-chlorophenyl group, a p-bromophenyl group, a p-hydroxyphenyl group, a m-carboxyphenyl group, an o-mercaptophenyl group, a p-cyanophenyl group, a m-nitrophenyl group, and a m-azidophenyl group. Examples of the heterocyclic group include an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, a benzopyrazolyl group, a triazolyl group, a thiazolyl group, a benzothiazolyl group, an isothiazolyl group, a benzisothiazolyl group, an oxazolyl group, a benzoxazolyl group, a thiadiazolyl group, a pyrrolyl group, a benzopyrrolyl group, an indolyl group, an isoxazolyl group, a benzisoxazolyl group, a thienyl group, a benzothienyl group, a furyl group, a benzofuryl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a cinnolinyl group, a phthalazinyl group, a quinazolinyl group, a quinoxalinyl group, and a triazinyl group. When the alkyl group, aryl group, or heterocyclic group has a substituent, examples of the substituent include an alkyl group, a hetero group, an aryl group, a halogen atom, a phenoxycarbonyl group, a phenoxyalkyl group, an acetyl group, an alkoxy group, an amido group, a sulfoalkyl group, and a sulfonamide group.

[0027] From the viewpoint of the aggregation-inhibiting ability of the phthalocyanine pigment of the present disclosure, among the above, a substituted or unsubstituted aryl group is preferred, and a substituted aryl group is more preferred. From the viewpoint of the aggregation-inhibiting ability, the substituent of the substituted aryl group is preferably an alkyl group, a phenoxycarbonyl group, a halogen atom, an alkoxycarbonyl group, a phenyl group, or an alkoxy group, more preferably an alkyl group, a phenoxycarbonyl group, or an alkoxy group, still more preferably an alkyl group or an alkoxy group, and particularly preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

[0028] From the viewpoint of aggregation suppression, in formula (1), R １０１ , R １０２ , R １０３ , R １０４ , R １０５ , R １０６ , R １０７ , and R １０８ Among these, preferably at least one, more preferably at least two, even more preferably at least three, particularly preferably at least four, and most preferably all are a group represented by the following formula (2).

[0029]

[0030] In formula (2), R ２０１ , R ２０２ , R ２０３ , R ２０４ , and R ２０５ each independently represents a hydrogen atom or a monovalent substituent, and * represents a linking portion to the oxygen atom. Examples of the monovalent substituent include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. From the viewpoint of aggregation suppression, preferably, in formula (2), R ２０１ , R ２０２ , R ２０３ , R ２０４ , and R ２０５ each independently represents any one selected from a hydrogen atom, a halogen atom, a phenyl group, an alkyl group, a phenoxycarbonyl group, and an alkoxy group; R ２０１ , R ２０２ , R ２０３ , R ２０４ , and R２０５ In view of the aggregation suppression property, it is more preferable that at least one of R ２０１ , R ２０２ , R ２０４ , and R ２０５ is a hydrogen atom, and R ２０３ represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, or a propyloxy group.

[0031] An example of the phthalocyanine pigment of the present disclosure is shown below. Note that the phthalocyanine pigment of the present disclosure is not limited to the following compound. Note that in the chemical formula in the present disclosure, Me represents a methyl group and Ph represents a phenyl group.

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] [Phthalocyanine Compound] The phthalocyanine compound of the present disclosure is represented by the following general formula (3).

[0047]

[0048] In formula (3), M represents zinc or copper, preferably zinc; ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ , R ３０６ , R ３０７ , and R ３０８ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ , R ３０６ , R ３０７ , and R ３０８ At least one of these is an aryl group represented by the following formula (4): The alkyl group, aryl group, and heterocyclic group are the same as those in the phthalocyanine pigment of the present disclosure, and therefore further description thereof will be omitted here.

[0049] In formula (4), R ４０１ , R ４０２ , R ４０４ , and R ４０５ is a hydrogen atom, and R ４０３ represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, or a propyloxy group, and * represents a linking point to an oxygen atom. The propyl group, the butyl group, and the propyloxy group may be linear or branched.

[0050] The phthalocyanine compound of the present disclosure has excellent light resistance and aggregation suppression properties. The reason for this effect is not clear, but is presumed to be as follows. The phthalocyanine compound of the present disclosure has a specific structure. This is presumed to increase the lattice spacing d of the crystal, thereby reducing the tendency for pigments to aggregate. Furthermore, the phthalocyanine compound has R 1 , which represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, or a propyloxy group. ４０３It is presumed that the presence of the group represented by formula (4) having the following structure effectively acts to dissipate light energy while appropriately alleviating the association and aggregation state of the phthalocyanine compound, thereby improving light resistance.

[0051] From the viewpoint of aggregation suppression, in formula (3), R ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ , R ３０６ , R ３０７ , and R ３０８ Among these, preferably at least two, more preferably at least three, even more preferably at least four, and particularly preferably all, are aryl groups represented by the above formula (4).

[0052] The solubility of the phthalocyanine compound of the present disclosure in acetone at 25° C. is preferably less than 0.01% by mass, and more preferably less than 0.005% by mass.

[0053] Examples of the phthalocyanine compound of the present disclosure include compounds (2) to (5) exemplified above as the phthalocyanine pigment, but the phthalocyanine compound of the present disclosure is not limited to these compounds.

