JP2513487B2 - Novel phthalocyanine compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a novel phthalocyanine compound, particularly a solvent-soluble phthalocyanine compound.

<Prior Art> Phthalocyanine compounds are stable to light, heat, etc., and have excellent robustness. Further, since it has a strong color tone, it is widely used as various dyes or pigments. On the other hand, since there is a large π-electron conjugation, conductivity, photoconductivity,
It has attracted attention as a material for photoelectric conversion, catalysts, optical disks, etc., and has been widely studied. In particular, it is used as an electrophotographic photoreceptor or a photoreceptor for laser printers.
Its importance is increasing year by year. In addition, as an electronic material, it has excellent photoconductivity and semiconductivity, and is an extremely valuable material industrially.

Further, if it is soluble in a solvent, a film can be formed on a substrate by a simple method such as spin coating and can also be used as a dye for an optical disk, which is an industrially very valuable material.

Furthermore, the composition of the gas sensor by the LB film of the phthalocyanine compound (Hank Wohltjen, William R. Barger, Arthur W.
Snow, N, Lynn Jarvis, IEEE Transaction on Electron De
vices, vol.ED-32, P1170-1174 (1985) etc.) There are many studies on LB films using solvent-soluble phthalocyanine compounds, and they are extremely valuable as materials for various devices such as sensors.

<Problems to be Solved by the Invention> Phthalocyanine compounds are almost insoluble and infusible, and these drawbacks are often encountered when studying applications. That is, to purify a phthalocyanine compound, so-called acid pasting using concentrated sulfuric acid must be used or sublimation purification must be used.
In these methods, the phthalocyanine compound is often decomposed, which is a purification method unsuitable for semiconductor applications, and it is difficult to obtain a high-purity product. In addition, in order to reduce the thickness, it is necessary to rely on a thin film method such as vacuum deposition or resin dispersion.

As described above, the conventional techniques have problems that it is difficult to obtain a high-purity product and that thinning is limited.

On the other hand, looking at phthalocyanine as an electronic material, the conventional techniques have problems such as low purity and limited means for forming a thin film.

The problem to be solved by the present invention is to provide a novel solvent-soluble phthalocyanine compound.

<Means for Solving Problems> In order to solve the above problems, the present invention provides a compound represented by the general formula MPc- (COOR) _m (1) (wherein, M is a hydrogen atom or halogenated or oxidized). Represents a metal atom, R represents a prenyl group or a polyprenyl group, m represents an integer of 1 to 8, and Pc represents a phthalocyanine ring.).

In the above formula (1), M represents a hydrogen atom or a metal atom which may be halogenated or oxidized, and the metal atom may be any, for example, Cu, F
Examples thereof include e, Ni, V, Pb, Si, Ge, Ti, Sn, Al, Ru, Zn, Mg, VO, TiO and AlCl.

In this case, 1 or 2 other ligands may be further coordinated above and below the phthalocyanine ring.

-(COOR) _m represents that the benzene ring of phthalocyanine is substituted with an ester group, and the number of ester groups substituted on one benzene ring is 2 or less, and the number of substituents on the entire phthalocyanine ring is , 8 or less.

Further, the position of the benzene ring to which-(COOR) _m is bonded is
Usually 4- or 5-(-4 ',-4 ", -4,-
5 ', -5 ", or -5), usually obtained as a mixture of these isomers.

R represents a prenyl group or a polyprenyl group, and isoprene units of 5 or less are preferable, and examples thereof include a prenyl group, a geranyl group, a neryl group, a t-nerolidol group, and a cis-nerolidol group.

Pc is a phthalocyanine ring represented by the following formula (2).

Specific examples of the phthalocyanine compound of the present invention are shown below, but the present invention is not limited to the specific examples shown below.

