JP6086841B2 - Phthalocyanine compounds - Google Patents

Description

  The present invention relates to a phthalocyanine compound and an inkjet ink containing the compound. More specifically, the present invention relates to a phthalocyanine compound having a strong bluish cyan color suitable for cyan ink and exhibiting excellent solubility in a solvent, and an inkjet ink containing the compound.

  Ink-jet printing has become widespread in industrial use and OA use in recent years because it is non-contact with the substrate and enables high-speed printing. Particularly in OA applications, there is an increasing demand for obtaining high-quality, full-color, high-quality printed matter. As ink-jet inks, inks in which water-soluble dyes such as acid dyes, direct dyes and basic dyes are dissolved in a solvent such as a glycol solvent and water are often used. However, ink jet inks that use water-soluble dyes do not provide sufficient water resistance for printed matter.

  In addition, liquid compositions and inks containing an active energy ray-polymerizable substance have been applied to the production of graphic arts, signs, displays, label recordings, package recordings, electronic circuit boards, and display panels by inkjet. Many of these are applications that require extremely high image quality. Such ink-jet inks include a solvent type and a water type. Among these, solvent-type inks include oil-based inks in which pigments or dyes are dispersed in toluene, methyl ethyl ketone, or the like.

  On the other hand, phthalocyanine compounds are stable against light, heat, temperature, etc., and have excellent robustness. Therefore, they are used in optical recording media such as compact discs, optical memory discs, and optical cards using semiconductor lasers as light sources. As a near-infrared absorbing dye, as a heat ray shielding agent, it is used in various applications. Thus, conventionally known phthalocyanine compounds include alcohols such as methanol, ethanol and propanol, cellosolves such as ethyl cellosolve, glycols such as monoethylene glycol and diethylene glycol, ketones such as acetone and methyl ethyl ketone, ethers, chloroform, toluene and the like. It is known that these organic solvents are soluble (see, for example, Patent Documents 1 to 3).

JP 2010-077408 A JP 2010-265254 A International Publication No. 2011/105603

  However, it has been found that a conventionally known phthalocyanine compound has both a vivid cyan color and an excellent solubility property in a solvent used in an inkjet ink.

  Accordingly, an object of the present invention is to provide a phthalocyanine compound having a strong bluish color and a bright cyan color suitable for cyan ink. Another object of the present invention is to provide a phthalocyanine compound having high solubility in various solvents.

  Another object of the present invention is to provide a cyan inkjet ink containing a phthalocyanine compound as described above.

  As a result of intensive studies to solve the above problems, the present inventors have found that a phthalocyanine compound having a specific structure has a strong cyan blue color and solubility in various solvents. It came to complete.

  That is, the above object is achieved by the following formula (1):

In the above formula (1), Z _{1 to} Z ₁₆ are each independently a hydrogen atom, a halogen atom, the following formula (2):

In the above formula (2), R ¹ and R ² may be different, are a halogen atom or an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 4.
Or a substituent represented by the following formula (3):

In the above formula (3), X is an oxygen atom or a sulfur atom, Ar is a phenyl group or a naphthyl group which may be substituted with R ³ , and in this case, each R ³ is independently cyano A group, a nitro group, OY, a halogen atom, an aryl group, or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, where Y is an alkyl group having 1 to 8 carbon atoms A substituent (b) represented by:
At this time, _{1 to} 3.9 of Z _{1 to} Z ₁₆ are the substituent (a) or the substituent (b), 3 to 12 are hydrogen atoms, and the remainder is a halogen atom, Among 1 to 3.9 substituents (a) or (b), at least one or more is substituent (a),
M represents metal-free, metal, metal oxide or metal halide,
It is achieved by a phthalocyanine compound represented by

  The phthalocyanine compound of the present invention has a high absorption at 630 nm and a high transparency at 460 nm, and has a bluish cyan color suitable for cyan ink. Moreover, the phthalocyanine compound of the present invention is soluble in various solvents. Therefore, the phthalocyanine compound of the present invention can be suitably used for cyan inkjet ink.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
Hereinafter, the phthalocyanine compound represented by the above formula (1) is also simply referred to as “phthalocyanine compound” or “phthalocyanine compound of the present invention”. The reason why the number of substituents included in Z _{1 to} Z ₁₆ can be as small as 3.9, for example, is as follows. That is, the raw material (phthalonitrile derivative) for producing the “phthalocyanine derivative” of the present invention is mixed in a desired ratio. At this time, the produced “phthalocyanine derivative” is in the form of a mixture having various structures. That is, the number of the substituent (a) or the substituent (b), the “hydrogen atom”, or the remaining halogen atoms may be a decimal number.

  As described above, the phthalocyanine compound of the present invention is characterized in that a specific number of substituents (a), substituents (b), hydrogen atoms and halogen atoms are introduced into the phthalocyanine skeleton. The phthalocyanine compound having such a structure has a cyan color with excellent contrast and strong bluish tint. Here, the degree of blueness of the phthalocyanine compound can be expressed by high absorption at 630 nm and high transmittance at 460 nm. Specifically, the cyan color becomes stronger as the light of 630 nm, which is a typical red light, is absorbed, and the vivid cyan color is exhibited as the light of 460 nm, which is a typical blue light, is transmitted. Specifically, the ratio of absorbance at 630 nm {Abs (630 nm)} to the absorbance at 460 nm {Abs (460 nm)} {Abs (630 nm) / Abs (460 nm)} can represent the degree of bluishness. A larger value means a cyan color with a stronger bluish tint. Further, it means that the smaller the absorbance value at 460 nm, that is, the greater the value of transmittance {% T (460 nm)} at 460 nm, the brighter the cyan color. More specifically, the ratio of the absorbance at 630 nm to the absorbance at 460 nm {Abs (630 nm) / Abs (460 nm)} of the phthalocyanine compound of the present invention usually exceeds 40, more preferably 50 or more, and particularly preferably. Is 60 or more. In addition, since Abs (630nm) / Abs (460nm) is so preferable that it is high, the upper limit is not specifically limited. Preferably, the upper limit is 100 and more preferably 80. Further, the transmittance value at 460 nm of the phthalocyanine compound of the present invention usually exceeds 90%, preferably 94% or more, and is ideal as it approaches 100%.

  Furthermore, the phthalocyanine compound of the present invention exhibits excellent solubility in various solvents. Here, the “solvent” is not particularly limited, but may be a solvent generally used for ink-jet ink. Specifically, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec- Alcohol solvents such as butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, n-hexanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl Glycol solvents such as ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol mono t-butyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, propylene glycol monomethyl ether acetate (PGMEA); toluene, Examples include hydrocarbon solvents such as xylene; ester solvents such as ethyl lactate, ethyl 3-ethoxypropionate, ethyl acetate, and butyl acetate. Among these, the phthalocyanine compound of the present invention is preferably excellent in solubility in a glycol solvent, a ketone solvent, or an alcohol solvent, more preferably excellent in solubility in a glycol solvent or a ketone solvent, It is particularly preferable that the solubility in a glycol solvent, particularly PGMEA is excellent.

  In addition to the above advantages, the phthalocyanine compound of the present invention is excellent in at least one characteristic of compatibility with a resin, heat resistance, light resistance and weather resistance. Further, the phthalocyanine compound of the present invention has a high extinction coefficient per gram (hereinafter referred to as gram extinction coefficient) because the total number of substitutions of the substituents (a) and (b) is small. Therefore, the phthalocyanine compound of the present invention has functions as a cyan dye (contrast, bluish strength, vividness, etc.), solubility in various solvents, durability (heat resistance, light resistance, weather resistance), It has an excellent balance of absorbance per gram and can be suitably used for cyan inkjet ink. In this specification, the absorbance {Abs (630 nm)} at 630 nm and the absorbance {Abs (460 nm)} at 460 nm are values measured according to the measurement method used in the following examples, and the transmittance {% at 460 nm T (460 nm)} is a value calculated based on the measured absorbance {Abs (460 nm)} at 460 nm.

In the phthalocyanine compound of the present invention, among Z _{1 to} Z ₁₆ , _{1 to} 3.9 are substituents (a) or (b), 3 to 12 are hydrogen atoms, and the balance is halogen It is an atom, and at least one or more of 1 to 3.9 substituents (a) or substituents (b) is the substituent (a). The phthalocyanine compound having such a structure has the following advantages: (i) It has a high absorption at 630 nm and a high transmittance at 460 nm. That is, the ratio of the absorbance at 630 nm to the absorbance at 460 nm is high. In addition, the transmittance value at 460 nm is large. Since the value of the ratio of the absorbance at 630 nm to the absorbance at 460 nm is large, the phthalocyanine compound of the present invention has a more bluish cyan color. In addition, since the transmittance value at 460 nm is large, the phthalocyanine compound of the present invention has a brighter cyan color; (ii) it has solubility in various solvents such as glycol solvents, ketone solvents, and alcohol solvents. (Iii) Excellent compatibility with the resin. Among these, thanks to having the above (i), the phthalocyanine compound of the present invention can be suitably used for cyan inkjet ink. Also, thanks to the above (ii) and (iii), it is possible to use a combination of a resin having high solubility in a solvent such as a glycol solvent and a dye, and it can be dissolved in a solvent other than the solvent to be used. Even when a plastic is used, a pigment can be applied on the plastic.