[0054] [Coloring Composition] The coloring composition of the present disclosure contains at least one of the phthalocyanine pigment and the phthalocyanine compound.

[0055] From the viewpoint of aggregation inhibition and storage stability, the viscosity of the colored composition of the present disclosure at 25° C. is preferably 1.0 MPa·s to 15.0 MPa·s, more preferably 2.0 MPa·s to 10.0 MPa·s, and even more preferably 3.0 MPa·s to 8.0 MPa·s. In the present disclosure, the viscosity is measured with a viscometer, and for example, a viscometer RE85L (rotor: 1°34′×R24, measurement range 0.6 to 1200 mPa·s) manufactured by Toki Sangyo Co., Ltd. can be used.

[0056] (Phthalocyanine Pigment and Phthalocyanine Compound) Details of the phthalocyanine pigment and the phthalocyanine compound have been described above, so further description will be omitted here. The colored composition of the present disclosure may contain multiple types of the phthalocyanine pigment and the phthalocyanine compound. For example, the colored composition may contain one or more types of phthalocyanine pigment and one or more types of phthalocyanine compound, or may contain multiple types of phthalocyanine pigments having different structures, or may contain multiple types of phthalocyanine compounds having different structures. From the viewpoint of light fastness and aggregation inhibition, the sum of the contents of the phthalocyanine pigment and the phthalocyanine compound relative to the total mass of the colored composition is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 8% by mass, and even more preferably 3% by mass to 6% by mass.

[0057] (Solvent) From the viewpoint of aggregation suppression, the colored composition of the present disclosure preferably contains a solvent having a boiling point of less than 160°C at 1013.2 hPa (hereinafter also referred to as "specific solvent"). The boiling point is preferably 60°C to 158°C, and more preferably 80°C to 150°C. In the present disclosure, the boiling point is a value measured with a boiling point meter, and can be measured using, for example, a DosaTherm 300 manufactured by Titan Technologies Co., Ltd. Examples of the specific solvent include methyl alcohol, ethyl alcohol, butyl alcohol, isobutyl alcohol, tert-butyl alcohol, propyl alcohol, isopropyl alcohol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, and ethylene glycol methyl ether.

[0058] The coloring composition of the present disclosure may contain a solvent other than the specific solvent (hereinafter also referred to as "other solvent"). The solvent may contain at least one selected from water, alcohol, ketone, carboxylic acid ester, and ether. Examples of the alcohol include methyl alcohol, ethyl alcohol, butyl alcohol, isobutyl alcohol, tert-butyl alcohol, propyl alcohol, isopropyl alcohol, 1-methoxy-2-propanol, benzyl alcohol, 1,2-hexanediol, glycerin, fluorinated alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, trimethylolethane, and trimethylolpropane. Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the carboxylic acid ester include propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, and ethyl propionate. Examples of the ether include diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, etc. Among the above, the solvent preferably contains at least one selected from alcohols, ketones, and carboxylic acid esters, and more preferably contains a carboxylic acid ester.

[0059] The colored composition of the present disclosure may contain only one type of solvent, or may contain multiple types. The content of the solvent relative to the total mass of the colored composition is preferably adjusted appropriately depending on the application of the colored composition, and can be, for example, 1% by mass to 50% by mass. From the viewpoint of aggregation suppression, the content of the specific solvent relative to the total mass of the solvents contained in the colored composition of the present disclosure is preferably 50 to 100% by mass, more preferably 80 to 100% by mass.

[0060] (Amide solvent) From the viewpoint of aggregation suppression, the colored composition of the present disclosure preferably does not contain an amide solvent, or contains an amide solvent, and the content of the amide solvent relative to the total mass of the colored composition is preferably 10% by mass or less, more preferably does not contain an amide solvent, or contains an amide solvent, and the content of the amide solvent relative to the total mass of the colored composition is 5% by mass or less, even more preferably does not contain an amide solvent, or contains an amide solvent, and the content of the amide solvent relative to the total mass of the colored composition is 3% by mass or less, particularly preferably does not contain an amide solvent, or contains an amide solvent, and the content of the amide solvent relative to the total mass of the colored composition is 1% by mass or less, and most preferably does not contain an amide solvent. In the present disclosure, amide solvent means a solvent having an amide bond, and examples thereof include dimethylformaldehyde, diethylformaldehyde, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, 3-methoxy-N,N-dimethylpropanamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, and the like. It should be noted that compounds having an amide bond, such as yellow dyes, are not solvents and are therefore not included in the amide solvents in the present disclosure.

[0061] (Dispersant) From the viewpoint of aggregation suppression property and storage stability, the colored composition of the present disclosure preferably contains a dispersant.

[0062] The type of dispersant is not particularly limited as long as it can disperse the pigment in the coloring composition and maintain that state stably. For example, cationic, anionic, nonionic, amphoteric, and other dispersants can be used.

[0063] From the viewpoint of aggregation suppression and storage stability, the dispersant is preferably a polymer dispersant. In the present disclosure, a polymer dispersant means a dispersant having a weight average molecular weight of 500 or more.

[0064] Examples of dispersants include modified acrylic copolymers, acrylic copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate ester salts of polymeric copolymers, and cationic comb-type graft polymers.

