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

Abstract

The present invention relates to a phthalocyanine pigment or the like which has at least one diffraction peak at 3 DEG < = 2 [theta] < = 7 DEG in a powder X-ray diffraction spectrum, and which is represented by general formula (1). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a phthalocyanine pigment, a phthalocyanine compound, a coloring composition, a method for producing a phthalocyanine pigment, and a method for producing a coloring composition. Background Art

[0002] In the past, the coloring composition contained various pigments, dyes, etc. For example, in Japanese Patent Publication No. 2016-141792, as a pigment, a coloring composition containing CI Pigment Green 58 (hereinafter also referred to as "PG58") having a true density of 2.985 to 3.005 is disclosed. In addition, in International Publication No. 2020 / 171139, a coloring composition containing a dye instead of a pigment for the purpose of improving brightness is disclosed. Summary of the invention

[0003] Technical issues to be solved by the invention

[0004] The pigment contained in the coloring composition is required to have various properties depending on its use. For example, in recent years, it has been required to be able to suppress the change in color tone caused by long-term exposure to sunlight (hereinafter also referred to as "light resistance").

[0005] In addition, from the viewpoint of forming an image well, it is required that the pigment can suppress aggregation over time (hereinafter also referred to as "aggregation inhibition".). Pigments with excellent aggregation inhibition can improve ejection stability when used in, for example, inkjet printing, and as a result, can suppress the occurrence of blurring of images formed by inkjet printing.

[0006] An object of one embodiment of the present invention is to provide a phthalocyanine pigment, a phthalocyanine compound, and a coloring composition having excellent light resistance and aggregation inhibition properties.

[0007] Another embodiment of the present invention aims to provide a method for producing a phthalocyanine pigment and a method for producing a coloring composition having excellent light resistance and aggregation inhibition properties.

[0008] Means for solving technical problems

[0009] The present invention includes the following aspects.

[0010] <1> A phthalocyanine pigment having at least one diffraction peak in 3°≤2θ≤7° in a powder X-ray diffraction spectrum and represented by the following general formula (1).

[0011] [Chemical formula 1]

[0012]

[0013] In formula (1),

[0014] M represents zinc or copper,

[0015] 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.

[0016] <2> According to the above <1> The phthalocyanine pigment, wherein

[0017] In formula (1),

[0018] M is zinc,

[0019] 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).

[0020] [Chemical formula 2]

[0021]

[0022] In formula (2),

[0023] 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,

[0024] R 201 , R 202 , R 203 , R 204 and R 205 At least one of them is an alkyl group, a phenoxycarbonyl group or an alkoxy group,

[0025] * indicates a linking portion with an oxygen atom.

[0026] <3> According to the above <2> The phthalocyanine pigment, wherein

[0027] In formula (2),

[0028] R 201 , R 202 , R204 and R 205 is a hydrogen atom,

[0029] R 203 represents an alkyl group, a phenoxycarbonyl group or an alkoxy group.

[0030] <4> According to the above <2> or <3> The phthalocyanine pigment, wherein

[0031] In formula (2),

[0032] R 201 , R 202 , R 204 and R 205 is a hydrogen atom,

[0033] R 203 represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group or a propoxy group.

[0034] <5> According to the above <1> to <4> The phthalocyanine pigment described in any one of the above aspects has a solubility in acetone at 25° C. of less than 0.005% by mass.

[0035] <6> A phthalocyanine compound represented by the following general formula (3).

[0036] [Chemical formula 3]

[0037]

[0038] In formula (3),

[0039] M represents zinc or copper,

[0040] 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.

[0041] Among them, R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 and R 308 At least one of them is an aryl group represented by the following formula (4).

[0042] [Chemical formula 4]

[0043]

[0044] In formula (4),

[0045] R 401 , R 402 , R 404 and R 405 is a hydrogen atom,

[0046] R 403 represents a methyl, ethyl, propyl, butyl, methoxy, ethoxy or propoxy group,

[0047] * indicates a linking portion with an oxygen atom.

[0048] <7> A coloring composition comprising the above <1> to <5> Any one of the phthalocyanine pigments and the above <6> At least one of the phthalocyanine compounds.

[0049] <8> According to the above <7> The coloring composition comprises a solvent having a boiling point of less than 160° C. at 1013.2 hPa.

[0050] <9> According to the above <8> The coloring composition, wherein

[0051] The solvent includes at least one selected from alcohols, ketones, carboxylic acid esters, and ethers.

[0052] <10> According to the above <7> or <8> The coloring composition, wherein

[0053] The above solvents contain carboxylic acid esters.

[0054] <11> According to the above <7> to <10> The colored composition described in any one of the preceding claims does not contain an amide solvent, or contains an amide solvent in which the content of the amide solvent relative to the total mass of the colored composition is 10% by mass or less.

[0055] <12> According to the above <7> to <11> The colored composition described in any one of the above aspects, comprising a dispersant.

[0056] <13> According to the above <12> The coloring composition, wherein

[0057] The above dispersant is a polymer dispersant having a weight average molecular weight of 1,000 to 100,000.

[0058] <14> According to the above <7> to <13> The colored composition described in any one of the above is an inkjet ink.

[0059] <15> A method for producing a phthalocyanine pigment, comprising a mixing step of mixing a phthalonitrile compound represented by the following general formula (5) to (8), a metal salt of at least one of zinc and copper, and a solvent.

[0060] In the mixing step, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used is set to 2.0 times or less on a mass basis.

[0061] [Chemical formula 5]

[0062]

[0063] In formula (5) to formula (8),

[0064] 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.

[0065] <16> A method for producing a coloring composition, comprising: <1> The phthalocyanine pigment and the above <6> A mixing step of mixing at least one of the phthalocyanine compounds with a solvent. <17> According to the above <16> The method for producing the coloring composition, wherein:

[0066] In the mixing step, at least one of the phthalocyanine pigment and the phthalocyanine compound is dispersed in the solvent.

[0067] Effects of the Invention

[0068] According to one embodiment of the present invention, a phthalocyanine pigment, a phthalocyanine compound, and a coloring composition having excellent light resistance and aggregation inhibition properties can be provided.

[0069] According to another embodiment of the present invention, a method for producing a phthalocyanine pigment and a method for producing a coloring composition having excellent light resistance and aggregation inhibition properties can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 This is an X-ray diffraction spectrum obtained by subjecting the pigment G-1 produced in Example 1 to powder X-ray diffraction. DETAILED DESCRIPTION

[0071] Hereinafter, an embodiment as an example of the present invention will be described. These descriptions and examples are for exemplifying the embodiment and do not limit the scope of the invention.