  In addition, the phthalocyanine compound of the present invention includes, as the substituent (a) or (b), a substituent containing an oxygen atom (—OE; where E represents an arbitrary substituent) or a substituent containing a sulfur atom. (-SE; E represents an optional substituent) is introduced into the phthalocyanine skeleton. Here, the characteristics of the phthalocyanine compound generally vary depending on the type of substituent, the number of introduction, the introduction location (α-position, β-position), and the like. In order to impart solubility, introduction of a substituent is indispensable. For example, as the type of substituent, a substituent containing a nitrogen atom (—NE; where E represents an arbitrary substituent) ), A sulfur atom-containing substituent (—SE), and an oxygen atom-containing substituent (—OE) in this order, the absorption wavelength of the phthalocyanine compound is shifted to the longer wavelength side. Also, the greater the number of substituents introduced into the phthalocyanine skeleton, the more the absorption wavelength shifts to the longer wavelength side. Therefore, the phthalocyanine compound of the present invention introduces an appropriate number of substituents containing an oxygen atom (—OE) or sulfur atoms (—SE) in consideration of the balance between the absorption wavelength and solubility, so that 630 nm. The selective absorption / permeability can be enhanced, such as high absorption at 460 nm and high transmission at 460 nm. In addition, the phthalocyanine compound in which a substituent containing an oxygen atom (-OE) or a substituent containing a sulfur atom (-SE) is introduced in the β-position is compared with the case where these substituents are introduced in the α-position, The maximum absorption wavelength can be shifted to the shorter wavelength side.

In addition, the phthalocyanine compound of the present invention is represented by Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ in the above formula (1) (in this specification, simply “β-position”). And Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ (in this specification, simply “substituents in the α-position”). ”Or“ α-position ”), the substituent (a) and the substituent (b) are introduced by appropriately selecting the number of substituents and the type of the substituents, thereby providing a vivid and bluish cyan color. In addition, the phthalocyanine compound having such an arrangement may have solubility in various solvents (herein, simply referred to as “solvent solubility”) (particularly, it is soluble in a glycol solvent). Furthermore, the phthalocyanine compound having such an arrangement is excellent in at least one characteristic of compatibility with a resin, heat resistance, light resistance, and weather resistance.

  Hereinafter, preferred embodiments of the present invention will be described.

In the present invention, among the substituents Z _{1 to} Z ₁₆ of the above formula (1), _{1 to} 3.9 are substituents (a) or (b), and 3 to 12 are hydrogen atoms. And the balance is a halogen atom. In this case, the substituent (a) and the substituent (b) are different substituents. Of these, considering the high absorption at 630 nm, the high transmittance at 460 nm, and the Gram extinction coefficient, the total number of substituents (a) or substituents (b) introduced is preferably small. Of the groups Z _{1 to} Z ₁₆ , 1.1 to 3.7 are the substituent (a) or the substituent (b), 3 to 12 are hydrogen atoms, and the remainder is a halogen atom It is more preferable that 1.2 to 3.5 is the substituent (a) or the substituent (b), 3 to 12 are hydrogen atoms, and the remainder is a halogen atom, more preferably 1.2. -3 are the substituent (a) or the substituent (b), 3-11 are hydrogen atoms, and the remainder is more preferably a halogen atom, and 1.2-2.8 are substituted. Group (a) or substituent (b), 3.5 to 9 Is hydrogen and it is most preferred balance is a halogen atom.

Here, when the total number of substituents (a) and (b) among Z _{1 to} Z ₁₆ is less than 1, the substituent (a) or (b) is introduced into the phthalocyanine skeleton. As a result, the solubility in a solvent is lowered, and it is not suitable for use in an inkjet ink.

The introduction position of 1 to 3.9 substituents (a) or substituents (b) in the phthalocyanine skeleton is not particularly limited as long as the total number of substitutions is in the above range. Therefore, as described _below, the constituent units comprising _{Z 1 ~Z 4, Z 5 ~Z} 8, Z 9 ~Z 12, Z 13 ~Z 16, respectively constitutional units A, B, C, and D In the structural units A to D, the substituent (a) or the substituent (b) may be introduced almost uniformly or non-uniformly. Preferably, the substituent (a) or (b) is introduced heterogeneously in the structural units A to D. The presence of such substituents balances high absorption at 630 nm and high transmittance at 460 nm, solubility in various solvents, wavelength control, durability (light resistance, heat resistance), and absorbance per gram. This is preferable. Although the detailed mechanism is unknown, the presence of an appropriate number of non-uniform substituents (a) and substituents (b) increases the absorption at 630 nm, the high transmittance at 460 nm, and the solubility in solvents. It is thought that both can be achieved. When a plurality of types of substituents (a) or (b) are present, these substituents (a) and (b) may be the same or different.

  Of the 1 to 3.9 substituents (a) or the substituents (b), at least one is the substituent (a). Here, among 1 to 3.9 substituents (a) or substituents (b), at least one or more may be substituents (a), and substituents (b) may be present. Alternatively, the substituent (b) may not be present. The case where the substituent (a) and the substituent (b) coexist is preferable. In this case, 0.1 to 2.9 of 1 to 3.9 substituents (a) or (b) are present. It is preferable that it is a substituent (b), and it is more preferable that 0.1-2.5 pieces are a substituent (b). When only the substituent (a) is present in such a ratio or the substituent (a) and the substituent (b) coexist, the resulting phthalocyanine compound has a ratio of absorbance at 630 nm to absorbance at 460 nm and at 460 nm. It has a high transmittance and can be soluble in various solvents. Moreover, the combination of the introduction position of each substituent (a) and (b) is not specifically limited, Any combination is applicable.

In the present invention, among the substituents Z _{1 to} Z ₁₆ of the above formula (1), 3 to 12 are hydrogen atoms in addition to the substituent (a) and the substituent (b). When the number of hydrogen atoms is within this range, although depending on the combination with other substituents, the phthalocyanine compound obtained shifts to the short wavelength side and the absorption near 630 nm increases, that is, 630 nm with respect to the absorbance at 460 nm. The ratio of absorbance increases. Moreover, the obtained phthalocyanine compound has good solubility in a solvent, particularly PGMEA. Further, in the case where the substituents Z _{1 to} Z ₁₆ are the structural units A to D, respectively, the structural unit A is all hydrogen atoms, and the structural unit B is all hydrogen atoms. It is preferable that the total number of the structural units A to D when the units C are all hydrogen atoms and the structural units D are all hydrogen atoms is more than 0 and less than 2.4. More preferably, the number is 0.5 to 2.0. By adopting such a configuration, the phthalocyanine compound shifts to the short wavelength side and has a cyan color with a strong blue tint.

In the present invention, among the substituents Z _{1 to} Z ₁₆ of the above formula (1), the substituent (a) or the substituent (b), or the remainder to which no hydrogen atom is introduced is a halogen atom. Although the detailed mechanism is unknown, it is considered that the durability (light resistance, heat resistance) or solubility of the obtained phthalocyanine compound is improved by arranging an appropriate number of halogen atoms in the balance as described above. . Here, the halogen atom is not particularly limited, and may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Preferably, they are a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom and a bromine atom are more preferable. By arranging the halogen atom as described above in the balance, durability (light resistance, heat resistance) and solubility can be further improved. Moreover, the halogen atoms introduced into the remainder may be the same or different.

In the present invention, the substituent (a) is represented by the above formula (2). As is clear from the above formula, the substituent (a) is a phenoxy group having one substituent R ¹ and, if necessary, ¹ to 4 R ² .

In the above formula (2), R ¹ is a halogen atom substituted at the 2-position or an alkyl group having 1 to 4 carbon atoms. By having a substituent at the 2-position, solubility in a solvent is increased.

In the above formula (2), R ² may be the same as or different from R ^1, and is a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferably R ² and R ¹ are the same.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Among these, considering the above properties such as solvent solubility and heat resistance, R ¹ is preferably fluorine or chlorine, and more preferably chlorine.

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and t-butyl group. Among these, considering the above properties such as solvent solubility and heat resistance, R ¹ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

Further, in the above formula, m is the number of manufacturing of 0-4, a number of the substituents R ^2. In consideration of the above properties such as high absorption at 630 nm, high transmittance at 460 nm, solvent solubility, and heat resistance, m is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1. When m is 1, R ² may be introduced at any of the 3, 4, 5 and 6 positions of the phenoxy group. In this case, the 5th or 6th position is preferable in consideration of the above characteristics such as high absorption at 630 nm, high transmittance at 460 nm, solvent solubility, and heat resistance. A preferred formula of the substituent (a) is specifically represented by the following chemical formula (4) or (5).