[0065] From the viewpoint of aggregation suppression and storage stability, the weight-average molecular weight of the dispersant is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 10,000 to 45,000. In the present disclosure, unless otherwise specified, the weight-average molecular weight is a molecular weight calculated using a gel permeation chromatography (GPC) analyzer with a column of TSKgel Super HM-H (trade name of Tosoh Corporation) in a solvent of PFP (pentafluorophenol) / chloroform = 1 / 2 (mass ratio) and a differential refractometer, and converted using polystyrene as a standard substance.

[0066] From the viewpoint of aggregation suppression property and storage stability, the content of the dispersant relative to the total mass of the colored composition is preferably 1% by mass to 20% by mass, more preferably 5% by mass to 15% by mass, and even more preferably 8% by mass to 13% by mass.

[0067] (Resin) The coloring composition of the present disclosure may contain a resin. Examples of the resin include an acrylic resin, a styrene-(meth)acrylic resin, a vinyl resin, a polyurethane, a polyester, a polyamide, and a fluororesin.

[0068] Examples of the acrylic resin include a homopolymer of a monomer selected from the group consisting of (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, and a (meth)acrylonitrile, and a copolymer obtained by using two or more of these monomers. In addition, the acrylic resin may have a functional group selected from the group consisting of a methylol group, a hydroxyl group, a carboxyl group, and an amino group so as to be crosslinkable with other compounds.

[0069] Examples of vinyl resins include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, vinyl chloride / (meth)acrylic acid ester copolymer, and ethylene / vinyl acetate copolymer.

[0070] Examples of polyurethanes include compounds obtained by reacting at least one selected from the group consisting of polyols (e.g., ethylene glycol, propylene glycol, glycerin, trimethylolpropane, etc.), polyester polyols, polyether polyols (e.g., poly(oxypropylene ether) polyols, poly(oxyethylene-propylene ether) polyols, etc.), and polycarbonate polyols with polyisocyanate.

[0071] Examples of polyesters include compounds obtained by reacting a polyol (for example, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, etc.) with a polybasic acid.

[0072] From the viewpoint of aggregation suppression property and storage stability, the content of the resin relative to the total mass of the coloring composition is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and even more preferably 3% by mass to 10% by mass.

[0073] (Additives) The colored composition of the present disclosure may contain components (hereinafter also referred to as "additives") other than the above-described components, and examples thereof include surfactants, colloidal silica, inorganic salts, solid wetting agents (urea, etc.), anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, anti-fungal agents, pH adjusters, antifoaming agents, viscosity adjusters, dispersion stabilizers, rust inhibitors, chelating agents, and water-soluble polymer compounds.

[0074] (Applications) The coloring composition of the present disclosure can be used as an inkjet ink. The phthalocyanine pigment and the phthalocyanine compound contained in the coloring composition of the present disclosure have excellent aggregation suppression properties, and therefore can improve ejection stability, making the coloring composition of the present disclosure suitable for use as an inkjet ink. The applications of the coloring composition are not limited thereto, and the coloring composition can be used for thermal transfer recording sheets, printing inks other than inkjet inks, paints, etc.

[0075] [Method for Producing Phthalocyanine Pigment] The method for producing a phthalocyanine pigment according to the present disclosure includes a mixing step of mixing a phthalonitrile compound represented by any one of the following general formulas (5) to (8), a metal salt of at least one of zinc and copper, and a solvent. In the mixing step, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used (amount of solvent used / amount of phthalonitrile compound used) is set to 2.0 times or less by mass.

[0076]

[0077] In formulas (5) to (8), R １０１ , R １０２ , R １０３ , R １０４ , R １０５ , R １０６ , R １０７ , and R １０８ R 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 , R１０７ , and R １０８ Preferred embodiments of (1) to (8) are the same as those of the phthalocyanine pigment of the present disclosure described above, and therefore will not be described here. The phthalonitrile compounds represented by general formulas (5) to (8) may be different compounds or the same compound. It is preferred that the phthalonitrile compounds represented by general formulas (5) to (8) used in the method for producing the phthalocyanine pigment of the present disclosure are the same compound.

[0078] According to the method for producing a phthalocyanine pigment of the present disclosure, a phthalocyanine pigment having excellent lightfastness and aggregation inhibition properties can be produced. The reason for this effect is not clear, but is presumed to be as follows. In the method for producing a phthalocyanine pigment of the present disclosure, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used in the mixing step is set to 2.0 times or less, on a mass basis. By setting the amount of the phthalonitrile compound used relative to the amount of the solvent used high in this way and performing the mixing step, it is presumed that it is possible to increase the lattice spacing d of the crystals of the resulting phthalocyanine pigment, thereby reducing the tendency for the pigments to aggregate. According to the method for producing a phthalocyanine pigment of the present disclosure, the above-mentioned phthalocyanine pigment of the present disclosure can be produced. Furthermore, the above-mentioned phthalocyanine compound of the present disclosure can also be produced by referring to this.

[0079] (Mixing Step) Examples of solvents used in the synthesis of the phthalocyanine pigment include benzonitrile, nitrobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and sulfolane. From the viewpoint of aggregation suppression, the ratio of the amount of solvent used to the amount of phthalonitrile compound used is preferably 1.0 to 2.0 times, more preferably 1.2 to 2.0 times, and even more preferably 1.5 to 1.9 times, by mass. Furthermore, the method for producing the phthalocyanine pigment of the present disclosure is preferably carried out under an inert atmosphere.