[0072] In the present invention, "to" indicating a numerical range is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0073] In the numerical ranges recorded in stages in the present invention, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical ranges recorded in the present invention, the upper limit or lower limit of its numerical range can be replaced by the value shown in the embodiments.

[0074] In the present invention, the "pigment" refers to a compound having a solubility of less than 0.01% by mass in acetone at 25° C. The solubility is preferably less than 0.005% by mass.

[0075] In the present invention, the "dye" refers to a compound having a solubility in acetone at 25°C of 0.01% by mass or more.

[0076] Here, the crystallinity of pigments and dyes is different, and depending on the crystallinity, the degree of interaction between compounds changes, and the solubility in the solvent changes. That is, even if the compounds have the same structure, one can be classified as a pigment and the other can be classified as a dye depending on the difference in crystallinity.

[0077] As one of the evaluation methods of the crystallinity, in the present invention, powder X-ray diffraction spectrum is used.

[0078] Each component may contain a plurality of corresponding substances.

[0079] When referring to the amount of each component in a composition, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the amount refers to the total amount of the plurality of substances present in the composition.

[0080] In the present invention, 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 can be achieved.

[0081] In the present invention, "(meth)acrylic acid" means acrylic acid and methacrylic acid.

[0082] In the present invention, a more preferred embodiment is a combination of two or more preferred embodiments.

[0083] In the present invention, when the embodiments are described with reference to the drawings, the structure of the embodiments is not limited to the structure shown in the drawings.

[0084] [Phthalocyanine Pigments]

[0085] The phthalocyanine pigment of the present invention has at least one diffraction peak in 3°≤2θ≤7° in a powder X-ray diffraction spectrum and is represented by the following general formula (1).

[0086] [Chemical formula 6]

[0087]

[0088] In formula (1),

[0089] M represents zinc or copper, preferably zinc,

[0090] 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.

[0091] The phthalocyanine pigment of the present invention is excellent in light resistance and aggregation inhibition. The reason why the above effects are exerted is not clear, but is presumed as follows.

[0092] The phthalocyanine pigment of the present invention has at least one diffraction peak in the range of 3°≤2θ≤7° in the powder X-ray diffraction spectrum. This indicates a crystalline state in which the lattice plane spacing d is large, and it is expected that the proportion of the phthalocyanine rings showing strong association per unit area is reduced. Therefore, it is speculated that the influence caused by the π-π interaction of the phthalocyanine rings is reduced when the pigment particles are close to each other, so the aggregation of the pigments can be reduced.

[0093] Furthermore, it is presumed that the phthalocyanine pigment of the present invention has a smaller particle surface area than dyes and is less susceptible to attack by active oxygen and the like, and therefore has excellent light resistance.

[0094] The phthalocyanine pigment of the present invention has at least one diffraction peak in the range of 3°≤2θ≤7° in a powder X-ray diffraction spectrum, and may have two or more diffraction peaks.

[0095] The diffraction peak of the phthalocyanine pigment of the present invention can be adjusted by adjusting the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used in the production of the phthalocyanine pigment. Furthermore, the diffraction peak can also be adjusted by the type of the phthalonitrile compound used.

[0096] In the present invention, the diffraction peak is observed as follows.

[0097] Using the phthalocyanine pigment powder of the present invention, X-ray diffraction is performed under the following conditions to confirm the number of diffraction peaks in the diffraction angle: 2θ3° to 7°. As a measuring device, a known device can be used. As an example of an X-ray device, smartlab manufactured by Rigaku Corporation, D8 Discover manufactured by Bruker, and Empyrean manufactured by Malvern and Panalytical can be used.

[0098] Furthermore, when the maximum peak intensity in the obtained X-ray diffraction spectrum (diffraction angle 2θ=2° to 60°) is defined as Z, a peak having an intensity of 1 / 4Z or more is identified as a diffraction peak.

[0099] (Measurement conditions)

[0100] ·Radiation source: Cu

[0101] Diffraction angle 2θ: 2°~60°

[0102] ·θ step: 0.01°

[0103] From the viewpoint of the aggregation inhibitory property, the phthalocyanine pigment of the present invention preferably has at least one diffraction peak in the range of 3.8°≤2θ≤6° in the powder X-ray diffraction spectrum.

[0104] In formula (1), R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

[0105] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, etc. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched.

[0106] Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 9-anthryl, 2-phenanthryl, 3-phenanthryl, 9-phenanthryl, 1-pyrenyl, 5-naphthyl, 1-indenyl, 2-heptadienyl, 1-acenaphthyl, 2-fluorenyl, 9-fluorenyl, 3-pentaphenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,5-xylyl, m-trisyl, p-cumyl, p-dodecylphenyl, p-cyclohexylphenyl, 4-biphenyl, o-fluorophenyl, m-chlorophenyl, p-bromophenyl, p-hydroxyphenyl, m-carboxyphenyl, o-mercaptophenyl, p-cyanophenyl, m-nitrophenyl, and m-azidophenyl.

[0107] Examples of the heterocyclic group include imidazolyl, benzimidazolyl, pyrazolyl, benzopyrazolyl, triazolyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, oxazolyl, benzoxazolyl, thiadiazolyl, pyrrolyl, benzopyrrolyl, indolyl, isoxazolyl, benzisoxazolyl, thienyl, benzothienyl, furanyl, benzofuranyl, pyridyl, quinolyl, isoquinolyl, pyridazinyl, pyrimidinyl, pyrazinyl, cinnolinyl, o-phthalazinyl, quinazolinyl, quinoxalinyl and triazinyl.

[0108] 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 amide group, a sulfoalkyl group and a sulfonamide group.

[0109] From the viewpoint of the aggregation inhibition of the phthalocyanine pigment of the present invention, among the above, a substituted or unsubstituted aryl group is also preferred, and a substituted aryl group is more preferred. From the viewpoint of the aggregation inhibition, as the substituent possessed by the substituted aryl group, an alkyl group, a phenoxycarbonyl group, a halogen atom, an alkoxycarbonyl group, a phenyl group or an alkoxy group is preferred, an alkyl group, a phenoxycarbonyl group or an alkoxy group is more preferred, an alkyl group or an alkoxy group is further preferred, and an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms is particularly preferred.

