JP4512543B2 - Method for producing metal phthalocyanine compound - Google Patents

Description

  The present invention relates to a novel method for producing a metal phthalocyanine compound. In particular, the present invention relates to a method for producing a metal phthalocyanine compound stably and in good yield under mild conditions.

Metal phthalocyanine compounds are compounds useful as materials for paints, printing inks, colorants, electrophotographic photoreceptors, and optical disks, and so far a great number of compounds have been synthesized and produced. The industrial production of metal phthalocyanine compounds is described in detail in Non-Patent Document 1. These methods are roughly classified into the following two types.
1) Weiler method: A method in which phthalic anhydride or phthalic anhydride imide is used as a raw material, and urea and a metal salt are reacted at 160 ° C. to 180 ° C. in the presence of a condensing agent. In the past, arsenic inorganic salts have been used as condensing agents, but recently, molybdates are generally used. In this method, there is a method that uses urea melt instead of a solvent as a solid phase method, but in addition to the risk of foaming and defects due to solidification when the temperature drops, the yield is low and the impurity ratio in the product is low. It is expensive and is not preferred as a mass production method.
On the other hand, the liquid phase method using an inert organic solvent such as nitrobenzene or polyhalogenated benzene tends to have a higher yield and more stable quality than the solid phase method. It is thought that it occupies the mainstream of the current industrial production method of phthalocyanine. However, on the other hand, this liquid phase method requires complicated unit operations such as separation and recovery of the reaction solvent. In addition, from the viewpoint of safety, nitrobenzene is toxic, and polyhalogenated benzene is a small amount of halogenated biphenyl. The selection of an appropriate high boiling point solvent is one of the problems in the industrial production of phthalocyanine.

2) Phthalonitrile method: This method uses highly reactive phthalonitrile as a starting material. In this method, a solid phase method or a baking method called a method of heating a mixture of phthalonitrile and a metal salt, using molten urea as a solvent, and a liquid phase method in which heat condensation is performed in a suitable high boiling point solvent. There is. In this case, quinoline and the like were sometimes used because of the condensation promoting action of the basic solvent, but at present, industrial use should be avoided from the viewpoint of safety. Moreover, it can be said that it is one of the problems like the liquid phase method of the Weiler method. Since the price of phthalonitrile is approximately 10 times that of phthalic anhydride, there is a disadvantage that it is considerably higher than that of the Weiler method in consideration of the raw material cost by this method. However, in the production of functional phthalocyanines having high added value in recent years, this method is an optimum method if importance is attached to various merits in the manufacturing method even if the terminal price as a product is taken into consideration.
Patent Document 1 discloses a reaction condition relaxation method using a base in the present phthalonitrile method. For example, when phthalonitrile and cuprous chloride in ethylene glycol are reacted at a temperature of about 100 ° C. under bubbling of ammonia, copper phthalocyanine is obtained in a high yield. Moreover, various phthalocyanines are industrially produced by using a high boiling point amine such as a secondary or tertiary amine as a condensing agent instead of ammonia as a base. Patent Document 2 discloses a general industrial production method of metal-free phthalocyanine. In addition to alcoholates as condensing agents, amines are high-boiling amines such as tributylamine, diazabicycloundecene and diazobicyclononene. Uses.

However, when a relatively strong base such as these is used, decomposition occurs depending on phthalonitrile, and the yield of the desired phthalocyanine compound is deteriorated. For example, phthalonitrile substituted with an electron-withdrawing group does not improve the condensation rate of the metal phthalocyanine compound because the target condensation reaction and the decomposition of the phthalonitrile by the attack of a nucleophilic agent such as a hydroxide ion occur in concert. In addition, in the production of metal phthalocyanine compounds using metal chloride, hydrochloric acid is generated as the condensation progresses, which inhibits the attack of the nucleophilic species that act as a catalyst for the condensation. The reaction will eventually stop even if remains. In this case, it is difficult to isolate only the target product from the reaction mixture by a recrystallization or reprecipitation method suitable for production, and a purification method with poor productivity such as column chromatography is required. For this reason, the manufacturing process is lengthened, which has the disadvantage that it leads to high costs from an industrial point of view.
Further, Patent Document 3 well-known is a method in which a reaction is performed in the presence of a strong base such as DBU with a high-boiling alcohol (n-butanol or the like) solvent, or Patent Document 4 is a method using a metal alkoxide. However, since the reaction system becomes strongly basic, a substrate having a substituent that easily decomposes under basic conditions cannot be used. In addition, the reaction substrate may be decomposed by moisture contained in the reaction substrate or the solvent, and the yield may be significantly reduced.
Patent Document 5 also discloses a method of performing a reaction in the presence of a dehydrating agent, and Patent Document 6 discloses a method of performing a reaction in the presence of an acid having a pKa of 7.0 or less in combination with a metal oxide. However, although the yield is improved by the use of these, the actual situation is that the level has not reached a satisfactory level. Patent Document 7 discloses a method for producing a phthalocyanine compound in the presence of an alkaline earth metal compound, but has a problem in terms of yield and purity.
In order to solve the above problems, Patent Document 8 discloses a rational production method with greatly improved reactivity and purity. However, further improvement in yield and operability on the production scale (reactions) Time shortening, crystallization, filterability, etc.) Improvement methods have been desired.
Shirai Yasuyoshi and Kobayashi Nagao, "Phthalocyanine -Chemistry and Function-", IPC Corporation (1997) JP 49-49759 A Japanese Patent No. 2520476 JP-A-11-269399 Japanese Patent Laid-Open No. 11-209380 JP-A-11-116835 Japanese Patent Laid-Open No. 11-263919 JP 2000-169743 A JP 2005-41856 A

  An object of the present invention is to solve the above-described conventional problems relating to the method for producing a metal phthalocyanine compound and to achieve the following object. That is, an object of the present invention is to produce a metal phthalocyanine compound by heating and reacting at least two selected from the compounds A to F represented by the general formula (I) with a metal compound in the presence of a dehydrating agent. An object of the present invention is to provide a method for producing a metal phthalocyanine compound which is industrially stable and has high yield, high purity and good operability.

As a result of detailed examination of a production method that gives a high reaction yield under mild conditions, the present inventors have found that the above-mentioned problems can be solved by conducting the reaction in a buffer solution in the presence of a dehydrating agent. The invention has been completed. That is, according to the present invention, a manufacturing method having the following configuration can be provided, and the above object has been achieved.
1. A method for producing a metal phthalocyanine compound from at least two compounds selected from the compounds represented by the following general formula (I) (compound A to compound F) and a metal compound, wherein an organic base is used in the presence of a dehydrating agent. Or it is a manufacturing method of the metal phthalocyanine compound characterized by reacting in the buffer solution of an inorganic base and an acid.
Formula (I)

In general formula (I), R represents a hydrogen atom or a substituent. l represents an integer of 0 to 4. When l is 2 to 4, a plurality of R may be the same as or different from each other. G represents an atomic group constituting a 5- or 6-membered aromatic ring and / or hetero ring.

2. 2. The metal phthalocyanine according to 1 above, wherein the compounds represented by the general formula (I) (compounds A to F) are compounds (compounds G to L) represented by the following general formula (II): It is a manufacturing method of a compound.
Formula (II)

In general formula (II), a and b each independently represent a substituent, and the sum of Hammett's substituent constant σp values is 0.20 or more. m and n represent integers satisfying 0 ≦ m ≦ 4, 0 ≦ n ≦ 3, and 0 ≦ m + n ≦ 4. G represents an atomic group constituting a 5- or 6-membered aromatic ring and / or hetero ring.

3. 3. The compound represented by the general formula (II) (compounds G to L) is a compound (compound M to compound Q) represented by the following general formula (III): It is a manufacturing method of a metal phthalocyanine compound.
General formula (III)

In the general formula (III), a ₁ is independently a sulfinyl group, a sulfonyl group, a sulfamoyl group, an acyl group, or an carbamoyl group, which may have a substituent. m ₁ represents an integer of 0 to 2. G represents an atomic group constituting a 5- or 6-membered aromatic ring and / or hetero ring.

4). Any of the above 1 to 3, wherein the compound represented by the general formula (III) (compound M to compound Q) is a compound represented by the following general formula (IV) (compound R to compound S) A method for producing the metal phthalocyanine compound according to claim 1.
Formula (IV)

In general formula (IV), a ₁ each independently represents any of a sulfinyl group, a sulfonyl group, a sulfamoyl group, an acyl group, and a carbamoyl group, and may have a substituent. m ₁ represents an integer of 0 to 2. G represents an atomic group constituting a 6-membered nitrogen-containing heterocycle.

5). 5. The method for producing a metal phthalocyanine compound according to any one of 1 to 4 above, wherein at least one selected from glycerin and a compound represented by the following general formula (V) is used as a reaction solvent. .
General formula (V)

However, s and t each independently represent a positive integer. X represents a hydrogen atom or a methyl group.

6). 6. The metal phthalocyanine compound according to any one of 1 to 5 above, wherein the dehydrating agent is selected from an acetal compound, an ortho ester compound, an alkenyl ether compound, an alkenyl ester compound, an epoxide compound, and an oxetane compound. It is a manufacturing method.

7). 7. The method for producing a metal phthalocyanine compound according to any one of 1 to 6 above, wherein the base is at least one selected from alkali metal salts, ammonium salts and tertiary amine salts of carboxylic acids. It is.

8). 7. The method for producing a metal phthalocyanine compound according to any one of 1 to 6 above, wherein the base is at least one selected from compounds represented by the following general formula (VI).
General formula (VI)

Represents in the general formula (VI), Y _1, Y ₂ and Y ₃ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, Y ₁ , Y ₂ and Y ₃ may be combined to form a condensed ring organic base. Each group may further have a substituent.

  According to the method of the present invention, a high-yield, high-purity, metal phthalocyanine compound can be produced with good operability in an industrially stable manner.

