Mixture, composition, and compound

Abstract

To provide a mixture containing a phthalocyanine compound and exhibiting excellent temporal stability and light resistance, a composition containing the mixture, and a novel phthalocyanine compound.SOLUTION: A mixture contains a compound represented by the following general formula (1) and a compound represented by the following general formula (2). A composition comprises the mixture and a solvent such as water, glycerin, ethylene glycol, diethylene glycol, or diethylene glycol monobutyl ether.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to mixtures, compositions, and compounds. [Background technology]

[0002] Phthalocyanine compounds are useful as dye compounds, and various compounds are known. A novel phthalocyanine compound having absorption in the near-infrared region has been proposed (see Patent Document 1), and it is described that it is useful, for example, as an optical recording medium. Also, as a phthalocyanine dye, a phthalocyanine dye obtained by reacting at least two kinds selected from phthalonitriles and phthalic acid derivatives having different soluble groups or precursors thereof with a metal derivative has been proposed (see Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 5-345861 [Patent Document 2] Japanese Patent Application Laid-Open No. 2003-12952 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the phthalocyanine compound described in Patent Document 1 has room for improvement in terms of suppressing precipitation, aggregation, and the like over time. Furthermore, the phthalocyanine dye described in Patent Document 2 has room for improvement in terms of light resistance as a dye compound.

[0005] An object of one embodiment of the present disclosure is to provide a mixture containing a phthalocyanine compound and having good stability over time and light resistance, and a composition containing the mixture. Another problem to be solved by one embodiment of the present disclosure is to provide a novel phthalocyanine compound having an ester side chain. [Means for solving the problem]

[0006] The present disclosure includes the following aspects. <1> The compound includes a compound represented by the following general formula (1) and a compound represented by the following general formula (2): mixture.

[0007] [ka]

[0008] In general formula (1), A 1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and a plurality of A 1 are all identical. X represents a hydrogen atom or a halogen atom. M represents a metal atom or an oxide of a metal atom.

[0009] [ka]

[0010] In general formula (2), A 1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and a plurality of A 1 are all the same, and A in general formula (2) 1 represents A in general formula (1). 1 is the same as A 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. 1 and A 2 are different from each other. X represents a hydrogen atom or a halogen atom and is the same as X in general formula (1). M represents a metal atom or an oxide of a metal atom, and is the same as M in general formula (1).

[0011] <2> A in the above general formula (1) and general formula (2) 1 is a substituent selected from an alkoxycarbonyl-substituted phenyl group which may have a substituent, and an aryloxycarbonyl-substituted phenyl group which may have a substituent; <1> The mixture according to claim 1. <3> A in the above general formula (1) and general formula (2) 1 is a substituent represented by the following general formula (1p): <1> or <2> The mixture according to claim 1.

[0012] [ka]

[0013] In the above general formula (1p), R 1 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. <4> A in the above general formula (2) 2 is a substituent selected from an optionally substituted carboxy-substituted phenyl group, an optionally substituted alkoxycarbonyl-substituted phenyl group, and an optionally substituted aryloxycarbonyl-substituted phenyl group; <1> ~ <3> 10. The mixture according to any one of the preceding claims. <5> A in the above general formula (2) 2 is a substituent represented by the following general formula (2p): <1> ~ <4> 10. The mixture according to any one of the preceding claims.

[0014] [ka]

[0015] In the general formula (2p) above, R 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. 2 and R in general formula (1)1 are different from each other. <6> The content ratio of the compound represented by the general formula (1) to the compound represented by the general formula (2) is in the range of 90:10 to 99.9:0.1 by mass ratio. <1> ~ <5> 10. The mixture according to any one of the preceding claims.

[0016] <7> <1> ~ <6> A composition comprising the mixture according to any one of the above and a solvent. <8> the solvent contains at least one selected from water, glycerin, ethylene glycol, diethylene glycol, diethylene glycol monobutyl ether, ethyl acetate, butyl acetate, 2-butanone, cyclohexanone, propylene glycol monomethyl ether acetate, 1,2-hexanediol, and diisopropyl adipate; <7> The composition described in <9> Further comprising a dispersant, <7> or <8> The composition described in <10> Further, a surfactant is included. <7> ~ <9> The composition according to any one of the preceding claims.

[0017] <11> A compound represented by the following general formula (2A):

[0018] [ka]

[0019] In general formula (2A), R 1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and a plurality of R 1 are all the same. R 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. 1 and R 2 are different from each other. [Effects of the Invention]

[0020] According to one embodiment of the present disclosure, it is possible to provide a mixture containing a phthalocyanine compound and having good stability over time and light resistance, and a composition containing the mixture. According to another embodiment of the present disclosure, there can be provided a novel phthalocyanine compound having an ester side chain. [Brief explanation of the drawings]

[0021] [Figure 1] 1 shows a spectrum obtained by MALDI-TOFMS mass spectrometry of Exemplary Compound 2-13. DETAILED DESCRIPTION OF THE INVENTION

[0022]

[0033] The following describes exemplary embodiments of the mixtures, compositions, and compounds of the present disclosure. These descriptions and examples are intended to illustrate the embodiments and are not intended to limit the scope of the invention. In the present disclosure, the use of "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower limit and upper limit. In the 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. In addition, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

[0023] Each component may contain multiple types of the corresponding substance. When referring to the amount of each component in a mixture or composition, if there are multiple substances corresponding to each component in the mixture or composition, the total amount of those multiple substances present in the mixture or composition is meant, unless otherwise specified. In the present 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.

