WO2008038679A1 - Phthalocyanine compound and process for production thereof - Google Patents

Abstract

Disclosed is a process for producing a phthalocyanine compound which is soluble to a hydrophilic solvent or water and is useful even in use applications to which phthalocyanine compounds have not ever been applicable. Specifically disclosed is a process for producing a phthalocyanine compound, which comprises reacting a phthalocyanine compound (1) represented by the formula (1) with at least one member selected from the group consisting of a pyridinol which may have a substituent, an imidazole which may have a substituent and a pyrazole which may have a substituent. (1) wherein Z1 to Z16 independently represent a hydrogen atom, SR1, NHR2, OR3 or a halogen atom, provided that each of at least two members among Z1 to Z16 represents a halogen atom; R1, R2 and R3 independently represent a phenyl group which may have a substituent, an aralkyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent; two or more of R1, R2 and R3 may be the same as or different from each other; and M represents a non-metal, a metal, a metal oxide or a metal halide.

Description

 Specification

 Phthalocyanine compound and method for producing the same

 Technical field

 [0001] The present invention relates to a phthalocyanine compound, particularly a phthalocyanine mixture, particularly a phthalocyanine mixture and a method for producing the same, having a selective absorption ability in the near-infrared wavelength region of UOOnm, solubility in a hydrophilic solvent, and water solubility. is there. The phthalocyanine compound (phthalocyanine mixture) of the present invention is a color toner, inkjet ink, household inkjet ink, anti-counterfeiting barcode ink, goggles lens or shielding plate, and dyeing for sorting during plastic recycling. Agents, optical recording media, photosensitive dyes for laser therapy, preheating aids during molding of PET bottles, photothermal exchange agents such as thermal transfer and thermal stencil, photothermal exchange agents for thermal rewritable recording, ID card Various applications such as anti-counterfeiting, photothermal exchange agents for laser transmission welding of plastics (LTW), heat ray shielding agents, and near infrared absorption filters, preferably for inkjet inks and household inkjets Ink, optical recording media, anti-counterfeit bar code ink, goggles label It can be suitably used for a screen, a shielding plate, and a photosensitive dye for laser therapy, particularly an inkjet ink.

 Background art

[0002] In recent years, phthalocyanine compounds are stable against light, heat, temperature, etc. and are excellent in robustness. Therefore, compact discs, laser discs, optical memory discs, optical cards using a semiconductor laser as a light source. It is used as a near-infrared absorbing dye used for optical recording media. In recent years, PDP (Plasma Display Panel), which is thin and applicable to large screens, has attracted attention. S, PDP generates near infrared light during plasma discharge. Inducing malfunction of electrical equipment such as video decks is a problem, and in order to solve such problems, selection of near-infrared regions with high near-infrared ray cutting efficiency with high visible light transmittance is high. Developments have been made on phthalocyanine compounds having excellent absorption ability and heat resistance, light resistance, and weather resistance. [0003] In this way, various phthalocyanine compounds have been studied. 'Except for the developed phthalocyanine for CD-R, most of the conventional phthalocyanine compounds are organic solvents such as acetone, chloroform, toluene and methyl ethyl ketone. Although it is soluble in water, it is hardly soluble in lower alcohols such as methanol or their aqueous solutions or even water, and this limits the choice of the solvent used and the type of resin used. there were.

 [0004] For this reason, color toner, inkjet ink, household inkjet ink, anti-counterfeiting barcode ink, goggles lens and shielding plate, dyeing agent for sorting when recycling plastic, light Photosensitive dyes for recording media, laser treatment photosensitive dyes, PET bottle pre-heating aids, thermal transfer, thermal stencil and other photothermal exchange agents, thermal rewritable recording photothermal exchange agents, forgery of ID cards If it is used as a photothermal exchanger, heat ray shielding agent, near-infrared absorption filter, etc. for prevention, plastic laser transmission welding (LTW), the organic solvent evaporates, and workers and users The product has an unpleasant odor and is flammable, which may be unfavorable for safety and has limited applications. Therefore, there has been a high demand for phthalocyanine compounds that can be dissolved in lower alcohols such as methanol or hydrophilic solvents such as aqueous solutions thereof, or water, and have utility in applications that cannot be applied conventionally.

 [0005] For the above purpose, phthalocyanine compounds having improved water solubility by introducing a sulfonic acid group have been reported (see, for example, US-A-4, 824, 948). According to US—A— 4, 824, 948 above, SO M (M is H, metal or optionally substituted

 Three

 Incorporation of 1 to 16 nitriles) into the phthalocyanine skeleton can provide moderate water solubility. In addition, by introducing carboxyl groups (including salts thereof) or sulfonic acid groups (including salts thereof) into the phthalocyanine compound skeleton, compatibility with excellent resins, heat resistance, light resistance, weather resistance, etc. In addition to various properties, phthalocyanine compounds have been reported that are soluble in lower alcohols such as methanol and ethanol or hydrophilic solvents such as aqueous solutions thereof (see, for example, JP-A-2005-220060).

[0006] However, in the above US—A—4, 824, 948, there are many reasons for the introduction of sulfonic acid groups. Since an amount of sulfuric acid is used, it is necessary to treat the waste acid after production, which is not preferable in the production process. In addition, the phthalocyanine compounds described in JP-A-2005-220060 are not sufficiently soluble in lower alcohols or aqueous solutions thereof, and the solubility in water is very low. For this reason, the development of phthalocyanine compounds that are superior in water solubility and hydrophilicity for the purposes described above has been sought after.

 [0007] On the other hand, for the purpose of improving the water solubility of the phthalocyanine compound, a 3-pyridyloxy group in the form of a pyridinium cation that imparts water solubility during protonation is introduced at the / 3-position of the phthalocyanine compound skeleton. Methods have been devised (see, for example, HETEROCYCLE S, Vol. 22, No. 9, p. 2047-2052, 1984). According to the method described in HETERO CYCLES, Vol. 22, No. 9, p. 2047-2052, 1984, as shown in the scheme on page 2048, the target Zn ( II) Since tetra- (3-pyridyloxy) phthalocyanine is produced through a very complicated process of 7 steps, there is a disadvantage that the yield of the final product is low and economically undesirable. In addition to the above disadvantages, a pyridyloxy group is added to the 3-position of the benzene ring in advance, and then the cyclization reaction is performed, so that the final product is a single structure bonded to the / 3-position of the individual phthalocyanine skeleton. Is obtained. For this reason, the maximum absorption wavelength of the final product is one. However, in any application, it is usually necessary to cut multiple wavelengths without cutting a single wavelength. In this case, a dye having a desired absorption wavelength is separately added. It is necessary to mix, which is also economically undesirable.

 [0008] iifHHETEROCYCLES, Vol. 22, No. 9, p. 2047—2052, 1984, released from Calo, the ability to produce phthalocyanine compounds in which a pyridyloxy group was introduced at the β-position of the phthalocyanine compound skeleton SYNTHESIS, Issue 02 , Vol. 1993, p. 194-196, 1993. In this method, as in HETEROCYCLES, Vol. 22, No. 9, p. 2047-2052, 1984, a pyridinoleic oxy group was previously added to positions 3 and 4 of the benzene ring. After that, since the cyclization reaction is a multistage reaction, the yield of the final product is low, and the final product can be obtained only as a single structure. Disclosure of the invention

[0009] Therefore, the present invention has been made in view of the above circumstances, and can be easily performed in a hydrophilic solvent or water. An object of the present invention is to provide a phthalocyanine compound (especially a phthalocyanine mixture) that can be dissolved and is useful for applications that cannot be applied conventionally.

Another object of the present invention is to provide a method for producing a phthalocyanine compound capable of producing such a phthalocyanine compound excellent in hydrophilicity and water solubility by a simple method.

 [0011] Still another object of the present invention is to provide a method for producing a phthalocyanine mixture excellent in hydrophilicity and water-solubility that can produce a plurality of phthalocyanine compounds in a simple manner in the form of a mixture.

 [0012] As a result of intensive studies to achieve the above-mentioned objects, the present inventor has reacted pyridinol, imidazole and pyrazole with a phthalocyanine compound having a halogen atom introduced at a desired position, respectively. Group, an imidazolyl group or a pyrazolyl group is substituted with a part or all of the above halogen atoms, and the phthalocyanine compound into which the desired substituent is introduced is used as it is or in the form of a mixture in one step without complicated steps. We found that it can be manufactured. Further, the phthalocyanine compound (phthalocyanine mixture) having such a structure and thus produced is superior to at least one of a lower alcohol such as methanol and ethanol, a hydrophilic solvent such as an aqueous solution thereof, and water. It was found to be highly soluble. Based on the above findings, the present invention has been completed.

 That is, the objects of the present invention are as follows:

[0014] [Chemical 1]

[0015] in the formula Rogen atom R ² and

R ^{3 and} R ³ may each independently have a phenyl group which may have a substituent, may have a substituent, may have a V aralkyl group or a substituent! /, The number of carbon atoms; ~ 20 alkyl groups represented

R ² and R ³ may be the same or different from each other; M represents a metal-free, metal, metal oxide or metal halide,

 The phthalocyanine compound (1) represented by the formula is selected from the group consisting of pyridinol which may have a substituent, may have a substituent! /, Imidazole and may have a substituent, and pyrazole This is achieved by a method for producing a phthalocyanine compound having a reaction with at least one selected from the group consisting of:

 [0016] Further, various objects of the present invention are such that the phthalocyanine compound (1) represented by the above formula (1) may have a substituent! /, Pyridinol, or a substituent! / It is also achieved by a phthalocyanine compound produced by reacting with at least one selected from the group consisting of imidazole and optionally substituted pyrazole.