In the above formulas (4) and (5), R ¹ and R ² are each independently a halogen atom or an alkyl group having 1 to 4 carbon atoms.

  In the present invention, the substituent (b) has the following formula (3):

It is represented by

  In the present invention, in the above formula (3), X is an oxygen atom (—O—) or a sulfur atom (—S—), preferably an oxygen atom. When X is an oxygen atom, the maximum absorption wavelength of the obtained phthalocyanine compound can be shifted to the short wavelength side, and thus the obtained phthalocyanine compound has high absorption at 630 nm and high transmittance at 460 nm. In this case, the substituent (b) is a substituent different from the substituent (a). Moreover, when X is a sulfur atom, the obtained phthalocyanine compound has an advantage of high solvent solubility.

Further, in the above formula (3), Ar is substituted with R ³ is also phenyl or naphthyl group, preferably a phenyl group. Here, when Ar is a phenyl group which may be substituted with R ³ , Ar is a group represented by the following formula.

In the above formula, X and R ³ are the same as defined in the above formula (3), and n is an integer of 0 to 5.

In the above formulas (3) and (6), R ³ is a substituent which may be introduced into a phenyl group or a naphthyl group, and is a cyano group (—CN), a nitro group (—NO ₂ ), OY, halogen An alkyl group having 1 to 8 carbon atoms which may be substituted with an atom, an aryl group, or a halogen atom; When a plurality of R ³ are present, the plurality of R ³ may be the same or different. Among the above ^{R 3,} where ^{R 3} is OY, Y is an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include straight-chain, branched or cyclic alkyl groups having 1 to 8 carbon atoms, and more specifically, those having 1 to 8 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- Examples thereof include straight chain, branched or cyclic alkyl groups such as hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Among these, in consideration of the above properties such as solvent solubility and heat resistance, a linear or branched alkyl group having 1 to 5 carbon atoms is particularly preferable.

In addition, when R ³ is a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable in consideration of the above characteristics such as high absorption at 630 nm, high transmittance at 460 nm, solvent solubility, and heat resistance. Further, when R ³ is a fluorine atom or a chlorine atom, the molecular weight of the dye is decreased, and the absorbance per gram can be increased.

Examples of the aryl group in the case where R ³ is an aryl group include aryl groups such as a phenyl group, a p-methoxyphenyl group, a pt-butylphenyl group, and a p-chlorophenyl group. Among them, a phenyl group is preferable because the molecular weight of the dye is reduced and the absorbance per gram is increased.

In addition, when R ³ is an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, the alkyl group having 1 to 8 carbon atoms which may be substituted is not particularly limited, Examples thereof include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms, and more specific examples are the same as those described above for Y. Among these, a linear or branched alkyl group having 1 to 5 carbon atoms is particularly preferable in consideration of the above properties such as solvent solubility and heat resistance. Examples of the halogen atom that is a substituent of the alkyl group that may be present include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom or a chlorine atom is more preferable. There may be a plurality of halogen atoms as substituents for the alkyl group, and when there are a plurality of halogen atoms, they may be the same or different. The number of substituents on the alkyl group is not particularly limited, but is preferably 1 to 3.

In the above formula (6), the number n of substituents R ³ in Ar is not particularly limited, and desired effects (high absorption at 630 nm, high transmittance at 460 nm, solvent solubility, gram extinction coefficient, heat resistance, etc. ) Can be selected as appropriate. For example, when Ar is a phenyl group which may be substituted with R ³ , n is an integer of 1 to 5, more preferably an integer of 1 to 3.

In the substituent (b) of the above formulas (3) and (6), the bonding position of the substituent R ^{3 to} the benzene ring is not particularly limited. The meta position (3rd position) and the para position (4th position) are preferred. Here, when the substituent R ³ is arranged at the meta position (3rd position) and the para position (4th position), the resulting phthalocyanine compound is particularly preferable because high absorption at 630 nm and high transmittance at 460 nm can be obtained. Moreover, when the substituent R ³ is arranged at the ortho position (position 2), the resulting phthalocyanine compound can improve the solvent solubility.

When n is 2, the two substituents R ³ may be introduced at any position of the benzene ring. In this case, considering the above characteristics such as high absorption at 630 nm, high transmittance at 460 nm, solvent solubility, and heat resistance, the 2,4th, 3,4th, 3,5th and the like are preferable, and the 2,4th position 3 and 4 are more preferable. In view of solvent solubility, 2,3-position, 2,5-position and 2,6-position are preferred, and 2,6-position is particularly preferred. When n is 3, the three substituents R ³ may be introduced at any position of the benzene ring. In this case, considering the above characteristics such as high absorption at 630 nm, high transmittance at 460 nm, solvent solubility, heat resistance, etc., 2,4,6, 2,5,6 and the like are preferable, The 6th position is more preferable.

Further, in the above formula (3), Ar in each case is a naphthyl group which may be substituted by R ^3, the number n of the substituents R ³ in Ar is not particularly limited, the desired effect (630 nm High absorption, high transmittance at 460 nm, solvent solubility, heat resistance, gram extinction coefficient, etc.). For example, when Ar is a naphthyl group which may be substituted with R ³ , n represents an integer of 1 to 7, preferably an integer of 1 to 5, more preferably 1 to 3, particularly preferably. 1 or 2. Further, the bonding position of the substituent R ^{3 to} the naphthalene ring is not particularly limited and can be appropriately selected depending on the desired effect. For example, when n is 1 and Ar is a 1-naphthyl group, the bonding position of R ^{3 to} the naphthalene ring may be any, but high absorption at 630 nm, high transmittance at 460 nm, solvent solubility, Considering the above characteristics such as heat resistance, the second, third and fourth positions are preferable, and the second position is more preferable. Further, when Ar is a 2-naphthyl group, the bonding position of R ^{3 to} the naphthalene ring may be any, but preferably the 1-position, the 3-position, and the 6-position, and the high absorption at 630 nm is at 460 nm. Considering the above properties such as high transmittance, solvent solubility, and heat resistance, the 3rd and 6th positions are more preferable.

  In the above formula (1), M represents a metal-free, metal, metal oxide or metal halide. Here, metal-free means an atom other than a metal, for example, two hydrogen atoms. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, aluminum, germanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, and tin (IV) chloride. Preferred are metals, metal oxides or metal halides, more preferred are cobalt, copper, and zinc, more preferred are zinc and copper, and particularly preferred is zinc. It is particularly preferable that the central metal is zinc because the absorption wavelength can be easily controlled to cyan and the solubility in a solvent or resin is excellent.

In the present specification, in formula (1), Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ are substitutions substituted at eight α positions of the phthalocyanine nucleus. In order to represent a group, these substituents are also referred to as α-position substituents. Similarly, in formula (1), Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ are substituents substituted at eight β positions of the phthalocyanine nucleus. These substituents are also referred to as β-position substituents. The β-position substituent is effective in improving heat resistance, and the α-position substituent is effective in improving solvent solubility. Therefore, it is preferable to mix the two in a balanced manner.

  Furthermore, the phthalocyanine compound of the present invention has good solubility in various solvents. For example, it has high solubility in an alcohol solvent, a ketone solvent, a glycol solvent, an ester solvent, or the like. Here, examples of the alcohol solvent include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol. , N-hexanol and the like. As the ketone solvent, branched or linear ketones and cyclic ketones are effectively used. Specific examples include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol and the like. Of these, acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone are often used in ink jet inks. Examples of glycol solvents include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol mono Examples thereof include t-butyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, propylene glycol monomethyl ether acetate (PGMEA) and the like. Examples of the ester solvent include hydrocarbon solvents such as toluene and xylene; ethyl lactate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate and the like. Among these solvents, general phthalocyanine compounds are hardly soluble in glycol solvents, particularly PGMEA, but the phthalocyanine compounds of the present invention have high solubility. The phthalocyanine compound of the present invention has a solubility in the above solvent of preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit of solubility is not particularly limited, but is usually about 30% by mass or less. Particularly when the solvent is a glycol solvent such as PGMEA, the phthalocyanine compound of the present invention is dissolved in a desired solvent so as to have a concentration of 5 wt%, and this solution is prepared with a magnetic stirrer for 1 hour. After stirring, when the whole amount is collected with a syringe and filtered using a membrane filter (φ = 0.45 μm), it is preferable that the solution can pass through the membrane filter without clogging. More specifically, the solubility of the phthalocyanine compound of the present invention in a glycol solvent is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit of solubility is not particularly limited, but is usually about 30% by mass or less.

  In addition, the phthalocyanine compound of the present invention is excellent in at least one characteristic of compatibility with a resin, heat resistance, light resistance and weather resistance.

  The characteristics as described above are attributed to the presence of the substituent (a) and substituent (b) substituted on the phthalocyanine nucleus and the number of substitutions. And the phthalocyanine compound of various absorption wavelengths can be obtained by selection of the kind, number, and central metal of a substituent.

  Therefore, the phthalocyanine compound of the present invention can be suitably used for cyan inkjet ink.