[0024] In the present disclosure, the group of substituents referred to as "substituent S" refers to the group of substituents shown below. (Substituent S) Examples of the substituent S include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (which may be linear, branched, or cyclic), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a silyl group, a hydroxy group, a nitro group, an amino group, an alkylamino group, an alkoxy group, an aryloxy group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imido group, a heterocyclic thio group, a phosphoryl group, an acyl group, a carboxy group, or a sulfo group. Each of these groups may further have a substituent.

[0025] [Mixture] The mixture of the present disclosure contains a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

[0026] [ka]

[0027] In general formula (1), A 1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and a plurality of A 1 are all the same. X represents a hydrogen atom or a halogen atom. M represents a metal atom or an oxide of a metal atom.

[0028] [ka]

[0029] In general formula (2), A 1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and a plurality of A 1 are all the same, and A in general formula (2) 1 represents A in general formula (1). 1 It is the same as A 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. 1 and A 2 are different from each other. X represents a hydrogen atom or a halogen atom, and is the same as X in general formula (1). M represents a metal atom or an oxide of a metal atom, and is the same as M in general formula (1).

[0030] (Compound represented by general formula (1)) The compound represented by the general formula (1) is a phthalocyanine compound, and is useful as a compound having excellent hue. In general formula (1), A 1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. A 1 When represents an alkyl group, the alkyl group is preferably, for example, an alkyl group having 1 to 10 carbon atoms. When the alkyl group has a substituent, the substituent is not particularly limited, and examples thereof include substituents selected from the substituents S, and among these, an alkoxy group or a halogen atom is preferred. A 1 When represents an aryl group, examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferred. When the aryl group has a substituent, the substituent is not particularly limited, and examples thereof include substituents selected from the substituents S, among which alkyl groups, halogen atoms, alkoxycarbonyl groups, and aryloxycarbonyl groups are preferred, and alkoxycarbonyl groups and aryloxycarbonyl groups are more preferred. When the aryl group is a phenyl group, the substitution position of these substituents may be the ortho-position, meta-position, or para-position of the phenyl group, and the para-position is preferred. In addition, the number of substituents may be one or more.

[0031] Among them, in the general formula (1), A 1 is preferably a substituent selected from an alkoxycarbonyl-substituted phenyl group which may have a substituent and an aryloxycarbonyl-substituted phenyl group which may have a substituent. In the alkoxycarbonyl-substituted phenyl group which may have a substituent or the aryloxycarbonyl-substituted phenyl group which may have a substituent, the substitution position of the alkoxycarbonyl group or the aryloxycarbonyl group relative to the phenyl group may be the ortho-position, meta-position, or para-position of the phenyl group, and from the viewpoint of the aggregation-inhibiting effect in the mixture, the para-position is preferred. From the viewpoint of achieving a more excellent effect of the present disclosure, in general formula (1), A 1 is more preferably a substituent represented by the following general formula (1p).

[0032] [ka]

[0033] In the above general formula (1p), R 1 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and from the viewpoint of light resistance, an unsubstituted alkyl group having 1 to 5 carbon atoms, a phenyl group, or a phenyl group substituted with a halogen atom is preferred. In general formula (1), a plurality of A 1 are all identical.

[0034] In general formula (1), X represents a hydrogen atom or a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. X is preferably a hydrogen atom or a fluorine atom from the viewpoint of the hue and color value of the phthalocyanine compound.

[0035] M represents a metal atom or an oxide of a metal atom. The metal atom is not particularly limited as long as it is a metal that can be a central atom of the phthalocyanine compound. Among them, from the viewpoints of the hue and light resistance of the phthalocyanine compound, Cu, Zn, Mg, Al, or V═O is preferred, Cu or Zn is more preferred, and Zn is even more preferred.

[0036] (Examples of compounds represented by general formula (1)) Specific examples of compounds represented by general formula (1) are listed below by clearly indicating the skeleton and substituents. The following exemplary compounds are examples of compounds represented by general formula (1) of the present disclosure, and it goes without saying that compounds represented by general formula (1) of the present disclosure are not limited to the exemplary compounds listed below.

[0037] [ka]

[0038] [ka]

[0039] (Compound represented by general formula (2)) The compound represented by the general formula (2) has the same phthalocyanine skeleton as the compound represented by the above-mentioned general formula (1), and is useful as a compound having excellent hue. Here, A in the compound represented by general formula (2) 1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and A in general formula (1) 1 In the compound represented by general formula (2), a plurality of A 1are all the same. That is, from the viewpoint of achieving a more excellent effect of the present disclosure, in general formula (2), A 1 is more preferably a substituent represented by the above general formula (1p). In general formula (2), A 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. 1 and A 2 are different from each other.

[0040] A in general formula (2) 2 The alkyl group in the formula (I) is preferably, for example, an alkyl group having 1 to 10 carbon atoms. The substituent substituted on the alkyl group is not particularly limited, and examples thereof include a substituent selected from the substituents S, and among these, a carboxy group, an alkoxy group, or a halogen atom is preferred. A in general formula (2) 2 The aryl group in the formula (I) includes, for example, a phenyl group or a naphthyl group, and a phenyl group is preferred. The substituent substituted on the aryl group is not particularly limited, and examples thereof include a substituent selected from the substituents S. Among them, an alkyl group, a halogen atom, a carboxy group, an alkoxycarbonyl group, or an aryloxycarbonyl group is preferable, and a carboxy group, an alkoxycarbonyl group, or an aryloxycarbonyl group is more preferable. When the aryl group is a phenyl group, the substitution position of these substituents may be the ortho-, meta-, or para-position of the phenyl group, preferably the para-position, and the number of substituents may be one or more.