[0017] The phthalocyanine compound (phthalocyanine mixture) of the present invention has a hydrophilic solvent such as a lower alcohol such as methanol or ethanol or an aqueous solution thereof, while exhibiting high near-infrared cut efficiency in the wavelength range of 650-; UOOnm. And / or soluble in water. In addition, the method for producing a phthalocyanine compound of the present invention can be simplified without requiring complicated steps. Can be manufactured by a convenient process. In particular, according to the method of the present invention, a plurality of phthalocyanine compounds excellent in hydrophilicity and water solubility can be produced in the form of a mixture by a simple method. In the present specification, “the phthalocyanine compound is in the form of a mixture” and “a phthalocyanine mixture” mean that two or more phthalocyanine compounds according to the present invention are included.

 Therefore, the phthalocyanine compound (phthalocyanine mixture) according to the present invention is used for color toner, inkjet ink, household inkjet ink, anti-counterfeit barcode ink, goggles lens and shielding plate, and plastic recycling. Dyes for sorting, optical recording media, photosensitive dyes for laser therapy, preheating aids during molding of PET bottles, photothermal exchange agents such as thermal transfer and thermal stencil, thermal rewritable recording Photo heat exchangers, ID card anti-counterfeiting, plastic heat transfer agents for laser transmission welding (LTW), heat ray shields, and near infrared absorption filters, especially for inkjet It can be suitably used for ink.

 [0019] Still other objects, features and characteristics of the present invention will become apparent by referring to the following description and preferred embodiments exemplified in the accompanying drawings.

 Brief Description of Drawings

 FIG. 1 is a diagram showing the results of liquid chromatography of the reaction product obtained in Example 1.

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

[0022] The first of the present invention is the following formula (1):

[0023] [Chemical 2]

 [0024] A group consisting of a phthalocyanine compound (1) represented by the following: a pyridinol which may have a substituent, may have a substituent! /, Imidazole and a substituent which has a substituent, and pyrazole The present invention relates to a method for producing a phthalocyanine compound having a reaction with at least one selected from the group consisting of:

 [0025] Since the phthalocyanine compound produced by the method of the present invention exhibits excellent hydrophilicity and / or water solubility, a hydrophilic solvent such as a lower alcohol such as methanol or ethanol or an aqueous solution thereof, and / or water Can be easily dissolved. In addition, according to the method of the present invention, such a phthalocyanine compound having excellent hydrophilicity and water solubility can be produced in the form of a plurality of mixtures by a simple method. In the present specification, the term “hydrophilic” means that the solubility in a lower alcohol having 1 to 4 carbon atoms such as methanol, ethanol, 2-ethoxyethanol or an aqueous solution thereof is 0.1% by mass or more. Preferably, the solubility power in these hydrophilic solvents is 1.0% by mass or more, more preferably 5.0% by mass or more. In the present specification, “water-soluble” means that the solubility in water (water solubility) is 0.1% by mass or more, and preferably, the solubility in water is 1S 1.0% by mass or more. Preferably it is 5.0 mass% or more. In the present specification, “hydrophilic and / or water-soluble” is also collectively referred to as “hydrophilic”.

[0026] Further, as described above, according to the method of the present invention, a plurality of phthalocyanine compounds can be easily produced in the form of a mixture without complicated steps, and these phthalocyanine compounds can be produced. Indicate different maximum absorption wavelengths. Further, the maximum absorption wavelength of each phthalocyanine compound depends on the structure of the phthalocyanine compound (1) of the formula (1), particularly the type and number of halogen atoms shown in the formula (1), and other substituents other than the nitrogen atom. Type: May have a substituent! / ヽ Type of pyridinol, optionally substituted imidazole, optionally substituted pyrazole; and phthalocyanine compound (1) It may be adjusted by the mixing ratio of pyridinol, which may be substituted, may have a substituent! /, Imidazole, and may have a substituent! /, And pyrazole. Therefore, a phthalocyanine mixture having various colors can be easily produced by appropriately selecting the above factors.

 [0027] Therefore, the phthalocyanine compound and the phthalocyanine mixture according to the present invention are used in power toners, inkjet inks, household inkjet inks, anti-counterfeiting barcode inks, goggles lenses and shielding plates, and plastic recycling. Dyeing agents for sorting, optical recording media, photosensitive dyes for laser therapy, preheating aids during molding of PET bottles, photothermal exchangers such as thermal transfer and thermal stencil, and thermal rewritable recording Various applications such as photothermal exchange agents, anti-counterfeiting of ID cards, photothermal exchange agents for laser transmission welding (LTW), heat ray shielding agents, and near-infrared absorption filters, preferably inkjet inks Ink-jet ink for home use, optical recording media, anti-counterfeit bar It can be suitably used for cord inks, goggle lenses and shielding plates, and photosensitive dyes for laser therapy, particularly ink jet inks.

[0028] The phthalocyanine compound of the present invention includes a phthalocyanine compound (1) of the formula (1), which may have a substituent! /, Pyridinol, may have a substituent! /, Imidazole, and a substituent. It is produced by reacting with at least one selected from the group consisting of pyrazoles, and preferably in the form of a mixture. In the present specification, the phthalocyanine compound (1) of the formula (1) has a “phthalocyanine compound (1)” and a substituent, and pyridinol has a “pyridinol derivative” and a substituent. The imidazole that may be substituted is also referred to as “imidazole derivative”, the pyrazole that may have a substituent is also referred to as “pyrazole derivative”, and the pyridinol derivative, imidazole derivative, and pyrazole derivative are also collectively referred to as “derivative”. . [0029] In the above formula (1), Z to Z may be the same or different from each other.

 1 16

 May be. In the present invention, in the above formula (1), Z, Z, Z, Z of phthalocyanine skeleton

 2 3 6 7

, Z, Z, Z, Z substituents are substituted at 8 positions of the phthalocyanine nucleus at the / 3-position

10 11 14 15

 Or simply “substituent at β-position” and ζ, ζ, ζ, ζ, ζ, ζ, ζ of phthalocyanine skeleton

 1 4 5 8 9 12

, 置換 substituents at the eight α-positions of the phthalocyanine nucleus or simply “

13 16

 It may be referred to as “substituent at position a”.

[0030] 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. In addition, examples of the metal include iron, magnesium, nickel, cobalt, copper, noradium, zinc, vanadium, titanium, 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, tin (IV) chloride, and silicon chloride. Preferably, it is a metal, metal oxide or metal halide, specifically copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper. , Vanadinole and zinc. In particular, when a phthalocyanine compound (including a mixture form; the same applies hereinafter) is used for an ink jet ink, the central metal M is preferably copper, vanadyl, or zinc from the viewpoint of hydrophilicity. That's right.

In the above formula (1), Z to Z are a hydrogen atom, SR ¹ , NHR ² , OR ³ or a halogen atom.

 1 16

 Represents a child. In this case, at least two of Z to Z represent halogen atoms. According to the present invention

 1 16

 Then, by reaction of the phthalocyanine compound (1) with at least one selected from the group consisting of a pyridinol derivative, an imidazole derivative and a pyrazole derivative, part or all of the halogen atoms present in the phthalocyanine compound (1). Is replaced with the above derivative (a group derived from the above derivative is introduced at a position where a halogen atom is present), and the phthalocyanine compound obtained thereby exhibits hydrophilicity / water solubility. For this reason, the hydrophilicity / water solubility of phthalocyanine compounds depends on the number of halogen atoms in z to z.

 1 16

The more the number of halogen atoms is adjusted, that is, the more these derivatives are introduced into the phthalocyanine skeleton, the higher the hydrophilicity / water solubility of the resulting phthalocyanine compound. Become. Therefore, the number of halogen atoms in z to z is the desired hydrophilic / water-soluble level.

1 16

Different colors, especially color toners, inkjet inks, household inkjet inks, anti-counterfeiting barcode inks, goggles lenses and shielding plates, plastic dyes for sorting, optical recording media, For applications such as photosensitive dyes for laser therapy and preheating aids during the molding of PET bottles, 4-16, more preferred <8 ~; 16, more preferred <12 ~ 16 and most preferably <16, where Z to Z, Z to Z, Z to Z and Z to Z

 1 4 5 8 9 12 13 16

The number of halogen atoms occupying Z to Z in formula (1) is 4, 8,

 1 16

 Particularly preferred are 12 and 16. In addition, halogen as Z to Z in the above formula (1)

 1 16

The nitrogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom and a chlorine atom, particularly preferably a fluorine atom. Also, the absorption wavelength is 700 ~ in the near infrared region;! OOOnm wavelength is preferred, especially the wavelength range of 750 ~ 850nm, which is near the wavelength of semiconductor laser, and the wavelength of 770 ~ 820nm is more preferred. The area is most preferred!

 In the above formula (1), the number of halogen atoms in Z to Z is 2 to 15

 1 16

 The bonding position of the halogen atom is not particularly limited and varies depending on the type and number of halogen atoms. For example, when there are four halogen atoms, one halogen atom is present in each benzene ring of the phthalocyanine skeleton, and each benzene ring, for example, Z position in Z to Z,

 1 4 2

It is preferably present at the Z position. For example, when there are 8 halogen atoms,

Three

Two halogen atoms exist in each benzene ring of the phthalocyanine skeleton, and each benzene ring, for example, Z to Z, Z position and Z position, Z position and Z position, Z position and Z position, Z position and Z , Z and Z

 1 4 1 2 1 3 2 3 2 4 It is preferred that they are present at the 3rd position, most preferably at the z position and the Z position. In addition, the halogen atom is 1

4 2 3

 In the case of two, three halogen atoms are present in each benzene ring of the phthalocyanine skeleton, and each benzene ring, for example, Z to Z, Z position and Z position and Z position, Z position and Z Position and Z position

 The force s is preferably present in 1 4 1 2 3 2 3 4. If the number of halogen atoms is other than the above, the same number of halogen atoms are present in each benzene ring as much as possible, and the excess halogen atom force s is at least at the z-position or z-position in the benzene ring of the phthalocyanine skeleton. Like to exist

 twenty three

Good. [0033] Further, in the above formula (1), when the number of halogen atoms in Z to Z is 2 to 15; it is z NHR ² or OR ³ other than halogen atoms.