[0110] From the viewpoint of agglutination inhibition, in formula (1), R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 Among them, preferably at least 1, more preferably at least 2, further preferably at least 3, particularly preferably at least 4, and most preferably all are groups represented by the following formula (2).

[0111] [Chemical formula 7]

[0112]

[0113] 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 with an oxygen atom.

[0114] 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.

[0115] From the viewpoint of agglutination inhibition, it is preferred that 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, and R 201 , R 202 , R 203 , R 204 and R 205 At least one of them is an alkyl group, a phenoxycarbonyl group or an alkoxy group, and more preferably an alkyl group or an alkoxy group.

[0116] From the viewpoint of agglutination inhibition, it is further preferred that in formula (2), R 201 , R 202 , R 204 and R 205 is a hydrogen atom, R 203 represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group or a propoxy group.

[0117] An example of the phthalocyanine pigment of the present invention is shown below. In addition, the phthalocyanine pigment of the present invention is not limited to the following compounds. In the chemical formula of the present invention, Me represents a methyl group, and Ph represents a phenyl group.

[0118] [Chemical formula 8]

[0119]

[0120] [Chemical formula 9]

[0121]

[0122] [Chemical formula 10]

[0123]

[0124] [Chemical formula 11]

[0125]

[0126] [Chemical formula 12]

[0127]

[0128] [Chemical formula 13]

[0129]

[0130] [Chemical formula 14]

[0131]

[0132] [Chemical formula 15]

[0133]

[0134] [Chemical formula 16]

[0135]

[0136] [Chemical formula 17]

[0137]

[0138] [Chemical formula 18]

[0139]

[0140] [Chemical formula 19]

[0141]

[0142] [Chemical formula 20]

[0143]

[0144] [Chemical formula 21]

[0145]

[0146] [Phthalocyanine compounds]

[0147] The phthalocyanine compound of the present invention is represented by the following general formula (3).

[0148] [Chemical formula 22]

[0149]

[0150] In formula (3),

[0151] M represents zinc or copper, preferably zinc,

[0152] R 301 , R 302 , R 303 , R304 , 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.

[0153] Among them, R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 and R 308 At least one of them is an aryl group represented by the following formula (4).

[0154] The above-mentioned alkyl group, aryl group and heterocyclic group are the same as those of the phthalocyanine pigment of the present invention, and description thereof is omitted here.

[0155] [Chemical formula 23]

[0156]

[0157] In formula (4),

[0158] R 401 , R 402 , R 404 and R 405 is a hydrogen atom,

[0159] R 403 represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group or a propoxy group, and * represents a linking portion with an oxygen atom.

[0160] The propyl group, butyl group and propoxy group may be linear or branched.

[0161] The phthalocyanine compound of the present invention is excellent in light resistance and aggregation inhibition. The reason why the above effects are exerted is not clear, but is presumed as follows.

[0162] The phthalocyanine compound of the present invention has a specific structure, and it is presumed that the lattice spacing d of the crystal becomes larger, and the aggregation of pigments can be reduced.

[0163] Furthermore, it is presumed that the phthalocyanine compound has a group represented by formula (4), which appropriately relaxes the association and aggregation state of the phthalocyanine compound and effectively acts to dissipate light energy, thereby improving light resistance. 403 .

[0164] From the viewpoint of agglutination inhibition, in formula (3), R301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 and R 308 Of these, preferably at least 2, more preferably at least 3, further preferably at least 4, and particularly preferably all are aryl groups represented by the above formula (4).

[0165] The solubility of the phthalocyanine compound of the present invention in acetone at 25° C. is preferably less than 0.01% by mass, more preferably less than 0.005% by mass.

[0166] Examples of the phthalocyanine compound of the present invention include the compounds (2) to (5) exemplified as the above-mentioned phthalocyanine pigments, etc. The phthalocyanine compound of the present invention is not limited to these compounds.

[0167] [Coloring composition]

[0168] The coloring composition of the present invention contains at least one of the above-mentioned phthalocyanine pigment and the above-mentioned phthalocyanine compound.

[0169] From the viewpoint of aggregation inhibition and storage stability, the viscosity of the colored composition of the present invention 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.

[0170] In the present invention, the viscosity is measured by a viscometer. For example, a viscometer RE85L (rotor: 1°34'×R24, measuring range 0.6 to 1200 mPa·s) manufactured by TOKI SANGYO CO., LTD. can be used.

[0171] (Phthalocyanine pigments and phthalocyanine compounds)

[0172] The details of the phthalocyanine pigment and the phthalocyanine compound have been described above, and therefore their description is omitted here.

[0173] The coloring composition of the present invention may contain a plurality of the above-mentioned phthalocyanine pigments and phthalocyanine compounds. For example, it may contain one or more phthalocyanine pigments and phthalocyanine compounds respectively, or may contain a plurality of phthalocyanine pigments having different structures, or may contain a plurality of phthalocyanine compounds having different structures.

[0174] From the viewpoint of light resistance and aggregation inhibition, the sum of the contents of the phthalocyanine pigment and the phthalocyanine compound is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass, and even more preferably 3 to 6% by mass based on the total mass of the coloring composition.

[0175] (Solvent)

[0176] From the viewpoint of aggregation inhibition, the colored composition of the present invention preferably contains a solvent having a boiling point of less than 160°C at 1013.2 hPa (hereinafter also referred to as a "specific solvent"). The boiling point is preferably 60°C to 158°C, more preferably 80°C to 150°C.

[0177] In the present invention, the boiling point is a value measured by an ebulliometer, and can be measured using, for example, DosaTherm300 manufactured by Titan Technologies, KK.

[0178] Examples of the specific solvent include methanol, ethanol, butanol, isobutanol, tert-butanol, propanol, isopropanol, 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.

[0179] The coloring composition of the present invention may contain a solvent other than the specific solvent (hereinafter, also referred to as “other solvent”).

[0180] The solvent may contain at least one selected from the group consisting of water, alcohol, ketone, carboxylic acid ester, and ether.

[0181] Examples of the alcohol include methanol, ethanol, butanol, isobutanol, tert-butanol, propanol, isopropanol, 1-methoxy-2-propanol, benzyl alcohol, 1,2-hexanediol, glycoside oil, fluorinated alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butanediol, 1,2,6-hexanetriol, thioglycolic acid, hexanediol, trimethylolethane, and trimethylolpropane.