[0041] In general formula (2), A 2is preferably a substituent selected from a hydrogen atom, an optionally substituted carboxy-substituted phenyl group, an optionally substituted alkoxycarbonyl-substituted phenyl group, and an optionally substituted aryloxycarbonyl-substituted phenyl group. In the optionally substituted carboxy-substituted phenyl group, the optionally substituted alkoxycarbonyl-substituted phenyl group, or the optionally substituted aryloxycarbonyl-substituted phenyl group, the substitution position of the carboxy-substituted phenyl group, the alkoxycarbonyl group, or the aryloxycarbonyl group relative to the phenyl group may be the ortho-position, meta-position, or para-position of the phenyl group, and is preferably the para-position from the viewpoint of light resistance. From the viewpoint of achieving a more excellent effect of the present disclosure, in general formula (1), A 2 is more preferably a substituent represented by the following general formula (2p).

[0042] [ka]

[0043] In the general formula (2p) above, R 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and from the viewpoint of the aggregation suppression effect, a hydrogen atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, a phenyl group, or a phenyl group substituted with a halogen atom, etc. are preferred. However, R in general formula (2) 2 and R in general formula (1) 1 are different from each other.

[0044] In the general formula (2), X represents a hydrogen atom or a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. X is preferably a hydrogen atom or a fluorine atom from the viewpoint of the hue and color value of the phthalocyanine compound.

[0045] M represents a metal atom or an oxide of a metal atom. The metal atom is not particularly limited as long as it is a metal that can be a central atom of the phthalocyanine compound. Among them, from the viewpoints of the hue, light resistance, etc. of the phthalocyanine compound, Cu, Zn, Mg, Al, or V═O is preferred, Cu or Zn is more preferred, and Zn is even more preferred.

[0046] A in general formula (2) 1 , X, and M are the same as the compounds represented by general formula (1) used in combination in the mixture. That is, the compound represented by general formula (1) and the compound represented by general formula (2) contained in the mixture of the present disclosure are the same as those of the substituent in general formula (2) and A 2 These compounds have the same skeleton except for the difference in

[0047] (Examples of compounds represented by general formula (2)) Specific examples of compounds represented by general formula (2) are listed below by clearly indicating the skeleton and substituents. The following exemplary compounds are examples of compounds represented by general formula (2) of the present disclosure, and it goes without saying that compounds represented by general formula (2) of the present disclosure are not limited to the exemplary compounds listed below.

[0048] [ka]

[0049] [ka]

[0050] The mass ratio of the compound represented by general formula (1) to the compound represented by general formula (2) in the mixture of the present disclosure is preferably 80:20 to 99.9:0.1, more preferably 90:10 to 99.9:0.1, and even more preferably 90:10 to 99.8:0.2.

[0051] The mechanism by which the precipitation or aggregation of the phthalocyanine compound is inhibited in the mixture of the present disclosure is not clear, but is presumed to be as follows. Phthalocyanine compounds are compounds that can achieve excellent hues, but depending on, for example, their solubility in the coexisting solvent, they may behave as a pigment in some cases or as a dye in other cases. When a phthalocyanine compound represented by general formula (1) coexists with a solvent in which it has low solubility, the phthalocyanine compound exists as a pigment dispersed in the medium. It is speculated that the coexistence of a compound represented by general formula (1) and a compound represented by general formula (2), which has a similar structure but differs only in a specific substituent, prevents the pigment particles from aggregating with each other over time due to the presence of the similar but different phthalocyanine compound on the pigment surface. Furthermore, because the compound represented by general formula (2) is identical to the compound represented by general formula (1) except for one substituent, it is speculated that the compound does not interfere with the arrangement of the pigment in the pigment, thereby maintaining high lightfastness. On the other hand, when the phthalocyanine compound represented by general formula (1) coexists with a solvent in which it has high solubility, the phthalocyanine compound exists as a dye dissolved in the solvent. As mentioned above, phthalocyanine compounds possess excellent hue and durability due to their strong aggregation ability. However, it is speculated that the coexistence of a compound represented by general formula (1) and a compound represented by general formula (2), i.e., the inclusion of phthalocyanines with similar structures but different substituents, inhibits the interaction between the phthalocyanine dyes, which tend to cause excessive aggregation and precipitate, thereby preventing sedimentation over time. Furthermore, since the compound represented by general formula (2) is identical to the compound represented by general formula (1) except for one substituent, it is speculated that the compound does not excessively inhibit the aggregation that contributes to improved lightfastness, thereby maintaining high lightfastness. It should be noted that this effect is speculative and does not affect the interpretation of the present disclosure.

[0052] The mixture of the present disclosure can be used in various applications, for example, as a colorant, it can be suitably used in dye compositions, inkjet inks, thermal transfer recording sheets, printing inks, paints, colored resin moldings, etc. For example, when the mixture of the present disclosure is applied to the production of a colored resin molded body, the mixture of the present disclosure as a coloring material is kneaded with a resin substrate, and the kneaded mixture is molded into a molded body by a known molding method (e.g., extrusion method or mold molding method), thereby obtaining a colored resin molded body colored with the mixture of the present disclosure.