Preferably a hydrogen atom or OR ³ , more preferably a hydrogen atom, a phenoxy group which may have a substituent, or an alkoxy group, and particularly preferably a phenoxy group which may have a substituent.

[0034] In the above formula (1),

R ² and R ³ represent an optionally substituted phenyl group, an optionally substituted aralkyl group, or an optionally substituted alkyl group having 1 to 20 carbon atoms. . In addition,

When there are multiple R ² and R ³ , these may be the same or different! /.

[0035] where

Examples of the aralkyl group in R ² and R ³ include a benzyl group, a phenethyl group, and a diphenylmethyl group.

 [0036] Examples of the substituent of the phenyl group or the aralkyl group include, for example, a halogen atom, an acylol group, an arolequinol group, a phenyl group, an alkoxyl group, a halogenated alkyl group, a halogenated alkoxyl group, a nitro group, and an amino group. Group, anolenoquinamino group, alkylcarbonylamino group, allylamino group, allylcarbonylamino group, carbonyl group, alkoxy group, norbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, rubamoyl group, allyl group Examples thereof include an oxycarbonyl group, an oxyalkyl ether group, and a cyan group. These substituents can be substituted with 1 to 5 phenyl groups or aralkyl groups, and the types of these substituents may be the same or different when there are multiple substitutions. ! /

 [0037] First, the halogen atom that can be substituted on the phenyl group or aralkyl group includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom, a chlorine atom, more preferably a fluorine atom. is there.

 [0038] Examples of the acyl group include a acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a petitenorecanolinore group, a pentinorecanoreponinole group, a hexinorecanoreponinore group, a benzoinole group, and a ptbutylbenzoyl group. Of these, acetyl and ethylcarbonyl groups are preferred.

[0039] The alkyl group is a straight chain having a number of carbon atoms;! -20, preferably a carbon atom;!-8 A branched or cyclic alkyl group, methyl group, ethyl group, n propyl group, isopropylene group, n butyl group, isobutyl group, sec butyl group, tert butyl group, n pentynole group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexenole group, cyclohexyl group, 1,3-dimethylbutyl group, 1 isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4 dimethylpentyl group, 2 —Methyl-1 isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like. Of these, a methyl group and an ethyl group are preferred.

 [0040] The alkoxyl group is a linear, branched or cyclic alkoxyl group having carbon atoms;! -20, preferably carbon atoms;! -8, methoxy group, ethoxy group, n propoxy group, Isopropoxy group, n butoxy group, isobutoxy group, sec butoxy group, tert butoxy group, n pentyloxy group, isopentyloxy group, neopentyloxy group, 1,2 dimethyl-propyloxy group, n hexyloxy group, cyclohexane Examples include a hexyloxy group, a 1,3-dimethylbutoxy group, and a 1-isopropylpropoxy group. Of these, methoxy and ethoxy groups are preferred.

 [0041] The rogenated alkyl group is a halogenated part of a linear, branched or cyclic alkyl group having carbon atoms;! To 20, preferably carbon atoms;! To 8 carbon atoms. Examples include chloromethyl group, bromomethyl group, trifunoleolomethylenole group, chlorodiethyl group, 2,2,2-trichlorodiethyl group, bromoethyl group, clopropropyl group, and bromopropyl group.

[0042] The rogenated alkoxyl group is a halogenated part of a linear, branched or cyclic alkoxyl group having carbon atoms;! -20, preferably carbon atoms;! -8. Examples include chloromethoxy, bromomethoxy, trifluoromethoxy, black ethoxy, 2,2,2-trichloro ethoxy, bromoethoxy, black propoxy, and bromopropoxy. It is done.

[0043] The alkylamino group is an alkylamino group having an alkyl moiety having! -20, preferably 1-8 carbon atoms, and includes a methylamino group, an ethylamino group, an n-propylamino group, n Butynoleamino group, sec Butylamino group, n-pentylamino group, n- Hexylamino group, n-heptylamino group, n-octylamino group, 2-ethylhexylamino group and the like can be mentioned. Of these, a methylamino group, an ethylamino group, an n-propylamino group, and an n-butylamino group are preferable.

 [0044] The alkylcarbonylamino group includes an acetylylamino group, an ethylcarbonylamino group, an n-propylcarbonylamino group, an isopropylcarbonylamino group, an n-butylcarbonylaminoamino group, and an isobutylcarbonylamino group. , Sec butylcarbonylamino group, t butylcarbonylamino group, n pentylcarbonylamino group, n hexylcarbonylamino group, cyclohexylcarbonylamino group, n-heptylcarbonylamino group, 3-heptylcarbonylamino And mino group, n-octylcarbonylamino group and the like.

 [0045] The arylamino group includes a phenylamino group, p-methylphenylamino group, p-t-butylphenylamino group, diphenylamino- group, di-p-methylphenylamino group, di-p-butyl-phenylphenyl. And a mino group.

 [0046] The arylylcarbonylamino group includes a benzoylamino group, p-chlorobenzoylamino group, p-methoxybenzoylamino group, p-t-butylbenzoylamino group, p-trifluoromethylbenzilamino group, Examples include m-trifluoromethylbenzoylamino group.

 [0047] The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms which may contain a hetero atom in the alkyl group part of the alkoxyl group, or a carbon atom which may contain a hetero atom. A number of 3 to 8, preferably 5 to 8 cyclic alkoxycarbonyl is shown. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n butoxycarbonyl group, an isobutoxycarbonyl group, a sec butoxycarbonyl group, and a tert butoxycarbonyl group. Of these, a methoxycarbonyl group and an ethoxycarbonyl group are preferred.

[0048] Examples of the alkylaminocarbonyl group include methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, n-pentylaminocarbonyl group, and n Xylaminocarbo nino group, n-heptylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, jetylaminocarbo group Ninole group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, di-sec butylaminocarbonyl group, di-n pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n-heptyla Examples thereof include a minocarbonyl group and a di-n-octylaminocarbonyl group.

 [0049] Alkylthio groups include methylthiophenyl, ethylthiophenyl, tert-butylthiophenyl, di-tert-butylthiophenyl, 2-methyl-1-ethylthiophenyl, 2-butyl-1-methylthiol An enyl group etc. are mentioned.

[0050] Meanwhile,

The unsubstituted alkyl group having 1 to 20 carbon atoms in R ² and R ³ is a linear, branched or cyclic alkyl group having carbon atoms;! To 20, preferably 1 to 8, and Tinole 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, 1,2-dimethylpropyl group, n hexyl Group, cyclohexyl group, 1,3-dimethylbutynole group, 1 isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4 dimethylpentyl group, 2-methyl 1 isopropylpropyl group, 1-ethyl Examples include 3-methylbutyl group, n-octyl group, and 2-ethylhexyl group. Of these, methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred.

 [0051] Examples of the substituent of the alkyl group include a halogen atom, an alkoxyl group, a hydroxyalkoxyl group, an alkoxyalkoxyl group, a halogenated alkoxyl group, a nitro group, an amino group, an anolenoquinamino group, and an alkoxycarbonyl group. And an alkylaminocarbonyl group, an alkoxysulfonyl group, and the like. The types of these substituents are the same as those described for the above-mentioned phenyl group or aralkyl group. Also, when a plurality of these substituents are substituted, they are the same or different! / May be! /

[0052] The method for producing the phthalocyanine compound (1) used in the present invention is not particularly limited, and a conventionally known method such as Japanese Patent Application Laid-Open No. 2001-106689 and Japanese Patent Application Laid-Open No. 2005-220060 can be used. It can be used appropriately. Briefly, the phthalocyanine compound (1) is produced by cyclizing the phthalonitrile compound and the metal salt, preferably in a molten state or in an organic solvent. [0053] That is, the following formula (2):

[0054] [Chemical 3]

 [0055] A phthalonitrile compound (A) represented by the following formula (3):

[0056] [Chemical 4]

 [0057] A phthalonitrile compound (B) represented by the following formula (4)

[0058] [Chemical 5]

 [0059] a phthalonitrile compound (C) represented by the following formula (5):

[0060] [Chemical 6]

[0061] A group consisting of a metal oxide, a metal carbonyl, a metal halide, and an organic acid metal (also collectively referred to as “metal salt” in this specification). A phthalocyanine compound (1) can be produced by a cyclization reaction with one selected from the group consisting of: In the above formulas (2) to (5), Z to Z are the structures of the desired phthalocyanine compound (1).

 1 16

 The description is omitted here because it is defined by the structure and is the same as the definition of the above formula (1).

[0062] In the above embodiment, the phthalonitrile compounds (A) to (D) of the formulas (2) to (5) as the starting materials are conventionally used, such as the method disclosed in JP-A No. 64-45474. The compound can be synthesized by a known method, or a commercially available product can be used, but preferably the following formula (6):

 [0063] [Chemical 7]

 [0064] In the formula, X, X, X and X are each independently a fluorine atom, a chlorine atom, or a bromine atom.