[0080] Examples of zinc metal salts include zinc iodide, zinc chloride, zinc bromide, zinc acetate, zinc stearate, etc. Examples of copper metal salts include copper iodide, copper chloride, copper bromide, copper acetate, copper stearate, etc. Among the above, zinc metal salts are preferred, and zinc iodide is more preferred.

[0081] From the viewpoint of aggregation suppression, the ratio of the sum of the amounts of the metal salts of zinc and copper used to the amount of the phthalonitrile compound used (sum of the amounts of the metal salts of zinc and copper used / amount of the phthalonitrile compound used) is preferably 0.01 to 0.6 times, more preferably 0.05 to 0.5 times, and even more preferably 0.1 to 0.4 times, on a mass basis.

[0082] (Heating Step) The method for producing a phthalocyanine pigment according to the present disclosure may include a heating step in which the mixture obtained in the mixing step is heated to precipitate crystals of the phthalocyanine pigment. The heating method is not particularly limited, and can be carried out using a heating device (such as a heater). From the viewpoints of reactivity and aggregation suppression, the heating temperature is preferably 100°C to 250°C, and more preferably 130°C to 200°C. In the present disclosure, the heating temperature refers to the ambient temperature at which the mixture is heated. From the viewpoints of reactivity and aggregation suppression, the heating time is, for example, preferably 3 hours to 12 hours, and more preferably 4 hours to 8 hours.

[0083] (Cooling Step) The method for producing a phthalocyanine pigment according to the present disclosure may include a cooling step in which cooling is performed after the heating step. The cooling method is not particularly limited, and may be performed using a cooling device (such as a fan) or by allowing the mixture to cool naturally. The cooling temperature is not particularly limited, and may be, for example, 0°C to 30°C. In the present disclosure, the cooling temperature refers to the ambient temperature at which cooling is performed. After cooling, filtration or the like may be performed.

[0084] (Milling Step) The method for producing the phthalocyanine pigment of the present disclosure may include a milling step to microparticulate the phthalocyanine pigment of the present disclosure. The phthalocyanine pigment of the present disclosure may be particle-sized by the milling step. The milling step is not particularly limited, but preferably includes a salt milling step in which milling is performed using a salt. The milling method may be a wet method or a dry method, but a wet method is preferred, and the milling step more preferably includes a solvent salt milling step in which milling is performed using a salt and a solvent. The solvent salt milling step can be performed in accordance with the method described in paragraph 0064 of JP 2013-173883 A. To cite one example of the solvent salt milling step, for example, 1 part by mass of the phthalocyanine pigment of the present disclosure, 10 parts by mass of pulverized sodium chloride, and 2 parts by mass of diethylene glycol are charged into a double-arm kneader and kneaded at 100°C for 3 hours, and the kneaded mixture is then taken out into 100 parts by mass of water at 80°C, filtered, and washed, thereby obtaining a finely divided green phthalocyanine pigment.

[0085] [Method for Producing Colored Composition] The method for producing a colored composition of the present disclosure includes a mixing step of mixing at least one of the phthalocyanine pigment of the present disclosure and the phthalocyanine compound of the present disclosure with a solvent.

[0086] The phthalocyanine pigment of the present disclosure, the phthalocyanine compound of the present disclosure, and the solvent have been described above, and therefore further description thereof will be omitted here.

[0087] (Mixing Step) In the mixing step, the mixing method is not particularly limited as long as it is a mixing step in which at least one of the phthalocyanine pigment of the present disclosure and the phthalocyanine compound of the present disclosure is mixed with a solvent. In the mixing step, in addition to the components described above, the dispersant, the resin, the additives, etc. may be added. The mixing step preferably includes a step of dispersing at least one of the phthalocyanine pigment of the present disclosure and the phthalocyanine compound of the present disclosure. The dispersion can be performed in accordance with the method described in paragraph 0093 of JP 2013-173883 A. Specifically, at least one of the phthalocyanine pigment of the present disclosure and the phthalocyanine compound of the present disclosure can be dispersed in a solvent using a dispersing device. Dispersion equipment that can be used includes stirrer stirring, impeller stirring, in-line stirring, milling (e.g., colloid mill, ball mill, sand mill, bead mill, attritor, roll mill, jet mill, paint shaker, agitator mill, etc.), ultrasonic, high-pressure emulsification dispersion (high-pressure homogenizer; specific commercially available equipment includes Gaulin homogenizer, Microfluidizer, DeBEE2000, etc.), etc. In the dispersion step, it is preferable to add the above-mentioned dispersant in addition to the above-mentioned components and disperse the mixture.

[0088] The present disclosure will be described in detail below based on examples. However, the present disclosure is not limited to the following examples, and the contents described in the following examples (e.g., raw materials, conditions, and methods) may be appropriately modified within the scope of the present disclosure. In the following description, "%" means "% by mass" unless otherwise specified.