[0053] [Composition] A preferred use of the mixture of the present disclosure is in a composition. The composition of the present disclosure comprises the mixture of the present disclosure described above and a solvent. The term "solvent" in the composition of the present disclosure is used to encompass a medium in which the compound represented by general formula (1) and the compound represented by general formula (2) contained in the mixture are not necessarily completely dissolved, but in which some of the compounds are dissolved and the undissolved compounds are dispersed, i.e., a dispersion medium.

[0054] (solvent) The composition of the present disclosure comprises the mixture of the present disclosure and further comprises a solvent. The solvent in the present disclosure is not particularly limited as long as it can contain the compound represented by the general formula (1) and the compound represented by the general formula (2) in a dissolved or dispersed state. The solvent may be at least one selected from water, glycerin, ethylene glycol, diethylene glycol, diethylene glycol monobutyl ether, ethyl acetate, butyl acetate, 2-butanone, cyclohexanone, propylene glycol monomethyl ether acetate, 1,2-hexanediol, and diisopropyl adipate.

[0055] When the compound represented by the general formula (1) and the compound represented by the general formula (2) are contained as pigments in the composition, examples of the solvent include water, glycerin, ethylene glycol, diethylene glycol, diethylene glycol monobutyl ether, ethyl acetate, butyl acetate, and 1,2-hexanediol. Furthermore, when the compound represented by the general formula (1) and the compound represented by the general formula (2) are contained as dyes in a composition, examples of solvents that can be used in terms of solubility include ethyl acetate, butyl acetate, 2-butanone, cyclohexanone, propylene glycol monomethyl ether acetate, diethyl phthalate, diisopropyl adipate, and N,N-diethyldodecanamide. The solvent in the composition of the present disclosure may be one type or a mixture of two or more types.

[0056] The compositions of the present disclosure may contain other ingredients in addition to the mixtures and solvents of the present disclosure. (dispersant) The composition of the present disclosure preferably further contains a dispersant from the viewpoint of suppressing aggregation of components and further improving stability over time.

[0057] The type of dispersant is not particularly limited as long as it can disperse the phthalocyanine compound in the composition in a pigment state and stably maintain that state. For example, cationic, anionic, nonionic, amphoteric, or other dispersants can be used.

[0058] From the viewpoint of suppressing aggregation of components and further improving stability over time, 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.

[0059] 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.

[0060] From the viewpoint of suppressing aggregation of components and further improving stability over time, the weight average molecular weight of the dispersant is preferably from 1,000 to 100,000, more preferably from 5,000 to 50,000, and even more preferably from 10,000 to 45,000. In the present disclosure, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC). In one embodiment, the GPC measurement is performed using an HLC (registered trademark)-8220GPC (manufactured by Tosoh Corporation) as the measuring device, three columns connected in series: a TSKgel (registered trademark) Super HZ2000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), a TSKgel (registered trademark) Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), and a TSKgel (registered trademark) Super HZ-H (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), and NMP (N-methylpyrrolidone) as the eluent. The measurement conditions were a sample concentration of 0.3% by mass, a flow rate of 0.35 ml / min, a sample injection volume of 10 μL, and a measurement temperature of 40°C. A refractive index (RI) detector was used. A calibration curve was prepared using six samples of "TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-80," "F-20," "F-4," "F-2," "A-5000," and "A-1000."

[0061] From the viewpoint of suppressing aggregation of the components and further improving stability over time, the content of the dispersant relative to the total mass of the 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. That's fine.

[0062] (surfactant) The composition of the present disclosure preferably further comprises a surfactant. By including a surfactant in the composition of the present disclosure, the surface tension of the composition can be adjusted, and the handleability of the resulting composition becomes better. Examples of surfactants include nonionic, cationic, and anionic surfactants. When the composition of the present disclosure is used as an inkjet recording ink, the surface tension of the ink at 25°C is preferably 25 to 70 mPa·s, and more preferably 25 to 60 mN / m. By including a surfactant, it is possible to adjust the surface tension of the composition of the present disclosure according to the purpose. Preferred examples of the surfactant include anionic surfactants such as fatty acid salts, alkyl sulfate salts, alkylbenzenesulfonates, alkylnaphthalenesulfonates, dialkylsulfosuccinates, alkylphosphate salts, naphthalenesulfonate-formalin condensates, and polyoxyethylene alkyl sulfate salts; and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and oxyethyleneoxypropylene block copolymers. Also preferably used is SURFYNOLS (Air Products & Chemicals), an acetylene-based polyoxyethylene oxide surfactant. As the surfactant, an amine oxide type amphoteric surfactant such as N,N-dimethyl-N-alkylamine oxide is also preferred. The surfactant may be selected depending on the intended use of the composition. For example, surfactants listed on pages (37) to (38) of JP-A-59-157636 and Research Disclosure No. 308119 (1989) can be used. In the composition of the present disclosure, the type and content of the surfactant may be selected appropriately depending on the desired physical properties of the composition.

[0063] (Other ingredients) In addition to the above-mentioned preferred optional components, the composition of the present disclosure can contain various other components depending on the intended use of the composition.

[0064] [Compound represented by general formula (2A)] The compound of the present disclosure is a compound represented by the following general formula (2A). The following compound is a novel compound.

[0065] [ka]

[0066] In general formula (2A), R 1 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and a plurality of R 1 are all the same. R 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. 1 and R 2 are different from each other. The compound represented by general formula (2A) is a preferred embodiment of general formula (2).