[0182] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0183] 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.

[0184] 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 and the like.

[0185] Among the above, the solvent preferably contains at least one selected from alcohols, ketones, and carboxylic acid esters, and more preferably contains carboxylic acid esters.

[0186] The coloring composition of the present invention may contain only one type of solvent or may contain a plurality of types.

[0187] The content of the solvent relative to the total mass of the colored composition is preferably appropriately adjusted depending on the intended use of the colored composition, and can be, for example, 1% by mass to 50% by mass.

[0188] From the viewpoint of the aggregation inhibitory property, the content of the specific solvent contained in the colored composition of the present invention is preferably 50 to 100% by mass, and more preferably 80 to 100% by mass, relative to the total mass of the solvent.

[0189] (Amide solvent)

[0190] From the viewpoint of agglomeration inhibition, the colored composition of the present invention preferably contains no amide solvent, or contains an amide solvent and the content of the amide solvent relative to the total mass of the colored composition is 10% by mass or less, more preferably contains no 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, further preferably contains no 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 contains no 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 contains no amide solvent.

[0191] In the present invention, the amide solvent refers to a solvent having an amide bond, and examples thereof include dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, 3-methoxy-N,N-dimethylpropionamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, and the like.

[0192] In addition, compounds having an amide bond such as a yellow dye are not solvents and therefore are not included in the amide solvents in the present invention.

[0193] (Dispersant)

[0194] The colored composition of the present invention preferably contains a dispersant from the viewpoint of aggregation inhibition and storage stability.

[0195] The type of the dispersant is not particularly limited as long as the pigment can be dispersed and stably maintained in the coloring composition. For example, cationic, anionic, nonionic, amphoteric, and other dispersants can be used.

[0196] From the viewpoint of aggregation inhibition and storage stability, the dispersant is preferably a polymer dispersant. In the present invention, the polymer dispersant refers to a dispersant having a weight average molecular weight of 500 or more.

[0197] Examples of the dispersant include modified acrylic copolymers, acrylic copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate ester salts of high molecular weight copolymers, and cationic comb-type graft polymers.

[0198] From the viewpoint of aggregation inhibition 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.

[0199] In the present invention, unless otherwise specified, the weight average molecular weight is a molecular weight calculated by using a gel permeation chromatography (GPC) analysis apparatus using a TSKgel SuperHM-H (trade name manufactured by TOSOH CORPORATION) column, a solvent of PFP (pentafluorophenol) / chloroform = 1 / 2 (mass ratio), a differential refractometer, and polystyrene as a standard substance.

[0200] From the viewpoint of aggregation inhibition and storage stability, the content of the dispersant relative to the total mass of the colored composition is preferably 1 to 20% by mass, more preferably 5 to 15% by mass, and even more preferably 8 to 13% by mass.

[0201] (resin)

[0202] The coloring composition of the present invention may contain a resin.

[0203] Examples of the resin include acrylic resins, styrene-(meth)acrylic resins, vinyl resins, polyurethanes, polyesters, polyamides, and fluororesins.

[0204] Examples of acrylic resins include homopolymers of monomers selected from (meth)acrylic acid, (meth)acrylates, (meth)acrylamide and (meth)acrylonitrile, and copolymers obtained by using two or more of these monomers. In addition, in order to be cross-linked with other compounds, the acrylic resin may have a functional group selected from methylol, hydroxyl, carboxyl and amino groups.

[0205] Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, polyolefins, ethylene / butadiene copolymers, polyvinyl acetate, vinyl chloride / vinyl acetate copolymers, vinyl chloride / (meth)acrylate copolymers, and ethylene / vinyl acetate copolymers.

[0206] Examples of polyurethane include compounds obtained by reacting at least one selected from 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 polyisocyanates.

[0207] Examples of the polyester include compounds obtained by reaction of a polyol (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, etc.) with a polybasic acid.

[0208] From the viewpoint of aggregation inhibition and storage stability, the content of the resin relative to the total mass of the colored composition is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass.

[0209] (additive)

[0210] The coloring composition of the present invention may contain ingredients other than the above-mentioned ingredients (hereinafter also referred to as "additives"), such as surfactants, colloidal silica, inorganic salts, solid wetting agents (such as urea), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, mildew inhibitors, pH adjusters, defoamers, viscosity adjusters, dispersion stabilizers, rust inhibitors, chelating agents, water-soluble polymer compounds, etc.

[0211] (use)

[0212] The coloring composition of the present invention can be used as an inkjet ink. The above-mentioned phthalocyanine pigment and the above-mentioned phthalocyanine compound contained in the coloring composition of the present invention have excellent agglomeration inhibition, so the ejection stability can be improved, so the coloring composition of the present invention can be appropriately used as an inkjet ink. In addition, the use of the coloring composition is not limited thereto, and it can be used for thermal transfer recording paper, printing inks other than inkjet inks, coatings, etc.

[0213] [Method for producing phthalocyanine pigment]

[0214] The method for producing a phthalocyanine pigment of the present invention includes a mixing step of mixing a phthalonitrile compound represented by the following general formula (5) to (8), a metal salt of at least one of zinc and copper, and a solvent.

[0215] In the mixing step, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used (the amount of the solvent used / the amount of the phthalonitrile compound used) is set to 2.0 times or less on a mass basis.

[0216] [Chemical formula 24]

[0217]

[0218] In formula (5) to formula (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.

[0219] About R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 The preferred embodiment of is the same as that of the phthalocyanine pigment of the present invention, and therefore description thereof is omitted here.

[0220] The phthalonitrile compounds represented by the general formula (5) to the general formula (8) may be different compounds or the same compound.

[0221] The phthalonitrile compounds represented by the above-mentioned general formula (5) to (8) used in the method for producing the phthalocyanine pigment of the present invention are preferably the same compounds.

[0222] According to the method for producing a phthalocyanine pigment of the present invention, a phthalocyanine pigment having excellent light resistance and aggregation inhibition can be produced. The reason for the above-mentioned effects is not clear, but it is presumed as follows.

[0223] In the method for producing a phthalocyanine pigment of the present invention, in the mixing step, the ratio of the amount of the solvent used to the amount of the phthalonitrile compound used is set to 2.0 times or less on a mass basis. In this way, it is presumed that by setting the amount of the phthalonitrile compound used to be higher than the amount of the solvent used and performing the mixing step, the lattice plane spacing d of the crystal of the obtained phthalocyanine pigment can be increased, thereby reducing the aggregation of the pigments.