[0089] Example 1 Zinc iodide (1.74 g), 3,6-difluoro-4,5-bisphenoxyphthalonitrile (6.20 g), and benzonitrile (12 mL) were placed in a 100 mL recovery flask and mixed (mixing step). The mixture was reacted at 160°C for 5 hours under a nitrogen atmosphere to precipitate crystals (heating step). The contents of the recovery flask were cooled to room temperature (25°C) (cooling step), and the precipitated crystals were collected by filtration. The obtained crystals were washed with 60 mL of methanol to obtain Pigment G-1 (green pigment). The yield was 2.64 g, a 41% yield, and the solubility in acetone at 25°C was less than 0.005% by mass, confirming that the product was a pigment and not a dye. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOFMS) identified Pigment G-1 as the following compound (MALDI-TOFMS: 1459 ([M+1] ＋ )) In the production of the pigment G-1, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used was 1.9 times on a mass basis.

[0090]

[0091] Powder X-ray diffraction was performed on Pigment G-1 under the following conditions, and the number of diffraction peaks at 3° to 7° was confirmed. The diffraction angles at which peaks were observed are shown in Table 1. When the maximum peak intensity in the obtained X-ray diffraction spectrum (diffraction angle 2θ = 2° to 60°) is designated as Z, peaks having an intensity of ¼Z or greater were recognized as diffraction peaks. FIG. 1 also shows the X-ray diffraction spectrum obtained by performing powder X-ray diffraction on Pigment G-1. (Measurement Conditions) ・Radiation source: Cu ・Diffraction angle 2θ: 2° to 60° ・θ step: 0.01° The above conditions are the settings for the X-ray diffraction device. Known X-ray diffraction devices can be used. In the present disclosure, examples of X-ray diffraction devices that can be used for powder X-ray diffraction include the SmartLab manufactured by Rigaku Corporation, the D8 Discover manufactured by Bruker, and the Empyrean manufactured by Malvern Panalytical.

[0092] A stainless steel container was charged with 40 parts by mass of pigment G-1, 23 parts by mass of an acrylic resin (dispersant, average molecular weight 23,000) synthesized with reference to [Synthesis Example 1] described in JP 2016-141792 A (dispersant), 34 parts by mass of a 5% by mass aqueous sodium hydroxide solution, 7 parts by mass of isopropyl alcohol, and 75 parts by mass of ion-exchanged water. Next, the mixture was dispersed for 2 hours using zirconia beads having a diameter of 0.5 mm manufactured by Nikkato Corporation in a paint conditioner, thereby obtaining pigment dispersion 1 (mixing step).

[0093] Example 2 Tetrafluorophthalonitrile (20.0 g), potassium fluoride (13.9 g), and acetone (72 mL) were placed in a three-necked flask and stirred at 25°C to dissolve. The mixture was then cooled, and a solution of p-cresol (21.6 g) in 48 mL of acetone was added dropwise at an internal temperature of -11°C to -5°C. The mixture was then gradually returned to 25°C while stirring was continued for 5 hours. Insoluble matter in the reaction solution was filtered off, and the filtrate was concentrated. The resulting residue was purified by silica gel column chromatography to obtain Intermediate G-2a. The yield was 37.6 g, or 48%. Intermediate G-2a was identified by MALDI-TOFMS as the following compound (MALDI-TOFMS: 377([M+1] ＋ )).

[0094]

[0095] Pigment G-2 (green pigment) was obtained in the same manner as in Example 1, except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was replaced with Intermediate G-2a (15.0 g). The yield was 10.3 g, a yield of 66%, and the solubility in acetone at 25°C was less than 0.005% by mass, confirming that it was a pigment and not a dye. Pigment G-2 was identified by MALDI-TOFMS as the following compound (MALDI-TOFMS: 1572 ([M+1] ＋ )) In the production of the pigment G-2, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used was 1.8 times on a mass basis.

[0096]

[0097] Pigment G-2 was subjected to powder X-ray diffraction to confirm the number of diffraction peaks at angles from 3° to 7° in the same manner as in Example 1. The results are shown in Table 1.

[0098] Pigment dispersion 2 was obtained in the same manner as in Example 1, except that pigment G-1 was changed to pigment G-2.

[0099] Example 3: 14.6 g of Intermediate G-3a was obtained (yield 46%) in the same manner as in Example 2, except that p-cresol in the synthesis of Intermediate G-2a was changed to p-ethylphenol (19.2 g). Intermediate G-3a was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 405 ([M+1] ＋ )).

[0100]

[0101] Pigment G-3 (green pigment) was obtained in the same manner as in Example 1, except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was replaced with Intermediate G-3a (10.0 g). The yield was 7.78 g, a yield of 75%, and the solubility in acetone at 25°C was less than 0.005% by mass, confirming that it was a pigment and not a dye. Pigment G-3 was identified by MALDI-TOFMS as the following compound (MALDI-TOFMS: 1684 ([M+1] ＋ In the production of the pigment G-3, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used was 1.8 times by mass.

[0102]

[0103] Pigment G-3 was subjected to powder X-ray diffraction to confirm the number of diffraction peaks at angles from 3° to 7° in the same manner as in Example 1. The results are shown in Table 1.

[0104] Pigment dispersion 3 was obtained in the same manner as in Example 1, except that pigment G-1 was changed to pigment G-3.