[0067] It has been found that the use of the compound represented by general formula (2A) in combination with a known zinc phthalocyanine fluoride compound having an ester side chain contributes to stability over time. The compound represented by the general formula (2A) above can be said to be the best example of the compound represented by the general formula (2) contained in the mixture of the present disclosure. The synthesis method of the compound represented by the above general formula (2A) will be explained in the examples below. [Example]

[0068] [Synthesis examples of exemplary compounds] 1. Synthesis of Example Compound 2-1 Exemplary compound 2-1 was synthesized according to the following scheme.

[0069] [ka]

[0070] Zinc iodide (0.17 g), 3,6-difluoro-4,5-bis(4-methoxycarbonylphenoxy)phthalonitrile (1.00 g), and benzonitrile (10 mL) were placed in a 100 mL recovery flask, mixed, and reacted at 160° C. for 5 hours. The contents of the recovery flask were cooled to room temperature (25°C), 10 mL of methanol was added dropwise, and the precipitated solid was collected by filtration. 10 mL of benzonitrile, 1 mL of water, and 100 mg of sulfuric acid were mixed in a 100 mL recovery flask, and the solid obtained above was added. The mixture was stirred at 150 °C for 48 hours. The recovery flask was cooled to room temperature (25 °C), and 10 mL of methanol was added dropwise. The precipitated solid was collected by filtration. 500 mg of the resulting solid was separated and purified by recycling preparative HPLC (column: JAIGEL-ODS-AP-50L, mobile phase: water / THF). The collected fractions were concentrated under reduced pressure to obtain compound 2-1 (125.2 mg) as a solid. (MALDI-TOFMS: 1907 ([M+1]+))

[0071] 2. Synthesis of Example Compound 2-3 Zinc iodide (0.16 g), 3,6-difluoro-4,5-bis(4-ethoxycarbonylphenoxy)phthalonitrile (1.00 g), and benzonitrile (10 mL) were placed in a 100 mL recovery flask, mixed, and reacted for 5 hours at 160° C. The recovery flask was cooled to room temperature (25° C.), 10 mL of methanol was added dropwise, and the precipitated solid was collected by filtration. 10 mL of benzonitrile, 1 mL of water, and 100 mg of sulfuric acid were mixed in a 100 mL recovery flask, and the solid obtained above was added. The mixture was stirred at 150 °C for 48 hours. The recovery flask was cooled to room temperature (25 °C), and 10 mL of methanol was added dropwise. The precipitated solid was collected by filtration. 500 mg of the resulting solid was separated and purified by recycling preparative HPLC (column: JAIGEL-ODS-AP-50L, mobile phase: water / THF). The collected fractions were concentrated under reduced pressure to give compound 2-3 (125.7 mg) as a solid. (MALDI-TOFMS: 1861 ([M+1]+))

[0072] 3. Synthesis of Example Compound 2-11 Zinc iodide (0.14 g), 3,6-difluoro-4,5-bis(4-butoxycarbonylphenoxy)phthalonitrile (1.00 g), and benzonitrile (10 mL) were placed in a 100 mL recovery flask, mixed, and reacted for 5 hours at 160° C. The recovery flask was cooled to room temperature (25° C.), 10 mL of methanol was added dropwise, and the precipitated solid was collected by filtration. 10 mL of benzonitrile, 1 mL of methanol, and 100 mg of sulfuric acid were mixed in a 100 mL recovery flask, and the solid obtained above was added. The mixture was stirred at 150 °C for 48 hours. The recovery flask was cooled to room temperature (25 °C), and 10 mL of methanol was added dropwise. The precipitated solid was collected by filtration. 500 mg of the resulting solid was separated and purified by recycling preparative HPLC (column: JAIGEL-ODS-AP-50L, mobile phase: water / THF). The collected fractions were concentrated under reduced pressure to obtain compound 2-11 (112.1 mg) as a solid. (MALDI-TOFMS: 2071 ([M+1]+))

[0073] 4. Synthesis of Example Compound 2-13 Zinc iodide (0.13 g), 3,6-difluoro-4,5-bis(4-phenoxycarbonylphenoxy)phthalonitrile (1.00 g), and benzonitrile (10 mL) were placed in a 100 mL recovery flask, mixed, and reacted for 5 hours at 160° C. The recovery flask was cooled to room temperature (25° C.), 10 mL of methanol was added dropwise, and the precipitated solid was collected by filtration. 10 mL of benzonitrile, 1 mL of water, and 100 mg of sulfuric acid were mixed in a 100 mL recovery flask, and the solid obtained above was added. The mixture was stirred at 150 °C for 48 hours. The recovery flask was cooled to room temperature (25 °C), and 10 mL of methanol was added dropwise. The precipitated solid was collected by filtration. 500 mg of the resulting solid was separated and purified by recycling preparative HPLC (column: JAIGEL-ODS-AP-50L, mobile phase: water / THF). The collected fractions were concentrated under reduced pressure to obtain compound 2-13 (133.4 mg) as a solid. (MALDI-TOFMS: 2341 ([M+1]+)) 1 shows the spectrum obtained by MALDI-TOFMS mass spectrometry of Exemplary Compound 2-13 obtained in the above Synthesis Example. The MALDI-TOFMS conditions will be described later.