[0224] According to the method for producing a phthalocyanine pigment of the present invention, the phthalocyanine pigment of the present invention can be produced. Furthermore, with reference to this, the phthalocyanine compound of the present invention can also be produced.

[0225] (Mixing process)

[0226] Examples of the solvent used for 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.

[0227] From the viewpoint of aggregation inhibition, the ratio of the amount of the solvent used to the amount of the 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, on a mass basis.

[0228] Furthermore, the method for producing the phthalocyanine pigment of the present invention is preferably carried out under an inert atmosphere.

[0229] 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.

[0230] From the viewpoint of agglomeration inhibition, the ratio of the sum of the amounts of the zinc and copper metal salts used to the amount of the phthalonitrile compound used (the sum of the amounts of the zinc and copper metal salts used / the 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.

[0231] (Heating process)

[0232] The method for producing the phthalocyanine pigment of the present invention may include a heating step of heating the mixture obtained in the above-mentioned mixing step to precipitate crystals of the phthalocyanine pigment.

[0233] The heating method is not particularly limited, and the heating can be performed by using a heating device (heater, etc.) or the like.

[0234] From the viewpoint of reactivity and aggregation inhibition, the heating temperature is preferably 100° C. to 250° C., and more preferably 130° C. to 200° C. In the present invention, the heating temperature refers to the ambient temperature at which the mixture is heated.

[0235] From the viewpoint of reactivity and aggregation inhibition, the heating time is, for example, preferably 3 hours to 12 hours, and more preferably 4 hours to 8 hours.

[0236] (Cooling process)

[0237] The method for producing the phthalocyanine pigment of the present invention may include a cooling step of cooling after the heating step.

[0238] The cooling method is not particularly limited, and the cooling may be performed using a cooling device (such as a blower) or the like, or may be performed by natural cooling.

[0239] The cooling temperature is not particularly limited, and can be, for example, 0° C. to 30° C. In the present invention, the cooling temperature refers to the ambient temperature of the cooling environment.

[0240] After cooling, filtration etc. may also be performed.

[0241] (Grinding process)

[0242] The method for producing the phthalocyanine pigment of the present invention may include a grinding step for finely dividing the phthalocyanine pigment of the present invention.

[0243] The phthalocyanine pigment of the present invention can be granulated by the grinding step.

[0244] The grinding process is not particularly limited, but preferably includes a salt grinding process using salt for grinding. The grinding method may be a wet method or a dry method, but preferably a wet method, and the grinding process more preferably includes a solvent salt grinding process using salt and a solvent for grinding.

[0245] The solvent salt grinding step can be performed according to the method described in paragraph 0064 of JP-A-2013-173883.

[0246] As an example of the solvent salt grinding step, for example, 1 part by mass of the phthalocyanine pigment of the present invention, 10 parts by mass of ground sodium chloride and 2 parts by mass of diethylene glycol are placed in a double-arm kneader, kneaded at 100° C. for 3 hours, and the kneaded product is taken out into 100 parts by mass of water at 80° C., filtered and washed, thereby obtaining a micronized green phthalocyanine pigment.

[0247] [Method for producing coloring composition]

[0248] The method for producing the coloring composition of the present invention includes a mixing step of mixing at least one of the above-mentioned phthalocyanine pigment of the present invention and the above-mentioned phthalocyanine compound of the present invention with a solvent.

[0249] The phthalocyanine pigment of the present invention, the phthalocyanine compound of the present invention, and the solvent have been described above, and thus description thereof will be omitted here.

[0250] (Mixing process)

[0251] In the mixing step, as long as at least one of the phthalocyanine pigment of the present invention and the phthalocyanine compound of the present invention is mixed with a solvent, the mixing method is not particularly limited. In the mixing step, in addition to the above-mentioned components, the above-mentioned dispersant, the above-mentioned resin, the above-mentioned additives, etc. may also be added.

[0252] The mixing step preferably includes a step of dispersing at least one of the phthalocyanine pigment of the present invention and the phthalocyanine compound of the present invention.

[0253] The above dispersion can be performed according to the method described in paragraph 0093 of JP-A-2013-173883.

[0254] Specifically, at least one of the phthalocyanine pigment of the present invention and the phthalocyanine compound of the present invention can be dispersed in a solvent using a dispersing device. As the dispersing device, a paddle stirring method, an impeller stirring method, an online stirring method, a grinding method (for example, a colloid mill, a ball mill, a sand mill, a bead mill, a grinder, a roller mill, a jet mill, a paint oscillator, a stirring mill, etc.), an ultrasonic method, a high-pressure emulsification dispersion method (a high-pressure homogenizer; as a specific commercially available device, a Gaulin homogenizer, a microfluidizer, a DeBEE2000, etc. can be used).

[0255] In the dispersing step, it is preferred that the above-mentioned dispersant is added in addition to the above-mentioned components for dispersion.

[0256] Example

[0257] Hereinafter, the present invention will be described in detail based on the examples. However, the present invention is not limited to the following examples, and the contents (e.g., raw materials, conditions and methods) described in the following examples can be appropriately changed within the scope of the purpose of the present invention. In the following description, unless otherwise specified, "%" means "mass %".

[0258] <Example 1>

[0259] Zinc iodide (1.74 g), 3,6-difluoro-4,5-bisphenoxyphthalonitrile (6.20 g) and benzonitrile (12 mL) were placed in a 100 mL eggplant-shaped flask and mixed (mixing step), and reacted at 160° C. for 5 hours under a nitrogen atmosphere to precipitate crystals (heating step).

[0260] The interior of the eggplant-shaped flask was cooled to room temperature (25° C.) (cooling step), and the precipitated crystals were collected by filtration.

[0261] The obtained crystals were washed with 60 mL of methanol to obtain Pigment G-1 (green pigment).

[0262] The yield was 2.64 g, the yield was 41%, and the solubility in acetone at 25°C was 0.005 mass%.

[0263] And it is a pigment rather than a dye.

[0264] Pigment G-1 was identified as the following compound by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOFMS) (MALDI-TOFMS: 1459 ([M+1]+)).

[0265] 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.