For example, 4-prenoxycarbonyl copper phthalocyanine 4,4′-di (prenoxycarbonyl) copper phthalocyanine 4,5′-di (prenoxycarbonyl) copper phthalocyanine 5,4′-di (prenoxycarbonyl) Copper Phthalocyanine 4,4 ', 4 "-Tri (Prenoxycarbonyl) Copper Phthalocyanine 4,5', 5" -Tri (Plenoxycarbonyl) Copper Phthalocyanine 4,4 ', 4 ", 4-Tetra (Pleno) Xycarbonyl) copper phthalocyanine 4,5,4 ′, 5 ′, 4 ″, 5 ″, 4,5-octa (prenoxycarbonyl) copper phthalocyanine, etc., in which copper is not halogenated or oxidized as described above. It may be replaced with a metal atom which may be present.

In addition, in the present specification, such a compound is, for example,
It may be abbreviated as CuPc- (COO-Prenyl) ₈ or CuPc- (COO-Geranyl) ₄ .

Such a phthalocyanine compound is synthesized as follows.

That is, trimellitic anhydride or pyromellitic anhydride or a predetermined amount mixture of both, phthalic anhydride, metal chloride and urea are mixed and reacted in nitrobenzene using ammonium molybdate as a catalyst.

In this case, the mixing ratio of trimellitic anhydride and phthalic anhydride or trimellitic anhydride and pyromellitic anhydride and phthalic anhydride or pyromellitic anhydride and phthalic anhydride is determined by the number of substituents of the target compound.

Then, take the product was filtered off, thoroughly washed with methanol, followed by drying MPC-(CONH _{2) m} (here, M, Pc and m are as defined M, and Pc and m in Formula (1) Is obtained).

The obtained MPc- (CONH ₂ ) _m is hydrolyzed with potassium hydroxide, for example, at a temperature of about 100 ° C., the precipitate is filtered off and washed with water to give an aqueous solution, and the aqueous solution is made acidic. This gives MPc- (COOH) _m as a solid.
By further purifying with potassium hydroxide, high purity MPc- (CO
OH) _m can be obtained.

Next, this is reacted with thionyl chloride (SOCl ₂ ) to form an acid chloride, which is then reacted with prenol or polyprenyl alcohol (ROH) to obtain the target compound, MPc.
− (COOR) _m is obtained. By recrystallizing this MPc- (COOR) _m from, for example, benzene-n-hexane, high-purity MPc- (COOR) _m can be obtained.

In addition, MPc- (COOR) _m is dissolved in chloroform, for example, and developed with silica gel column chromatography or the like using chloroform-ethanol or the like as a developing solvent, and a blue liquid is evaporated to obtain a highly purified product by drying. MPc− (COOR) _m is obtained.

The MPc- (COOR) _m thus obtained is a mixture of isomers as described above, and its infrared absorption spectrum shows ν (C =
0) 1720 cm ^-1 , ν (C-0) 1275 cm ^-1 , ν (CH) 2950 cm
There is an absorption of ^-1 .

Further, the LB film of these compounds can be formed by the following method.

For example, double distilled water is added to FILM BALANCE manufactured by LAUDA and kept at 20 ° C. MPc- (COOR) _m is dissolved in, for example, benzene and adjusted to a concentration of 0.1 mmol / 1. After dropping this solution on the surface of the water and adjusting the barrier so that the surface pressure becomes 20 dynes / cm, dip a microscope slide glass well cleaned with isopropanol gradually (1 mm / min) in water to form the phthalocyanine layer. (1 layer) is coated. At this time, the barrier is automatically adjusted to maintain the surface pressure.

Then, the slide glass is pulled up in the same manner. By repeating this operation, a plurality of coatings can be formed.

<Examples> Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples.

Example 1 Synthesis of CuPc- (CONH ₂ ) ₄ A 200 ml four-necked flask was charged with 10.0 g of trimellitic anhydride, 30.0 g of urea, 3.0 g of copper (I) chloride, 1.0 g of ammonium molybdate and 150 ml of nitrobenzene, and a nitrogen atmosphere. The mixture was allowed to react at 160 ° C. for 3.5 hours with strong stirring. The reaction was a solid black color and adhered to the flask wall.