[0074] 5. Synthesis of Example Compound 2-14 Zinc iodide (0.13 g), 3,6-difluoro-4,5-bis(4-phenoxycarbonylphenoxy)phthalonitrile (1.00 g), and benzonitrile (10 mL) were placed in a 100 mL recovery flask, mixed, and reacted for 5 hours at 160° C. The recovery flask was cooled to room temperature (25° C.), 10 mL of methanol was added dropwise, and the precipitated solid was collected by filtration. 10 mL of benzonitrile, 1 mL of methanol, and 100 mg of sulfuric acid were mixed in a 100 mL recovery flask, and the solid obtained above was added. The mixture was stirred at 150 °C for 48 hours. The recovery flask was cooled to room temperature (25 °C), and 10 mL of methanol was added dropwise. The precipitated solid was collected by filtration. 500 mg of the resulting solid was separated and purified by recycling preparative HPLC (column: JAIGEL-ODS-AP-50L, mobile phase: water / THF). The collected fractions were concentrated under reduced pressure to obtain compound 2-14 (112.7 mg) as a solid. (MALDI-TOFMS: 2355 ([M+1]+))

[0075] 6. Synthesis of Example Compound 2-18 Zinc iodide (0.18 g), 4,5-bis(4-methoxycarbonylphenoxy)phthalonitrile (1.00 g), and benzonitrile (10 mL) were placed in a 100 mL recovery flask, mixed, and reacted at 160° C. for 5 hours. The contents of the recovery flask were cooled to room temperature (25°C), 10 mL of methanol was added dropwise, and the precipitated solid was collected by filtration. 10 mL of benzonitrile, 1 mL of water, and 100 mg of sulfuric acid were mixed in a 100 mL recovery flask, and the solid obtained above was added. The mixture was stirred at 150 °C for 48 hours. The recovery flask was cooled to room temperature (25 °C), and 10 mL of methanol was added dropwise. The precipitated solid was collected by filtration. 500 mg of the resulting solid was separated and purified by recycling preparative HPLC (column: JAIGEL-ODS-AP-50L, mobile phase: water / THF). The collected fractions were concentrated under reduced pressure to give compound 2-18 (102.8 mg) as a solid. (MALDI-TOFMS: 1763 ([M+1]+))

[0076] 7. Synthesis of Example Compound 2-20 Zinc iodide (0.12 g), 3,6-difluoro-4,5-bis(4-(4-chlorophenoxycarbonyl)phenoxy)phthalonitrile (1.00 g), and benzonitrile (10 mL) were placed in a 100 mL recovery flask, mixed, and reacted at 160° C. for 5 hours. The recovery flask was cooled to room temperature (25° C.), 10 mL of methanol was added dropwise, and the precipitated solid was collected by filtration. 10 mL of benzonitrile, 1 mL of water, and 100 mg of sulfuric acid were mixed in a 100 mL recovery flask, and the solid obtained above was added. The mixture was stirred at 150 °C for 48 hours. The recovery flask was cooled to room temperature (25 °C), and 10 mL of methanol was added dropwise. The precipitated solid was collected by filtration. 500 mg of the resulting solid was separated and purified by recycling preparative HPLC (column: JAIGEL-ODS-AP-50L, mobile phase: water / THF). The collected fractions were concentrated under reduced pressure to obtain compound 2-20 (118.5 mg) as a solid. (MALDI-TOFMS: 2435 ([M+1]+))

[0077] 8. Synthesis of Example Compound 2-27 Tetrafluorophthalonitrile (10 g), 1-butanol (75 ml), and tetrahydrofuran (10 ml) were dissolved in a 200 ml three-neck flask, and 3.3 g of potassium hydroxide was added in three portions over 30 minutes at an internal temperature of -7°C to -3°C, followed by stirring for 30 minutes. The reaction solution was concentrated, and water (40 mL) was added to the resulting residue. The extracts obtained by three extractions with ethyl acetate were combined and dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was filtered off, and the filtrate was concentrated. The resulting residue was purified by silica gel column chromatography to obtain 10.3 g of 3,4,6-trifluoro-5-butoxyphthalonitrile.

[0078] 3,4,6-trifluoro-5-butoxyphthalonitrile (10 g), potassium fluoride (2.5 g), and acetone (45 ml) were added to a 100 ml three-neck flask, stirred at room temperature, and dissolved. After cooling, the mixture was stirred at an internal temperature of -11 to -9 °C to dissolve 3-methoxy-1-propanol. (5.0 g) was added dropwise, and then the mixture was stirred for 7 hours while gradually returning to room temperature. Insoluble matter in the reaction mixture was filtered off, and the filtrate was concentrated. The resulting residue was purified by silica gel column chromatography to obtain 9.2 g of 3,6-difluoro-4-methoxypropyloxy-5-butoxyphthalonitrile.

[0079] Tetrafluorophthalonitrile (10 g) and acetone (40 mL) were added to a 300 mL three-neck flask, and the flask was cooled to an internal temperature of -11°C and stirred. A solution prepared by stirring 1-butanol (8.2 g), tetrahydrofuran (100 mL), and potassium t-butoxide (11.6 g) was added dropwise to the flask at an internal temperature of -10°C to -7°C and stirred. Thereafter, the mixture was stirred for another 6 hours while gradually raising the temperature to 25°C, and toluene (100 mL) was added to the obtained reaction liquid, and the liquid volume was concentrated to about one-third. Water (50 mL) and saturated saline (50 mL) were added to the obtained residue, and the liquids were separated. Subsequently, the toluene solution layer was washed with water (50 mL) and saturated saline (50 mL), and this operation was repeated three times. The toluene solution layer was dried over anhydrous sodium sulfate, and the anhydrous sodium sulfate was filtered off, followed by concentration. The obtained residue was purified by silica gel column chromatography, and 8.9 g of 3,6-difluoro-4,5-butoxyphthalonitrile was obtained.