  The method for producing the phthalocyanine compound of the present invention is not particularly limited, and a conventionally known method can be appropriately used. Preferably, the phthalonitrile compound and the metal salt are used in a molten state or in an organic solvent. A method of cyclization reaction is particularly preferably used. Hereinafter, particularly preferred embodiments of the production method for the phthalocyanine compound of the present invention will be described. However, the present invention is not limited to the following preferred embodiments.

  That is, the following formula (I):

A phthalonitrile compound (1) represented by the following formula (II):

A phthalonitrile compound (2) represented by the following formula (III):

A phthalonitrile compound (3) represented by formula (IV):

Is selected from the group consisting of metals, metal oxides, metal carbonyls, metal halides, and organic acid metals (also collectively referred to as “metal compounds” in this specification). The phthalocyanine compound of the present invention can be produced by cyclization reaction with one kind. Alternatively, during the reaction, a phthalonitrile derivative of the following formula (V) (particularly, tetrafluorophthalonitrile, tetrachlorophthalonitrile, or tetrabromophthalonitrile) is converted to any of the phthalonitrile compounds of the above formulas (1) to (4). The reaction may be carried out with substitution. By using such a phthalonitrile derivative in the reaction, the number of fluorine atoms, chlorine atoms or bromine atoms introduced into the phthalocyanine skeleton is appropriately adjusted, and the substituent (a) and / or the substituent (b ) Can be produced with a suitable number of substituents and substituent species. In the above reaction, the phthalonitrile compounds (1) to (4) are described in accordance with the structure of the phthalocyanine compound of the formula (1), but depending on the structure of the target phthalocyanine compound, there are 1 to 3 types of phthalonitrile compounds. Sometimes it becomes. For this reason, for example, when the structural units A to D including Z _{1 to} Z ₄ , Z _{5 to} Z ₈ , Z _{9 to} Z ₁₂ , and Z _{13 to} Z ₁₆ are the same, the phthalonitrile compound used as a raw material is One type.

In the above formulas (I) to (IV), Z _{1 to} Z ₁₆ are defined by the structure of the desired phthalocyanine compound. Specifically, in the above formulas (I) to (IV), Z _{1 to} Z ₁₆ are the same as the definitions of Z _{1 to} Z _{16 in} the above formula (1), respectively, and thus description thereof is omitted here. To do.

  In the above embodiment, the starting phthalonitrile compounds of formulas (I) to (IV) can be synthesized by a conventionally known method such as the method disclosed in JP-A No. 64-45474, or commercially available. Can be used, but preferably, the following formula (V):

A phthalonitrile derivative represented by the following (in this specification, simply referred to as “phthalonitrile derivative”) is represented by the following formula (2a):

A substituent (a) -containing precursor represented by the formula (herein also simply referred to as “substituent (a) -containing precursor”), and / or the following formula (3a):

It is obtained by reacting with a substituent (b) -containing precursor represented by the formula (herein also simply referred to as “substituent (b) -containing precursor”). In the following, the substituent (a) -containing precursor and the substituent (b) -containing precursor are collectively referred to as “precursor”.

In the above formula (2a), R ¹ , R ² and m are the same as the definitions of R ¹ , R ² and m in the above formula (2), respectively, and thus description thereof is omitted here. Similarly, in the above formula (3a), X, Ar, and R ³ are the same as the definitions of X, Ar, and R ^{3 in} the above formula (3), respectively, and thus description thereof is omitted here. .

In the above reaction, a phthalonitrile derivative of the formula (V) is used as a starting material. In the above formula (V), X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a halogen atom or a nitro group. Here, X ₁ , X ₂ , X ₃ and X ₄ may be the same or different. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, X ₁ , X ₂ , X ₃ and X ₄ particularly preferably represent a fluorine atom, a chlorine atom or a bromine atom. In particular, when tetrafluorophthalonitrile (hereinafter abbreviated as TFPN), tetrachlorophthalonitrile (hereinafter abbreviated as TCPN) or tetrabromophthalonitrile (hereinafter abbreviated as TBPN) is used as a starting material, the substituent (a ) -Containing precursor or substituent (b) -containing precursor reacts randomly with the fluorine atom, chlorine atom or bromine atom at the 3-6 position of the TFPN, TCPN or TBPN. For this reason, by using TFPN, TCPN, or TBPN as a starting material, substituents (a) and (b) can be randomly introduced into the α-position and β-position of the phthalocyanine skeleton. For this reason, when TFPN, TCPN or TBPN is used as a starting material for a phthalonitrile derivative, the phthalonitrile derivative is optionally a precursor of four fluorine atoms, chlorine atoms or bromine atoms of TFPN, TCPN or TBPN. Obtained in the form of a substituted mixture. Moreover, 3-nitrophthalonitrile or 4-nitrophthalonitrile can also be used as a starting material. In this case, the substituent (a) -containing precursor or the substituent (b) -containing precursor reacts preferentially with the nitro group. Therefore, by using 3-nitrophthalonitrile or 4-nitrophthalonitrile as a starting material, the substituents (a) and (b) can be selectively introduced into the α-position or β-position of the phthalocyanine skeleton. Here, as described above, high absorption at 630 nm and high transmittance at 460 nm, solubility in various solvents, wavelength control, durability (light resistance, heat resistance), absorbance per gram, particularly high absorption at 630 nm In view of the high transmittance at 460 nm, the substituent (a) or (b) includes each of the structural units A to Z including Z _{1 to} Z ₄ , Z _{5 to} Z ₈ , Z _{9 to} Z ₁₂ , and Z _{13 to} Z _16. In D, it is preferably introduced non-uniformly. For this reason, it is particularly preferable to use TFPN, TCPN or TBPN as a starting material.

In the reaction of the phthalonitrile derivative with the substituent (a) -containing precursor or the substituent (b) -containing precursor, the proportion of the precursor can be appropriately selected depending on the structure of the target phthalonitrile compound. The total amount of the precursor used is not particularly limited and can be appropriately selected depending on the structure of the desired phthalonitrile compound. In the phthalocyanine skeleton according to the present invention, 3 to 12 are hydrogen atoms. Therefore, when a phthalonitrile compound is produced by reacting TFPN, TCPN or TBPN with a substituent (a) -containing precursor or a substituent (b) -containing precursor, the phthalonitrile compound is represented by the above formula ( In V), hydrogen atoms are introduced into the phthalocyanine skeleton by using phthalonitrile in which X ₁ , X ₂ , X ₃ and X ₄ are all hydrogen atoms in a cyclization reaction with a metal compound. However, as described above, the structural unit A in which Z _{1 to} Z ₄ are all hydrogen atoms, the structural unit B in which Z _{5 to} Z ₈ are all hydrogen atoms, and the structural unit in which all of Z _{9 to} Z ₁₂ are hydrogen atoms. It is preferable that the total number of structural units D in which C and Z _{13 to} Z ₁₆ are all hydrogen atoms is more than 0 and less than 2.4. For this reason, when performing the said cyclization reaction, it is preferable that the addition amount of a phthalonitrile is more than 0 mol% and less than 60 mol% with respect to all the phthalonitrile compounds, and is 20-50 mol%. It is more preferable. Thereby, the ratio for which the structural units AD which are all hydrogen atoms in all the structural units AD can be adjusted to the above ranges.

  The reaction between the phthalonitrile derivative and the precursor may be performed in the absence of a solvent or in an organic solvent, but is preferably performed in an organic solvent. Examples of the organic solvent that can be used in this case include nitriles such as acetonitrile and benzonitrile; polar solvents such as acetone and 2-butanone. Of these, acetonitrile, benzonitrile and acetone are preferred. The amount of the organic solvent used when using the solvent is such an amount that the concentration of the phthalonitrile derivative is usually 2 to 50% by mass, preferably 10 to 40% by mass. Further, in the reaction of the phthalonitrile derivative and the precursor, it is preferable to use these trapping agents in order to remove hydrogen halide (for example, hydrogen chloride or hydrogen fluoride) generated during the reaction. Specific examples of the trapping agent when using the trapping agent include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride and magnesium carbonate. Of these, potassium carbonate, calcium carbonate and calcium hydroxide are preferred. Further, the amount of the trapping agent used when using the trapping agent is not particularly limited as long as it is an amount capable of efficiently removing hydrogen halide generated during the reaction, but is usually 1 to 1 mol of the precursor. 4 moles, preferably 1-2 moles.

  In addition, the reaction conditions for the phthalonitrile derivative and the precursor are not particularly limited as long as the reaction of both proceeds to obtain a desired phthalonitrile compound. Specifically, the reaction temperature is usually 20 to 150 ° C, preferably 40 to 120 ° C. Moreover, reaction time is 0.5 to 60 hours normally, Preferably it is 1 to 50 hours.

  The phthalonitrile compounds (1) to (4) of the above formulas (I) to (IV) are obtained by the above reaction. After the reaction, crystallization, filtration, washing and drying are performed according to a conventionally known method. Also good. By such an operation, the phthalonitrile compound can be obtained efficiently and with high purity.