Details of the present invention will be described below.
First, the compound represented by formula (I) will be described.
In the general formula (I), R represents a hydrogen atom or a substituent. Specific examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group (a linear or branched substituent). Or an unsubstituted alkyl group, preferably having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl. , 3- (2,4-di-t-amylphenoxy) propyl), an aralkyl group (preferably a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms such as benzyl, phenethyl), a cycloalkyl group (preferably carbon A substituted or unsubstituted cycloalkyl group having a number of 3 to 30, for example, cyclohexyl, cyclopentyl, 4-n-dodo Decylcyclohexyl), alkenyl groups (straight or branched substituted or unsubstituted alkenyl groups, preferably having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably C3-C30 substituted or unsubstituted cycloalkenyl group such as 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), alkynyl group (straight or branched substituted or unsubstituted alkynyl group) And preferably having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group [preferably 5 A 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atoms are carbon atoms, nitrogen atoms, oxygen atoms and A heterocyclic group selected from sulfur atoms and having at least one hetero atom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered aromatic heterocycle having 3 to 30 carbon atoms Cyclic groups (eg 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), and even 4 A heterocyclic group containing a substituted nitrogen atom (for example, a pyridinio group, an imidazolio group, a quinolinio group, or an isoquinolinio group), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms) , A substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an alkoxycarbonyl group (preferably, A substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), aryloxycarbonyl group (preferably a 7 to 30 carbon atom substitution) Or leave Aryloxycarbonyl group of, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), carbamoyl group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) A carbamoyl group such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), a carboxy group or a salt thereof, a sulfonylcarbamoyl group (preferably Is a substituted or unsubstituted sulfonylcarbamoyl group having 2 to 30 carbon atoms, such as methanesulfonylcarbamoyl, octanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), an acylcarbamoyl group (preferably having a carbon number) 2-30 acylcarbamoyl groups such as formylcarbamoyl, methylcarbamoyl, phenylcarbamoyl), sulfamoylcarbamoyl groups (preferably sulfamoylcarbamoyl groups having 1 to 30 carbon atoms such as methylsulfamoylcarbamoyl, Phenylsulfamoylcarbamoyl), a carbazoyl group (preferably a carbazoyl group having 1 to 30 carbon atoms, such as carbazoyl, 3-ethylcarbazoyl, 3,3-dimethylcarbazoyl, 2-ethyl-3-phenylcarbazoyl) An oxalyl group (preferably an oxalyl group having 2 to 30 carbon atoms, for example, methyl oxalyl, phenyl oxalyl, ethoxy oxalyl, phenoxy oxalyl), an oxamoyl group (preferably an oxamoyl group having 2 to 30 carbon atoms, for example, Xamoyl, N-ethyloxamoyl, N-phenyloxamoyl, N, N-diethyloxamoyl), cyano group, thiocarbamoyl group (preferably a thiocarbamoyl group having 1 to 30 carbon atoms such as thiocarbamoyl, N- Ethylthiocarbamoyl, N-phenylthiocarbamoyl),

A hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit, preferably an alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, octyloxy, hexadecyloxy), aryloxy group (Preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenyloxy, naphthyloxy), a heterocyclic oxy group (a heterocyclic oxy group of the aforementioned heterocyclic group is preferable, for example, pyridyloxy , Imidayloxy, piperidyloxy), acyloxy groups (preferably acyloxy groups having 1 to 30 carbon atoms, such as formyloxy, acetyloxy, benzoyloxy), (alkoxy or aryloxy) carbonyloxy groups (preferably carbon Number 1-30 Xyloxycarbonyloxy or aryloxycarbonyloxy group having 6 to 30 carbon atoms, for example, methoxycarbonyloxy, phenoxycarbonyloxy), carbamoyloxy group (preferably carbamoyloxy group having 1 to 30 carbon atoms, carbamoyloxy, ethylcarbamoyl) Oxy, phenylcarbamoyloxy), a sulfonyloxy group (preferably a sulfonyloxy group having 2 to 30 carbon atoms, such as methanesulfonyloxy, benzenesulfonyloxy), an amino group, an (alkyl, aryl, or heterocyclic) amino group [ (Preferably alkyl having 1 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, heterocyclic ring in the aforementioned heterocyclic group) Amino group is preferable, for example, methylamino, diethylamino, phenylamino, pyridylamino An acylamino group (preferably an acylamino group having 1 to 30 carbon atoms, such as formylamino, acetylamino, benzoylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 30 carbon atoms, such as ethanesulfonamide, benzene Sulfoneamide), ureido group (preferably a ureido group having 1 to 30 carbon atoms, for example, ureido, methylureido, phenylureido), thioureido group (preferably a thioureido group having 1 to 30 carbon atoms, for example, methylthioureido, phenyl Thioureido), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms such as N-succinimide and N-phthalimide), (alkoxy or aryloxy) carbonylamino group (preferably having 2 carbon atoms) ~ 30 alkoxycals Bonylamino or aryloxycarbonylamino group having 7 to 30 carbon atoms, such as methoxycarbonylamino, phenoxycarbonylamino), sulfamoylamino group (preferably sulfamoylamino group having 1 to 30 carbon atoms, such as methane Sulfamoylamino, benzenesulfamoylamino), semicarbazide group (preferably a semicarbazide group having 1 to 30 carbon atoms, such as semicarbazide, N-ethylsemicarbazide, N-phenylsemicarbazide), thiosemicarbazide group (preferably carbon number) 1-30 thiosemicarbazide groups such as thiosemicarbazide, N-butylthiosemicarbazide, N-phenylthiosemicarbazide, hydrazino groups (preferably 1-30 hydrazino groups such as hydrazino, Ruhydrazino, phenylhydrazino), ammonio group, oxamoylamino group (preferably an oxamoylamino group having 2 to 30 carbon atoms, for example, oxamoyl, ethyloxamoyl, phenyloxamoyl), (alkyl or aryl) sulfonylureido group (Preferably an alkylsulfonylureido group having 2 to 30 carbon atoms or an arylsulfonylureido group having 7 to 30 carbon atoms, such as methanesulfonylureido or benzenesulfonylureido), acylureido group (preferably an acylureido group having 2 to 30 carbon atoms) For example, formylureido, acetylureido, benzoylureido), acylsulfamoylamino group (preferably an acylsulfamoylamino group having 1 to 30 carbon atoms such as acetylsulfamoylamino, Down benzoyl sulfamoylamino),

A nitro group, a mercapto group, an (alkyl, aryl or heterocyclic) thio group (preferably an alkyl having 1 to 30 carbon atoms, an aryl having 6 to 30 carbon atoms, a heterocyclic ring in the aforementioned heterocyclic group) thio group, , Methylthio, phenylthio, pyridylthio], (alkyl, aryl or heterocyclic) sulfonyl group [(preferably alkyl having 1 to 30 carbons, aryl having 6 to 30 carbons, heterocyclic in the above heterocyclic group) sulfonyl group , For example, methylsulfonyl, phenylsulfonyl, pyridylsulfonyl], (alkyl, aryl or heterocyclic) sulfinyl group [(preferably alkyl having 1 to 30 carbons, aryl having 6 to 30 carbons, heterocycle in the above heterocyclic group] Ring) sulfinyl group, for example, methylsulfinyl, phenylsulfinyl , Pyridylsulfinyl], a sulfo group or a salt thereof, a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms, such as sulfamoyl, ethanesulfamoyl, benzenesulfamoyl), an acylsulfamoyl group (preferably An acylsulfamoyl group having 1 to 30 carbon atoms, such as formylsulfamoyl, acetylsulfamoyl, benzoylsulfamoyl), a sulfonylsulfamoyl group or a salt thereof (preferably having 0 to 30 carbon atoms, Groups containing methanesulfonylsulfamoyl, benzenesulfonylsulfamoyl), phosphoric acid amide or phosphoric acid ester structures (preferably having 0 to 30 carbon atoms such as phosphoric acid amide, methylphosphoric acid amide, phenylphosphoric acid amide, ethoxyphosphorus) Acid amide, phenoxyphosphate ), A silyloxy group (preferably a silyloxy group having 1 to 30 carbon atoms such as trimethylsilyloxy, t-butyldimethylsilyloxy), a silyl group (preferably a silyl group having 1 to 30 carbon atoms such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl) and the like.

  When R is a substituent, preferably a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, oxalyl group, oxamoyl group , Cyano group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, sulfonyloxy group, (alkyl, aryl or heterocyclic) amino group, acylamino group, sulfonamide group, mercapto group, (alkyl, aryl or hetero Rings) thio groups, (alkyl, aryl or heterocyclic) sulfonyl groups, (alkyl, aryl or heterocyclic) sulfinyl groups, sulfo groups or salts thereof, sulfamoyl groups, groups containing phosphoric acid amides or phosphoric ester structures are used. . More preferably, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, a carboxy group or a salt thereof, an oxamoyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, (alkyl, aryl or heterocyclic ring) ) Amino group, acylamino group, sulfonamido group, (alkyl, aryl or heterocycle) thio group, (alkyl, aryl or heterocycle) sulfonyl group, (alkyl, aryl or heterocycle) sulfinyl group, sulfo group or a salt thereof, Sulfamoyl groups are used. More preferably, a halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, carbamoyl group, oxamoyl group, alkoxy group, aryloxy group, heterocyclic oxy group, (alkyl, aryl or heterocyclic) amino group, acylamino group , Sulfonamido group, (alkyl, aryl or heterocycle) thio group, (alkyl, aryl or heterocycle) sulfonyl group and sulfamoyl group are used.

  When R is a substituent, particularly preferred are a halogen atom, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, and a sulfonyl group, and more preferred are a carbamoyl group, a sulfamoyl group, a sulfinyl group, and a sulfonyl group. A sulfamoyl group and a sulfonyl group are particularly preferable, and a sulfonyl group is most preferable.