[0080] Zinc iodide (0.25 g), 3,6-difluoro-4-methoxypropyloxy-5-butoxyphthalonitrile (0.26 g), 3,6-difluoro-4,5-butoxyphthalonitrile (1.00 g), and benzonitrile (10 mL) were placed in a 100 mL recovery flask, mixed, and reacted for 5 hours at 160° C. The recovery flask was cooled to room temperature (25° C.), 10 mL of methanol was added dropwise, and the precipitated solid was collected by filtration. A 500 mg portion of the solid was purified by recycle preparative HPLC (JAIGEL-ODS-AP-50L column, water / THF mobile phase), and the collected fractions were concentrated under reduced pressure to give compound 2-27 (178.4 mg) as a solid (MALDI-TOFMS: 1313 ([M+1]+)).

[0081] The above exemplary compounds (2-1), (2-3), (2-11), (2-13), (2-14), (2-18) and (2-20) are all novel compounds represented by the above general formula (2A). The exemplified compounds (2-1), (2-3), (2-11), (2-13), (2-14), (2-18), and (2-20) obtained in the above synthesis examples were confirmed for their structures by the following method. <MALDI-TOF MS Conditions> The compounds synthesized above were each dissolved (or dispersed) in THF, and a sample solution was prepared using ditranol as the matrix. The sample solution was placed on a target plate, air-dried, and then measured. Apparatus: UltrafleXtreme manufactured by Bruker Measurement mode: Reflector, Posi. & Nega

[0082] Hereinafter, the present disclosure will be described in detail based on examples. However, the present disclosure is not limited to the following examples, and the contents described in the following examples (for example, raw materials, conditions, and methods) may be appropriately changed within the scope of the object of the present disclosure. Unless otherwise specified in the following description, “%” means “mass %”.

[0083] <Examples 1 to 8, Comparative Example 1, Comparative Example 2> Examples 1 to 8, Comparative Example 1, and Comparative Example 2 are examples related to compositions using exemplified compound 1, which is a compound represented by the general formula (1), and exemplified compound 2, which is a compound represented by the general formula (2), as pigments, respectively. The structures of the exemplified compounds are as described above. Comparative compound used in Comparative Example 2 *1 is compound 40 described in paragraph

[0053] [Table 4] of JP-A No. 2003-12952.

[0084] 1. Preparation of Pigment Dispersion Exemplified compound 1 or the comparative compound and exemplified compound 2 were weighed in the types and contents shown in Table 1. Exemplified compound 1 is a compound represented by the general formula (1), and exemplified compound 2 is a compound represented by the general formula (2). Exemplary Compound 1 and Exemplary Compound 2, 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, 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 were charged into a stainless steel container. Next, the mixture was dispersed for 2 hours in a paint conditioner using zirconia beads with a diameter of 0.5 mm manufactured by Nikkato Corporation, to obtain a pigment dispersion.

[0085] The obtained pigment dispersion was mixed with a polyurethane resin (HYDRAN (registered trademark) AP-40F (manufactured by DIC Corporation)) and ion-exchanged water to produce an aqueous pigment dispersion with a pigment content of 10% by mass and a polyurethane resin non-volatile content of 2% by mass. The pigment content of the coloring composition was 4% by mass.

[0086] The following components were mixed with the obtained aqueous pigment dispersion in the amounts shown below to obtain colored compositions of the respective Examples and Comparative Examples. (Composition of Coloring Composition) Pigment dispersion 40 parts by weight 1,2-Hexanediol 5 parts by mass Glycerin 10 parts by weight Surfynol 465 (surfactant, manufactured by Air Products and Chemicals Co.) 1 part by mass Ion-exchanged water 44 parts by weight

[0087] 2. Evaluation 2-1. Stability over time Each of the colored compositions of Examples 1 to 8 and Comparative Examples 1 and 2 was stored for 7 days in an environment maintained at 45° C. using an oven. The viscosity of the colored composition 1 was measured before and after storage, and the viscosity increase rate (viscosity after storage−viscosity before storage) / viscosity before storage×100 was calculated and evaluated based on the following evaluation criteria. The viscosity of each colored composition was measured using a viscometer RE85L (rotor: 1°34'×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%. Here, the term "good stability over time of a composition" means that the mixture contained in the composition has good stability over time.

[0088] 2-2.Lightfastness Using an inkjet printer (manufactured by Fujifilm Corporation, product name: Material Printer DMP-2850), images were formed on OK topcoat paper (manufactured by Oji Paper Co., Ltd.) using each of the coloring compositions of Examples 1 to 8 and Comparative Examples 1 and 2. The image was irradiated with xenon light (100,000 lux) for 168 hours using a weather meter (Atlas, Ci65), and the reflection density after irradiation with xenon light was measured using a reflection densitometer (X-Rite, product name: X-Rite i1Pro). The reflection density of the image before irradiation with xenon light was set to 1.0±0.2. 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: A higher compound remaining rate (%) indicates that the phthalocyanine compound contained in the image has better light resistance. Compound remaining rate (%) = (reflection density of solid image after irradiation with xenon light) / (reflection density of solid image before irradiation with xenon light = 1.0) × 100 (Evaluation criteria) A: The compound remaining rate was 80% or more. B: The compound remaining rate was 70% or more and less than 80%. C: The compound remaining rate was less than 70%.

[0089] In Tables 1 and 2, "-" means that the component is not included.

[0090] [Table 1]

[0091] As is clear from Table 1, the compositions (coloring compositions) of Examples 1 to 8, which contained a compound represented by general formula (1) and a compound represented by general formula (2), were good in both stability over time and lightfastness. On the other hand, the composition of Comparative Example 1, which contained only a compound represented by general formula (1) but not a compound represented by general formula (2), had poor stability over time, and Comparative Example 2, which contained neither a compound represented by general formula (1) nor a compound represented by general formula (2) and contained a known phthalocyanine compound, had poor lightfastness.