  Next, the cyclization reaction is selected from the group consisting of phthalonitrile compounds (1) to (4) of formulas (I) to (IV) and a metal, metal oxide, metal carbonyl, metal halide, and organic acid metal. It is preferable to react one species in a molten state or in an organic solvent. The metal, metal oxide, metal carbonyl, metal halide, and organic acid metal that can be used at this time are not particularly limited as long as those corresponding to M of the phthalocyanine compound of the formula (1) obtained after the reaction can be obtained. For example, metals such as iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, aluminum, germanium, indium and tin listed in the M section in the above formula (1), Metal halides such as chloride, bromide and iodide, metal oxides such as vanadium oxide, titanyl oxide and copper oxide, organic acid metals such as acetate, and complex compounds such as acetylacetonate and carbonyl iron And metal carbonyl such as Specifically, vanadium chloride, titanium chloride, copper chloride, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, germanium chloride, magnesium chloride, copper iodide, zinc iodide, iodine Metal halides such as cobalt iodide, indium iodide, aluminum iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide; vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, dioxide Titanium, iron monoxide, iron sesquioxide, iron tetroxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt sesquioxide, cobalt dioxide, cuprous oxide, cupric oxide, copper sesquioxide, palladium oxide and Metal oxides such as zinc oxide; organic acids such as copper acetate, zinc acetate, cobalt acetate, copper benzoate, zinc benzoate Genus; and complex compounds and cobalt carbonyl such as acetyl acetonate, iron carbonyl, and metal carbonyls such as nickel carbonyl. Of these, preferred are metals, metal oxides and metal halides, more preferred are metal halides, still more preferred are cobalt chloride, copper chloride and zinc iodide, and more preferred are copper chloride and Zinc iodide, particularly preferably zinc iodide. When zinc iodide is used, the central metal is zinc. Among metal halides, it is preferable to use iodide because it is excellent in solubility in solvents and resins, and the spectrum of the obtained phthalocyanine compound is sharp and easily fits in a desired wavelength. The detailed mechanism of sharpening the spectrum when using iodide during the cyclization reaction is unknown, but when iodide is used, the iodine remaining in the phthalocyanine compound after the reaction may have some interaction with the phthalocyanine compound. It is presumed that iodine is present between the layers of the phthalocyanine compound due to the action. However, the mechanism is not limited to the above mechanism. In order to obtain the same effect as when metal iodide is used for the cyclization reaction, the obtained phthalocyanine compound may be treated with iodine.

  In the above embodiment, the cyclization reaction can be carried out in the absence of a solvent, but it is preferably carried out using an organic solvent. The organic solvent may be any inert solvent that has low reactivity with the phthalonitrile compound as a starting material, and preferably does not exhibit reactivity. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o -Inert solvents such as chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol, 1-hexanol, 1-pentanol, 1-octanol; and pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, Triethylamine, tri n- butylamine, dimethyl sulfoxide, aprotic polar solvents such as sulfolane. Of these, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile are preferably used, and more preferably 1-octanol, dichlorobenzene and benzonitrile are used. These solvents may be used alone or in combination of two or more.

  The reaction conditions of the phthalonitrile compounds (1) to (4) of the formulas (I) to (IV) and the metal compound in the above embodiment are not particularly limited as long as the reaction proceeds, but for example, The phthalonitrile compound (1) to (4) is 1 to 500 parts by weight, preferably 10 to 350 parts by weight in total with respect to 100 parts by weight of the organic solvent, and the metal compound is the phthalonitrile compound. The amount is preferably 1 to 2 mol, more preferably 1 to 1.5 mol with respect to 4 mol. The cyclization is not particularly limited, but the reaction is preferably performed at a reaction temperature of 30 to 250 ° C, more preferably 80 to 200 ° C. The reaction time is not particularly limited, but is preferably 3 to 48 hours. Moreover, although the said reaction may be performed in air | atmosphere atmosphere, it is preferable to carry out in inert gas atmosphere (For example, under distribution | circulation of nitrogen gas, helium gas, argon gas, etc.).

  After the cyclization reaction, crystallization, filtration, washing and drying may be performed according to a conventionally known method. By such an operation, the phthalocyanine compound can be obtained efficiently and with high purity.

  The phthalocyanine compound of the present invention exhibits excellent solubility in various solvents such as alcohol-based solvents, ketone-based solvents, glycol-based solvents, ester-based solvents, particularly glycol-based solvents, and therefore is used for various applications. Can do.

The phthalocyanine compound of the present invention is a heat ray shielding material for shielding heat rays, a heat ray absorbing laminated glass for automobiles, a heat ray shielding film or a heat ray shielding resin glass, a filter for plasma display, a non-contact fixing toner such as flash fixing. As an infrared absorber, a near-infrared absorber for heat-retaining and storing fibers, an infrared absorber for fibers that have camouflage performance (camouflage performance) for reconnaissance by infrared rays, an optical recording medium using a semiconductor laser, and a filter for liquid crystal display Filters for organic EL displays, near-infrared absorbing dyes for writing or reading in optical character readers, near-infrared photosensitizers, photothermal exchange agents such as thermal transfer and thermal stencil, resin using laser beam Laser heat fusion heat exchanger, near infrared absorption filter, eye Anti-falsification agents or photoconductive materials, photosensitive dyes for tumor treatment that absorb light in a long wavelength range with good tissue permeability, color toner, ink for ink, anti-counterfeiting ink, anti-counterfeiting bar code iNK, near infrared absorbing ink, positioning marking agent photos or films, and goggle lenses and the shielding plate, preheating aids during molding of sorting for dyeing colorant, and PET bottles during plastic recycling It exhibits an excellent effect when used in, for example.

  The phthalocyanine compound having a specific structure as described above efficiently transmits blue light near 460 nm and efficiently absorbs red light near 630 nm. Presents. For this reason, the phthalocyanine compound of the present invention can exhibit a deep cyan color in a small amount. The phthalocyanine compound of the present invention also has excellent compatibility with resins, heat resistance, light resistance and weather resistance. In addition, the phthalocyanine compound of the present invention exhibits excellent solubility in various solvents such as alcohol solvents, ketone solvents, glycol solvents and ester solvents, particularly glycol solvents.

  Considering the above characteristics, the phthalocyanine compound of the present invention can be suitably used for cyan inkjet ink. Therefore, the present invention also provides a cyan inkjet ink containing the phthalocyanine compound of the present invention.

  The inkjet ink of the present invention is the same as the conventional inkjet, such as JP 2010-195904 A, JP 2009-132812 A and JP 11-106693 A, except that it contains the phthalocyanine compound of the present invention as a pigment. Can be an ink.

  The composition of the inkjet ink of the present invention can be the same as a known composition except that it contains the phthalocyanine compound of the present invention as a pigment. For example, the inkjet ink of the present invention contains a pigment, a resin, and a solvent.

  The ink-jet ink of the present invention must contain the phthalocyanine compound of the present invention as a pigment. Here, the blending amount of the phthalocyanine compound of the present invention is not particularly limited, but is preferably 5 to 30% by weight, more preferably 10 to 25% by weight based on the total weight of the ink. If it is such a range, the printing surface of sufficient density | concentration will be obtained and it can melt | dissolve stably in ink. In addition, the phthalocyanine compound of the present invention may be used alone or in the form of a mixture of two or more.

  The ink-jet ink of the present invention must contain the phthalocyanine compound of the present invention as a coloring matter, but other blue pigments or dyes may be used. Other blue pigments or dyes are not particularly limited as long as they exhibit a blue color (preferably having a maximum absorption wavelength (λmax) at 600 to 750 nm), and known blue pigments or dyes can be used. Specifically, bromocresol green, bromophenol blue, 1-ethyl-2- [3-chloro-5- (1-ethyl-2 (1H) -quinolinylidene) -1,3-pentadienyl] quinolium bromide (λmax = 694.4 nm), 1,3,3-trimethyl-2- [5- (1,3,3-trimethyl-2 (1H) -benz [e] indolinylidene) -1,3-pentadienyl] -3H Benz [e] indolinium perchlorate (λmax = 675.6 nm), 3-ethyl-2- [5- (3-ethyl-2-benzothiazolinylidene) -1,3-pentadienyl] benzothiazolium And cyanine dyes such as iodide (λmax = 651.6 nm). In the above, the maximum absorption wavelength (λmax) is shown in parentheses. Here, the blending amount of the other pigment or dye is not particularly limited, but is preferably 1 to 20% by weight based on the total weight of the ink. In addition, the said other pigment or dye may be used independently or may be used with the form of 2 or more types of mixtures.