[0266] [Chemical formula 25]

[0267]

[0268] Powder X-ray diffraction of Pigment G-1 was performed under the following conditions, and the number of diffraction peaks at 3° to 7° was confirmed. Table 1 shows the diffraction angle results at which the peaks were observed.

[0269] In addition, when the maximum peak intensity in the obtained X-ray diffraction spectrum (diffraction angle 2θ=2° to 60°) is defined as Z, a peak having an intensity of 1 / 4Z or more is identified as a diffraction peak. Figure 1 ] The X-ray diffraction spectrum obtained by subjecting Pigment G-1 to powder X-ray diffraction is shown in FIG.

[0270] (Measurement conditions)

[0271] ·Radiation source: Cu

[0272] Diffraction angle 2θ: 2°~60°

[0273] ·θ step: 0.01°

[0274] The above conditions are set values ​​in the X-ray diffraction device. The X-ray diffraction device can use a known device. In the present invention, examples of X-ray diffraction devices that can be used for powder X-ray diffraction include SmartLab manufactured by Rigaku Corporation, D8 Discover manufactured by Bruker, and Empyrean manufactured by Malvern Panalytical.

[0275] 40 parts by mass of pigment G-1, 23 parts by mass of acrylic resin (dispersant, average molecular weight 23,000) synthesized with reference to [Synthesis Example 1] described in Japanese Patent Application Laid-Open No. 2016-141792, 34 parts by mass of 5% sodium hydroxide aqueous solution, 7 parts by mass of isopropyl alcohol and 75 parts by mass of ion exchange water were placed in a stainless steel container. Next, zirconium oxide beads with a diameter of 0.5 mm manufactured by NIKKATO CORPORATION were used and dispersed for 2 hours using a paint conditioner to obtain a pigment dispersion 1 (mixing step).

[0276] <Example 2>

[0277] 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.

[0278] The mixture was then cooled, and a solution prepared by dissolving p-cresol (21.6 g) in 48 mL of acetone was added dropwise at an internal temperature of -11°C to -5°C, and then stirring was continued for 5 hours while gradually returning the temperature to 25°C.

[0279] The insoluble matter in the reaction solution was filtered off, and the filtrate was concentrated. The obtained residue was purified by silica gel column chromatography to obtain intermediate G-2a. The yield was 37.6 g, and the yield was 48%.

[0280] The intermediate G-2a was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 377 ([M+1]+)).

[0281] [Chemical formula 26]

[0282]

[0283] Pigment G-2 (green pigment) was obtained in the same manner as in Example 1 except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was changed to intermediate G-2a (15.0 g).

[0284] The yield was 10.3 g, the yield was 66%, the solubility in acetone at 25° C. was less than 0.005 mass %, and it was confirmed that the product was a pigment rather than a dye.

[0285] Pigment G-2 was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 1572 ([M+1]+)).

[0286] 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.

[0287] [Chemical formula 27]

[0288]

[0289] Powder X-ray diffraction was performed on Pigment G-2 in the same manner as in Example 1, and the number of diffraction peaks at 3° to 7° was confirmed. The results are shown in Table 1.

[0290] Pigment dispersion 2 was obtained in the same manner as in Example 1 except that pigment G-1 was changed to pigment G-2.

[0291] <Example 3>

[0292] 14.6 g (yield 46%) of Intermediate G-3a was obtained in the same manner as in Example 2 except that p-cresol was replaced with p-ethylphenol (19.2 g).

[0293] The intermediate G-3a was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 405 ([M+1]+)).

[0294] [Chemical formula 28]

[0295]

[0296] Pigment G-3 (green pigment) was obtained in the same manner as in Example 1 except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was changed to intermediate G-3a (10.0 g).

[0297] The yield was 7.78 g, the yield was 75%, the solubility in acetone at 25° C. was less than 0.005% by mass, and it was confirmed that the product was a pigment rather than a dye.

[0298] Pigment G-3 was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 1684 ([M+1]+)).

[0299] 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 on a mass basis.

[0300] [Chemical formula 29]

[0301]

[0302] Powder X-ray diffraction was performed on Pigment G-3 in the same manner as in Example 1, and the number of diffraction peaks at 3° to 7° was confirmed. The results are shown in Table 1.

[0303] Pigment dispersion 3 was obtained in the same manner as in Example 1 except that pigment G-1 was changed to pigment G-3.

[0304] <Example 4>

[0305] Pigment G-4 (green pigment) was obtained in the same manner as in Example 1 except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was changed to 3,6-difluoro-4,5-bis[4-(1,1-dimethylethyl)phenoxy]phthalonitrile (12.0 g).

[0306] The yield was 8.00 g, the yield was 65%, the solubility in acetone at 25° C. was less than 0.005% by mass, and it was confirmed that the product was a pigment rather than a dye.

[0307] Pigment G-4 was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 1908 ([M+1]+)).

[0308] 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 on a mass basis.

[0309] [Chemical formula 30]

[0310]

[0311] Powder X-ray diffraction was performed on Pigment G-4 in the same manner as in Example 1, and the number of diffraction peaks at 3° to 7° was confirmed. The results are shown in Table 1.

[0312] Pigment dispersion 4 was obtained in the same manner as in Example 1 except that pigment G-1 was changed to pigment G-4.

[0313] <Example 5>

[0314] 8.16 g (yield 55%) of Intermediate G-5a was obtained in the same manner except that p-cresol in the synthesis of Intermediate G-2a in Example 2 was replaced with p-methoxyphenol (9.47 g).

[0315] The intermediate G-5a was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 409 ([M+1]+)).

[0316] [Chemical formula 31]

[0317]

[0318] Pigment G-5 (green pigment) was obtained in the same manner as in Example 1 except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was changed to intermediate G-5a (8.16 g).

[0319] The yield was 6.71 g, the yield was 70%, the solubility in acetone at 25° C. was less than 0.005 mass %, and it was confirmed that the product was a pigment rather than a dye.

[0320] Pigment G-5 was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 1700 ([M+1]+)).

[0321] 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 on a mass basis.

[0322] [Chemical formula 32]

[0323]

[0324] Powder X-ray diffraction was performed on Pigment G-5 in the same manner as in Example 1, and the number of diffraction peaks at 3° to 7° was confirmed. The results are shown in Table 1.

[0325] Pigment dispersion 5 was obtained in the same manner as in Example 1 except that pigment G-1 was changed to pigment G-5.

