JPS61246393A - Production of metallophthalocyanine crystal - Google Patents

Abstract

PURPOSE:To easily produce crystals of a metallophthalocyanine compound having sperior crystallizability and electric conductivity by placing two electrodes in a soln. of a metallophthalocyanine compound and carrying out constant-current electrolysis. CONSTITUTION:A metallophthalocyanine compound represented by a general formula MPc(L)n (where M is a transition metal belonging to the group VIII in the periodic table or other metal such as Al, IN, Ga or Sn, L is an N-contg. org. compound group acting as a ligand such as cyano, piperidino or 1- methylimidazole, Pc is a phthalocyanine ring, and n=1 or 2) is dissolved in a solvent such as acetone or methyl ethyl ketone to 10<-5>-10<-10>M concn. Electrodes of Au, Pt, NI, Cu or the like are placed in the resulting soln. as an electrolytic soln., and constant-current electrolysis is carried out with 1mum-1mA electric current. When the metallophthalocyanine compound is acidic, crystals of a metallophthalocyanine compound having high crystallizability and electric conductivity are formed on the surface of the anode to 0.1- several mm length. When the metallophthalocyanine compound is basic, the crystals are formed on the surface of the cathode.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for producing crystals of organometallic compounds, and more specifically, to a method for easily producing crystals of metal phthalocyanine compounds having high crystallinity and high conductivity. (Prior Art) Conventionally, polycyclic compounds, particularly metal phthalocyanine compounds, have been variously studied due to their various unique physical, chemical and electrical properties, and some of these studies have focused on these metal phthalocyanines. Research is being conducted to improve the conductivity of metal phthalocyanine compounds by turning them into polymers, and other research has focused on the polycrystalline nature of metal phthalocyanine compounds, and various crystal forms of metal phthalocyanine crystals have been disclosed. . Generally speaking, metal phthalocyanine polymers are produced by a method in which an addition polymerizable group is introduced into a metal phthalocyanine compound and then polymerized, a functional group is introduced into a benzene ring of a phthalocyanine ring and these are condensed and polymerized, and as a manufacturing raw material. , a method of making a polymer using a tetracarboxylic acid compound, etc. In addition, in the crystallization of metal phthalocyanine compounds, there are various methods: crystal growth of metal phthalocyanine in various organic solvents to form α, β, γ, and other crystal forms, a method by heat sublimation under vacuum, and a method in which metal phthalocyanine compounds are combined. There are methods such as modifying the initial temperature, dissolving it in a suitable solvent, and performing constant voltage electrolysis. (Problem to be solved by the invention) The above phthalocyanine polymer has a low degree of polymerization because the metal phthalocyanine compound that is its raw material is poorly soluble in solvents, and the resulting polymer is even more poorly soluble in solvents. Therefore, in terms of conductivity, a sufficiently high value has not been obtained. On the other hand, regarding the crystallization of phthalocyanine, metal phthalocyanine compounds are similarly poorly soluble in solvents, so crystallization using solvents is difficult.Also, in the sublimation method, metal phthalocyanine has a high melting point, so it requires high vacuum conditions, heating, etc. Since it is difficult to set appropriate conditions such as temperature and sublimation rate, there is a problem that sufficiently grown or highly purified crystals cannot be easily obtained using a simple device. Furthermore, the constant voltage electrolysis method does not require high temperatures or high vacuum, and is an extremely effective method for obtaining metal phthalocyanine crystals with a size of 100 gm or less, but it is difficult to form larger crystals. There is a problem. The present inventor has solved the problems of the prior art as described above, and as a result of intensive research to obtain extremely large metal phthalocyanine crystals, the present inventor has developed various metal phthalocyanine compounds by coordinating an organic group to the metal of the metal phthalocyanine compound. When these compounds are easily soluble in solvents and are dissolved in various solvents and electrolyzed with a constant current, no other expensive equipment or processes, such as high temperature, high pressure, high vacuum equipment or settings, are required. Metal phthalocyanine crystals that are significantly larger than those using conventional constant voltage electrolysis methods can be easily formed without using difficult conditions, and the resulting metal phthalocyanine crystals have a size that would not be expected from conventional techniques. The present invention was completed by discovering that it has electrical conductivity. (Disclosure of the Invention) That is, the present invention provides a solution of a phthalocyanine compound represented by the general formula MPc(L)n (M is a metal, L is a ligand, n is 1 or 2, and Pc is a phthalocyanine ring). This is a method for producing metal phthalocyanine crystals, which is characterized by depositing metal phthalocyanine crystals on electrodes by performing constant current electrolysis between counter electrodes. Next, to explain the present invention in more detail, the first feature of the present invention is that a metal phthalocyanine compound represented by the general formula MPc(L)n is used as a raw material for obtaining metal phthalocyanine crystals, The second feature is that these metal phthalocyanine compounds of general formula MPc(L)n are easily dissolved in various solvents, and the third feature is that the obtained general formula MPc(L)n is easily dissolved. (L)
It is a method of constant current electrolysis using a solution of a metal phthalocyanine compound represented by n as an electrolyte, and due to these characteristics, it was completely unexpected that significantly larger crystals were grown on the electrode than in the conventional method. This is what I found out. Therefore, the present invention will be described in more detail below, focusing mainly on the above-mentioned features. The phthalocyanine compound with the general formula MPc(L)n used in the present invention itself can be obtained by a conventionally known method, and M in the general formula MPc(L)n is preferably a trivalent or higher valent metal. For example, aluminum, indium, gallium, tin, lead, titanium, germanium, silicon, thorium, antimony, vanadium, chromium, molybdenum, uranium, manganese, iron, cobalt, nickel, hafnium, rhodium, palladium, osmium, platinum, etc. The metals are trivalent or higher, and transition metals belonging to Group 1 of the periodic table are particularly preferred. Metal phthalocyanines made of these metals can be easily obtained, for example, by the method described in "Phthalocyanine Compounds" by Moser and Torts. The ligand L in the general formula MPc(L)n is 1 or 2, that is, n is 1 or 2, and these ligands are preferably nitrogen-containing organic compound groups, For example, cyan group, piperidine group, l-methylimidazole group, pyridine group, 2-methylpyrazine group,
piperidine group, 3.4-dimethylpyridine group, 3.5-
Dimethylpyridine group, 4-methylpyridine group, 3-chloropyridine group, pyrazine group, 3-ethylpyridine group, 4
- Aliphatic amine groups such as ethylpyridine group, 3-7 cetylpyridine group, 4-acetylpyridine group, bipyridine group, dicyanobenzene group, cyanobenzene group, methylamine group, ethylamine group, propylamine group, butylamine group, aniline group, an aromatic amine group such as a methylaniline group, a dimethylaniline group, or a naphthylamine group, or a halogen atom such as chlorine or bromine, and when n is 2, these ligands may be the same or different. The method of coordinating such various ligands to metal phthalocyanine can be carried out in accordance with any known method, for example, the method of simply coordinating the above-mentioned ligand to metal phthalocyanine, When synthesizing metal phthalocyanine compounds from metals such as Using polyhalide metal as
A metal phthalocyanine having one or two halogens is prepared, and the halogen is used to introduce the above-mentioned ligand, or a metal-free phthalocyanine is synthesized. Examples include a method similar to that described above by introducing a polyhalogenated metal, but the method is not limited to these methods. In addition, the benzene nucleus of these metal phthalocyanines can have 1 to 16 substituents at most, such as a halogen atom, a methyl group, a nitro group, a carboxyl group, and other substituents. The general formula M P c (L
) The metal phthalocyanine compound represented by n can be represented as follows, to give one example.