  The resin used in the inkjet ink of the present invention is not particularly limited, and a known resin used in the inkjet ink can be used. The resin can be appropriately selected in consideration of properties such as viscosity and adhesion. Specifically, polyvinyl chloride, acrylic resin, epoxy resin, urethane resin, cellulose derivatives (for example, ethyl cellulose, cellulose acetate, nitrocellulose), vinyl acetal resin, diallyl phthalate resin, butadiene-acrylonitrile copolymer, styrene- Acrylic resin, styrene-maleic acid resin, rosin resin, rosin ester resin, ethylene-vinyl acetate resin, petroleum resin, coumarone indene resin, terpene phenol resin, phenol resin, melamine resin, urea resin, Examples thereof include epoxy resins, vinyl acetate resins, xylene resins, alkyd resins, aliphatic hydrocarbon resins, butyral resins, silicone resins, maleic resins, fumaric resins, amide resins, and the like. The weight average molecular weight of the resin is not particularly limited and can be appropriately selected in consideration of a desired ink viscosity and the like. Specifically, the weight average molecular weight of the resin is preferably 1000 to 30000. Within such a range, the viscosity of the ink can be adjusted to an appropriate level. Further, the blending amount of the resin (resin content of the ink) is not particularly limited, but is preferably 1 to 60% by weight and more preferably 5 to 60% by weight based on the total weight of the ink. In such a range, an appropriate ink viscosity can be obtained, so that ink can be stably ejected without causing droplet ejection or direction disturbance, and adhesion to a printing medium without peeling from the printing surface. And the dye can be retained well. In addition, the said resin may be used independently or may be used with the form of a 2 or more types of mixture. Alternatively, a higher molecular weight resin may be used in combination for the purpose of further improving properties such as viscosity and adhesion.

  The solvent used in the inkjet ink of the present invention is not particularly limited as long as it can dissolve other components (pigment, resin, etc.). Specifically, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n butyl alcohol, sec-butyl Alcohol, tert? Butyl alcohol, n? Amyl alcohol, isoamyl alcohol, sec? Amyl alcohol, n? Alcohol solvents such as hexanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol Glycol solvents such as mono t-butyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, propylene glycol monomethyl ether acetate (PGMEA); hydrocarbon solvents such as toluene and xylene; ethyl lactate, 3 -Ethyl ethoxypropionate, ethyl acetate, And ester type solvents such as Le like. Of these, ketone solvents and glycol solvents are preferable, glycol solvents are more preferable, and PGMEA is particularly preferable. The amount of the solvent is not particularly limited, but is preferably 30 to 90% by weight, more preferably 40 to 80% by weight, based on the total weight of the ink. If it is such a range, other components (a pigment | dye, resin, etc.) can be melt | dissolved efficiently. In addition, the said solvent may be used independently or may be used with the form of a 2 or more types of mixture.

  The ink-jet ink of the present invention may contain other additives. Here, the other additives are not particularly limited, and the additives used for the ink jet ink can be used in the same manner. For example, a conductivity adjusting agent, an amine, a dispersing agent, a polymerization inhibitor, a surface adjusting agent, a leveling agent, an ultraviolet absorber, and an antioxidant for increasing printability and printed matter resistance.

  Of these, the conductivity adjusting agent is particularly effective when the ink of the present invention is used for high-speed printing by a continuous type ink jet printer. Here, it does not restrict | limit especially as an electrical conductivity regulator, A well-known electrical conductivity regulator can be used. Specific examples include potassium iodide, ammonium thiocyanate, potassium thiocyanate, and lithium nitrate. These conductivity adjusting agents are preferred because they do not show discoloration due to heat due to the residue on the printing surface. The blending amount of the conductivity adjusting agent is not particularly limited, but is preferably 0.1 to 2% by weight based on the total weight of the ink. In such a range, sufficient conductivity can be obtained, so that moderate charge deflection can be obtained, and no discoloration is induced. In addition, the said electrical conductivity modifier may be used independently or may be used with the form of 2 or more types of mixtures.

  An amine can be added for the purpose of coloring blue more vividly. Here, the amine is not particularly limited. For example, triethanolamine, cetylamine, pentadecylamine, tetradecylamine, tridecylaminedodecylamineoctylamine, diamylamine, dibutylamine, tributylamine, tripropylamine, triallylamine, Examples include cyclohexylamine, dibenzylamine, naphthylamine, and benzylamine. The amine can develop blue more favorably, and these amines disappear from the printing surface due to the history of heat, so that they can also act as a slow-drying component in the printer. The compounding amount of the amine is not particularly limited, and can be appropriately set in consideration of the coloring of the dye on the printing surface, the concentration, the stable elapsed time of the heat, and the like. Specifically, the blending amount of the amine is preferably 0.5 to 15% by weight with respect to the total weight of the ink. If it is such a range, discoloration will not be induced, even if it is an impermeable to-be-printed body, it can dry quickly, and the water resistance of a printing surface can be ensured moderately. In addition, the said amine may be used independently or may be used with the form of 2 or more types of mixtures.

  The dispersant may be added for the purpose of improving the dispersibility of the dye and the storage stability of the ink composition. Here, it does not restrict | limit especially as a dispersing agent, A well-known dispersing agent can be used. Specifically, a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester, a high Molecular copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl Examples include phenyl ether and stearylamine acetate. More specifically, styrene-acrylic acid copolymer, styrene-acrylic acid-alkyl acrylate ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid-acrylic acid alkyl ester copolymer, Salt: Styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, salts thereof; styrene-maleic acid half ester copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic Examples include acid copolymers, styrene-maleic anhydride-maleic acid half ester copolymers, salts thereof; benzyl methacrylate-methacrylic acid copolymers, salts thereof, and the like. A commercially available product may be used as the dispersant. In this case, “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylic acid) manufactured by BYK Chemie Co., Ltd. Salt) "," Disperbyk-101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163 , 164, 165, 166, 170 (polymer copolymer) ”,“ 400 ”,“ Bykumen ”(high molecular weight unsaturated acid ester),“ BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ” , “P104S, 240S (high molecular weight unsaturated acid polycarboxylic acid and silicone system)”, “Lactimon” Long chain amine, unsaturated acid polycarboxylic acid and silicone) ";" Efka CHEMICALS "" Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766 ", “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine)”, Kyoeisha Chemical Co., Ltd. “Floren TG-710 (urethane oligomer)”, “Flonon SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, manufactured by Enomoto Kasei Co., Ltd.” 873SN, 874 (polymer dispersant), # 2150 (aliphatic polycarboxylic acid) , # 7004 (polyether ester type); “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP, manufactured by Kao Corporation "Homogenol L-18 (polycarboxylic acid type polymer)", "Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 24 (coconut amine acetate), 86 (stearyl) Amine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000GR, 32000, 33000, 39000, 41000, 53000 ", Nikko Chemi "Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate)" manufactured by Luo, "Ajisper PB821, 822," manufactured by Ajinomoto Fine Techno Commercially available products such as “824, 827, 711” and “TEGODisper685” manufactured by Tego Chemi Service Corporation can be used. The blending amount of the dispersant is not particularly limited, and can be appropriately set in consideration of desired dispersibility. Specifically, the blending amount of the dispersant is preferably 0.01 to 10% by weight with respect to the total weight of the ink. If it is such a range, components, such as a pigment | dye, can be disperse | distributed favorably. In addition, the said dispersing agent may be used independently or may be used with the form of 2 or more types of mixtures.

  The polymerization inhibitor can be added for the purpose of enhancing the storage stability of the ink and the stability in the recording apparatus. Here, it does not restrict | limit especially as a polymerization inhibitor, A well-known polymerization inhibitor can be used. Specific examples include hydroquinone, p-methoxyphenol, t-butylcatechol, and di-t-butylhydroxytoluene. The blending amount of the polymerization inhibitor is not particularly limited, and can be appropriately set in consideration of desired characteristics. Specifically, the blending amount of the polymerization inhibitor is preferably 0.01 to 5% by weight with respect to the total weight of the ink. If it is such a range, sclerosis | hardenability can be maintained and the storage stability of an ink can be improved. In addition, the said polymerization inhibitor may be used independently or may be used with the form of 2 or more types of mixtures.

  The inkjet ink of the present invention can be produced by a known method. For example, the ink-jet ink of the present invention can be prepared by adding a resin to a solvent and dissolving it by stirring, and then adding a dye and, if necessary, other additives and sufficiently dissolving them. If necessary, the liquid mixture thus obtained may be filtered with a filter having a pore diameter of 3 μm or less, and further 1 μm or less.

  Alternatively, the inkjet ink of the present invention may be an ink used for active energy ray-curable inkjet printing. In this case, the inkjet ink includes a coloring matter, a polymerizable monomer, and a polymerization initiator.

  Here, the pigment is the same as described above.