[0092] <Examples 9 to 11, Comparative Examples 3 and 4> Examples 9 to 11 and Comparative Examples 3 and 4 are examples relating to compositions in which the above-mentioned exemplary compound 1 and exemplary compound 2 are used as dyes. The structures of the exemplary compounds are as described above. Comparative compound used in Comparative Example 2 *2 is compound 40 described in paragraph

[0053] [Table 4] of JP-A No. 2003-12952.

[0093] 1. Preparation of dye-containing composition The following components were dissolved with stirring to obtain a colored composition. Exemplary Compound 1: The type and content shown in Table 2 Exemplary Compound 2: Type and content as listed in Table 2 Diethyl phthalate 30 parts by mass Diisopropyl adipate 44 parts by mass N,N-diethyldodecanamide 20 parts by mass

[0094] 2. Evaluation of coloring compositions 2-1. Stability over time Each of the colored compositions of Examples 9 to 11 and Comparative Examples 3 and 4 was stored for 7 days in an environment maintained at 45° C. using an oven. The viscosity of the colored composition 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 viscosity of the colored composition was measured using a viscometer RE85L (rotor: 1°34'×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%.

[0095] 2-2.Lightfastness Using an inkjet printer (manufactured by Fujifilm Corporation, product name: Material Printer DMP-2850), images were formed on OK topcoat paper (manufactured by Oji Paper Co., Ltd.) using each of the coloring compositions of Examples 10 to 12, Comparative Examples 3 and 4. The image was irradiated with xenon light (100,000 lux) for 48 hours using a weather meter (Atlas, Ci65), and the reflection density after irradiation with xenon light was measured using a reflection densitometer (X-Rite, trade name: X-Rite i1Pro). The reflection density of the image before irradiation with xenon light was set to 1.0±0.2. 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: A higher compound remaining rate (%) indicates that the phthalocyanine compound contained in the image has better light resistance. Compound remaining rate (%) = (reflection density of solid image after irradiation with xenon light) / (reflection density of solid image before irradiation with xenon light = 1.0) × 100 (Evaluation criteria) A: The compound remaining rate was 80% or more. B: The compound remaining rate was 70% or more and less than 80%. C: The compound remaining rate was less than 70%.

[0096] [Table 2]

[0097] As is clear from Table 2, the compositions of Examples 9 to 11, which contained a compound represented by general formula (1) and a compound represented by general formula (2) as dyes, exhibited good stability over time and good lightfastness. On the other hand, the composition of Comparative Example 3, which contained only a compound represented by general formula (1) but no compound represented by general formula (2), exhibited poor stability over time, and Comparative Example 4, which contained neither a compound represented by general formula (1) nor a compound represented by general formula (2) but a known phthalocyanine compound, exhibited poor lightfastness.

Claims

1. The compound includes a compound represented by the following general formula (1) and a compound represented by the following general formula (2): mixture. 【Chemical 1】 In general formula (1), A １ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and a plurality of A １ are all identical. X represents a hydrogen atom or a halogen atom. M represents a metal atom or an oxide of a metal atom. 【Chemistry 2】 In general formula (2), A １ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and a plurality of A １ are all the same, and A in general formula (2) １ represents A in general formula (1). １ is the same as A ２ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. 1 and A ２ are different from each other. X represents a hydrogen atom or a halogen atom and is the same as X in general formula (1). M represents a metal atom or an oxide of a metal atom, and is the same as M in general formula (1).

2. A in the general formula (1) and general formula (2) １ The mixture according to claim 1 , wherein is a substituent selected from an optionally substituted alkoxycarbonyl-substituted phenyl group and an optionally substituted aryloxycarbonyl-substituted phenyl group.

3. A in the general formula (1) and general formula (2) １ The mixture according to claim 1 or 2, wherein is a substituent represented by the following general formula (1p): 【Chemistry 3】 In general formula (1p), R １ represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

4. A in the general formula (2) ２ is a substituent selected from an optionally substituted carboxy-substituted phenyl group, an optionally substituted alkoxycarbonyl-substituted phenyl group, and an optionally substituted aryloxycarbonyl-substituted phenyl group.

5. A in the general formula (2) ２ The mixture according to claim 1 or 2, wherein is a substituent represented by the following general formula (2p): 【Chemistry 4】 In general formula (2p), R ２ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. ２ and R in general formula (1) １ are different from each other.

6. 3. The mixture according to claim 1, wherein the content ratio of the compound represented by the general formula (1) to the compound represented by the general formula (2) is in the range of 90:10 to 99.9:0.1 by mass ratio.

7. A composition comprising the mixture of claim 1 or claim 2 and a solvent.

8. 8. The composition of claim 7, wherein the solvent comprises at least one selected from water, glycerin, ethylene glycol, diethylene glycol, diethylene glycol monobutyl ether, ethyl acetate, butyl acetate, 2-butanone, cyclohexanone, propylene glycol monomethyl ether acetate, 1,2-hexanediol, and diisopropyl adipate.

9. The composition of claim 7 further comprising a dispersant.

10. The composition of claim 7 further comprising a surfactant.

11. A compound represented by the following general formula (2A): 【Chemistry 5】 In general formula (2A), R １ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and a plurality of R １ are all the same. ２ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. １ and R ２ are different from each other.

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