The nitrobenzene was decanted off and the solid washed well with methanol then water. The remaining solid was dried to obtain 21.37 g of a black-green solid.

Synthesis of CuPc- (COOH) ₄ 21.37 g of CuPc- (CONH ₂ ) ₄ and 200 g of 50% aqueous potassium hydroxide solution were charged in a 200 ml four-necked flask and heated at 100 ° C. for 20 hours while stirring. After the reaction was completed, the mixture was left overnight, the supernatant was decanted, and then filtered.
CuPc- (COOK) ₄ was obtained. Dissolve it with water 1,
The insoluble matter was filtered off and then adjusted to pH 3 with an aqueous hydrochloric acid solution.
The precipitated blue precipitate was filtered off, dissolved in 1% aqueous potassium hydroxide solution 1, filtered, and adjusted to pH 3 with an aqueous hydrochloric acid solution, and the precipitated blue precipitate was filtered off. This operation was repeated 3 times to purify CuPc- (COOH) ₄ . At 100 ° C under reduced pressure
After drying for 24 hours, 7.12 g of CuPc- (COOH) ₄ was obtained.

Synthesis of CuPc- (COO-Prenyl) ₄ A four-necked flask was charged with 0.75 g of CuPc- (COOH) ₄ , 10 ml of thionyl chloride and 3 drops of pyridine, and in a nitrogen atmosphere,
The reaction was carried out at reflux temperature for 8 hours. Then, the excess thionyl chloride was completely distilled off under reduced pressure. A mixed solution of 0.86 g of prenol, 0.32 g of pyridine and 10 ml of benzene was added to the flask residue from a dropping funnel, and the mixture was reacted in a nitrogen atmosphere at reflux temperature for 20 hours.

After adding 100 ml of benzene to the reaction mixture, the insoluble matter was filtered off, and the filtrate was mixed with 100 ml of a 1% aqueous potassium hydroxide solution and then with water (1 ml).
It was washed 3 times with 00 ml and dried over anhydrous sodium sulfate.

Benzene was distilled off under reduced pressure to obtain 0.35 g of a blue solid. This solid was dissolved in 6.0 g of hot benzene, and n-hexane was added.
6.0 g was added, and the mixture was filtered while hot. The filtrate was left overnight in the refrigerator, the precipitated solid was filtered and dried, and blue crystal CuPc- (C
OO-Prenyl) ₄ 0.15 g was obtained.

The crystals obtained by recrystallization are subjected to silica gel column chromatography (developing solvent; chloroform: ethanol = 100: 2).
It was purified using.

Yield: 10.6% IR: 1720 cm ^-1 {ν of COOR} Elemental analysis C H N Cu% Analytical value 65.4 4.9 10.8 6.1 Calculated value 65.7 4.7 10.9 6.2 Example 2 Synthesis of CuPc- (CONH ₂ ) ₃ 500 ml four-necked A flask was charged with 14.4 g of trimellitic anhydride, 3.7 g of phthalic anhydride, 60.0 g of urea, 3.0 g of copper (I) chloride, 2.0 g of ammonium molybdate and 300 g of nitrobenzene, and the mixture was stirred at 150 ° C. under a nitrogen atmosphere at 3 ° C. for 3 days. Then, the reaction was carried out at 170 ° C. for 5 hours. The reaction was a solid black color and adhered to the flask wall. The nitrobenzene was decanted off and the solid was removed with methanol,
Then, it was thoroughly washed with water. The remaining solid was dried to obtain a black green solid.

Synthesis of CuPc- (COOH) ₃ CuPc- (CONH ₂ ) ₃ Total amount and 50% potassium hydroxide aqueous solution
300 g was charged into a 500 ml four-necked flask and heated at 100 ° C. for 14 hours while stirring. After the reaction, the mixture was left to stand overnight, the supernatant was decanted, and then filtered, and CuPc- (C
OOK) ₃ got. This was dissolved with water 1, the insoluble material was filtered off, and the pH was adjusted to 3 with aqueous hydrochloric acid. After filtering off the blue precipitate that had formed, 1% aqueous potassium hydroxide solution 1
After being dissolved in water and filtered, the pH was adjusted to 3 with an aqueous hydrochloric acid solution, and the precipitated blue precipitate was filtered off. This operation is repeated 3 times, and CuPc
-(COOH) ₃ was purified. It dried under reduced pressure at 100 degreeC for 24 hours, and obtained 3.87g of CuPc- (COOH) ₃ .