  The polymerizable monomer used in the inkjet ink of the above form is not particularly limited, and is an active energy ray polymerizable substance represented by the formula (1) described in JP2009-132812A, JP2010-195904A. Polymerizable monomer (A) having one triazine ring and two or more polymerizable groups described in the publication [for example, bis (acryloxyethyl) hydroxyethyl isocyanurate, tris (methacryloxyethyl) isocyanurate, tris ( Acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, etc.], benzyl (meth) acrylate, (ethoxy (or propoxy)) 2-phenoxyethyl (meth) acrylate, dicyclopentenyl (oxyethyl) ( (Meth) acrylate, Enoxydiethylene glycol (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxydipropylene glycol (meth) ) Acrylate, dipropylene glycol (meth) acrylate, β-carboxylethyl (meth) acrylate, trimethylolpropane formal (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Isoboronyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1,4-cyclohexanedimethanol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Monofunctional monomers such as (meth) acrylate, acryloylmorpholine, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, N-acryloyloxyethylhexahydrophthalimide, dimethylol-tricyclodecandi (meth) acrylate, (ethoxy) (Or propoxy)) bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (ethoxy (or pro Xylation) 1,6-hexanediol di (meth) acrylate, (ethoxy (or propoxy)) neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, pentaerythritol tri (or tetra) (meth) acrylate, trimethylolpropane tri (or tetra) (meth) acrylate, tetramethylolmethane Known monomers such as polyfunctional monomers such as tri (or tetra) (meth) acrylate and dipentaerythritol hexa (meth) acrylate can be used. The polymerizable monomers may be used alone or in the form of a mixture of two or more.

  The polymerization initiator used in the inkjet ink of the above form is not particularly limited, and can be appropriately selected in consideration of the curing speed, the cured coating film properties, the coloring material, and the like. Specifically, compounds represented by formulas (8) and (10) to (13) described in JP2009-132812; benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,4,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), 1,2-octanedione, 1- (4- (phenylthio) ) -2,2- (O-benzoyloxime)) and the like; 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropane-1 -One and molecular cleavage type polymerization initiators such as 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one; benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4 ' -Hydrogen abstraction type polymerization initiators such as methyl-diphenyl sulfide. Although the compounding quantity of the said polymerization initiator is not restrict | limited in particular, It is preferable that it is 2-25 weight% with respect to a polymerizable monomer. In such a range, an appropriate curing speed (polymerization of the polymerizable monomer can be efficiently achieved), and an appropriate ink viscosity can be obtained, so that the ink can be discharged without causing droplet ejection or direction disturbance. It can be ejected stably, has excellent adhesion to the printing medium without being peeled off from the printing surface, and the dye can be held well. In addition, the said polymerization initiator may be used independently or may be used with the form of 2 or more types of mixtures. When the compounds represented by the above formulas (8) and (10) to (13) are used as a polymerization initiator, a hydrogen donor such as triethanolamine or monoethanolamine is used in combination with a polymerizable substance. Also good. Thereby, the radical generating efficiency of a polymerization initiator can be improved.

  A sensitizer may be used in combination with or in place of the hydrogen donor. The sensitizer is not particularly limited, and examples thereof include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethyl. Examples include amines that do not cause an addition reaction with the polymerizable monomer, such as benzylamine and 4,4′-bis (diethylamino) benzophenone.

  The ink jet ink of the above form may contain an organic solvent. The organic solvent is not particularly limited as long as it can dissolve other components (pigment, polymerizable monomer, polymerization initiator, etc.). Specifically, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol monobutyl ether propionate, die Rudiglycol, diethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, diethylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether propionate, diethylene glycol monobutyl ether propionate, propylene glycol monomethyl ether propionate, ethylene glycol monomethyl ether butyrate, Ethylene glycol monoethyl ether butyrate, ethylene glycol monobutyl ether butyrate, diethylene glycol monomethyl ether butyrate, diethylene glycol monoethyl ether butyrate, diethylene glycol monobutyl ether butyrate, propylene glycol monomethyl ether butyrate, etc. Coal monoacetate solvent: ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, ethylene glycol propionate butyrate, ethylene glycol dipropionate, ethylene glycol acetate Dibutyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, diethylene glycol propionate butyrate, diethylene glycol dipropionate, diethylene glycol acetate dibutyrate, propylene glycol acetate propionate, propylene glycol acetate butyrate, propylene glycol propionate Glycol diacetate solvents such as nate butyrate, propylene glycol dipropionate, propylene glycol acetate dibutyrate; glycol solvents such as ethylene glycol, diethylene glycol, propylene glycol; ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether , Glycol ether solvents such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol n-propyl ether; esters such as methyl lactate, ethyl lactate, propyl lactate, butyl lactate, ethyl 3-ethoxypropionate System solvents and the like. Of these, ketone solvents and glycol solvents are preferable, glycol solvents are more preferable, and PGMEA is particularly preferable. The amount of the solvent is not particularly limited, but is preferably 30 to 90% by weight, more preferably 40 to 80% by weight, based on the total weight of the ink. If it is such a range, other components (a pigment | dye, a polymerizable monomer, a polymerization initiator, etc.) can be dissolved efficiently. In addition, the said solvent may be used independently or may be used with the form of a 2 or more types of mixture.

  In addition, the ink jet ink of the above form may contain other additives. Here, the other additives are not particularly limited, and the additives used for the ink jet ink can be used in the same manner. For example, a conductivity adjusting agent, an amine, a dispersing agent, a polymerization inhibitor, a surface adjusting agent, a leveling agent, an ultraviolet absorber, and an antioxidant for increasing printability and printed matter resistance. In addition, since these other additives are the same as the above, description is abbreviate | omitted here.

  The ink jet ink of the above form can be produced by a known method. For example, it can be prepared by thoroughly dispersing a dye, a polymerizable monomer, a polymerization initiator, and, if necessary, other additives using a normal dispersing machine such as a sand mill. At this time, a high concentration concentrate of the dye may be prepared in advance and then diluted with a polymerizable monomer. If necessary, the dispersion thus obtained may be filtered with a filter having a pore size of 3 μm or less, and further 1 μm or less.

The usage form of the inkjet ink of the present invention is not particularly limited, and a known inkjet printing method can be applied. For example, the ink-jet ink of the present invention is supplied to a printer head of a printer for an ink-jet recording system, ejected from the printer head onto a substrate, and then irradiated with active energy rays such as ultraviolet rays and electron beams. Thereby, the ink on the printing medium is quickly cured. In addition, when irradiating an ultraviolet-ray as a light source of an active energy ray, a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, LED, and sunlight can be used, for example. The light source is preferably selected appropriately according to the sensitivity of the polymerization initiator used. The ultraviolet intensity that can be used for curing the ink of the present invention is preferably 500 to 5,000 mW / cm ² in a wavelength region effective for curing. Such irradiation intensity does not damage the recording medium and does not induce color fading.

Hereinafter, examples and comparative examples will be described. However, the technical scope of the present invention is not limited only to the following examples. In the names of the following compounds, Pc represents a phthalocyanine nucleus, and PN represents phthalonitrile. In the names of the following compounds, “α- (substituent A) _a , β- (substituent A) _x-a PN (0 <a <x)” or “α- (substituent A) _a , β- (Substituent A) _x-a Pc (0 <a <x) ”is described because the obtained phthalonitrile compound or phthalocyanine compound has an average of a at the α-position and an average of x-a at the β-position. Means that a total of x substituents A have been introduced at the α-position and the β-position.

Example 1: [ZnPc- {α- (2,5-Cl ₂ ) C ₆ H ₄ O} _x , {β- (2,5-Cl ₂ ) C ₆ H ₄ O} _1.5-x {α -(4-CN) C ₆ H ₄ O} _y , {β- (4-CN) C ₆ H ₄ O} _0.9-y Cl _9.6 H _4.0 ] (0 ≦ x <1.5 ) (0 ≦ y <0.9) Synthesis In a 100 ml flask, 5.98 g of tetrachlorophthalonitrile (hereinafter abbreviated as TCPN), 1.83 g of 2,5-dichlorophenol, 0.80 g of 4-cyanophenol, benzo 23.2 g of nitrile (hereinafter abbreviated as BN) was added and stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 100 ° C., and then 2.74 g of potassium carbonate was added for about 4 hours. By making it react, the reaction liquid containing the desired phthalonitrile compound was obtained. After cooling, 0.96 g of phthalonitrile (hereinafter abbreviated as PN) was added to the solution obtained by suction filtration to prepare a total concentration of nitrile compounds in the liquid of 40 wt%. Next, the reaction solution obtained above was stirred for about 1 hour using a magnetic stirrer under a nitrogen flow (10 ml / min) until the internal temperature was stabilized at 160 ° C. Then, 1.12 g of zinc chloride was added. The reaction was performed for about 24 hours. After cooling, it was added dropwise to methanol (302.3 g) corresponding to 30 times the sum of the weight of the phthalocyanine compound from which the reaction solution was obtained and stirred for 30 minutes. Thereafter, distilled water (100.8 g) corresponding to 10 times the sum of the weight of the phthalocyanine compound was added dropwise over 30 minutes, and after completion of the addition, the mixture was further stirred for 30 minutes to precipitate crystals. The obtained crystals were subjected to suction filtration, and then washed and purified by adding the same amount of methanol and distilled water as in the crystallization and stirring the mixture at 40 ° C. for 30 minutes. After suction filtration, the taken out crystals were vacuum-dried at about 90 ° C. overnight to obtain about 9.17 g (yield 97.4 mol%).