[M and L in the above formula are as defined above. According to the inventor's detailed research, the general formula M
The metal phthalocyanine represented by Pc(L)n is acidic or basic as a whole molecule and tends to form salts with bases or acids, respectively, and these metal phthalocyanine compounds can be used in various organic solvents, preferably dipolar It has been found that the metal phthalocyanine is significantly more soluble in organic solvents or mixed solvents of these and water than conventional metal phthalocyanines. In the present invention, acetone, methyl ethyl ketone, methyl-n-
Propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, methyl cellosolve, butyl cellosolve, cellosolve acetate , formamide, dimethylformamide, dimethyl sulfoxide, or mixtures thereof with water, or with pentane, hexane. Cyclohexane, heptane, octane, mineral spirits, petroleum ether, gasoline, benzene, toluene,
Mixtures with xylene, chloroform, carbon tetrachloride, chlorobenzene, perchloroethylene, trichlorethylene, etc. are mentioned. In the present invention, the general formula
A metal phthalocyanine compound represented by MPc(L)n is dissolved to form a solution. The concentration is preferably a concentration,
In addition, in order to increase the conductivity of these solutions, KCI, NaBr, KI, LtC 04, LiB
F4. Any electrolyte can be added, such as tetra-n-butylammonium verchlorate, tetra-n-butylammonium perfluoroporate, tetramethylammonium chloride, sodium p-)luenesulfonate, Na, SO, etc. These electrolytes are about 10 to
It is preferable to dissolve it at a concentration of about 10M. Furthermore, in the constant current electrolysis of the present invention, various conventionally known doping agents, such as the electrolyte described above, iodine, arsenic oxide, sulfuric acid, trifluorosulfuric acid, etc., are added to the solution as described above to any desired concentration. By dissolving the metal phthalocyanine crystal, the electrical properties of the obtained metal phthalocyanine crystal can be modified. Moreover, these doping agents may be doped after crystal formation. In the present invention, the general formula M P c (L
) By using a solution of a metal phthalocyanine compound represented by Excellent metal phthalocyanine crystals can be formed in a short time using inexpensive equipment and easy operation. The above-mentioned crystal formation method is carried out by using the above-mentioned metal phthalocyanine compound solution as an electrolytic solution, inserting a pair of electrodes into the solution, and applying a constant current. When the metal phthalocyanine compound of the general formula MPc(L)n used is acidic, crystals are deposited on the surface of the anode, and when the metal phthalocyanine compound of the general formula MPc(L)n used is basic. , crystals are deposited on the surface of the cathode. Electrolytic conditions vary depending on the type of phthalocyanine compound used, the material and shape of the electrode, the type and concentration of the electrolytic solution and electrolyte, and the size of the electrode, but generally: a constant current of 1 gk to 1 mA. Then, crystals with a length of about 0.1 to several 1 intestines are formed on the electrode surface in a few seconds to more than ten hours. In addition, the electrodes used as anodes or cathodes in the above are metals such as gold, platinum, nickel, and copper, or those metals deposited on insulating substrates such as plastic or glass plates, and tin oxide and indium oxide. Any conventionally known electrode material such as an insulating substrate coated with a conductive metal fusion layer such as , indium tin oxide or the like can be used, and any shape thereof may be used. As described above, metal phthalocyanine compounds of the general formula MPc(L)n are selected from needle-shaped, columnar, plate-like, etc. Crystals of various shapes, such as These crystals have the general formula MPc(L