 1 2 3 4

 Represents a halogen atom such as a child atom and an iodine atom, preferably a fluorine atom and a chlorine atom, particularly preferably a fluorine atom,

Is obtained by reacting with one or more selected from the group consisting of HSR ¹ and HOR ^ R ¹ and R ³ as defined in the above formula (1). At this time, the ratio of HSR ¹ and HOR ³ is appropriately selected according to the structure of the target phthalonitrile compound. The total amount of HSR ¹ and / or HOR ³ is not particularly limited as long as these reactions can proceed to produce the desired phthalonitrile compound, but with respect to 1 mol of the phthalonitrile derivative, Usually 1.0 to 6.0 monoliths, preferably 1.1 to 2.5 monoles.

[0065] The phthalonitrile compound can be obtained by reacting the phthalonitrile derivative represented by the formula (6) with one or more selected from the group consisting of HSR ¹ and HOR ³ . In this case, the reaction between the phthalonitrile derivative and HSR ¹ and / or HOR ³ may be performed in the absence of a solvent or in an organic solvent! /, But is preferably performed in an organic solvent. Examples of organic solvents that can be used in this case include nitriles such as acetonitrile and benzonitrile; Examples include polar solvents such as acetone and 2-butanone. Of these, preferably acetonitrile, benzonitrile and acetone. The amount of the organic solvent used when the solvent is used is such that the concentration of the phthalonitrile derivative is usually 2 to 40 (w / v)%, preferably 10 to 30 (w / v)%. . Also,

In the reaction with HSR ² and / or HOR ³ , it is preferable to use these trapping agents in order to remove hydrogen halide (eg, hydrogen fluoride) generated during the reaction. Specific examples of the trapping agent when using the trapping agent include potassium fluoride, potassium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride, and magnesium carbonate. Among these, Most preferred is potassium fluoride, with potassium fluoride, calcium carbonate and calcium hydroxide being preferred. Further, the amount of 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 limited to 1 mol of phthalonitrile derivative. 1. 0 to 4.0 monole, preferably (1.1 to 2.0 monole.

[0066] In addition, a phthalocyanine compound (1) in which all of Z to Z in the formula (1) are halogen atoms.

 1 16

In the case of reacting with a pyridinol derivative, imidazole derivative, or pyrazole derivative, the reaction of the phthalonitrile derivative of the above formula (6) with HOR ¹ is omitted, and the phthalol nitrile derivative of the above formula (6) is represented by the formula ( The phthalonitrile compounds (A) to (D) of 2) to (5) may be used directly for the cyclization reaction.

[0067] In the above embodiment, the cyclization reaction comprises the phthalonitrile compounds (A) to (D) of formulas (2) to (5) and a metal, metal oxide, metal carbonyl, metal halide, and organic acid metal. It is preferable to react one kind selected from the group in a molten state or in an organic solvent. Metals, metal oxides, metal carbonyls, metal halides and organic acid metals (hereinafter collectively referred to as “metal compounds”) that can be used at this time include those corresponding to M of the phthalocyanine compound obtained after the reaction. If it can be obtained, it is not particularly limited. For example, metals such as iron, copper, zinc, vanadium, titanium, indium and tin listed in the item M in the above formula (1), the metal Metal halide compounds such as chloride, bromide, iodide, etc., metal oxides such as vanadium oxide, titanyl oxide and copper oxide, organic acid metals such as acetate, and complex compounds such as acetylacetonate and carbo two And metal carbonyls such as iron. Of these, metals, metal oxides and metal halides are preferred.

 [0068] In addition, the cyclization reaction is preferably carried out using an organic solvent that can be used without a solvent. The organic solvent may be any inert solvent that has a low reactivity with the phthalonitrile compound as a starting material and preferably does not exhibit any reactivity.For example, benzene, toluene, xylene, nitrobenzene, monochrome Inert solvents such as benzene, dichlorobenzene, trichloro benzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycolanol, and benzonitrile; methanol, ethanol, 1 propanol, 2-propanol, 1-butanol, 1 Alcohols such as xanol, 1 pentanol, 1-octanol; and pyridine, N, N dimethylformamide, N, N dimethylacetamide N methyl 2-pyrrolidinone, N, N dimethylacetophenone, triethynoleamine, tri n Butyramine, dimethyl sulfoxide, Aprotic polar solvents such as Horan like. Of these, preferably 1-chloronaphthalene, 1-methylnaphthalene and benzonitrile force, more preferably benzonitrile is used.

 [0069] The reaction conditions of the phthalonitrile compound (A) (D) of the formula (2) (5) and the metal compound in the above embodiment are not particularly limited as long as the reaction proceeds. For example, with respect to 100 parts by mass of the organic solvent, the phthalonitrile compounds (A) to (D) are added in a total amount in the range of 240 parts by mass, preferably 20 35 parts by mass, and the metal compound is added to the lid. Charged in a range of 12 moles, preferably 1.;! 1.5 moles per 4 moles of tolyl compound, and reacted at a reaction temperature of 30 250 ° C, preferably 80 200 ° C. After the reaction, it is possible to obtain a phthalocyanine derivative which can be used in the next step efficiently and with high purity by filtering, washing and drying according to a conventionally known method for synthesizing phthalocyanine compounds.

[0070] Here, when the phthalocyanine compound (1) according to the present invention has NHR ² in the above formula (1), following the above method, the obtained reaction product and the formula: NHR ² If necessary, the reaction with the amino compound having the compound is preferably carried out by mixing in the presence of an inert liquid that is not reactive with the compound used for the reaction and heating to a certain temperature. More preferably, it is carried out by heating to a certain temperature in the amino compound to be reacted. Inert liquid For example, nitriles such as benzonitrile and acetonitrile, and amides such as N-methylpyrrolidone or dimethylformamide can be used alone or in the form of a mixture of two or more.

[0071] In the above reaction, a desired substituent is added to the Z to Z substitution positions of the phthalocyanine compound (1).

 1 16

The optimum range may be selected appropriately so that it can be introduced as designed. For example, the following conditions can be used. That is, an equimolar amount of an amino compound having a group of the formula: NHR ² is usually equimolar to 1 mol of a phthalocyanine compound derivative obtained by a cyclization reaction between a phthalonitrile compound (A) to (D) and a metal compound. Above, preferably 1.0 to 1.1; Next, with respect to 1 mol of the phthalocyanine compound derivative for the purpose of trapping the generated hydrogen halide, inorganic components such as calcium carbonate and calcium hydroxide are added to this reaction product; Charge the trapping agent in the range of 3-8 mol. Trapping agents that can be used at this time include potassium fluoride, potassium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride and magnesium carbonate. Of these, calcium carbonate and calcium hydroxide are included. preferable. The reaction temperature when the alkylamino compound is reacted is 20 to 200 ° C, preferably 30 to 150 ° C, and the reaction temperature when the arylamine compound is reacted is 80 to 250 ° C, Preferably it is the range of 100-200 degreeC. The reaction time when the alkylamino compound is reacted is !! to 20 hours, preferably 2 to 10 hours, and the reaction time when the aryloamino compound is reacted is !! to 30 hours, preferably Is in the range of 5 to 15 hours. By controlling the reaction temperature and time within the above range, it is possible to control the amount of ammine to be substituted. Usually, the amount of ammine is increased or the reaction temperature is increased to tighten the reaction conditions. It is possible to increase the number of ammine substitutions. After the reaction, according to a conventionally known synthesis method by substitution reaction of a phthalocyanine compound, the inorganic component is filtered and the amino compound is distilled off (washed) to produce a complex production of the desired phthalocyanine compound of the present invention. Without passing through the process, it is possible to obtain efficiency and high purity.

[0072] In the present invention, the pyridinol derivative is a pyridinol-substituted pyridinol, having a substituent in at least one of the four remaining positions not having a hydroxyl group of the pyridinol ring. Body, and salts thereof. Here, the bonding position of the hydroxyl group in the pyridinol to the pyridine ring is not particularly limited and may be 2, 3, or 4, but the 3rd position (3 pyridinol) and the 4th position (4 pyridinol) are preferred 4th position. Is particularly preferred. In addition, when the pyridinol derivative has a substituent at at least one of the remaining positions of the pyridinol ring, the substituent is not particularly limited, but an alkyl group, a halogenated alkyl group, an alkoxynole group, a halogenated alkoxyl. Group, hydroxyalkyl group, acylol group, phenyl group, amino group, anolenoquinamino group, alkylcarbonylamino group, alkoxycarbonyl group, alkylaminocarbonyl group, dimethylamino group, methylaminomethyl group, dimethylaminomethyl group, Examples thereof include hydroxyl group, carboxyl group, force rubamoyl group, piperidyl group, piperidinomethyl group, morpholino group, morpholinomethyl group, nitro group, cyano group and halogen atom. Among the above substituents, the same substituents as described above can be used for the substituents other than the hydroxyalkyl group. In addition, the hydroxyalkyl group is not particularly limited, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, a hydroxy n-propyl group, a hydroxyisopropyl group, a hydroxy-nbutyl group, etc. Among these, a hydroxymethyl group and A hydroxyethyl group is preferred. In this case, the bonding position of these substituents to the pyridinol ring is not particularly limited. For example, in the case of 4-pyridinol, the 2-position and the 6-position are preferable. In addition, when the pyridinol or pyridinol-substituted product has a salt form, the nitrogen atom of the pyridinol ring has a salt form. Specifically, the number of nitrogen nuclear carbon atoms of the pyridinol ring;! To 8 alkyls It is preferable to form a salt with the group (positively charged). At this time, it is more preferable that the nitrogen atom of the pyridinol ring forms a salt with a methyl group or an ethyl group. Of these pyridinol derivatives, pyridinol, more preferably 4 pyridinol, 2 methylpyridinol, especially 2 methynole 4 pyridinol is preferred, and 4 pyridinol is most preferred! /.