[0105] Example 4 Pigment G-4 (green pigment) was obtained in the same manner as in Example 1, except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was replaced with 3,6-difluoro-4,5-bis[4-(1,1 dimethylethyl)phenoxy]phthalonitrile (12.0 g). The yield was 8.00 g, a yield of 65%, and the solubility in acetone at 25°C was less than 0.005% by mass, confirming that it was a pigment and not a dye. Pigment G-4 was identified by MALDI-TOFMS as the following compound (MALDI-TOFMS: 1908([M+1] ＋ )) In the production of the pigment G-4, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used was 1.9 times by mass.

[0106]

[0107] Pigment G-4 was subjected to powder X-ray diffraction to confirm the number of diffraction peaks at angles from 3° to 7° in the same manner as in Example 1. The results are shown in Table 1.

[0108] Pigment Dispersion Liquid 4 was obtained in the same manner as in Example 1, except that Pigment G-1 was changed to Pigment G-4.

[0109] Example 5 Intermediate G-5a (8.16 g, 55% yield) was obtained in the same manner as in Example 2, except that p-cresol in the synthesis of intermediate G-2a was changed to p-methoxyphenol (9.47 g). Intermediate G-5a was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 409 ([M+1] ＋ )).

[0110]

[0111] Pigment G-5 (green pigment) was obtained in the same manner as in Example 1, except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was replaced with Intermediate G-5a (8.16 g). The yield was 6.71 g, a 70% yield, and the solubility in acetone at 25°C was less than 0.005% by mass, confirming that it was a pigment and not a dye. Pigment G-5 was identified by MALDI-TOFMS as the following compound (MALDI-TOFMS: 1700 ([M+1] ＋ In the production of the pigment G-5, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used was 1.8 times by mass.

[0112]

[0113] Pigment G-5 was subjected to powder X-ray diffraction to confirm the number of diffraction peaks at angles of 3° to 7° in the same manner as in Example 1. The results are shown in Table 1.

[0114] Pigment Dispersion Liquid 5 was obtained in the same manner as in Example 1, except that Pigment G-1 was changed to Pigment G-5.

[0115] Example 6 Pigment G-6 (green pigment) was obtained in the same manner as in Synthesis Example 1, except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was replaced with 3,6-difluoro-4,5-bis(4-chlorophenoxy)phthalonitrile (6.00 g). The yield was 4.43 g, a 71% yield, and the solubility in acetone at 25°C was less than 0.005% by mass, confirming that it was a pigment and not a dye. Pigment G-6 was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 1735([M+1] ＋ In the production of the pigment G-6, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used was 1.8 times by mass.

[0116]

[0117] Pigment G-6 was subjected to powder X-ray diffraction to confirm the number of diffraction peaks at angles of 3° to 7° in the same manner as in Example 1. The results are shown in Table 1.

[0118] Pigment Dispersion Liquid 6 was obtained in the same manner as in Example 1, except that Pigment G-1 was changed to Pigment G-6.

[0119] Example 7 Pigment G-7 (green pigment) was obtained in the same manner as in Example 1, except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was replaced with 3,6-difluoro-4,5-bis(4-methoxycarbonylphenoxy)phthalonitrile (1.40 g). The yield was 0.810 g, a yield of 56%, and the solubility in acetone at 25°C was less than 0.005% by mass, confirming that it was a pigment and not a dye. Pigment G-7 was identified by MALDI-TOFMS as the following compound (MALDI-TOFMS: 1924([M+1] ＋ )) In the production of the pigment G-7, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used was 1.9 times by mass.

[0120]

[0121] Pigment G-7 was subjected to powder X-ray diffraction to confirm the number of diffraction peaks at angles of 3° to 7° in the same manner as in Example 1. The results are shown in Table 1.

[0122] Pigment Dispersion Liquid 7 was obtained in the same manner as in Example 1, except that Pigment G-1 was changed to Pigment G-7.

[0123] Example 8 3,6-Difluoro-4,5-bis(4-phenoxycarbonylphenoxy)phthalonitrile (2.00 g) and benzonitrile (4 mL) were placed in a 100 mL recovery flask and stirred at 125°C for 1 hour under a nitrogen atmosphere. Subsequently, zinc iodide (0.326 g) was added and the mixture was stirred at 170°C for 4 hours to cause a reaction, resulting in the precipitation of crystals. The contents of the recovery flask were cooled to 25°C and filtered. The resulting crystals were washed with 50 mL of benzonitrile to obtain Pigment G-8 (green pigment). The yield was 0.246 g, a 10% yield, and the solubility in acetone at 25°C was less than 0.005% by mass, confirming that the product was a pigment and not a dye. Pigment G-8 was identified by MALDI-TOFMS as the following compound (MALDI-TOFMS: 2420([M+1] ＋)) In the production of the pigment G-8, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used was 2.0 times on a mass basis.

[0124]

[0125] Pigment G-8 was subjected to powder X-ray diffraction to confirm the number of diffraction peaks at 3° to 7° in the same manner as in Example 1. The results are shown in Table 1.

[0126] Pigment dispersion 8 was obtained in the same manner as in Example 1, except that pigment G-1 was changed to pigment G-8.

[0127] Comparative Example 1 C.I. Pigment Green 58 (hereinafter also referred to as "PG58") was prepared. The structure of PG58 is shown below. The solubility of PG58 in acetone at 25°C was less than 0.005% by mass, confirming that it was a pigment, not a dye. Pigment dispersion A was obtained in the same manner as in Example 1, except that pigment G-1 was changed to PG58.