[0326] <Example 6>

[0327] 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 changed to 3,6-difluoro-4,5-bis(4-chlorophenoxy)phthalonitrile (6.00 g).

[0328] The yield was 4.43 g, the yield was 71%, the solubility in acetone at 25° C. was less than 0.005% by mass, and it was confirmed that the product was a pigment rather than a dye.

[0329] Pigment G-6 was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 1735 ([M+1]+)).

[0330] 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 on a mass basis.

[0331] [Chemical formula 33]

[0332]

[0333] Powder X-ray diffraction was performed on Pigment G-6 in the same manner as in Example 1, and the number of diffraction peaks at 3° to 7° was confirmed. The results are shown in Table 1.

[0334] Pigment dispersion 6 was obtained in the same manner as in Example 1 except that pigment G-1 was changed to pigment G-6.

[0335] <Example 7>

[0336] Pigment G-7 (green pigment) was obtained in the same manner as in Example 1 except that 3,6-difluoro-4,5-bisphenoxyphthalonitrile was changed to 3,6-difluoro-4,5-bis(4-methoxycarbonylphenoxy)phthalonitrile (1.40 g).

[0337] The yield was 0.810 g, the yield was 56%, the solubility in acetone at 25° C. was less than 0.005% by mass, and it was confirmed that the product was a pigment rather than a dye.

[0338] Pigment G-7 was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 1924 ([M+1]+)).

[0339] 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 on a mass basis.

[0340] [Chemical formula 34]

[0341]

[0342] Powder X-ray diffraction was performed on Pigment G-7 in the same manner as in Example 1, and the number of diffraction peaks at 3° to 7° was confirmed. The results are shown in Table 1.

[0343] Pigment dispersion 7 was obtained in the same manner as in Example 1 except that pigment G-1 was changed to pigment G-7.

[0344] <Example 8>

[0345] 3,6-difluoro-4,5-bis(4-phenoxycarbonylphenoxy)phthalonitrile (2.00 g) and benzonitrile (4 mL) were added to a 100 mL eggplant-shaped flask, and the mixture was stirred at 125° C. for 1 hour under a nitrogen atmosphere.

[0346] Next, zinc iodide (0.326 g) was added and stirred at 170° C. for 4 hours to cause crystals to precipitate during the reaction. The contents of the eggplant-shaped flask were cooled to 25° C. and filtered out, and the obtained crystals were washed with 50 mL of benzonitrile to obtain Pigment G-8 (green pigment).

[0347] The yield was 0.246 g, the yield was 10%, the solubility in acetone at 25° C. was less than 0.005 mass %, and it was confirmed that the compound was a pigment rather than a dye.

[0348] Pigment G-8 was identified as the following compound by MALDI-TOFMS (MALDI-TOFMS: 2420 ([M+1]+)).

[0349] 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.

[0350] [Chemical formula 35]

[0351]

[0352] Powder X-ray diffraction was performed on Pigment G-8 in the same manner as in Example 1, and the number of diffraction peaks at 3° to 7° was confirmed. The results are shown in Table 1.

[0353] Pigment dispersion 8 was obtained in the same manner as in Example 1 except that pigment G-1 was changed to pigment G-8.

[0354] <Comparative Example 1>

[0355] CI Pigment Green 58 (hereinafter also referred to as "PG58") was prepared. The structure of PG58 is shown below. It was confirmed that the solubility of PG58 in acetone at 25°C was less than 0.005 mass %, and that PG58 was a pigment rather than a dye.

[0356] Pigment dispersion A was obtained in the same manner as in Example 1 except that pigment G-1 was changed to PG58.

[0357] [Chemical formula 36]

[0358]

[0359] <Comparative Example 2>

[0360] The following compound G-9 was synthesized according to Example 30 of Japanese Patent Application Laid-Open No. 05-345861. The solubility in acetone at 25°C was 5% by mass, and it was confirmed to be a dye.

[0361] Compound G-9 was subjected to powder X-ray diffraction in the same manner as in Example 1. As a result, no peak was observed in the diffraction angle 2θ: 2° to 60°.

[0362] [Chemical formula 37]

[0363]

[0364] <Comparative Example 3>

[0365] 3,6-difluoro-4,5-bis(4-phenoxycarbonylphenoxy)phthalonitrile (6.50 g) and benzonitrile (26 mL) were added to a 100 mL eggplant-shaped flask, and the mixture was stirred at 120° C. for 1 hour under a nitrogen atmosphere.

[0366] Next, zinc iodide (1.06 g) was added, and the mixture was stirred at 140° C. for 2 hours and further stirred at 170° C. for 9 hours to allow the mixture to react. The interior of the eggplant-shaped flask was cooled to 25° C., and reprecipitation was performed with 60 mL of methanol, and the precipitated crystals were collected by filtration.

[0367] The obtained crystals were purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1 / 1 [v / v]) to obtain compound G-10.

[0368] The yield was 3.02 g, the yield was 45%, and the solubility in acetone at 25° C. was 2.0% by mass. It was confirmed that the product was a dye.

[0369] Compound G-10 was identified as a compound having the same structure as pigment G-8 by MALDI-TOFMS (MALDI-TOFMS: 2420 ([M+1]+)).

[0370] 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.

[0371] Compound G-10 was subjected to powder X-ray diffraction in the same manner as in Example 1. As a result, no peak was observed in the diffraction angle 2θ: 2° to 60°.

[0372] 《Lightfastness Evaluation》

[0373] Pigment dispersion 1, polyurethane resin (HYDRAN (registered trademark) AP-40F (manufactured by DIC Corporation)) and ion exchange water were mixed to prepare aqueous pigment dispersion 1 having a pigment content of 10% by mass and a polyurethane resin nonvolatile content of 2% by mass.

[0374] The following components were mixed to obtain a coloring composition 1.

[0375] (Composition of Coloring Composition 1)

[0376] · Aqueous pigment dispersion 1 (non-volatile content 4.5% by mass) 40 parts by mass

[0377] 5 parts by mass of 1,2-hexanediol

[0378] 10 parts by mass of glycerol

[0379] Surfynol 465 (surfactant, manufactured by Air Products and Chemicals, Inc.) 1 part by mass

[0380] ·44 parts by mass of ion exchange water

[0381] Colored compositions 2 to 8 were obtained in the same manner as the above method except that the pigment dispersion 1 was changed to the pigment dispersions 2 to 8.