The imidazole derivatives include imidazole, imidazole-substituted products having a substituent at at least one of the 2, 4, and 5 positions of the imidazole ring, and salts thereof. When the imidazole derivative has a substituent at at least one of the 2, 4, and 5 positions of the imidazole ring, the substituent is not particularly limited, but is an alkyl group, a halogenated alkynole group, an alkoxyl group, a halogenated group. Alkoxyl group, hydroxyalkyl group, Sil group, phenyl group, amino group, anolenoquinamino group, alkylcarbonylamino group, alkoxycarbonyl group, alkylaminocarbonyl group, dimethylamino group, methylaminomethylol group, dimethylaminomethyl group, hydroxyl group, carboxyl Groups, rubamoyl groups, piperidyl groups, piperidinomethyl groups, morpholino groups, morpholinomethyl groups, nitro groups, cyan groups, groups, and rogen atoms. Since the substituent is the same as defined in the pyridinol derivative, description thereof is omitted here. Of the above substituents, an alkyl group, particularly a methyl group and an ethyl group are preferred. In this case, the bonding position of these substituents to the imidazole ring is not particularly limited. For example, the 2-position and the 4-position are preferred, but the 2-position is more preferred. In addition, when the imidazole or imidazole substitute has a salt form, the nitrogen atom at the 3-position of the imidazole ring forms a salt with an alkyl group having 8 to 8 carbon atoms, and is charged positively. Is preferred. At this time, it is more preferable that the nitrogen atom of the pyridinol ring forms a salt with a methyl group or an ethyl group. Of these imidazole derivatives, imidazole and 2-methylimidazole are preferred, and imidazole is particularly preferred.

The pyrazole derivatives include pyrazole, substituted pyrazoles having a substituent at at least one of the 3, 4, and 5 positions of the pyrazole ring, and salts thereof. In the case where the pyrazonole derivative has a substituent at at least one of the 3, 4, and 5 positions of the pyrazole ring, the substituent is not particularly limited, but is an alkyl group, a halogenated alkyl group, an alkoxyl group, a halogenated group. Alkoxyl group, hydroxyalkyl group, acyl group, phenyl group, amino group, anolenoquinamino group, alkylcarbonylamino group, alkoxycarbonyl group, alkylaminocarbonyl group, dimethylamino group, methylaminomethyl group, dimethyl group Examples include a ruaminomethyl group, a hydroxyl group, a carboxyl group, a strong rubamoyl group, a piperidyl group, a piperidinomethyl group, a morpholino group, a morpholinomethyl group, a nitro group, a cyano group, and a halogen atom. Since the substituent is the same as defined in the pyridinol derivative, description thereof is omitted here. Of the above substituents, an alkyl group, particularly a methyl group and an ethyl group are preferred. In this case, the bonding position of these substituents to the pyrazole ring is not particularly limited. For example, the 4-position and the 5-position are preferred, and the 4-position is more preferred. In addition, when a pyrazonol pyrazole substituent has a salt form, it can form a salt (positively charged) with an alkyl group having 2 to 8 nitrogen atoms in the pyrazole ring; Like Yes. At this time, the nitrogen atom of the pyrazole ring preferably forms a salt with a methyl group or an ethyl group. Of these pyrazole derivatives, pyrazole and 4-methylbiazole are preferred, and pyrazole is particularly preferred.

 [0075] In the present invention, any of pyridinol derivatives, imidazole derivatives and pyrazole derivatives may be reacted with the phthalocyanine compound (1). These may be used alone or in a mixture of two or more. It may be reacted with the phthalocyanine compound (1), or one or more of each derivative may be combined and reacted with the phthalocyanine compound (1). Preferably, the ability to react a pyridinol derivative and / or an imidazole derivative with a phthalocyanine compound (1).

 In the present invention, the reaction mixture ratio of the phthalocyanine compound (1) and the derivative is not particularly limited as long as it is a ratio in which the halogen atom in the phthalocyanine compound (1) is efficiently substituted with the derivative. Stoichiometrically, if one molecule is a derivative for one halogen atom in the phthalocyanine compound (1), the basic force derived from the above derivative at the position of the halogen atom in the phthalocyanine compound (1). Are introduced. Considering the mixed form of the phthalocyanine compound, which is the final product, the above derivative is 0.25 to 1 to 11 molecules of harm when the number of halogen atoms present in the phthalocyanine compound (1) is ¾. It is preferable to react with the phthalocyanine compound (1) in one group, and more preferably, when the number of halogen atoms present in the phthalocyanine compound (1) is ¾, 0 molecules, most preferably from 0.8; 1.0 molecules. In this case, “the above derivative reacts with the phthalocyanine compound (1) at a ratio of 0.25 x n to IX n molecules in the case of several halogen atoms present in the phthalocyanine compound (1). “Allows” means that the halogen atom present in the phthalocyanine compound (1) is 0.25 X i! ~ I X means reacting with η derivatives of the above. In such a mixing ratio, various groups derived from the above derivative are introduced into the position of the halogen atom of the phthalocyanine compound (1), and phthalocyanine compounds having different maximum absorption wavelengths depending on one production process are simultaneously produced. It can be produced in the form of a mixture.

[0077] The reaction between the phthalocyanine compound (1) and the derivative may be performed in the absence of a solvent or in an organic solvent, but is preferably performed in an organic solvent. The organic solvents that can be used at this time include benzene, toluene, xylene, nitrobenzene, monochrome benzene, dibenzene. Black benzene, Trichloro benzene, 1 chloronaphthalene, 1-methinolenaphthalene, benzonitrile, pyridine, N, N dimethylformamide, N, N dimethylacetamide, N-methyl 2-pyrrolidinone, N, N dimethylacetofu Enone, triethylamine, tri-n-butylamine, sulfolane, quinoline, methanol, ethanol, n-propanol, isoprono-norole, 1-butanol, 2-butanol, tert-butanol, 1-hexanol, 2-monohexanol , 3 hexanol, cyclohexanol, 2 methoxyethanol, 2 ethoxyethanol, 2- (2-methoxymethoxy) ethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, tetrahydrofuran, dioxane Aniso Examples include mononole, phenenole monole, 2-butanone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone or in the form of a mixture of two or more. Of these, 2-methoxyethanol, 2-ethoxyethanol, 2- (2-methoxymethoxy) ethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, dioxane are preferable. , Anisole, phenethyl alcohol, methyl isobutyl ketone, N, N dimethylacetamide and benzonitrile, more preferably 2-methoxyethanol, 2-ethoxyethanol, dioxane, anisole, methyl isobutyl ketone, Benzonitrile can be used, most preferably 2-methoxyethanol, anisole, and benzonitrile.

 [0078] The reaction between the phthalocyanine compound (1) and the derivative is preferably performed in the presence of a base. Thereby, the group derived from the derivative can be efficiently introduced at the position of the halogen atom in the phthalocyanine compound (1), and as a result, the solubility of the obtained phthalocyanine compound in the hydrophilic solvent and water can be improved.

[0079] The base used when the reaction between the phthalocyanine compound (1) and the derivative is carried out in the presence of a base, the group derived from the derivative is efficiently located at the position of the halogen atom in the phthalocyanine compound (1). There is no particular limitation as long as it can be introduced, but for example, potassium fluoride (KF), sodium fluoride (NaF), cesium fluoride (CsF), potassium carbonate (K CO)

 twenty three

, Sodium carbonate (Na CO), cesium carbonate (Cs CO), calcium carbonate (CaCO), water

 2 3 2 3 3 Calcium oxide (Ca (OH)), magnesium hydroxide (Mg (OH)), magnesium chloride (

 twenty two

MgCl), magnesium carbonate (MgC0), triethinoleamine, tri-n-propylamine, Jetyl-n-propylamine, tri-n-butylamine, tetramethylethylenediamine, tetraethylethylenediamine, N-methylbiperidine, N-ethylbiperidine, Nn-propylpiperidine, N, N-dimethylbiperidine, 1, 8- Diazabicyclo [5. 4. 0] u ndec— 7—ene, 1, 4— Diazabicyclo [2. 2. 2] octane, 1, 5—Diazabicyclo [4. 3. 0] non— 5— ene, salt Preferred examples include benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, and the like. Of these, potassium fluoride (KF), potassium carbonate, potassium carbonate, calcium carbonate, triethylamine, tri-n-propylamine, tetramethylethylenediamine, N-methylbiperidine, N-ethylbiperidine are more preferred. Potassium, calcium carbonate and N-methylbiperidine are particularly preferred. The above bases may be used alone or in the form of a mixture of two or more. The combination of bases in the latter case is not particularly limited as long as the group derived from the derivative can be efficiently introduced into the halogen atom in the phthalocyanine compound (1). Specifically, a combination with carbonate and N-alkylpiperidine is more preferable, a combination with calcium carbonate and N-methylbiperidine, and a combination with carbonated lithium and N-ethylbiperidine. A combination of calcium carbonate and N-methylpiperidine is particularly preferred. When two or more bases are used in the form of a mixture, each base may be dissolved / dispersed / suspended in the same solvent (preferably dissolved) or dissolved / dispersed / suspended in a different solvent ( It may be preferably dissolved) and subjected to a reaction between the phthalocyanine compound (1) and the above derivative. Furthermore, the amount of the base used in the above reaction is not particularly limited as long as the reaction between the phthalocyanine compound (1) and the above derivative can proceed efficiently, but is preferably 0.5 to 5 with respect to 1 mol of the derivative. 0 mol, more preferably 1.0 to 3.0 mol. With such an amount, the effect of improving the hydrophilicity / water solubility of the obtained phthalocyanine compound is the highest. In addition, the usage-amount of the said base means the total usage-amount of a base, when using combining 2 or more types of bases. Therefore, in the present invention, in the above formula (1), at least 12 of Z to Z are fluorine atoms.