) If a concentrated solution of the metal phthalocyanine compound (n) is electrolyzed in a relatively short time, relatively small-sized crystals will be produced, and if a dilute solution is used and the electrolysis takes a relatively long time, For example, it is possible to obtain up to several liters of crystals. According to the present invention as described above, the highly crystalline and highly conductive metal phthalocyanine crystal as described above can be provided in a very short time using a very simple device and operation, and therefore at a very low cost. When the conductivity of the metal phthalocyanine compound crystal of the present invention obtained was measured, it was found that it had a high conductivity that could not be expected from the metal phthalocyanine crystal of the prior art.
That is, it had high electrical conductivity, reaching as high as 10 to 10 S/cm. Therefore, the metal phthalocyanine crystals obtained by the method of the present invention can be used as advanced organic conductive materials in various conventionally known applications, such as resistance heating elements, resistors, antistatic agents,
Electromagnetic shielding bodies, electrode materials, conductive adhesives, conductive paints,
It is useful for sensors of various electric and electronic devices, electrophotographic photoreceptors, various recording materials, etc. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Sodium dicyanocobalt phthalocyanine (in the general formula MPc(L)n, M = cobalt, L = cyano group, n = 2) was dissolved in dimethylformamide at 2.5 x 1
It was dissolved to a concentration of 0M to form an electrolytic solution. A pair of platinum electrodes were inserted into this electrolyte, one was connected to the anode of a DC power supply, and the other was connected to the cathode. When electrolysis was carried out at a constant current (5 JLA) for 10 hours, a black color appeared on the anode surface. Needle-shaped crystals (Fig. 1) were precipitated. The size of this crystal is 5 x 10~
It was 5XlOc and the length was 3mm to 5m. The electrical conductivity of the obtained crystal in the direction of crystal growth was measured and found to be approximately 3°9 x 10 S/cm. Example 2 Sodium dicyanocobalt 7-talocyanine (in the general formula MPc(L)n, M = cobalt, L = cyan group, n = 2) (2,5X10M), tetrabutylammonium verchlorate (4,7X 10M) was dissolved in dimethylformamide to prepare an electrolyte. A pair of platinum electrodes were inserted into this electrolyte, one was connected to the anode of a DC power supply, and the other was connected to the cathode, and the electrodes were heated at a constant current (2 gA) for 10 minutes.
When time electrolysis was performed, black needle-like crystals were deposited on the anode surface. The size of this crystal was 0.1 mm in width and 3 to 4 meters in length. The electrical conductivity of the obtained crystal in the crystal growth direction is 1.0S/
It was cm. Examples 3 to 8 Crystals of metal phthalocyanine compounds were obtained in the same manner as in Examples 1 to 2 except that the following materials were used. -MPcLnc7) Hi, M=iron, L=pyrazine, n
=2 vu; Approx. 4X10S/cm Length 11A-MPcLn: M=iron, L=bipyridine, n=
2 Drunk ■; Approximately lXIO3/c+n Length 11j -MPcLn, M = Iron, L = Nidishyanobenzene n = 2 vu: Approximately 2X10S/Cm L = Pyridine, n = 2 Illusion u: Approximately lXl0S/cm Fruit. 111-MPcLn, M=cobalt, L=piperidine, n=2 vu; approximately 5X10S/ca+ length"111-MPcLn; M=cobalt,
L = piperidine and cyanogen group I; approximately LOS/cm

[Brief explanation of the drawing]

FIG. 1 shows a micrograph (magnification: 47) of the crystalline state of the metal phthalocyanine crystal obtained in Example 1, and FIG. 2 shows a micrograph (magnification: 47) of the crystalline state of the metal phthalocyanine crystal obtained in Example 2. Indicates 5,000 times. Patent applicant Canon Co., Ltd. agent Patent attorney Yoshi 1) Katsuhiro 'jj,'+',"
”、'：Made゛、゛1st figure 2nd circle

Claims (1)

[Claims] General formula MPc(L)n (M is metal, L is ligand, n is 1
or 2. Metal phthalocyanine, characterized in that metal phthalocyanine crystals are precipitated on an electrode by performing constant current electrolysis between counter electrodes in a solution of a metal phthalocyanine compound represented by (Pc is a phthalocyanine ring) Method of manufacturing crystals.