  The substituent represented by R may be further substituted. Such a substituted substituent includes a substituent substituted with any substituent, and preferably a substituent substituted with an ionic hydrophilic group. Specifically, it is also preferable that it is substituted with an ionic hydrophilic group such as a carboxyl group, a sulfo group, a phosphate group, a group having a quaternary salt structure of nitrogen, or a quaternary salt structure of phosphorus.

When the ionic hydrophilic group has a carboxyl group, a sulfo group, or a phosphate group, these groups may have a counter cation as necessary. A group having a quaternary salt structure or a group having a quaternary salt structure of phosphorus is used.
When the ionic hydrophilic group has a group having a quaternary salt structure of nitrogen or a quaternary salt structure of phosphorus, it may have a counter anion as necessary. Ions, sulfate ions, nitrate ions, phosphate ions, oxalate ions, alkanesulfonate ions, arylsulfonate ions, alkanecarboxylate ions, arylcarboxylate ions, and the like can be used.
The ionic hydrophilic group is preferably a carboxyl group, a sulfo group or a phosphate group, more preferably a carboxyl group or a sulfo group. In this case, Li, Na, K, and NH ₄ cations are preferably used as counter cations, more preferably Li and Na cations, and particularly preferably Li cations.

A particularly preferred counter cation of the phthalocyanine compound of the present invention is lithium ion. The counter cations may not be all lithium ions, but it is preferable that the counter cations having the highest abundance ratio are lithium ions.
Under such conditions, hydrogen ions, alkali metal ions (for example, sodium ions, potassium ions), alkaline earth metal ions (for example, magnesium ions, calcium ions, etc.), quaternary ammonium ions, quaternary phosphoniums Ions, sulfonium ions, and the like can be included as counter cations.
Regarding the types and ratios of the counter cation of the phthalocyanine compound, the Chemical Society of Japan “New Experimental Chemistry Course 9 Analytical Chemistry” (1977 Maruzen) and the Chemical Society of Japan “4th edition Experimental Chemistry Course 15 Analysis” (1991 Maruzen) ) Describes various theories about analysis methods and elements, so that analysis methods can be selected, analyzed and quantified by referring to them. In particular, it is easy to determine by an analytical method such as ion chromatography, atomic absorption, inductively coupled plasma emission spectrometry (ICP).
The amount of lithium ions in the phthalocyanine compound is preferably 50% or more, preferably 60% or more, more preferably 80% or more, and particularly preferably 90% or more with respect to the total counter ion. 100% is preferred.
When R is a group having a carbon atom, the total number of carbon atoms is preferably 1 to 100, more preferably 1 to 80, still more preferably 1 to 50, and particularly preferably 1 to 20. .

  l represents an integer of 0 to 4. Preferably l is 1-3, more preferably 1 or 2. When l is 2 to 4, a plurality of Rs exist. In this case, a plurality of Rs may be the same or different.

In the case of producing a phthalocyanine compound from the compound represented by the general formula (I), a stoichiometric amount of four compounds of the compound represented by the general formula (I) is required to produce one molecule of the phthalocyanine compound. is necessary.
Here, the compounds represented by the general formula (I) do not have to be the same for all four necessary molecules, and a plurality of types of compounds represented by the general formula (I) having different R are used in an arbitrary ratio. In the present invention, it is particularly preferable that at least two different Rs are present in four molecules of the compound represented by the general formula (I).

  When a plurality of types of compounds represented by the general formula (I) having different R are used in an arbitrary ratio, they may be selected from the compound A group represented by the general formula (I) of the present invention at an arbitrary ratio. It may be selected at any ratio from the compound A group to the compound F group, and preferably selected from the compound A group represented by the general formula (I) at an arbitrary ratio. It is more preferable for the purpose of managing a mixed distribution of R which is arbitrarily different during the production of the phthalocyanine compound.

The mixing ratio in the case where a plurality of types of compounds represented by formula (I) having different R are used in an arbitrary ratio has no upper limit to lower limit for the corresponding phthalocyanine compound, but more preferably the phthalocyanine compound. In this case, the four molecules of the compound represented by the general formula (I) necessary for the production of are used in the following ratio.
(1) When there are two different Rs: (R1 + R2 = 4)
R1: R2 = 0.01 to 3.99 (eq / eq): 3.99 to 0.01 (eq / eq)
(2) When there are three different Rs: (R1 + R2 + R3 = 4)
R1 = 0.01 to 3.98 (eq)
R2 = 0.01 to 3.98 (eq)
R3 = 0.01 to 3.98 (eq)
It can be arbitrarily selected from the minimum value to the maximum value of R1 to R3 that satisfy (R1 + R2 + R3 = 4).
(3) When there are four different Rs, each independently:
R1 = 0.01 to 3.97 (eq)
R2 = 0.01 to 3.97 (eq)
R3 = 0.01 to 3.97 (eq)
R4 = 0.01 to 3.97 (eq)
It can be arbitrarily selected from the minimum value to the maximum value of R1 to R3 that satisfy (R1 + R2 + R3 + R4 = 4).
The substitution position of R in the compound of the general formula (I) may be any position as long as substitution is possible, but it is preferably substituted at the 4-position or 5-position.

G in the compound represented by the general formula (I) represents a 5- or 6-membered aromatic ring and / or an atomic group constituting a heterocycle, preferably a 6-membered aromatic ring or a 6-membered nitrogen-containing heterocycle. Among them, a 6-membered aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring and a pyridazine ring are preferable, a 6-membered aromatic ring and a pyridine ring are particularly preferable, and a 6-membered aromatic ring is most preferable.
Among the compounds A to F represented by the general formula (I), the compound A, the compound B and the compound F are preferable, the compound A and the compound B are more preferable, and the compound A is particularly preferable.
Regarding the preferred combination of substituents of the compound represented by the general formula (I) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

Preferred combinations of the compounds represented by the general formula (I) of the present invention include the following (a) to (f).
(I) R represents a hydrogen atom or a substituent. Examples of preferable substituents are a halogen atom, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, and a sulfonyl group, and more preferably a carbamoyl group, a sulfamoyl group, a sulfinyl group, and a sulfonyl group, and among them, a sulfamoyl group, A sulfonyl group is particularly preferred, and a sulfonyl group is most preferred.
The substituent represented by R may be further substituted, and such a substituted substituent is preferably a substituent substituted with an ionic hydrophilic group.
Specifically, it is preferably substituted with a hydrophilic group such as a carboxyl group, a sulfo group, a phosphate group, a group having a quaternary salt structure of nitrogen, or a quaternary salt structure of phosphorus. Group is preferable, and among them, a sulfo group is most preferable.

When the ionic hydrophilic group has a carboxyl group, a sulfo group, or a phosphate group, these groups may have a counter cation as necessary. A group having a quaternary salt structure or a group having a quaternary salt structure of phosphorus is preferable, and a cation of Li, Na, K, or NH ₄ is preferable, and a cation of Li or Na is more preferable. A cation of Li is preferred.
The amount of the lithium ion is preferably 50% or more, preferably 60% or more, more preferably 80% or more, particularly preferably 90% or more, and the upper limit is 100% with respect to the total counter ion. preferable.

(B) G is preferably a 6-membered aromatic ring or a 6-membered nitrogen-containing heterocycle, and among them, a 6-membered aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring is preferable, and a 6-membered aromatic ring or pyridine Rings are particularly preferred and 6-membered aromatic rings are most preferred.
(C) l represents an integer of 0 to 4. Desirable l represents an integer of 0 to 3, more preferably 0 to 2, and most preferably l = 0 to 1. When l is 2 to 4, a plurality of R may be the same as or different from each other.
(D) The substitution position of R in the compound of the general formula (I) may be any position as long as it can be substituted, but it is preferably substituted at the 4-position or 5-position.

(E) Among the compounds A to F represented by the general formula (I), the compound A, the compound B and the compound F are preferable, the compound A and the compound B are more preferable, and the compound A is particularly preferable.

(F) When a plurality of types of compounds represented by the general formula (I) having different R are used at an arbitrary ratio, they are selected at an arbitrary ratio from the compound A group represented by the general formula (I) of the present invention. Alternatively, it may be selected at any ratio from the compound A group to the compound F group, and preferably selected from the compound A group represented by the general formula (I) at any ratio. Is more preferable for the purpose of managing a mixed distribution of R which is arbitrarily different during the production of the phthalocyanine compound.
Among the compounds A to F represented by the general formula (I), the compounds G to L represented by the general formula (II) are particularly preferable.

Next, the compound represented by formula (II) will be described.
In the compounds G to L represented by the general formula (II), a and b each independently represent a substituent, and the sum of the Hammett's substituent constants σp value is 0.20 or more. m and n represent integers satisfying 0 ≦ m ≦ 4, 0 ≦ n ≦ 3, and 0 ≦ m + n ≦ 4. G represents an atomic group constituting a 5- or 6-membered aromatic ring and / or hetero ring.
Here, in this specification, for example, in the general formula (II), Hammett's substituent constant σp value used will be described. Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. For example, JADean ed., “Lange's Handbook of Chemistry”, No. 12 Edition, 1979 (Mc Graw-Hill), “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it can be found in the above-mentioned book and is limited only to a substituent having a known value in the literature. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule. Further, the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value is used in this sense.
Preferred substituents represented by a and / or b in the compounds G to L represented by the general formula (II) are a halogen atom, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, and a sulfonyl group, and more preferably Is a carbamoyl group, a sulfamoyl group, a sulfinyl group, or a sulfonyl group. Among them, a sulfamoyl group or a sulfonyl group is particularly preferable, and a sulfonyl group is most preferable.
These groups preferably further have a substituent such as an ionic hydrophilic group and / or an alkyl group or an aryl group having the ionic hydrophilic group as a substituent.
Examples of the ionic hydrophilic group as a substituent in the general formula (II) are the same as the ionic hydrophilic group described in the general formula (I), and preferred examples are also the same.