[0382] Except having changed the pigment dispersion liquid 1 into the pigment dispersion liquid A, it carried out similarly to the above method, and obtained the coloring composition A.

[0383] A coloring composition B was obtained in the same manner as the above method except that the aqueous pigment dispersion 1 was changed to the compound G-9.

[0384] A coloring composition C was obtained in the same manner as the above method except that the aqueous pigment dispersion 1 was changed to the compound G-10.

[0385] Using the coloring compositions 1 to 8 and the coloring compositions A to C, images were formed on coated paper using an inkjet printer (manufactured by Fujifilm Corporation, trade name: Material Printer DMP-2850).

[0386] The image was irradiated with xenon light (85,000 lux) for 100 hours using a weather tester (Ci65, manufactured by Atlas), and the reflection density after irradiation with xenon light was measured using a reflection densitometer (manufactured by X-Rite, trade name: X-Rite ilPro).

[0387] In addition, the reflection density of the image before irradiation with xenon lamp light was set to 1.0.

[0388] The residual rate (%) of the compound before and after irradiation with xenon light was calculated according to the following formula, and evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 1.

[0389] In addition, the higher the compound residual rate (%) is, the more excellent the light resistance of the phthalocyanine compound contained in the image is.

[0390] Compound residual rate (%) = (reflection density of the solid image after irradiation with xenon light) / (reflection density of the solid image before irradiation with xenon light = 1.0) × 100

[0391] (Evaluation Criteria)

[0392] A: The residual rate of the compound is 80% or more.

[0393] B: The compound residual rate is 70% or more and less than 80%.

[0394] C: The residual rate of the compound is less than 70%.

[0395] 《Agglutination inhibition evaluation》

[0396] Coloring Compositions 1 to 8 and Coloring Compositions A to C were used to form images on 100 sheets of paper (A4 size) using the inkjet printer used in the above light fastness evaluation.

[0397] The formed images were observed with the naked eye and evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 1.

[0398] (Evaluation Criteria)

[0399] A: In the images formed on 100 sheets, disturbance such as blurring was not observed.

[0400] B: In the images formed on 100 sheets, disturbances such as blurring were slightly observed.

[0401] C: In the images formed on 100 sheets, disturbances such as blurring were observed.

[0402] D: In the images formed on 100 sheets, many disturbances such as blurring were observed.

[0403] 《Storage stability evaluation》

[0404] Coloring compositions 1 to 8 and coloring compositions A to C were stored for 7 days in an environment set to 45° C. in an oven.

[0405] The viscosity of the coloring composition before and after storage was measured, and the viscosity increase ratio (viscosity after storage - viscosity before storage) / viscosity before storage × 100 was calculated and evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 1.

[0406] The viscosity of the coloring composition was measured using a viscometer RE85L manufactured by Toki Sangyo Co., Ltd. (rotor: 1°34′×R24, measurement range 0.6 to 1200 mPa·s) in a state where the temperature was adjusted to 25°C.

[0407] (Evaluation Criteria)

[0408] A: The viscosity increase ratio is 10% or less.

[0409] B: The viscosity increase ratio exceeds 10%.

[0410] [Table 1]

[0411]

[0412] <Example 9>

[0413] 20 parts by mass of pigment G-1, 10 parts by mass of SOLSPERSE (registered trademark) 32000 (polymer dispersant, manufactured by The Lubrizol Corporation, weight average molecular weight 32,000) and 70 parts by mass of propylene glycol monomethyl ether acetate (solvent) were mixed, zirconium oxide beads with a diameter of 0.5 mm were filled, and dispersion was performed for 2 hours using a ball mill to obtain pigment dispersion 1A.

[0414] <Example 10>

[0415] Pigment dispersion 5A was obtained in the same manner as in Example 9 except that pigment G-1 was changed to pigment G-5.

[0416] <Example 11>

[0417] Pigment dispersion 1B was obtained in the same manner as in Example 9 except that propylene glycol monomethyl ether acetate was changed to ethyl 3-ethoxypropionate.

[0418] <Example 12>

[0419] 20 parts by mass of pigment G-1, 10 parts by mass of SOLSPERSE (registered trademark) 32000 (polymer dispersant, manufactured by The 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, and zirconium oxide beads with a diameter of 0.5 mm were filled and dispersed for 2 hours using a ball mill to obtain pigment dispersion 1C.

[0420] "evaluate"

[0421] The pigment dispersion 1A, the pigment dispersion 5A, the pigment dispersion 1B, and the pigment dispersion 1C were evaluated for light resistance, aggregation inhibition, and storage stability in the same manner as above.

[0422] [Table 2]

[0423]

[0424] The invention of Japanese Patent Application No. 2022-157096 filed on September 29, 2022 is incorporated herein by reference.

[0425] All documents, patent applications, and technical standards described in the present invention are incorporated herein by reference to the same extent as if each individual document, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A phthalocyanine pigment having at least one diffraction peak in 3°≤2θ≤7° in a powder X-ray diffraction spectrum and represented by the following general formula (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. The phthalocyanine pigment according to claim 1, wherein In formula (1), M is zinc, 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), 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 them is an alkyl group, a phenoxycarbonyl group or an alkoxy group, * indicates a linking portion with an oxygen atom.

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

4. The phthalocyanine pigment according to claim 2 or 3, wherein In formula (2), R 201 , R 202 , R 204 and R 205 is a hydrogen atom, R 203 represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group or a propoxy group. The phthalocyanine pigment according to claim 1 or 2, which has 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): 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, in, R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 and R 308 At least one of them is an aryl group represented by the following formula (4), In formula (4), R 401 , R 402 , R 404 and R 405 is a hydrogen atom, R 403 represents a methyl, ethyl, propyl, butyl, methoxy, ethoxy or propoxy group, * indicates 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 includes at least one selected from alcohols, ketones, carboxylates, and ethers.

10. The coloring composition according to claim 8, wherein The solvent comprises a carboxylic acid ester. 11 . The coloring composition according to claim 7 , which contains no amide solvent, or contains an amide solvent and the content of the amide solvent relative 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 with a weight average molecular weight of 1,000 to 100,000. 14 . The colored composition according to claim 7 , which is an inkjet ink.

15. A method for producing a phthalocyanine pigment, comprising: a mixing step of mixing a phthalonitrile compound represented by the following general formula (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 is set to 2.0 times or less on a mass basis, In formula (5) to formula (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, comprising 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.

Images