[0128]

[0129] Comparative Example 2 The following compound G-9 was synthesized based on Example 30 of JP-A-05-345861. The solubility in acetone at 25°C was 5% by mass, and it was confirmed to be a dye. When compound G-9 was subjected to powder X-ray diffraction in the same manner as in Example 1, no peaks were observed at diffraction angles 2θ of 2° to 60°.

[0130]

[0131] Comparative Example 3: 3,6-difluoro-4,5-bis(4-phenoxycarbonylphenoxy)phthalonitrile (6.50 g) and benzonitrile (26 mL) were placed in a 100 mL recovery flask and stirred at 120°C for 1 hour under a nitrogen atmosphere. Subsequently, zinc iodide (1.06 g) was added and stirred at 140°C for 2 hours, and then stirred at 170°C for 9 hours to allow the reaction to proceed. The contents of the recovery flask were cooled to 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 (developing solvent: ethyl acetate / hexane = 1 / 1 [v / v]) to obtain compound G-10. The yield was 3.02 g, a 45% yield, and the solubility in acetone at 25°C was 2.0% by mass, confirming that it was a dye. MALDI-TOFMS identified compound G-10 as a compound with the same structure as pigment G-8 (MALDI-TOFMS: 2420 ([M+1] ＋ )) In the production of the compound G-10, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used was 4.0 times on a mass basis.

[0132] When compound G-10 was subjected to powder X-ray diffraction in the same manner as in Example 1, no peaks were observed at diffraction angles 2θ of 2° to 60°.

[0133] <<Lightfastness Evaluation>> Pigment dispersion 1, polyurethane resin (Hydran (registered trademark) AP-40F (manufactured by DIC Corporation)), and ion-exchanged water were mixed to produce aqueous pigment dispersion 1 having a pigment content of 10% by mass and a polyurethane resin non-volatile content of 2% by mass. The following components were mixed to obtain colored composition 1. (Composition of colored composition 1) Aqueous pigment dispersion 1 (non-volatile content 4.5% by mass) 40 parts by mass 1,2-hexanediol 5 parts by mass Glycerin 10 parts by mass Surfynol 465 (surfactant, manufactured by Air Products and Chemicals Co., Ltd.) 1 part by mass Ion-exchanged water 44 parts by mass

[0134] Colored compositions 2 to 8 were obtained in the same manner as described above, except that pigment dispersion 1 was changed to pigment dispersions 2 to 8. Colored composition A was obtained in the same manner as described above, except that pigment dispersion 1 was changed to pigment dispersion A. Colored composition B was obtained in the same manner as described above, except that aqueous pigment dispersion 1 was changed to compound G-9. Colored composition C was obtained in the same manner as described above, except that aqueous pigment dispersion 1 was changed to compound G-10.

[0135] Using an inkjet printer (manufactured by Fujifilm Corporation, product name: Material Printer DMP-2850), images were formed on art paper using colored compositions 1 to 8 and colored compositions A to C.

[0136] The image was irradiated with xenon light (85,000 lux) for 100 hours using a weather meter (Atlas, Ci65), and the reflection density after irradiation with xenon light was measured using a reflection densitometer (X-Rite i1Pro, product name, manufactured by X-Rite). The reflection density of the image before irradiation with xenon light was set to 1.0. The compound remaining rate (%) before and after irradiation with xenon light was calculated using the following formula and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1. A higher compound remaining rate (%) indicates better light resistance of the phthalocyanine compound contained in the image. 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 (Evaluation criteria) A: The compound remaining rate was 80% or more. B: The compound remaining rate was 70% or more but less than 80%. C: The compound remaining rate was less than 70%.

[0137] <<Evaluation of Aggregation Inhibition Property>> Images were formed on 100 sheets of paper (A4 size) using coloring compositions 1 to 8 and coloring compositions A to C using the inkjet printer used in the lightfastness evaluation above. The formed images were visually observed and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1. (Evaluation Criteria) A: No disturbances such as fading were observed in the images formed on the 100 sheets of paper. B: Slight disturbances such as fading were observed in the images formed on the 100 sheets of paper. C: Disturbances such as fading were observed in the images formed on the 100 sheets of paper. D: Significant disturbances such as fading were observed in the images formed on the 100 sheets of paper.

[0138] <<Storage Stability Evaluation>> Colored compositions 1 to 8 and colored compositions A to C were stored for 7 days in an environment maintained at 45°C in an oven. The viscosity of the colored compositions was measured before and after storage, and the viscosity increase rate (viscosity after storage - viscosity before storage) / viscosity before storage x 100 was calculated and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1. The viscosity of the colored compositions was measured using a viscometer RE85L (rotor: 1°34' x R24, measurement range 0.6 to 1200 mPa s) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25°C. (Evaluation Criteria) A: The viscosity increase rate was 10% or less. B: The viscosity increase rate was more than 10%.

[0139]

[0140] Example 9 20 parts by mass of pigment G-1, 10 parts by mass of Solsperse (registered trademark) 32000 (polymer dispersant, manufactured by Lubrizol Corporation, weight average molecular weight 32,000), and 70 parts by mass of propylene glycol monomethyl ether acetate (solvent) were mixed, and zirconia beads having a diameter of 0.5 mm were filled into the mixture, followed by dispersion for 2 hours using a ball mill, thereby obtaining pigment dispersion liquid 1A.