G in the general formula (II) has the same meaning as G described in the general formula (I), and preferred examples thereof are also the same.
M in the general formula (II) represents an integer of 0 to 4, preferably 0 to 2, more preferably 1 or 2, and most preferably m = 1.
N in the general formula (II) represents an integer of 0 to 3, preferably 0 to 2, preferably 0 to 1, and most preferably n = 0.
Among the compounds G to L represented by the general formula (II), the compound G, the compound H and the compound L are preferable, the compound G and the compound H are more preferable, and the compound G is particularly preferable.

At least two compounds of the compound represented by the general formula (II) (compound G to compound L) may be selected from the compound G group represented by the general formula (II) of the present invention at any ratio. The phthalocyanine compound may be selected from the compound G group to the compound L group at an arbitrary ratio, and preferably selected from the compound G group represented by the general formula (II) at an arbitrary ratio. It is more preferable for the purpose of managing the distribution of arbitrarily mixed dyes at the time of production.
Regarding the preferred combination of substituents of the compound represented by the general formula (II) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

Preferred combinations of the compounds represented by the general formula (II) of the present invention include the following (A) to (G).
(A) Examples of preferable substituents represented by a or b are a halogen atom, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, and a sulfonyl group, and more preferably a carbamoyl group, a sulfamoyl group, a sulfinyl group, and a sulfonyl group. Among them, a sulfamoyl group and a sulfonyl group are particularly preferable, and a sulfonyl group is most preferable.
The substituent represented by a or b may be further substituted, and such a substituted substituent is preferably a substituent substituted with an ionic hydrophilic group.
The example of an ionic hydrophilic group is synonymous with the ionic hydrophilic group demonstrated in the said general formula (I), and its preferable example is also the same.
(B) G is preferably a 6-membered aromatic ring or a 6-membered nitrogen-containing heterocycle, and among them, a 6-membered aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring is preferable, and a 6-membered aromatic ring or pyridine Rings are particularly preferred and 6-membered aromatic rings are most preferred.
(C) m represents an integer of 0 to 4, preferably 0 to 2, more preferably 1 or 2, and most preferably m = 1.
(D) n represents an integer of 0 to 3, preferably 0 to 2, more preferably 0 to 1, and most preferably n = 0.
(E) The substitution position of a or b in the compound of the general formula (II) may be any position as long as it can be substituted, but it is preferably substituted at the 4-position or 5-position.
(F) Among compound G to compound L, compound G, compound H and compound L are preferable, compound G and compound H are more preferable, and compound G is particularly preferable.
(G) At least two compounds of the compound represented by the general formula (II) (compound G to compound L) are selected from the compound G group represented by the general formula (II) of the present invention at an arbitrary ratio. Alternatively, the compound G may be selected at any ratio from the compound G group to the compound L group. Among them, the compound G group represented by the general formula (II) is preferably selected at an arbitrary ratio. From the viewpoint of managing arbitrarily different dye mixture distributions during the production of the phthalocyanine compound.

Among the compounds G to L represented by the general formula (II), the compounds M to R represented by the general formula (III) are particularly preferable.
Next, the compound represented by formula (III) will be described.
Preferred substituents represented by a ₁ in the general formula (III) compounds represented by M~ compound R, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, a sulfonyl group, more preferably a carbamoyl group, a sulfamoyl Group, sulfinyl group and sulfonyl group, among which sulfamoyl group and sulfonyl group are particularly preferable, and sulfonyl group is most preferable.
These groups preferably further have a substituent such as an ionic hydrophilic group and / or an alkyl group or an aryl group having the ionic hydrophilic group as a substituent.
Examples of the ionic hydrophilic group as a substituent in the general formula (III) are the same as the ionic hydrophilic group described in the general formula (I), and preferred examples are also the same.
G in general formula (III) is synonymous with G demonstrated in the said general formula (I), and its preferable example is also the same.
M in the general formula (III) represents an integer of 0 to 2, preferably 1 or 2, and most preferably m = 1.
Among the compounds M to R represented by the general formula (III), the compound M, the compound N and the compound R are preferable, the compound M and the compound N are more preferable, and the compound M is particularly preferable.
At least two compounds of the compound represented by the general formula (III) (compound M to compound R) may be selected from the compound G group represented by the general formula (III) of the present invention at any ratio. The compound M group to the compound R group may be selected at an arbitrary ratio. Among them, the phthalocyanine compound is preferably selected at an arbitrary ratio from the compound M group represented by the general formula (III). It is more preferable for the purpose of managing the distribution of arbitrarily mixed dyes at the time of production.
As for the preferred combination of substituents of the compound represented by the general formula (III) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

Preferred combinations of the compounds represented by the general formula (III) of the present invention include the following (A) to (G).
(I) Examples of preferred substituents represented by a ₁ are acyl group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, more preferably carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, Of these, a sulfamoyl group and a sulfonyl group are particularly preferable, and a sulfonyl group is most preferable.
The substituent represented by a ₁ may be further substituted, and such a substituted substituent is preferably a substituent substituted with an ionic hydrophilic group.
The example of an ionic hydrophilic group is synonymous with the ionic hydrophilic group demonstrated in the said general formula (I), and its preferable example is also the same.
(B) G is preferably a 6-membered aromatic ring or a 6-membered nitrogen-containing heterocycle, and among them, a 6-membered aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring is preferable, and a 6-membered aromatic ring or pyridine Rings are particularly preferred and 6-membered aromatic rings are most preferred.
(C) m ₁ represents an integer of 0 to 2, preferably 1 or 2, and most preferably m ₁ = 1.
(D) The substitution position of a1 in the compound of the general formula (III) may be any position as long as it can be substituted, but is preferably substituted at the 4-position or 5-position.
(E) Among the compounds M to R, the compound M, the compound N and the compound R are preferable, the compound M and the compound N are more preferable, and the compound M is particularly preferable.
(G) At least two compounds of the compound represented by the general formula (III) (compound M to compound R) are selected from the compound M group represented by the general formula (III) of the present invention at an arbitrary ratio. Alternatively, it may be selected from the compound M group to the compound R group at an arbitrary ratio. Among them, it is preferably selected from the compound M group represented by the general formula (III) at an arbitrary ratio. From the viewpoint of managing arbitrarily different dye mixture distributions during the production of the phthalocyanine compound.

Among the compounds G to L represented by the general formula (III), the compounds S to X represented by the general formula (IV) are particularly preferable.
Next, the compound represented by formula (IV) will be described.
Preferable substituents represented by a _{1 of the} compounds M to R represented by the general formula (IV) are an acyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, and a sulfonyl group, and more preferably a carbamoyl group and a sulfamoyl group. Group, sulfinyl group and sulfonyl group, among which sulfamoyl group and sulfonyl group are particularly preferable, and sulfonyl group is most preferable.
These groups preferably further have a substituent such as an ionic hydrophilic group and / or an alkyl group or an aryl group having the ionic hydrophilic group as a substituent.
Examples of the ionic hydrophilic group as a substituent in the general formula (IV) are the same as the ionic hydrophilic group described in the general formula (I), and preferred examples are also the same.
G in the general formula (IV) has the same meaning as G described in the general formula (I), and preferred examples thereof are also the same.
M ₁ in the general formula (IV) represents an integer of 0 to 2, preferably 1 or 2, and most preferably m ₁ = 1.
Among the compounds S to X represented by the general formula (IV), the compound S, the compound U and the compound W are preferable, the compound S and the compound W are more preferable, and the compound S is particularly preferable.

At least two compounds of the compound represented by the general formula (IV) (compound S to compound X) may be selected from the compound S group represented by the general formula (IV) of the present invention at an arbitrary ratio. The phthalocyanine compound may be selected from the compound S group to the compound X group at an arbitrary ratio, and preferably selected from the compound S group represented by the general formula (IV). It is more preferable for the purpose of managing the distribution of arbitrarily mixed dyes at the time of production.
As for the preferred combination of substituents of the compound represented by the general formula (IV) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.
Preferred combinations of the compounds represented by the general formula (IV) of the present invention include the following (A) to (E).
(I) Examples of preferred substituents represented by a ₁ are acyl group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, more preferably carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, Of these, a sulfamoyl group and a sulfonyl group are particularly preferable, and a sulfonyl group is most preferable.
The substituent represented by a ₁ may be further substituted, and such a substituted substituent is preferably a substituent substituted with an ionic hydrophilic group.
The example of an ionic hydrophilic group is synonymous with the ionic hydrophilic group demonstrated in the said general formula (I), and its preferable example is also the same.
(B) G is preferably a 6-membered nitrogen-containing heterocycle, among which a pyridine ring, a pyrazine ring, a pyrimidine ring and a pyridazine ring are preferred, and a pyridine ring is most preferred.
(C) m ₁ represents an integer of 0 to 2, preferably 1 or 2, and most preferably m ₁ = 1.
(D) Among compounds S to X, compound S, compound T and compound W are preferable, compound S and compound W are more preferable, and compound S is particularly preferable.
(E) At least two kinds of compounds represented by the general formula (IV) (compound S to compound X) are selected from the compound S group represented by the general formula (IV) of the present invention at an arbitrary ratio. Alternatively, it may be selected at any ratio from the compound S group to the compound X group. Among them, it is preferably selected from the compound S group represented by the general formula (IV) at an arbitrary ratio. From the viewpoint of managing arbitrarily different dye mixture distributions during the production of the phthalocyanine compound.