 1 16

Or a phthalocyanine compound (1) representing a chlorine atom, in particular a fluorine atom, in the case where the derivative and the number of halogen atoms present in the phthalocyanine compound (1) are several. It is preferable to carry out the reaction with a harm of 8 11 1 molecules, particularly in the presence of potassium fluoride, potassium carbonate, potassium carbonate, N-methylbiperidine.

[0081] In the present invention, the reaction conditions of the phthalocyanine compound (1) and the derivative are not particularly limited as long as these reactions can sufficiently proceed. Preferably, the phthalocyanine compound (1) is reacted with the derivative at a temperature of 40 240 C, more preferably 60 200 C for 0.5-60 hours, more preferably 145 hours. The reaction may be performed under normal pressure, increased pressure, or reduced pressure, but is preferably performed at normal pressure.

[0082] In the present invention, in particular, when obtaining a phthalocyanine compound having a structure in which a derivative-derived group is introduced at the / 3-position of the phthalocyanine skeleton and an NHR ² substituent is introduced at the _α- position of the phthalocyanine skeleton. For example, after the reaction between the phthalocyanine compound (1) and the derivative, a reaction product of the phthalocyanine compound (1) and the derivative may be further reacted with the amine compound. In general, the α-position of the phthalocyanine skeleton is difficult to introduce a substituent compared to the / 3-position, and the amine compound is highly reactive, so the NHR ² substituent derived from the amine compound is Easily introduced into the phthalocyanine skeleton. For this reason, even after the phthalocyanine compound (1) is reacted with the derivative and the substituent derived from the derivative is previously introduced into the / 3-position, when reacted with the amine compound, the derivative derived from the amine compound is obtained. NHR ² substituents can be efficiently introduced into the α-position of the phthalocyanine skeleton. The reaction conditions between the reaction product of the phthalocyanine compound (1) and the derivative and the amine compound are the same as those described in the production of the phthalocyanine compound (1), and thus the description thereof is omitted here.

[0083] In the present invention, as described in detail below, an embodiment in which a quaternization reaction is further performed after the reaction between the phthalocyanine compound (1) and the derivative is also included in the present invention. In this case, either the reaction with the amine compound or the quaternization reaction may be performed, or both reactions may be performed. The order of the reaction with the amine compound and the quaternization reaction in the latter case is not particularly limited, and any order may be used, but after the reaction with the amine compound, the quaternization reaction is performed. Is preferred.

[0084] In the present invention, after the reaction between the phthalocyanine compound (1) and the derivative, further quaternization reaction is performed. May be performed. By such a quaternization reaction, the water solubility of the obtained phthalocyanine compound can be improved. The above effect is achieved particularly when an imidazole derivative is used. Although the mechanism of the quaternization reaction is not clear, for example, the mechanism of the quaternization reaction when imidazole is used is described below. However, the present invention is not limited by the following description. That is, after reacting the phthalocyanine compound (1) with imidazole, for example, when performing a quaternization reaction using methyl iodide, as shown in the following reaction formula, the nitrogen nuclear power at the 3-position of the imidazole ring is shown. It is considered to be in the form of a salt by combining with S methyl group.

[Chemical 8]

When a quaternization reaction is further performed after the reaction between the phthalocyanine compound (1) and the derivative, the quaternization reaction is appropriately selected depending on the structure of the salt of the resulting phthalocyanine compound. In addition to methyl chloride, acetyl chloride, n-propyl chloride, n-butyl chloride, n-pentyl chloride, n-hexyl chloride, methyl bromide, bromide tinol, n-propyl bromide, bromide n-butyl, n-pentyl bromide, n-hexyl bromide, iodinated tinole, iodinated n-propinole, iodinated n-butynole, iodinated n-pentinole, i-noxyhexyl iodide, etc .; ! ~ 8 using alkyl halide, jetyl sulfate, dimethyl sulfate, monochloroacetic acid, etc. Of these, methyl chloride, methyl chloride, methyl bromide, methyl bromide, methyl iodide, methyl iodide, and dimethyl sulfate are preferred. Methyl chloride, methyl bromide, methyl iodide, and dimethyl sulfate are more preferred. Particularly preferred is methyl iodide. At this time, the amount of the compound to be added is not particularly limited, but preferably 1 mol of the derivative present in the phthalocyanine compound obtained by the reaction between the phthalocyanine compound (1) and the derivative (approximately 1.0— 2.0 Monole, more preferably (1.1-1.1.5 Monole. With such an amount, the derivative present in the phthalocyanine compound is efficiently quaternized. The reaction may be carried out in the absence of a solvent or in an organic solvent, but it is preferred. Or in an organic solvent. Organic solvents that can be used at this time include alcohols such as methanol, ethanol, propanol, butanol, methoxyethanol, and ethoxyethanol; nitriles such as acetonitrile and benzonitrile; polar solvents such as acetone and 2-butanone; pyridine, N , N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, triethinoreamine, tri-n-butylamine, dimethyl sulfoxide, sulfolane, etc. Polar solvents and the like. Of these, methanol and ethanol are preferable, and methanol is particularly preferable. The amount of the organic solvent used when the solvent is used is such that the concentration of the reaction product of the phthalocyanine compound (1) and the derivative is usually 2 to 40 (w / v)%, preferably 10 to 30 (w / v ) The amount is%. The solvent used in the quaternization reaction may be the same as the solvent used in the reaction between the phthalocyanine compound (1) and the derivative, but may be different. The former case is preferred because the reaction can be carried out continuously as it is by simply adjusting the amount of the solvent if necessary without changing the solvent.

[0087] Further, the quaternization reaction conditions are not particularly limited as long as such quaternization can sufficiently proceed, but -10 to 100 ° C, more preferably 10 to 60 ° C. The quaternization reaction is preferably performed at a temperature of 0.5 to 24 hours, more preferably 1 to 6 hours. The quaternization reaction may be performed under normal pressure, increased pressure, or reduced pressure, but is preferably performed at normal pressure.

[0088] As described above, the phthalocyanine compound of the present invention is obtained by the reaction of the phthalocyanine compound (1) and the derivative. Since the phthalocyanine compound exhibits excellent hydrophilicity / water-solubility, it can be dissolved well in a lower alcohol such as methanol or ethanol or a hydrophilic solvent such as an aqueous solution thereof, and further in water. Various colors are shown to indicate the maximum absorption wavelength. Therefore, the phthalocyanine compound of the present invention is a color toner, inkjet ink, household inkjet ink, anti-counterfeiting barcode ink, goggles lens or shielding plate, dyeing agent for sorting when recycling plastic, light Recording media, photosensitive dyes for laser therapy, preheating aids during molding of PET bottles, photothermal exchange agents such as thermal transfer and thermal stencil, photothermal exchange agents for thermal rewritable recording, ID card Anti-counterfeit, plastic laser Various uses such as photothermal exchange agents, heat ray shielding agents, and near-infrared absorption filters for laser transmission welding (LTW), preferably inkjet inks, household inkjet inks, optical recording media, It can be suitably used for bar code ink for falsification prevention, goggle lenses and shielding plates, and photosensitive dyes for laser treatment, particularly ink jet ink.

 Therefore, the second aspect of the present invention relates to an ink-jet ink containing the phthalocyanine compound of the present invention. The second aspect of the present invention is characterized by the use of the phthalocyanine compound of the present invention, and other components such as other pigments and dispersants can be used in the same known manner. Components described in 08-337,745 and JP-A-2004-285,262 can be used.

 [0090] Examples

 Hereinafter, the present invention will be described in more detail with reference to examples.

 [0091] Synthesis Example 1: Synthesis of hexadecafluorozinc phthalocyanine

 100 ml four-necked flask ί こ Tetrafunole age 29, l lg (145. 45 mmol), Yowi Sya-ro, 12. 77 g (40 mmol) and Benzonitorinore 70 mL are added all at once, at 165 ° C Stir for 4 hours. After the reaction solution was cooled to room temperature, 700 mL of methanol and 210 mL of water were added to precipitate a solid content. This solid content was collected by filtration and dried under reduced pressure at 60 ° C. to obtain 31.09 g of hexadecafluorozinc phthalocyanine as a reaction product.

 [0092] Synthesis Example 2: Synthesis of hexadecafluorovanadyl phthalocyanine

 100 ml four-necked flask ί こ tetrafunole Loftaloni nitrore 29. l lg (145. 45 mmol), salt 匕 ノ nasium 6 29 g (40 mmol), otatano nore 5-2 g (40 mmol) 150 mL of tril was added all at once and stirred at 185 ° C for 9 hours. The reaction was cooled to room temperature. For the purification process! / When the same operation as that used for the synthesis of hexadecafluorochlorozinc phthalocyanine was performed, 29.20 g of hexadecafluorovanadyl phthalocyanine was obtained as a reaction product. .

 Synthesis Example 3: Synthesis of hexade strength fluorocopper phthalocyanine

In Synthesis Example 1 of hexadecafluorozinc phthalocyanine, the same operation was performed except that copper chloride was used instead of zinc iodide, and 22.16 g of hexadecafluorocopper Talocyanine was obtained as a target product.