(Evaluation of Abs (630 nm) / Abs (460 nm),% T (460 nm) and thermal change characteristic (ΔE))
0.073 g of the obtained phthalocyanine compound, 0.475 g of a binder polymer manufactured by Nippon Shokubai Co., Ltd., 1.03 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA), 0.113 g of dipentaerythritol hexaacrylate, Ciba Specialty -0.01 g of Chemicals Co., Ltd. (IRGACURE369) was added, and it melt | dissolved and mixed and prepared the resist coating liquid. The obtained coating liquid was applied to a glass plate using a spin coater (Mikasa Co., Ltd .: 1H-D7) so that the dye concentration in the dry film was 20 wt% and the dry film thickness was 2 μm, and the temperature was 100 ° C. And dried for 3 minutes. The absorption spectrum of the coating glass plate thus obtained was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: U-2910), and this was used as the spectrum before heating. Next, the coated glass plate whose spectrum before heating was measured was heat-treated at 180 ° C. for 20 minutes. The absorption spectrum of the heat-treated coated glass plate was measured with a spectrophotometer, and this was used as the spectrum after heating.

In the spectrum before heating measured in this way, the ratio of the absorbance at 630 nm (Abs (630 nm)) to the absorbance at 460 nm (Abs (460 nm)) (Abs (630 nm) / Abs (460 nm)) was calculated. Further, the transmittance at 460 nm (% T (460 nm)) in the spectrum before heating was calculated. Furthermore, the absorbance from 380 nm to 900 nm was integrated in each spectrum before and after heating, and the difference between the absorbance before and after heating was measured. Further, ΔE was calculated by the following equation, where E _{1 was} the spectrum before heating, E _{2 was} the spectrum after heating, and ΔE was the difference in measured absorbance.

(Evaluation of solubility in paint liquid)
A prepared solution having the same composition as the resist coating solution used in the above evaluation was collected with a syringe and filtered using a membrane filter (φ = 0.45 μm). When the prepared solution can pass through the membrane filter without clogging, a filtration test is performed to judge that the dye is dissolved in the prepared solution. Was evaluated as solubility evaluation. The results thus measured are summarized in Table 1 below.

Example 2: [ZnPc- {α- (2,6-Cl ₂ ) C ₆ H ₄ O} _x , {β- (2,5-Cl ₂ ) C ₆ H ₄ O} _1.0-x {α _{- (4-NO 2) C} 6 H 4 O} y, {β- (4-NO 2) C 6 H 4 O} 0.2-y Cl 10.8 H 4.0] (0 ≦ x <1 0.0) (0 ≦ y <0.2) In Example 1, 1.83 g of 2,5-dichlorophenol was added to 1.22 g of 2,6-dichlorophenol, and 0.80 g of 4-cyanophenol was 4- A reaction solution containing the desired phthalonitrile compound was obtained in the same manner as in Example 1 except that the amount was changed to 0.21 g of nitrophenol. Next, 0.96 g of PN was added, the same operation as in Example 1 was performed, and the reaction was allowed to proceed for about 24 hours. After cooling, the completely same operation as Example 1 was performed, and about 8.23 g (yield 96.4 mol%) was obtained. Thereafter, the solubility in the coating liquid, Abs (630 nm) / Abs (460 nm),% T (460 nm) and heat change characteristics were measured by exactly the same operation as in Example 1, and the results are summarized in Table 1.

Example 3: [ZnPc- {α- (2,5-Cl ₂ ) C ₆ H ₄ O} _x , {β- (2,5-Cl ₂ ) C ₆ H ₄ O} _1.5-x {α _{-C 6 H 5 O} y,} {β-C 6 H 5 O} 0.9-y Cl 9.6 H 4.0] (0 ≦ x <1.5) (0 ≦ y <0.9) In Example 1, a reaction solution containing the desired phthalonitrile compound was obtained in the same manner as in Example 1 except that 4-cyanophenol was changed to 0.64 g of phenol. Next, 0.96 g of PN was added and the same operation as in Example 1 was performed except that zinc chloride was changed to 2.63 g of zinc iodide, and the reaction was allowed to proceed for about 24 hours. After cooling, the completely same operation as Example 1 was performed, and about 9.17 g (yield 97.4 mol%) was obtained. Thereafter, the solubility in the coating liquid, Abs (630 nm) / Abs (460 nm),% T (460 nm) and heat change characteristics were measured by exactly the same operation as in Example 1, and the results are summarized in Table 1.

Example 4: [ZnPc- {α- (2,5- (CH 3) 2) C 6 H 4 O} x, {β- (2,5- (CH 3) 2) C 6 H 4 O} 1 _0.0-x {α-C ₆ H ₅ O} _y , {β-C ₆ H ₅ O} _0.9-y {α- (2,6- (CH ₃ ) ₂ ) C ₆ H ₄ O} _z , {Β- (2,6- (CH ₃ ) ₂ ) C ₆ H ₄ O} _0.5-z Cl _7.6 H _6.0 ] (0 ≦ x <1.0) (0 ≦ y <0 .9) Synthesis of (0 ≦ z <0.5) In Example 1, 2,5-dichlorophenol was changed to 0.92 g of 2,5-dimethylphenol and 0.46 g of 2,6-dimethylphenol to 4-cyano. A reaction solution containing the desired phthalonitrile compound was obtained in the same manner as in Example 1 except that phenol was changed to 0.64 g of phenol. Next, except for changing the addition amount of PN added to 1.44 g, the same operation as in Example 1 was performed, and the reaction was performed for about 24 hours. After cooling, the completely same operation as Example 1 was performed, and about 7.92 g (yield 95.8 mol%) was obtained. Thereafter, the solubility in the coating liquid, Abs (630 nm) / Abs (460 nm),% T (460 nm) and heat change characteristics were measured by exactly the same operation as in Example 1, and the results are summarized in Table 1.

Comparative Example 1
A phthalocyanine compound [ZnPc- {α- (4-CN) C ₆ H ₄ O} _x , {β- (4-CN) C ₆ H ₄ O} described in Example 9 of JP2012-15381A _2.4- xCl _13.6 ] (0 ≦ x <2.4) was subjected to exactly the same operation as in Example 1, so that the solubility in paint liquid, Abs (630 nm) / Abs (460 nm),% T ( 460 nm) and thermal change characteristics were measured, and the results are summarized in Table 1.

  It was shown that the phthalocyanine compounds synthesized in Examples 1 to 4 have improved transmittance with resin as compared with Comparative Example 1, and have excellent transmittance without cloudiness. Moreover, compared with the comparative example 1, heat resistance showed the same excellent value, and it was shown that it is excellent in heat resistance. Furthermore, the ratio (Abs (630 nm) / Abs (460 nm)) of the absorbance (Abs (630 nm)) at 630 nm, which is a typical red light wavelength, and the absorbance (Abs (460 nm)) at 460 nm, which is a typical blue light wavelength. ) Was greatly improved and showed a more vivid cyan color. Further,% T (460 nm) also showed an excellent value as compared with Comparative Example 1, indicating that it efficiently transmits the blue bright line.

  From the above, the phthalocyanine dye of the present invention exhibits a high-brightness and vivid cyan color, in addition, has high compatibility with the resin, and also has excellent heat resistance. It was shown to be suitable as.

Claims (4)

Following formula (1):

In the above formula (1), Z _{1 to} Z ₁₆ are each independently a hydrogen atom, a halogen atom, the following formula (2):

In said formula (2), R < ¹ > and R < ² > are respectively independently a halogen atom and a C1-C4 alkyl group, and m is an integer of 0-4,
Or a substituent represented by the following formula (3):

In the above formula (3), X is an oxygen atom or a sulfur atom, Ar is a phenyl group or a naphthyl group which may be substituted with R ³ , and in this case, each R ³ is independently cyano A group, a nitro group, OY, a halogen atom, an aryl group, or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, where Y is an alkyl group having 1 to 8 carbon atoms A substituent (b) represented by:
At this time, _{1 to} 3.9 of Z _{1 to} Z ₁₆ are the substituent (a) or the substituent (b), 3 to 12 are hydrogen atoms, and the remainder is a halogen atom, Among 1 to 3.9 substituents (a) or (b), at least one or more is substituent (a),
M represents metal-free, metal, metal oxide or metal halide,
A phthalocyanine compound represented by The phthalocyanine compound according to claim 1, wherein the substituent (a) represented by the formula (2) is the following formula (4) or (5).

In the above formulas (4) and (5), R ¹ and R ² are each independently a halogen atom or an alkyl group having 1 to 4 carbon atoms. The structural unit in which all of Z _{1 to} Z ₄ are hydrogen atoms, the structural unit in which Z _{5 to} Z ₈ are all hydrogen atoms, the structural unit in which all of Z _{9 to} Z ₁₂ are hydrogen atoms, and the Z ₁₃ to The phthalocyanine compound according to claim 1 or 2, wherein the total number of structural units in which Z ₁₆ is all hydrogen atoms is more than 0 and less than 2.4.   An inkjet ink comprising the phthalocyanine compound according to claim 1.