Next, the dehydrating agent will be described.
Examples of the dehydrating agent include those that adsorb water molecules (Molecular sieves, Drierite (registered trademark), magnesium sulfate, sodium sulfate, etc.), those that azeotrope with water and exhibit a dehydrating effect (benzene, toluene, xylene, ethanol, methanol, Acetonitrile, etc.), those that cause a chemical reaction with water [organometallic compounds (Grignard reactant, organolithium reactant, organozinc reactant, etc.), acid anhydrides (carboxylic anhydride, sulfonic anhydride, mixed acid anhydride] Acid halide, polyphosphoric acid, phosphorus pentoxide, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride, orthoester compound, acetal compound, alkenyl ether compound, alkenyl ester compound, oxirane compound, oxetane compound, etc.) Can be mentioned.

  As the dehydrating agent, those that cause a chemical reaction with water are preferably used. More preferably, an acetal compound, an ortho ester compound, an alkenyl ether compound, an alkenyl ester compound, an epoxide compound, or an oxetane compound is used. More preferably, an acetal compound, an ortho ester compound, or an alkenyl ether compound is used. When the dehydrating agent used here is a substance containing a carbon atom, the total carbon number is 1 to 50, preferably 1 to 30, more preferably 1 to 20.

  The following are particularly preferred as the dehydrating agent, but the present invention is not limited to these.

The dehydrating agent needs to be added in such an amount that the water in the reaction mixture can be removed to such an extent that it does not affect the phthalocyanine formation reaction, and the required amount depends on the amount of water in the reaction mixture and the dehydrating efficiency of the dehydrating agent used. Therefore, the required amount of the dehydrating agent is case-by-case and cannot be specified uniformly, but is preferably 0.1 to 500 equivalents relative to the compounds represented by the general formulas (I) to (IV).
The dehydrating agent may be added at any stage of the reaction, but is preferably added at the time of the reaction preparation. In addition, as an auxiliary operation for increasing the dehydrating efficiency of the dehydrating agent, when an operation such as heating, depressurization, or reaction under an inert gas stream is necessary, these appropriate operations may be performed.

The base that can be used in this reaction is an inorganic base containing an alkali metal or an organic base.
As the inorganic base, for example, inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable.
Other examples include lithium acetate, potassium acetate, lithium benzoate, ammonium benzoate, sodium oxalate, and disodium ethylenediaminetetraacetate.
In the present invention, alkali metal salts of these organic acids are also defined as inorganic bases.
Among these, carboxylic acid ammonium salt is particularly preferable.
The carboxylic acid ammonium salt used in the present invention is preferably an aliphatic carboxylic acid ammonium salt, an aromatic carboxylic acid ammonium salt, or a heterocyclic carboxylic acid ammonium salt. The carboxylic acid in these salts is a monocarboxylic acid. The polycarboxylic acid may be a dicarboxylic acid or higher, but is preferably a monocarboxylic acid.
The aliphatic carboxylic acid ammonium salt is preferably a saturated or unsaturated, linear, branched or cyclic substituted or unsubstituted aliphatic carboxylic acid ammonium having 1 to 30 carbon atoms (more preferably 1 to 10 carbon atoms). Examples of the salt include ammonium formate, diammonium oxalate, ammonium acetate, ammonium propionate, ammonium butanoate, ammonium butyrate, ammonium acrylate, and ammonium cyclohexanecarboxylate.
The ammonium salt of the aromatic carboxylic acid is preferably an ammonium salt of a substituted or unsubstituted aromatic carboxylic acid having 7 to 30 carbon atoms, and examples thereof include ammonium benzoate, ammonium toluate, and diammonium phthalate. The ammonium salt of a heterocyclic carboxylic acid is preferably a saturated or unsaturated, substituted or unsubstituted ammonium salt of a heterocyclic carboxylic acid having 1 to 30 carbon atoms (more preferably 3 to 10), such as nicotinic acid. Ammonium, ammonium isonicotinate, and ammonium 1-pyrrolecarboxylate are mentioned.

Among these carboxylic acid ammonium salts, preferably an ammonium salt of an aliphatic carboxylic acid or an ammonium salt of an aromatic carboxylic acid, more preferably an ammonium salt of a saturated aliphatic carboxylic acid having 1 to 6 carbon atoms, 7 carbon atoms. To 10 ammonium salts of aromatic carboxylic acids, more preferably ammonium acetate, ammonium propionate or ammonium benzoate, and particularly preferably ammonium acetate or ammonium benzoate.
As the organic base, it is preferable to use an amine (for example, triethylamine, tributylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, etc.).
More preferably, it is at least one selected from compounds represented by the following general formula (VI).
Formula (VI)

Wherein, Y _1, Y ₂ and Y ₃ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group. Examples of the substituent are preferably a linear or branched alkyl group having 1 to 30 (preferably 1 to 12) carbon atoms, preferably an aralkyl group having 7 to 30 (preferably 7 to 18) carbon atoms. , Preferably an alkenyl group having 2 to 30 (preferably 2 to 12) carbon atoms, preferably a linear or branched alkynyl group having 2 to 30 (preferably 2 to 12) carbon atoms, preferably a side chain A cycloalkyl group having 3 to 30 carbon atoms (preferably 3 to 12) which may have a cycloalkyl group, preferably a cycloalkenyl group having 3 to 30 carbon atoms (preferably 3 to 12) which may have a side chain A group (specific examples of the above group include, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), A reel group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms (preferably 6 to 18 carbon atoms) such as phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), hetero A cyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably 3 to 30 carbon atoms. And 5- or 6-membered aromatic heterocyclic groups such as imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl). Two or more of Y ₁ , Y ₂ and Y ₃ may form a ring. For example, pyridine, imidazole, diazabicycloundecene, piperidine, morpholine, and azacrown are preferable, pyridine, imidazole, piperidine, and morpholine are preferable, and pyridine, piperidine, and morpholine are more preferable.

Preferred groups for Y ₁ , Y ₂ and Y ₃ are alkyl groups, cycloalkyl groups, aryl groups and heterocyclic groups, more preferred are alkyl groups, aryl groups and heterocyclic groups, and most preferred are alkyl groups. . Each group may further have a substituent. Examples of the substituent are preferably a linear or branched alkyl group having 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms), preferably an aralkyl group having 7 to 30 carbon atoms (preferably 7 to 18 carbon atoms). , Preferably an alkenyl group having 2 to 30 (preferably 2 to 12) carbon atoms, preferably a linear or branched alkynyl group having 2 to 30 (preferably 2 to 12) carbon atoms, preferably a side chain A cycloalkyl group having 3 to 30 carbon atoms (preferably 3 to 12) which may have a cycloalkyl group, preferably a cycloalkenyl group having 3 to 30 carbon atoms (preferably 3 to 12) which may have a side chain A group (specific examples of the above group include, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), A reel group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms (preferably 6 to 18 carbon atoms) such as phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), hetero A cyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably 3 to 30 carbon atoms. 5- or 6-membered aromatic heterocyclic group such as imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), halogeno group (for example, fluorine atom, chlorine atom, bromine) Atom); an alkyloxy group (preferably a substituted or unsubstituted alkyloxy group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example, Xy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (preferably formylamino group, 1-30 carbon atoms (preferably 1-12) substituted or unsubstituted alkylcarbonylamino group, C6-C30 (preferably 6-18) substituted or unsubstituted arylcarbonylamino group such as formamide, acetamide, benzamide, 4- (3 -T-butyl-4-hydroxyphenoxy) butane Amide), alkylamino group (substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms, for example, methylamino, butylamino, diethylamino, methylbutylamino), arylamino group (preferably A substituted or unsubstituted arylamino group having 6 to 30 carbon atoms (preferably 6 to 18 carbon atoms), for example, phenylamino, 2-chloroanilino), a ureido group (preferably having 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms)). A substituted or unsubstituted ureido group such as phenylureido, methylureido, N, N-dibutylureido), a sulfamoylamino group (preferably having 0 to 30 carbon atoms (preferably 0 to 18 carbon atoms)) Sulfamoylamino groups such as N, N-dipropylsulfamoylamino), alkylthio A group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms) such as methylthio, octylthio, 2-phenoxyethylthio), an arylthio group (preferably having 6 to 30 carbon atoms (preferably Are substituted or unsubstituted arylthio groups such as phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino groups (preferably having 2-30 carbon atoms). (Preferably 2 to 12) substituted or unsubstituted alkyloxycarbonylamino group such as methoxycarbonylamino), sulfonamide group (preferably having 1 to 30 carbon atoms (preferably 1 to 12) substituted or unsubstituted Alkylsulfonylamino group, 6-30 carbon atoms (preferably 6-1 ) Substituted or unsubstituted arylsulfonylamino groups such as methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide), carbamoyl groups (preferably having 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms)) Substituted or unsubstituted carbamoyl groups such as N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl groups (preferably substituted or unsubstituted sulfamoyl groups having 0 to 30 carbon atoms such as N-ethylsulfuryl group). Famoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl), a sulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms (preferably 1 to 12), 6 ~ 30 (preferably 6-18) substitution or absence A substituted arylsulfonyl group, for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), an alkyloxycarbonyl group (preferably a substituted or unsubstituted alkyloxycarbonyl group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms)) , For example, methoxycarbonyl, butyloxycarbonyl), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms) such as 1-phenyltetrazole-5- Oxy, 2-tetrahydropyranyloxy), an azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms (preferably 6 to 18), a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms. Groups such as phenylazo, 4-methoxyphenylazo 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyl having 2 to 30 (preferably 2 to 12) carbon atoms) An oxy group, a substituted or unsubstituted arylcarbonyloxy group having 7 to 30 carbon atoms (preferably 7 to 18 carbon atoms such as acetoxy), a carbamoyloxy group (preferably having 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms)) Substituted or unsubstituted carbamoyloxy groups such as N-methylcarbamoyloxy, N-phenylcarbamoyloxy),