Synthesis of CuPc- (COO-Prenyl) ₃ A 4-necked flask was charged with 3.80 g of CuPc- (COOH) ₃ , 25 g of thionyl chloride and 3 drops of pyridine, in a nitrogen atmosphere,
The reaction was carried out at the reflux temperature for 20 hours. Then, the excess thionyl chloride was completely distilled off under reduced pressure. In the flask residue,
A mixed solution of 4.00 g of prenol, 1.89 g of pyridine and 20 g of benzene was added from the dropping funnel, and the mixture was reacted at a reflux temperature in a nitrogen atmosphere for 22 hours.

After adding 100 ml of benzene to the reaction mixture, the insoluble matter was filtered off, and the filtrate was mixed with 100 ml of a 1% aqueous potassium hydroxide solution and then with water (1 ml).
It was washed 3 times with 00 ml and dried over anhydrous sodium sulfate. Benzene was distilled off under reduced pressure to obtain 1.27 g of a blue solid. Dissolve this solid in 20.0 g of hot benzene and add 20.0 g of n-hexane.
Was added and filtered while hot. The filtrate was left overnight in the refrigerator, the precipitated solid was filtered and dried, and blue crystals CuPc- (COO-P
0.88 g of renyl) ₃ was obtained.

The crystals obtained by recrystallization were purified by silica gel column chromatography (developing solvent; chloroform: ethanol: ethyl acetate = 100: 2: 1).

IR: 1720 cm-1 {ν of COOR} Elemental analysis C H N Cu% Analytical value 64.9 4.6 12.1 6.91 Calculated value 65.8 4.4 12.3 6.96 Example 3 In Example 1, cobalt chloride (II) was used instead of copper chloride (I). And other steps are performed in the same manner, and CoPc− (COO-P
renyl) ₄ 0.51 g was obtained.

IR: 1720 cm-1 {ν of COOR} Elemental analysis C H N Co% Analytical value 65.2 4.9 12.2 5.68 Calculated value 65.9 4.7 12.6 5.78 Example 4 In Example 2, trimellitic anhydride 9.6 g and phthalic anhydride 7.4 g were added. Use the same procedure as above for CuPc- (COO-Pre
1.25 g of nyl) ₂ was obtained.

IR: 1720 cm ^-1 {ν of COOR} Elemental analysis C H N Cu% Analytical value 65.1 4.2 13.6 7.82 Calculated value 66.0 4.0 14.0 7.94 Example 5 Synthesis of CuPc- (CONH ₂ ) ₁ Anhydrous Trimerit in a 500 ml four-necked flask Acid 4.8g, phthalic anhydride 11.1g, urea 60.0g, copper (I) chloride 6.0g, ammonium molybdate 2.0g and nitrobenzene 300g were charged, and under strong stirring under nitrogen atmosphere at 150 ° C for 3 hours and then at 180 ° C. The reaction was carried out for 3 hours. The reaction product was a bluish solid.

The nitrobenzene was decanted off and the solid washed well with methanol then water. The remaining solid was dried to give a blue solid.

Synthesis of CuPc- (COOH) ₁ CuPc- (CONH ₂ ) ₁ Total amount and 50% potassium hydroxide aqueous solution
Charge 300g into a 500ml four-necked flask and stir 1 while
Heated at 00 ° C. for 16 hours. After the reaction, the mixture was left to stand overnight, the supernatant was decanted, and then filtered, and CuPc- (COOK) ₁
I got Since this solid was poorly soluble in water, it was adjusted to pH 3 with an aqueous hydrochloric acid solution, the blue solid was filtered off, and then thoroughly washed with water. Under reduced pressure, dried at 100 ℃ for 24 hours, CuPc- (COOH) ₁
Was obtained 9.16 g.