[0141] Example 10 Pigment dispersion 5A was obtained in the same manner as in Example 9, except that pigment G-1 was changed to pigment G-5.

[0142] Example 11 Pigment dispersion liquid 1B was obtained in the same manner as in Example 9, except that propylene glycol monomethyl ether acetate was changed to ethyl 3-ethoxypropionate.

[0143] Example 12 20 parts by mass of pigment G-1, 10 parts by mass of Solsperse (registered trademark) 32000 (polymer dispersant, manufactured by Lubrizol Corporation, weight average molecular weight 32,000), 70 parts by mass of propylene glycol monomethyl ether acetate (solvent), and 7 parts by mass of N-methylpyrrolidone (amide solvent) were mixed together, and zirconia beads having a diameter of 0.5 mm were filled into the mixture, followed by dispersion for 2 hours using a ball mill, thereby obtaining pigment dispersion liquid 1C.

[0144] <<Evaluation>> Pigment Dispersion Liquid 1A, Pigment Dispersion Liquid 5A, Pigment Dispersion Liquid 1B, and Pigment Dispersion Liquid 1C were evaluated for light resistance, aggregation suppression ability, and storage stability in the same manner as above. The results are shown in Table 2.

[0145]

[0146] The disclosure of Japanese Patent Application No. 2022-157096, filed on September 29, 2022, is incorporated herein by reference. All documents, patent applications, and technical standards mentioned in this disclosure 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 phthalocyanine pigment having at least one diffraction peak at 3° ≤ 2θ ≤ 7° in a powder X-ray diffraction spectrum and represented by the following general formula (1). 【Chemical 1】 In formula (1), M represents zinc or copper, 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.

2. In formula (1), where M is zinc, R １０１ , R １０２ , R １０３ , R １０４ , R １０５ , R １０６ , R １０７ , and R １０８ Among them, at least one is a group represented by the following formula (2). The phthalocyanine pigment according to claim 1. [Chemical 2] In formula (2), R ２０１ 、 R ２０２ 、 R ２０３ 、 R ２０４ 、 and R ２０５ each independently represents a hydrogen atom, an alkyl group, a phenoxycarbonyl group, or an alkoxy group, R ２０１ 、R ２０２ 、R ２０３ 、R ２０４ 、and R ２０５ at least one of which is an alkyl group, a phenoxycarbonyl group, or an alkoxy group, * represents a linking portion with an oxygen atom.

3. In formula (2), R ２０１ 、R ２０２ 、R ２０４ 、and R ２０５ are hydrogen atoms, R ２０３ The phthalocyanine pigment according to claim 2, wherein R represents an alkyl group, a phenoxycarbonyl group, or an alkoxy group.

4. In formula (2), R ２０１ 、R ２０２ 、R ２０４ 、and R ２０５ are hydrogen atoms, R ２０３ is a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, or represents a propyloxy group, the phthalocyanine pigment according to claim 2 or claim 3.

5. The phthalocyanine pigment according to claim 1 or claim 2, having a solubility in acetone at 25°C of less than 0.005% by mass.

6. A phthalocyanine compound represented by the following general formula (3). [Chemical Formula 3] In formula (3), M represents zinc or copper, R ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ , R ３０６ , R ３０７ , and R ３０８ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, R ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ , R ３０６ , R ３０７ , and R ３０８ Among them, at least one is an aryl group represented by the following formula (4). 【Chemical Formula 4】 In formula (4), R ４０１ 、R ４０２ 、R ４０４ 、and R ４０５ are hydrogen atoms, R ４０３ represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, or a propyloxy group, * represents a linking portion with an oxygen atom.

7. A coloring composition comprising at least one of the phthalocyanine pigment according to claim 1 and the phthalocyanine compound according to claim 6.

8. The coloring composition according to claim 7, comprising a solvent having a boiling point of less than 160°C at 1013.2 hPa.

9. The coloring composition according to claim 8, wherein the solvent contains at least one selected from alcohols, ketones, carboxylic acid esters, and ethers.

10. The coloring composition according to claim 8, wherein the solvent contains a carboxylic acid ester.

11. The coloring composition according to claim 7, which does not contain an amide solvent, or contains an amide solvent and the content of the amide solvent with respect to the total mass of the coloring composition is 10% by mass or less.

12. The coloring composition according to claim 7, comprising a dispersant.

13. The coloring composition according to claim 12, wherein the dispersant is a polymer dispersant having a weight average molecular weight of 1,000 to 100,000.

14. The coloring composition according to claim 7, which is an inkjet ink.

15. Including a mixing step of mixing a phthalonitrile compound represented by the following general formulas (5) to (8) with at least one metal salt of zinc and copper and a solvent, In the mixing step, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used is 2.0 times or less on a mass basis, a method for producing a phthalocyanine pigment. 【Chemical Formula 5】 In formulas (5) to (8), 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.

16. A method for producing a coloring composition, including a mixing step of mixing at least one of the phthalocyanine pigment according to claim 1 and the phthalocyanine compound according to claim 6 with a solvent.

17. The method for producing a colored composition according to claim 16, wherein in the mixing step, at least one of the phthalocyanine pigment and the phthalocyanine compound is dispersed in the solvent.

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