A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms (preferably 3 to 12 carbon atoms) such as trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms (preferably 7 carbon atoms)) To 18) substituted or unsubstituted aryloxycarbonylamino group, such as phenoxycarbonylamino), imide group (for example, N-succinimide, N-phthalimide), heterocyclic thio group (preferably having 2 to 30 carbon atoms (preferably 2-12) substituted or unsubstituted heterocyclic thio groups such as 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), A sulfinyl group (preferably substituted with 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms) or Substituted alkylsulfinyl groups, 6-30 (preferably 6-18) substituted or unsubstituted arylsulfinyl groups such as 3-phenoxypropylsulfinyl), phosphonyl groups such as phenoxyphosphonyl, octyloxyphosphonyl, phenyl Phosphonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms (preferably 7 to 18 carbon atoms such as phenoxycarbonyl)), an acyl group (preferably formyl group, carbon A substituted or unsubstituted alkylcarbonyl group having 2 to 30 (preferably 2 to 12), a substituted or unsubstituted arylcarbonyl group having 7 to 30 (preferably 7 to 18) carbon atoms, and 4 to 30 (preferably) Is a substituted or unsubstituted carbon atom of 4-12) Heterocyclic carbonyl groups bonded to the alkyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (eg, carboxyl group, phosphono group, sulfo group, and quaternary ammonium group), etc. A cyano group, a hydroxyl group, a nitro group, an amino group, etc. are mentioned. Preferred substituents include heterocyclic groups, alkyloxy groups, aryloxy groups, alkylamino groups, arylamino groups, alkylthio groups, arylthio groups, acyl groups, alkylcarbonyl groups, arylcarbonyl groups, heterocyclic carbonyl groups, ionicity A hydrophilic group, a hydroxyl group, and an amino group are preferable, and a heterocyclic group, an alkyloxy group, an aryloxy group, an alkylamino group, an arylamino group, an acyl group, an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl are more preferable. Group, ionic hydrophilic group, hydroxyl group and amino group, more preferably alkylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, ionic hydrophilic group, hydroxyl group and amino group.

Particularly preferred examples of Y ₁ , Y ₂ and Y ₃ are preferably a substituted alkyl group, cycloalkyl group, aryl group or heterocyclic group, more preferably an alkyl group, aryl group or heterocyclic group, An alkyl group is preferred. In addition, amines having chelating ability for metals are preferred.
Most preferred examples of the organic base include triethylamine, tributylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, ethanolamine, diethanolamine, triethanolamine, oxine, ethylenediamine, triethylenetriamine, glycine, iminoacetic acid, ethylenediaminetetraacetic acid. It is done. More preferred are triethylamine, pyridine, ethanolamine, diethanolamine, triethanolamine, oxine, ethylenediamine, triethylenetriamine, glycine, iminoacetic acid, ethylenediaminetetraacetic acid, and most preferred are ethanolamine, diethanolamine, triethanolamine, ethylenediamine, triamine. Ethylenetriamine and ethylenediaminetetraacetic acid.

In the present invention, these organic bases and inorganic bases can be used alone or in combination. However, since these bases act as a buffer solution by dissolving in a reaction solvent, a highly soluble base is preferable, and an inorganic base Among these, carboxylic acid ammonium salts and organic bases are more preferable, and organic acid salts having ammonium ions and alkali metal ions as cations are more preferable.
Among the carboxylic acid ammonium salts, aliphatic ammonium salts and aromatic ammonium salts are particularly preferable, and aromatic ammonium salts are most preferable.
The amount of the base used in the present invention is 0.05 to 30.0 equivalents, preferably 0.5 to 15.5, based on the amount of the compounds represented by the general formulas (I) to (IV). 0 equivalents.
A more preferred amount of the carboxylic acid ammonium salt used is in the range of 0.01 to 2000 equivalents relative to the compounds represented by the general formulas (I) to (IV) of the present invention.
Preferably it is the range of 1-1000 equivalent, More preferably, it is the range of 20-500 equivalent, More preferably, it is the range of 50-400 equivalent.
As described above, in the step of producing a metal phthalocyanine compound from at least one of the compounds A to F represented by the general formula (I) and a metal compound, the reaction is efficiently performed by using a base as a catalyst for the condensation of phthalocyanine. It is said that it is possible to make progress.
However, the compounds A to F represented by the general formula (I) also have an electron-withdrawing group, more specifically, the compounds G to L represented by the general formula (II) are bases, for example, the compound A and / or In the case of Compound G, decomposition of phthalonitrile is accelerated. In particular, decomposition was significant in metal phthalocyanine compounds substituted with electron-withdrawing groups having high σp values.
However, it was found that this decomposition can be suppressed by allowing an acid to coexist in the reaction system.
That is, as a result, the reaction system became a buffer solution consisting of an acid and a base, in which the reaction proceeded with good yield without decomposition of the compounds A to F represented by the general formulas (I) to (IV).
It was also found that the acid generated as a reaction by-product was maintained in pH because the reaction was carried out in a buffer solution, and the reaction proceeded stably.

The buffer solution refers to a solution having a large buffering effect against a change in a certain component concentration in the solution. For example, a mixed solution of a weak acid (AH) such as acetic acid and its conjugate base (A ⁻ ) can suppress the pH change slightly even if a small amount of H ⁺ or OH ⁻ is added. A system containing a weak base (B) and a conjugate acid (BH ⁺ ) exhibits the same action. As a practical pH buffer solution, it can be found in many general books. For example, it is detailed in the fifth edition of “Science and Chemistry Dictionary” edited by Saburo Nagakura (1999, Iwanami Shoten).

The acid used in the present invention is not particularly limited, and any organic compound or inorganic compound is preferable as long as the dissociation index pKa in the aqueous solution at 25 ° C. is 7.0 or less. pKa represents the logarithmic value of the reciprocal of the acid dissociation constant, and is a value obtained at an ionic strength of 0.1 and 25 ° C. The acid having a pKa of 0.0 to 7.0 may be any of an inorganic acid such as phosphoric acid and an organic acid such as acetic acid, malonic acid, and citric acid. The acid of ˜7.0 is an organic acid. Moreover, even in the organic acid, the organic acid having a carboxyl group is most preferable. The organic acid having a pKa of 0.0 to 7.0 may be a monobasic organic acid or a polybasic organic acid. In the case of a polybasic organic acid, if the pKa is in the range of 0.0 to 7.0, it can be used as a metal salt (for example, sodium salt or potassium salt) or ammonium salt. Two or more organic acids having a pKa of 0.0 to 7.0 can be used in combination.
Specific examples of preferred organic acids having a pKa of 0.0 to 7.0 used in the present invention include formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, and acrylic acid. Aliphatic monobasic organic acids such as butyric acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid, isovaleric acid; asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, leucine, etc. Amino acid compounds; benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy, and aromatic monobasic organic acids such as nicotinic acid; oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, Aliphatic dibasic organic acids such as oxaloacetic acid, glutaric acid, and adipic acid; aspartic acid, glutami Lists various organic acids such as acid, glutaric acid, cystine, ascorbic acid and other amino acid-based dibasic organic acids; phthalic acid, terephthalic acid and other aromatic dibasic organic acids; citric acid and other tribasic organic acids be able to.
The acid preferably used in the present invention is a carboxylic acid.
The carboxylic acid is preferably an aliphatic carboxylic acid, an aromatic carboxylic acid, or a heterocyclic carboxylic acid, and these carboxylic acids may be monocarboxylic acids or polycarboxylic acids of dicarboxylic acids or more, preferably Monocarboxylic acid.

The aliphatic carboxylic acid is preferably a saturated or unsaturated, linear, branched or cyclic substituted or unsubstituted aliphatic carboxylic acid having 1 to 30 carbon atoms (more preferably 1 to 10), such as formic acid. Oxalic acid, acetic acid, propionic acid, butanoic acid, butyric acid, acrylic acid, and cyclohexanecarboxylic acid. The aromatic carboxylic acid is preferably a substituted or unsubstituted aromatic carboxylic acid having 7 to 30 carbon atoms, and examples thereof include benzoic acid, toluic acid, and phthalic acid. The heterocyclic carboxylic acid is preferably a saturated or unsaturated, substituted or unsubstituted ammonium salt of a heterocyclic carboxylic acid having 1 to 30 carbon atoms (more preferably 3 to 10), such as nicotinic acid or isonicotitine. An acid and 1-pyrrole carboxylic acid are mentioned.

Among these carboxylic acids, preferably an aliphatic carboxylic acid or an aromatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid having 1 to 6 carbon atoms, an aromatic carboxylic acid having 7 to 10 carbon atoms, More preferably, it is a C1-C6 saturated aliphatic carboxylic acid.
In the present invention, among the organic acids, aliphatic monobasic organic acids are preferable, and formic acid, acetic acid, and propionic acid are most preferable.

  The amount of the compound (acid) having a pKa of 7.0 or less is 0.05 to 20 equivalents relative to the total amount of compound A to compound F represented by the general formula (I), preferably 0.8. By charging 1 to 10 times the amount, the decomposition inhibiting action of the compound represented by the general formula (I) can be obtained. When the amount of the acid having a pKa of 7.0 or less is less than 0.05 times the total amount of the compounds A to F represented by the general formula (I), the general formula (I) It is not sufficient to suppress the degradation of the compounds shown. On the other hand, when the amount of the acid having a pKa of 7.0 or less exceeds 20 times the total amount of the compound represented by the general formula (I), the reaction system is biased toward the acidic side, so that the reaction occurs. It becomes difficult to progress. Further, since the base is used excessively until it becomes a buffer solution, an acid-base salt is generated as crystals, which is not preferable.