CuPc- to (COO-Prenyl) ₁ Synthesis four-necked flask, were charged CuPc- (COOH) ₁ 8.00g, thionyl chloride 50g and pyridine 3 drops, in a nitrogen atmosphere, and 25 hours at reflux temperature. Then, the excess thionyl chloride was completely distilled off under reduced pressure. A mixed solution of 4.00 g of prenol, 1.89 g of pyridine and 20 g of benzene was added to the flask residue from a dropping funnel, and the mixture was reacted in a nitrogen atmosphere at reflux temperature for 22 hours.

100 ml of methanol was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour, and then the precipitate was separated by filtration. The solid was thoroughly washed with methanol, dried under vacuum at 100 ° C., and then extracted with benzene for 48 hours using a Soxhlet extractor.

Benzene was distilled off under reduced pressure to obtain 0.81 g of a blue solid. This solid was subjected to silica gel column chromatography (developing solvent; chloroform: ethanol: ethyl acetate =
100: 2: 1) and CuPc- (COO-Prenyl) ₁ at 0.61
g got.

IR: 1720 cm ^-1 {ν of COOR} Elemental analysis C H N Cu% Analytical value 65.1 3.0 15.5 8.97 Calculated value 66.3 3.5 16.3 9.23 Example 6 CuPc- (COOH) ₄ was obtained in the same manner as in Example 1.

A 4-necked flask was charged with 1.86 g of CuPc- (COOH) ₄ , 10 ml of thionyl chloride and 0.5 g of dimethylformamide, and reacted in a nitrogen atmosphere at reflux temperature for 10 hours. Then, the excess thionyl chloride was completely distilled off under reduced pressure. A mixed solution of 1.68 g of geraniol, 0.86 g of pyridine and 10 ml of benzene was added to the flask residue from a dropping funnel, and the mixture was reacted in a nitrogen atmosphere at reflux temperature for 17 hours.

After adding 100 ml of benzene to the reaction mixture, the insoluble matter was filtered off, and the filtrate was mixed with 100 ml of a 1% aqueous potassium hydroxide solution and then 100 ml of water.
The extract was washed 3 times with ml and dried over anhydrous sodium sulfate. Benzene was distilled off under reduced pressure to obtain blue crystals CuPc- (COO-Gerany
l) 1.82 g of ₄ was obtained.

This crystal was subjected to silica gel column chromatography (developing solvent; chloroform: ethanol: ethyl acetate = 100:
Purification was performed using 2: 1 to obtain 1.49 g of a purified product.

IR: 1720 cm ^-1 {ν of COOR} Elemental analysis C H N Cu% Analytical value 69.8 6.34 8.60 4.79 Calculated value 70.4 6.22 8.64 4.90 Examples 7 and 8 In Example 1, instead of copper chloride (I), iron chloride ( II) 3.84 g or nickel (II) chloride 3.89 g, but otherwise the same procedure is performed to obtain FePc- (COO-Prenyl) ₄ with 0.62 g.
0.58 g of NiPc- (COO-Prenyl) ₄ was obtained.

FePc- (COO-Prenyl) ₄ IR: 1720cm ^-1 {ν of COOR} Elemental analysis CHN Fe% Analytical value 65.2 4.92 10.4 5.33 Calculated value 66.1 4.76 11.0 5.49 NiPc- (COO-Prenyl) ₄ IR: 1720cm ^-1 {Ν of COOR} Elemental analysis C H N Ni% Analytical value 65.4 4.87 10.4 5.56 Calculated value 66.0 4.74 11.0 5.76 Example 9 In Example 2, pyromellitic anhydride 5.45 g and phthalic anhydride 11.1 g were used, but otherwise the same. Go to CuPc− (COO-
0.76 g of Prenyl) ₂ was obtained.