[0093] Example 1: Reaction of hexadecafluorozinc phthalocyanine and 4-pyridinol (base: KF)

 In a 100 ml three-necked flask, hexanedecafluorozinc lid mouth prepared in Synthesis Example 1 1.73 g (2 mmol), 4 pyridinanol 3.65 g (38.4 mmol), and hot potato rhodium (KF) 2.23 g (38.4 mmol) and 30 mL of benzonitrile were added all at once and stirred at 190 ° C for 3 hours. After the reaction solution was cooled to room temperature, the precipitated solid was separated by filtration and washed with acetone. Next, this solid matter was dissolved in methanol, and acetone was added to precipitate the solid content again. This solid content was dissolved in 30 mL of methanol, passed through a basic Al 2 O column, and then the methanol was distilled off with an evaporator. Remaining solid

 twenty three

 When the portion was dried under reduced pressure at 60 ° C., 2.6 g of a reaction product was obtained.

[0094] The reaction product thus obtained was analyzed by liquid chromatography under the following conditions, and the results are shown in FIG. As is clear from FIG. 1, the reaction product obtained by the above reaction contains a plurality of phthalocyanine compounds!

[0095] <Liquid chromatography conditions>

 Column: Inertsil ODS2 (GL Science Inc.)

 Eluent: acetonitrile 20% + 0.1% phosphoric acid aqueous solution 80%

 Detection wavelength: 750nm

 Further, when the maximum absorption wavelength (λ) in water and methanol was measured for the above reaction products using a spectrophotometer (manufactured by Shimadzu Corporation: UV1650PC),

 max

 And 810 nm.

 [0096] Further, the solubility of the reaction product in water and methanol was measured (measurement temperature:

 As a result, the solubility in water and methanol both exceeded 30% by mass.

 [0097] Example 2: Reaction of hexadecafluorozinc phthalocyanine and 4-pyridinol (base: none)

To a 100 ml three-necked flask, 0.43 g (0.5 mmol) of hexadecafluorozinc lid mouth prepared in Synthesis Example 1, 4 .97 g (9.6 mmol) of 4 pyridinanol, and 7.5 mL of benzonitrile. Were added all at once and stirred at 190 ° C for 3 hours. This reaction solution is placed in the chamber. After cooling to temperature, the precipitated solid was filtered off and washed with acetone. Next, this solid was dissolved in methanol, and acetone was added to precipitate the solid again (performed twice). When the remaining solid was dried under reduced pressure at 60 ° C, 1. Og reaction product was obtained.

 [0098] For the reaction product thus obtained, the maximum absorption wavelength (λ) in water and methanol and the solubility in water and methanol were measured in the same manner as in Example 1.

 The results are shown in Table 1 below.

[0099] Example 3: Reaction of hexadecafluorozinc phthalocyanine and 4-pyridinol (base: K 2 CO 3)

 twenty three

In a 100 ml three-necked flask, hexadecafluorozinc lid mouth produced in Synthesis Example 1 0 · 43 g (0.5 mmol), 4 pyridinol 0 · 97 g (9.6 mmol), carbonated lithium 1.33 g (38 . 4 mmol) and, 30 mL stated emission zone, and projecting human collectively two Torinore, 190 ο ^(ί iron 5 hours, and stirred. dissolved after the reaction solution was cooled to room temperature, the precipitated solids in methanol The insoluble matter was filtered, and the filtrate was concentrated to obtain a solid, which was dissolved in methanol, and acetone was added to precipitate the solid again. Is dissolved in 10 mL of methanol and passed through a basic Al 2 O column.

 twenty three

 Methanol was distilled off. The remaining solid was dried at 60 ° C under reduced pressure to obtain 0.26 g of reaction product.

 [0100] For the reaction product thus obtained, the maximum absorption wavelength (λ) in water and methanol and the solubility in water and methanol were measured in the same manner as in Example 1.

 The results are shown in Table 1 below.

[0101] Example 4: Reaction of hexadecafluorovanadyl phthalocyanine with 4-pyridinol (base: KF)

 In Example 1, except that hexadecafluorovanadyl phthalocyanine prepared in Synthesis Example 2 was used instead of hexadecafluorozinc phthalocyanine, the same operation as in Example 1 was performed, and 1.30 g of reaction product was gotten.

[0102] For the reaction product thus obtained, the maximum absorption wavelength (λ) in water and methanol and the solubility in water and methanol were measured in the same manner as in Example 1. The results are shown in Table 1 below.

Example 5: Reaction of hexadefluorofluorofluorocopper phthalocyanine with 4-pyridinol (base: KF)

 In Example 1, the same procedure as in Example 1 was used, except that hexadecafluorozinc phthalocyanine prepared in Synthesis Example 3 was used instead of hexadecafluorozinc phthalocyanine, and 0.92 g of reaction product was obtained. Obtained.

[0104] For the reaction product thus obtained, the maximum absorption wavelength (λ) in water and methanol and the solubility in water and methanol were measured in the same manner as in Example 1.

 max

 The results are shown in Table 1 below.

[0105] Example 6: Reaction of hexadecafluorozinc phthalocyanine and imidazole (base: KF)

In a 100 ml three-necked flask, hexadecafluorozinc lid-opened cyanine 0 · 87 g (lmmol), imidazole 1.20 g (17.6 mmol), potassium fluoride 2.67 g (45.9 mmol) prepared in Synthesis Example 1 and , 10 mL stated emission zone, and projecting human collectively two Torinore, 190 ^o (between ί trowel 2 days temple, and stirred. after the reaction solution was cooled to room temperature, it added acetone, acetic Echiru, in sequence, precipitation The solid was then dissolved in isopropyl alcohol, and the solid was reprecipitated by adding ethyl acetate, which was dissolved in 15 mL of methanol and added to the base. After passing through a porous Al O column, methano

 twenty three

 One liter was distilled off. The remaining solid was dried under reduced pressure at room temperature, and 1.47 g of reaction product was obtained.

 [0106] For the reaction product thus obtained, the maximum absorption wavelength (λ) in water and methanol and the solubility in water and methanol were measured in the same manner as in Example 1.

 max

 The results are shown in Table 1 below.

[0107] Synthesis Example 4: Synthesis of 4- (3 methoxycarboylphenoxy) -1,5,6 trifluorophthalonitol

To a 25 ml three-necked flask, 15.01 g (75 mmol) of tetrafluorophthalonitrile, 75 g of potassium fluoride (41.3 mmol), and 50 mL of acetonitrile were added and stirred at 0 ° C. To this, 5.71 g (37.5 mmol) of 3 hydroxybenzoic acid methyl ester was added dropwise with 20 mL of acetonitrile nitrile, and the mixture was stirred for 2 hours. This reaction solution is filtered. And the resulting filtrate was concentrated. Methanol was added to the obtained concentrated liquid to precipitate a solid content. When this solid content was dried under reduced pressure at room temperature, 2.18 g of a reaction product was obtained.

Synthesis Example 5: 2, 6, 10, 14-Tetra (3 methoxycarbonylphenoxy) -1,3,4,5,7,8

, 9, 11, 12, 13, 15, 16 Synthesis of dodecafluorozinc phthalocyanine

 In a 100 ml three-necked flask, 4 1 (3 methoxycarbourephenoxy) -3, 5, 6 trifnoreo phthalonitrinore 2 · 12 g (6.4 mmol) prepared in Synthesis Example 4, 0 .

53 g (l. 65 mmol) and 5 mL of benzonitrile were added and stirred at 180 ° C for 2 hours.

. The reaction solution was cooled to room temperature and then poured into methanol to precipitate a solid content. This solid content was washed with a mixture of acetone and water and then dried under reduced pressure at 60 ° C. to obtain 1.7 g of a reaction product.

Example 7: 2, 6, 10, 14-tetra (3 methoxycarbonylphenoxy) -1,3,4,5,7,8

, 9, 11, 12, 13, 15, 16 Dodekahunore's reaction, reaction of phthalocyanine with 4-pyridinanol (base: KF)

 To a 100 ml three-necked flask, 2, 6, 10, 14-tetra (3 methoxy decanonolephenoxy) 1, 3, 4, 5, 7, 8, 9, 11, 12 produced in Synthesis Example 5 , 13, 15, 16 Dodecafnorre rosin zinc phthalocyanine 0 · 7 g (0.5 mmol), 4 pyridinol 0 · 68 g (7.2 mmol), potassium fluoride (KF) 0.42 g (7.2 mmol) and benzonitrinole 5 mL Were added all at once and stirred at 190 ° C for 10 hours. After cooling the reaction solution to room temperature, the precipitated solid was separated by filtration and washed with acetone. Next, this solid substance was dissolved in methanol, and acetone was added to precipitate the solid content again. This solid content was dissolved in 6 mL of methanol, passed through a basic Al 2 O column, and then the methanol was distilled off with an evaporator. The rest

 twenty three

 When the solid content was dried under reduced pressure at 60 ° C, 1.32 g of reaction product was obtained.

[0110] For the reaction product thus obtained, the maximum absorption wavelength (λ) in water and methanol and the solubility in water and methanol were measured in the same manner as in Example 1.

 max

 The results are shown in Table 1 below.