  In the method for producing a metal phthalocyanine compound of the present invention, at least one of the compounds A to F represented by the general formula (I) and the metal compound are present in the presence of the base and the acid having a pKa of 7.0 or less. In this case, the reaction temperature is 30 to 220 ° C, preferably 40 to 200 ° C, more preferably 50 to 180 ° C. When the reaction temperature is less than 30 ° C., the reaction rate is remarkably slow and the time required for production is remarkably long, which is not economical, and when produced at a high temperature exceeding 220 ° C., This is not preferable because the production amount increases.

  As a metal compound to be added to the reaction of the present invention, a metal chloride, a metal acetate, a metal aco complex, and an ammine complex can be used in addition to a metal, a metal oxide, and a metal hydroxide. Examples of the metal or metal oxide that can be introduced include VO, TiO, Mn, Fe, Co, Ni, Cu, Zn, Pd, Cd, and Mg. Among these, Fe, Ni, Cu, and Zn are included. Ni, Cu, and Zn are more preferable. Preferable salt states are chloride (for example, copper chloride), acetate, and aco complex, and chloride and acetate are most preferable. The amount to be used is preferably 0.01 to 10 times equivalent, more preferably 0.05 to 5 times equivalent, particularly preferably relative to the total amount of compound A to compound F represented by the above general formula (I). The amount is 0.1 to 3 times equivalent.

  In the present invention, a catalyst may be used at the same time. As the catalyst of the present invention, all catalysts usually used for the production of metal phthalocyanine compounds can be used. Examples thereof include molybdenum compounds such as ammonium molybdate, molybdic acid, ammonium phosphomolybdate, and molybdenum oxide, tank stainless steel. There are tungsten compounds such as ammonium acid and ammonium phosphotungstate, arsenic vanadium compounds, boric acid, and titanium, tin, and antimony halides or oxyhalides. Among them, ammonium molybdate is excellent.

As the solvent used in the method of the present invention, a general organic solvent can be used. Among them, organic solvents having a hydroxyl group, polar solvents (eg, acetonitrile, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, propylene carbonate, N-methyl-2-pyrrolidone, N- Vinyl-2-pyrrolidone, N, N-diethyldodecanamide) are preferred. Examples of more preferable alcohols include methanol, ethanol, pentanol, heptanol, octanol, cyclohexanol, benzyl alcohol, phenethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, and anise alcohol. Also not only mono-, but also oligo- (especially di- and tri-) and poly-C ₂ -C ₄ -alkylene glycols (in short “glycols”) and their mono-C ₁ -C ₈ -alkyl- and Also suitable are monoaryl ethers (in short, “glycol monoethers”). Also advantageous are compounds based on ethylene. Examples include ethylene glycol, 1,2- and 1,3-propylene glycol, diethylene glycol, butylene glycol, di-, tri- and tetraethylene glycol, di-, tri- and tetrapropylene glycol, polyethylene- and polypropylene glycol, ethylene Glycol monomethyl-, -monoethyl-, -monopropyl-, -monobutyl- and -monohexyl ether and propylene glycol monomethyl-, -monoethyl-, -monopropyl-, -monobutyl- and -monohexyl ether, di-, tri- And tetraethylene glycol monomethyl-, -monoethyl- and -monobutyl ether and di-, tri- and tetrapropylene glycol monomethyl-, -monoethyl- and -monobutyl ether and ethyl - and it includes propylene glycol monophenyl ether. In the present invention, an industrially used inert solvent can also be used. Examples include nitrobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, naphthalene, alkylbenzene, paraffin, naphthene and kerosene.
These may be used alone or in combination of two or more as long as they do not affect each other. The usage-amount of a solvent is 1-100 mass times of the total usage-amount of the compound A-compound F shown by the said general formula (I), Preferably it is 1-20 mass times, More preferably, it is 1-5 mass times. .

  Further, a more preferable solvent in the method of the present invention is at least one selected from glycerin and a compound represented by the general formula (V), or an organic compound having a hydroxyl group described in the previous section as long as the combination does not affect each other. It is a solvent in which a solvent or a polar solvent is appropriately mixed. In the formula, s and t each independently represent a positive integer, but preferably s and t are each 1 to 10, more preferably 1 to 5. X represents a hydrogen atom or a methyl group. More preferable examples include ethylene glycol, diethylene glycol, triethylene glycol, polypropylene glycol, propylene glycol, dipropylene glycol, a 1: 2 (v / v) mixed solvent of ethylene glycol and diethylene glycol, and 3: 1 of propylene glycol and triethylene glycol. (V / v), 1: 5 (v / v) mixed solvent of methanol and triethylene glycol. The usage-amount of a solvent is 1-100 mass times of the total usage-amount of the compound A-compound F shown by the said general formula (I), Preferably it is 1-20 mass times, More preferably, it is 1-5 mass times. .

  Performing the reaction for a long time in this reaction is uneconomical because there is concern about the stability of the target product or the occurrence of side reactions. The reaction time is preferably less than 10 hours, more preferably less than 5 hours, and even more preferably less than 4 hours.

In summary, the production method of the metal phthalocyanine compound of the present invention is preferably a production method comprising the following combinations (a) to (h).
(B) The acid used in the present invention is not particularly limited, but an organic compound and an inorganic compound can be used as long as the dissociation index pKa of the acid or conjugate acid in an aqueous solution at 25 ° C. is 7.0 or less. Either of these is preferable. Among them, an organic acid that is an acid having a pKa of 0.0 to 7.0 is preferable, and an organic acid having a carboxyl group is most preferable. Among organic acids, aliphatic monobasic organic acids are preferable, and formic acid, acetic acid, and propionic acid are most preferable.
(B) An inorganic base or an organic base made of an alkali metal can be used as the base, and examples of the inorganic base include lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, lithium hydroxide, potassium hydroxide and the like. The inorganic base, carboxylate, and organic base are preferably at least one selected from the compounds represented by the general formula (IV), and particularly preferable examples include ethanolamine, diethanolamine, and triethanolamine. It is. Other examples include organic acid salts such as lithium acetate, potassium acetate, sodium oxalate, and disodium ethylenediaminetetraacetate.
In the present invention, these organic bases and inorganic bases can be used alone or in combination. However, since these bases act as a buffer solution by dissolving in a reaction solvent, a highly soluble base is preferable, and an inorganic base Among these, carboxylic acid ammonium salts and organic bases are more preferable, and organic acid salts having ammonium ions and alkali metal ions as cations are more preferable.
Among the carboxylic acid ammonium salts, aliphatic ammonium salts and aromatic ammonium salts are particularly preferable, and aromatic ammonium salts are most preferable. Of these, ammonium benzoate is most preferable.
(C) As reaction conditions, reaction temperature is 30-220 degreeC, Preferably it is 40-200 degreeC, Most preferably, it is 50-180 degreeC.
(D) Examples of metals or metal oxides that can be introduced include VO, TiO, Mn, Fe, Co, Ni, Cu, Zn, Pd, Cd, and Mg. Among these, Ni, Cu, Zn Is preferred. Particularly preferred as the salt state are chloride (for example, copper chloride) and acetate. As a usage-amount, 0.1-3 times equivalent is especially preferable with respect to the total usage-amount of the compound A-compound F shown by the said general formula (I).
(E) Most preferably, the solvent is ethylene glycol, diethylene glycol, triethylene glycol, polypropylene glycol, propylene glycol, dipropylene glycol, a mixed solvent of ethylene glycol and diethylene glycol 1: 2 (v / v), propylene glycol and triethylene. Glycol is a mixed solvent of 4: 1 (v / v), and the particularly preferred amount is 1 to 5 times the total amount of compound A to compound F represented by the above general formula (I).
(F) The reaction time is particularly preferably less than 4 hours.
(G) Among the compounds A to F of the present invention represented by the general formula (I), the compounds G to L represented by the general formula (II) are preferred, and further represented by the general formula (III). Compound M to Compound R are preferable, and Compound S to Compound X represented by the above general formula (IV) are preferable. Among them, Compound S and Compound W are particularly preferable, and Compound S is most preferable.
(H) In general formula (III) and general formula (IV), a ₁ is preferably a sulfinyl group, a sulfonyl group, a sulfamoyl group, an acyl group or a carbamoyl group, particularly preferably a sulfonyl group, a sulfamoyl group or a carbamoyl group. Of these, a sulfonyl group is particularly preferred. m ₁ is preferably 1 or 2, and most preferably m ₁ = 1.

  Regarding these preferable combinations, at least one of these is preferably the above-described preferable conditions, more preferably the above-mentioned preferable conditions, and most preferably all the above-mentioned preferable conditions.

  Examples (1) to (54) of the compounds represented by the general formulas (I) to (IV) used in the present invention are shown below. However, the present invention is not limited to these.

Hereinafter, the metal phthalocyanine compound manufactured by the manufacturing method of this invention is demonstrated.
The metal phthalocyanine compound produced by the production method of the present invention is represented by the following general formula.

In the general formula, rings A, B, C and D have the same meaning as G described in the general formula (I), and preferred examples are also the same.
M represents a metal atom. In the case of representing a metal atom, any metal can be used as long as it forms a stable complex. Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe , Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, etc. . Further, the metal atom may form a complex with the phthalocyanine compound in the state of oxide, hydroxide, or halide. Examples of the oxide include VO and GeO. Examples of the hydroxide include Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _{2 and the} like. The _{halides, AlCl, SiCl 2, VCl,} VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like. Mg, Ca, Co, Zn, Pd and Cu are preferably used as the metal atom, more preferably Co, Pd, Zn and Cu are used, and Cu is particularly preferably used.
Although the specific example of the phthalocyanine compound manufactured with the method of this invention is shown, this invention is not limited to these. The following is the case where M is Cu.

  In the production of the phthalocyanine compound of the present invention, there are two theoretically necessary compounds represented by the general formula (I), and two different Rs (R1 + R2 = 4) and R1: R2 = 3: When used at a ratio of 1 (eq / eq), for example, the reaction proceeds according to the following scheme.