IR: 1720 cm ^-1 {ν of COOR} Elemental analysis C H N Cu% Analytical value 64.8 4.3 13.4 7.77 Calculated value 66.0 4.0 14.0 7.94 Examples 10, 11, 12 In Example 1, instead of copper chloride (I) chloride Zinc (II) 3.85 g or magnesium (II) chloride 3.76 g or aluminum (III) chloride was used in the same manner as above, and 0.55 g of ZnPc- (COO-Prenyl) ₄ or MgPc- (C
0.28 g of OO-Prenyl) ₄ or AlPcCl- (COO-Prenyl) ₄
0.18 g was obtained.

ZnPc- (COO-Prenyl) ₄ IR: 1720cm ^-1 {ν of COOR} Elemental analysis CHN Zn% Analytical value 65.2 4.82 10.4 6.21 Calculated value 65.5 4.71 10.9 6.37 MgPc- (COO-Prenyl) ₄ IR: 1720cm ^-1 {Ν of COOR} Elemental analysis CHN Mg% Analytical value 67.4 4.97 10.9 2.33 Calculated value 68.3 4.91 11.4 2.47 AlPcCl- (COO-Prenyl) ₄ IR: 1720cm ^-1 {COORν} Elemental analysis CHN Al% analysis Value 64.4 4.86 10.4 2.42 Calculated value 65.7 4.73 10.9 2.64 Example 13 The same procedure as in Example 1 was repeated except that 10.9 g of pyromellitic anhydride was used instead of trimellitic anhydride in Example 1, and CuPc- (COOH ) ₈ 5.25 g was obtained.

A 100 ml flask was charged with 1.0 g of CuPc- (COOH) ₈ , 0.1 g of P-toluenesulfonic acid and 50 ml of mesitylene,
The temperature was maintained at 150-160 ° C for 96 hours. The solvent was removed under reduced pressure, and the remaining solid was purified by silica gel column chromatography using a developing solvent of n-hexane: tetrahydrofuran = 1: 1 to obtain 0.52 g of CuPc- (COO-Prenyl) ₈ .

IR: 1720 cm ^-1 {ν of COOR} Elemental analysis C H N Cu% Analytical value 64.4 5.66 7.52 4.18 Calculated value 65.2 5.47 7.61 4.31 Reference example 1 CuPc- (COO-Prenyl) ₄ obtained in Example 1 was 1 mmol / 1
Benzene solution.

FILM BALANCE made by LAUDA was charged with distilled water twice and kept at 20 ° C. The above solution was dropped on the water surface, the barrier was adjusted so that the surface pressure was 20 dynes / cm, and a microscope slide glass well cleaned with isopropanol was gradually immersed (1 mm / min) in water. At this time, the barrier is automatically adjusted to maintain the surface pressure.

Then, the slide glass is pulled up in the same manner. By repeating this operation, a plurality of coatings could be formed.

Similarly, a film could be formed by the horizontal deposition method.

<Effects of the Invention> As described above, the solvent-soluble phthalocyanine compound of the present invention,-(COOR) _m is bonded to the phthalocyanine ring, compared to a phthalocyanine compound without a substituent, the solubility is significantly improved. To do. That is, it dissolves very well in benzene, chloroform, toluene, tetrahydrofuran, dioxane, dimethylformamide, acetone, methyl ethyl ketone, etc., and it also contains polymers such as vinyl chloride, vinyl chloride-vinyl acetate copolymer, polyester resin, epoxy resin. It has a very high compatibility with, and so on.

Therefore, the compound of the present invention can be efficiently dissolved in a solvent and purified by recrystallization or liquid chromatography. The compound of the present invention can be easily purified, and a highly pure product can be easily obtained. Furthermore, thinning by the LB method, thinning by spin coating, etc. become easy, and the industrial value is high.

Claims (1)

(57) [Claims] 1. A general formula MPc- (COOR) _m (wherein M represents a hydrogen atom or an optionally halogenated or oxidized metal atom, R represents a prenyl group or a polyprenyl group, and m represents 1 to 1). Represents an integer of 8 and Pc represents a phthalocyanine).