[0111] Example 8: Reaction of hexadecafluorozinc phthalocyanine with 4-pyridinol (base: N-methylbiperidine and calcium carbonate)

Into a 200 ml two-necked flask, the hexadecafluorozinc lid produced in Synthesis Example 1 4.33 g (5 mmol) of cyanine and 50 mL of anisole were added all at once, and the temperature was raised to 110 ° C. with stirring. To this was added dropwise a solution in which 9.13 g (96 mmol) of 4-pyridinol, 9.52 g (96 mmol) of N-methylbiperidine, 9.61 g (96 mmol) of canolesic carbonate and lOOmL of 2 methoxyethanol were added dropwise, and then stirred for 44 hours. did. The reaction solution was cooled to room temperature, the precipitated solid was filtered off, and the resulting filtrate was concentrated. The resulting concentrated solution was diluted with ethanol, and then acetone was added to precipitate a solid. After this solid content was dissolved in methanol, acetone was added to precipitate the solid content again. The obtained solid was dried under reduced pressure at 60 ° C. to obtain 5.51 g of a reaction product.

 [0112] For the reaction product thus obtained, the maximum absorption wavelength (λ) in water and methanol and the solubility in water and methanol were measured in the same manner as in Example 1.

 The results are shown in Table 1 below.

Example 9: Reaction of hexadecafluorozinc phthalocyanine with 4-pyridinol (base: N-methylbiperidine and calcium carbonate)

 Into a 200 ml two-necked flask, hexadecafluorozinc phthalate prepared in Synthesis Example 1 2.16 g (2.5 mmol), calcium carbonate 4.80 g (48 mmol), and 25 ml of methyloisobutyl ketone were added together and stirred. The temperature was raised to 115 ° C. To this was added dropwise a liquid mixture of 4-pyridinanol 4.56 g (48 mmol), N methenorepiperidine 4.76 g (48 mmol) and 2-methoxyethanol 50 mL, and then the mixture was stirred for 40 hours. The reaction solution was cooled to room temperature, the precipitated solid was filtered off, and the obtained filtrate was concentrated. The concentrated solution obtained was diluted with ethanol, and acetone was added to analyze the solid content. After this solid content was dissolved in methanol, acetone was added to precipitate the solid content again. The obtained solid content was dissolved in a mixed solvent of water and methanol, and then stirred for 30 minutes in the presence of calcium carbonate. Calcium carbonate was filtered off, and the resulting filtrate was concentrated to dryness. The obtained solid was dried under reduced pressure at 60 ° C, and 2.27 g of reaction product was obtained.

[0114] For the reaction product thus obtained, the maximum absorption wavelength (λ) in water and methanol and the solubility in water and methanol were measured in the same manner as in Example 1. The results are shown in Table 1 below.

[0115] Synthesis Example 6: Synthesis of 4- (2, 6 dimethylphenoxy) 3, 5, 6 trifluorophthalonitrile

 To a 25 ml three-necked flask, 15.01 g (75 mmol) of tetrafluorophthalonitrile, 75 g of potassium fluoride (41.3 mmol), and 50 mL of acetonitrile were added and stirred at 0 ° C. A solution prepared by dissolving 2,58 dimethylenophenol 4 · 58 g (37.5 mmol) in 20 mL of acetonitrile was added dropwise thereto, followed by stirring for 2 hours. The reaction solution was filtered, and the obtained filtrate was concentrated. Methanol was added to the obtained concentrated liquid to precipitate a solid content. When this solid content was dried under reduced pressure at room temperature, 11.3 g of a reaction product was obtained.

 [0116] Synthesis Example 7: 2, 6, 10, 14-tetra (2, 6 dimethylphenoxy) 1, 3, 4, 5, 7, 8, 9, 11, 12, 13, 15, 16 dodecafluorozinc phthalocyanine Synthesis of

 In a 100 ml three-necked flask, 4 (2, 6 dimethylphenoxy) 3, 5, 6 trifanolate Lofta Lutrinore 5 g (16.5 mmol) prepared in Synthesis Example 6, 0.82 g (4.26 mmol) and benzonitrile (10 mL) were added, and the mixture was stirred at 180 ° C. for 2 hours. After cooling this reaction liquid to room temperature, solid content was deposited by throwing it into methanol. This solid content was washed with a mixture of acetone and water, and then dried under reduced pressure at 60 ° C. to obtain 4.2 g of a reaction product.

 Example 10: 2, 6, 10, 14 Tetra (2, 6 dimethylphenoxy) 1, 3, 4, 5, 7, 8, 9, 1 1, 12, 13, 15, 16 Reaction of Loa t ^ phthalocyanine with 4-pyridinanol (base: KF)

In a 100 ml three-necked flask, 2, 6, 10, 14-tetra (2, 6-dimethylenophenoxy) 1, 3, 4, 5, 7, 8, 9, 11, 12, 13, 15, 16 Dodecafonore, Roth, Phthalocyanine lg (0.8 mmol), 4 Pyridinol 1.00 g (10.6 mmol), Lithium fluoride (KF) 0.62 g (10.6 mmol) and Benzonitrile 5 mL was added all at once and stirred at 190 ° C for 10 hours. After the reaction solution was cooled to room temperature, the precipitated solid was separated by filtration and washed with acetone. Next, this solid substance was dissolved in methanol, and acetone was added to precipitate the solid content again. This solid content was dissolved in 20 mL of methanol and passed through a basic Al 2 O column, and then methanol was distilled off with an evaporator. The remaining solid When the form was dried at 60 ° C under reduced pressure, 1.43 g of reaction product was obtained.

[0118] For the reaction product thus obtained, the maximum absorption wavelength (λ) in water and methanol and the solubility in water and methanol were measured in the same manner as in Example 1. Is shown in Table 1 below.

[0119] [Table 1]

 [0120] From Table 1 above, it is clear that the phthalocyanine compound according to the present invention exhibits good solubility in at least one of water and methanol.

 Industrial applicability

[0121] Since the phthalocyanine compound (including phthalocyanine mixture) according to the present invention is excellent in hydrophilicity / water solubility, color toner, inkjet ink, household inkjet ink, anti-counterfeit barcode ink, goggles Lenses, shielding plates, plastic dyes for sorting during recycling, optical recording media, photosensitive dyes for laser therapy, preheating aids during the molding of PET bottles, thermal transfer, thermal stencils, etc. Photothermal heat exchanger, heat-sensitive rewritable recording photothermal exchanger, ID card forgery prevention, plastic laser transmission welding (LTW: Laser Transmission Welding) photothermal exchanger, heat ray shielding agent, and near infrared absorption It can be suitably used for various applications such as filters, particularly ink jet ink. Furthermore, this application is based on Japanese Patent Application No. 2006-263 318 filed on Sep. 27, 2006, the disclosure of which is incorporated by reference and incorporated in its entirety.

Claims

Claim [1] Formula (1) below

 [Chemical 1]

In the formula, Z to Z are each independently a hydrogen atom, SR ¹ , NHR ² , OR ³ or halogen.

1 16

Atom, where ZR ² and

R ^{3 and} R ³ may each independently have a phenyl group which may have a substituent, may have a substituent, may have a V aralkyl group or a substituent! /, The number of carbon atoms; ~ 20 alkyl groups represented

R ² and R ³ may be the same or different from each other; M represents a metal-free, metal, metal oxide or metal halide,

 The phthalocyanine compound (1) represented by the formula is selected from the group consisting of pyridinol which may have a substituent, may have a substituent! /, Imidazole and may have a substituent, and pyrazole For producing a phthalocyanine compound having a reaction with at least one selected from the group

[2] At least one selected from the group consisting of pyridinol which may have a substituent, imidazole which may have a substituent and pyrazole which may have a substituent is the phthalocyanine compound (1 ) The number of halogen atoms present in ¾, 0.25 X n

The method according to claim 1, wherein the phthalocyanine compound (1) is reacted at a ratio of ˜1Χ η molecule.

[3] From the group consisting of the phthalocyanine compound (1), pyridinol which may have the substituent, may have a substituent! /, Imidazole, and may have a substituent, pyrazole. The method according to claim 1 or 2, wherein the reaction with at least one selected is performed in the presence of a base.

 [4] In the formula (1), at least 12 of Z to Z represent a fluorine atom or a chlorine atom,

 1 16

 And at least one selected from the group consisting of the above-mentioned substituent group, pyridinol, may have a substituent group! /, Imidazole, and optionally substituted pyrazole group, In the case of ¾ number of halogen atoms present in compound (1), 0.8 X i! ~

The method according to claim 1, wherein the phthalocyanine compound (1) is reacted at a ratio of 分子 η η molecule.

[5] From the group consisting of the phthalocyanine compound (1), pyridinol which may have the substituent, may have a substituent! /, Imidazole, and may have a substituent, pyrazole. The method according to any one of claims 1 to 4, further comprising performing a quaternization reaction after reacting with at least one selected from the reaction.

[6] Formula (1) below:

 [Chemical 2]

In the formula, Z to Z each independently represent a hydrogen atom, SR ¹ , NHR ² , OIT or halogen.

1 16

In which at least two of Z to Z represent halogen atoms; R ² and R ^{3 and} R ³ may each independently have a phenyl group which may have a substituent, may have a substituent, may have a V aralkyl group or a substituent! /, The number of carbon atoms; ~ 20 alkyl groups represented

R ² and may be the same or different; M represents a metal-free, metal, metal oxide or metal halide;

 The phthalocyanine compound (1) represented by the formula is selected from the group consisting of pyridinol which may have a substituent, may have a substituent! /, Imidazole and may have a substituent, and pyrazole A phthalocyanine compound produced by reacting with at least one of the above.

[7] The phthalocyanine compound according to claim 6, which is in the form of a mixture.

[8] An inkjet ink comprising the phthalocyanine compound produced by the method according to any one of claims 1 to 5, or the phthalocyanine compound according to claim 6 or 7.