  Other examples of the production of metal phthalocyanine compounds using Compound B, Compound C, Compound D, Compound E, and Compound F include, for example, “phthalocyanine as a functional dye (basic edition / application edition)” ICP Corporation (2004) Publisher), Ryo Takahashi, Keiichi Sakamoto, Eiko Okumura (p-30-33), C.I. C. Leznoff-A. B. P. Lever co-authored and published in VCH, 'Phthalogians-Properties and Applications' (p-1 to 54), etc., can be used while combining or quoting these similar methods.

  Hereinafter, the present invention will be described in more detail based on examples. The present invention is not limited to these examples. Compound 2 and Compound 5 in Examples can be produced by the methods described in JP-A No. 2004-2670, JP-A No. 2005-41856, Japanese Patent Application No. 2004-094413, and JP-A No. 2003-119415. It belongs to the compounds represented by formulas (I) to (IV).

Production Example 1: Production of a dye compound containing phthalocyanine compound 1 as a main component

After adding 0.6 mL of acetic acid and 21.2 g of triethyl orthoacetate to 120 mL of diethylene glycol at room temperature, 21.44 g of compound 2 (water content 3%) and 8.29 g of compound 5 (water content 1%) were continuously mixed. The internal temperature was heated to 100 ° C. After adding 3.0 g of CuCl2 and 24.8 g of ammonium benzoate to the reaction mixture, the mixture was stirred at an internal temperature of 100 ° C. for 1.5 hours.
Next, the internal temperature was cooled to 90 ° C., and 7.7 mL of concentrated hydrochloric acid was added dropwise. Subsequently, 4.28 g of lithium chloride was added, and the mixture was stirred at an internal temperature of 90 ° C. for 30 minutes. Thereafter, 360 mL of isopropanol was dropped and crystallized. After stirring at an internal temperature of 80 ° C. for 1 hour, after cooling to 30 ° C., the precipitate was filtered by suction and washed with 500 mL of isopropanol. After drying, 31.44 g of crude crystals were obtained.
After dissolving 30.0 g of crude crystals in 38.3 mL of ion exchange water and 90.7 g of methanol, a 2.5N-LiOH aqueous solution was added at 50 ° C. until the pH reached 9.5. After stirring at 50 ° C. for 60 minutes, dust removal filtration was performed, the temperature was raised to an internal temperature of 90 ° C., and 450 mL of isopropanol was added dropwise for crystallization. After cooling to an internal temperature of 30 ° C., the purified crystals were suction filtered and washed with 250 mL of isopropanol. Yield 27.3 g (91% yield).
Solution absorption: λmax = 624.7 nm, ε59000 (H ₂ O) (phthalocyanine compound 1 2.5 mg / 100 mL of ultrapure water).

Production Example 2: Production of a dye compound containing phthalocyanine compound 2 as a main component

After adding 0.6 mL of acetic acid and 21.2 g of triethyl orthoacetate to 120 mL of diethylene glycol at room temperature, 14.29 g (water content 3%) of compound 2 and 16.58 g (water content 1%) of compound 5 were continuously mixed. The internal temperature was heated to 100 ° C. After adding 3.0 g of CuCl2 and 24.8 g of ammonium benzoate to the reaction mixture, the mixture was stirred at an internal temperature of 100 ° C. for 1.5 hours.
Next, the internal temperature was cooled to 90 ° C., and 7.7 mL of concentrated hydrochloric acid was added dropwise. Subsequently, 4.28 g of lithium chloride was added, and the mixture was stirred at an internal temperature of 90 ° C. for 30 minutes. Thereafter, 360 mL of isopropanol was dropped and crystallized. After stirring at an internal temperature of 80 ° C. for 1 hour, after cooling to 30 ° C., the precipitate was filtered by suction and washed with 500 mL of isopropanol. After drying, 33.5 g of crude crystals were obtained.
After dissolving 30.0 g of crude crystals in 120 mL of 0.1N-LiOH aqueous solution at 60 ° C., dust removal filtration was carried out, stirring was performed for 30 minutes at the same temperature, 30 mL of methanol was injected, and 1.0 N-LiOH was added at 50 ° C. The aqueous solution was added until pH 8.5. The temperature was raised to an internal temperature of 60 ° C., and 6000 mL of isopropanol was added dropwise for crystallization. After cooling to an internal temperature of 30 ° C., the purified crystals were suction filtered and washed with 300 mL of isopropanol. Yield 27.0 g (90% yield).
Solution absorption: λmax = 615.8 nm, ε52000 (H ₂ O) (phthalocyanine compound 2 2.4 mg / 100 mL of ultrapure water).

Production Example 3: Production of a dye compound containing phthalocyanine compound 3 as a main component

After adding 0.6 mL of acetic acid and 21.2 g of triethyl orthoacetate to 120 mL of diethylene glycol at room temperature, 27.7 g of compound 2 (water content 0.8%) and 8.29 g of compound 5 (water content 1%) were continued. The mixture was mixed and heated to an internal temperature of 100 ° C. After adding 3.0 g of CuCl2 and 24.8 g of ammonium benzoate to the reaction mixture, the mixture was stirred at an internal temperature of 100 ° C. for 1.5 hours.
The reaction solution was cooled to room temperature and crystallized in 300 mL of 1.0N hydrochloric acid, filtered, washed with 800 mL of water, and dried to obtain 35.6 g of crude crystals.
After 30 g of the dried crude crystals were dissolved in 300 mL of methanol, dust was collected and filtered, and 600 mL of isopropanol was added dropwise for crystallization. The mixture was filtered with suction, and the solid was washed with isopropanol. Yield 27 g (yield 90.0%). Solution absorption: λmax = 595.6 nm, ε35200 (ethyl acetate) (phthalocyanine compound 3 2.7 mg / ethyl acetate 100 mL).

Production Examples 4 to 10
In Table 3, the result of having operated according to manufacture example 1 except having changed the compound represented by general formula (I)-(IV), a base, etc. is described collectively.
[Comparative example]
Comparative Examples 1 to 5
Table 3 summarizes the results of operation according to Production Example 1 except that the compounds represented by general formulas (I) to (IV), acids, bases, and dehydrating agents were changed.

  In Table 3, the phthalocyanine compounds obtained in Production Examples 5 to 7 were the same as in Production Example 1. In Production Examples 8, 9 and 10, phthalocyanine compounds represented by the following chemical formulas were obtained. The yield after purification in Table 3 is the yield of the compound represented by the following chemical formula.

As is clear from the above results, the phthalocyanine compound can be obtained in a high yield and high purity in a short time under mild conditions in the configuration of the present invention.

Claims (8)

A method for producing a metal phthalocyanine compound from at least two compounds selected from the compounds represented by the following general formula (I) (compound A to compound F) and a metal compound, wherein an organic base is used in the presence of a dehydrating agent. Alternatively, a method for producing a metal phthalocyanine compound, wherein the reaction is carried out in a buffer solution of an inorganic base and an acid.
Formula (I)

In general formula (I), R represents a hydrogen atom or a substituent. l represents an integer of 0 to 4. When l is 2 to 4, a plurality of R may be the same as or different from each other. G represents an atomic group constituting a 5- or 6-membered aromatic ring and / or hetero ring. 2. The metal according to claim 1, wherein the compound represented by the general formula (I) (compound A to compound F) is a compound represented by the following general formula (II) (compounds G to L). A method for producing a phthalocyanine compound.
Formula (II)

In general formula (II), a and b each independently represent a substituent, and the sum of Hammett's substituent constant σp values is 0.20 or more. m and n represent integers satisfying 0 ≦ m ≦ 4, 0 ≦ n ≦ 3, and 0 ≦ m + n ≦ 4. G represents an atomic group constituting a 5- or 6-membered aromatic ring and / or hetero ring. The compound (compounds G to L) represented by the general formula (II) is a compound (compound M to compound R) represented by the following general formula (III). Of producing a metal phthalocyanine compound.
General formula (III)

In general formula (III), each a ₁ independently represents any of a sulfinyl group, a sulfonyl group, a sulfamoyl group, an acyl group, and a carbamoyl group, and may have a substituent. m ₁ represents an integer of 0 to 2. G represents an atomic group constituting a 5- or 6-membered aromatic ring and / or hetero ring. The compound (compound M to compound R) represented by the general formula (III) is a compound (compound S to compound X) represented by the following general formula (IV): The manufacturing method of the metal phthalocyanine compound of any one.
Formula (IV)

In general formula (IV), a ₁ each independently represents any of a sulfinyl group, a sulfonyl group, a sulfamoyl group, an acyl group, and a carbamoyl group, and may have a substituent. m ₁ represents an integer of 0 to 2. G represents an atomic group constituting a 6-membered nitrogen-containing heterocycle. The method for producing a metal phthalocyanine compound according to any one of claims 1 to 4, wherein at least one selected from glycerin and a compound represented by the following general formula (V) is used as a reaction solvent.
General formula (V)

In general formula (V), s and t each independently represent a positive integer. X represents a hydrogen atom or a methyl group.   The metal phthalocyanine according to any one of claims 1 to 5, wherein the dehydrating agent is selected from an acetal compound, an ortho ester compound, an alkenyl ether compound, an alkenyl ester compound, an epoxide compound, and an oxetane compound. Compound production method.   The said base uses at least 1 sort (s) chosen from the alkali metal salt, ammonium salt, or tertiary amine salt of carboxylic acid, The manufacture of the metal phthalocyanine compound of any one of Claims 1-6 characterized by the above-mentioned. Method. The method for producing a metal phthalocyanine compound according to any one of claims 1 to 6, wherein the base is at least one selected from compounds represented by the following general formula (VI).
General formula (VI)

Represents in the general formula (VI), Y _1, Y ₂ and Y ₃ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, Y ₁ , Y ₂ and Y ₃ may be combined to form a condensed ring organic base. Each group may further have a substituent.