JP2853546B2 - Method for producing phthalocyanine ring-containing compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a phthalocyanine ring-containing compound having a light absorption band in the visible region.

[0002]

BACKGROUND OF THE INVENTION Phthalocyanines are compounds similar to porphyrins and are generally used as dyes and organic pigments. However, due to its unique structure, it is difficult to mix with solvents and other substances except for special solvents such as quinoline, so that it is difficult to handle and its use is limited.

On the other hand, siloxanes having a phthalocyanine ring in the side chain are already known (Schoch; J. Am.
Chem. Soc. , 1979, 97, 3039: Ha
yashita et al; Synthetic M
et al., 1991, 41-43) have not yet been obtained which is bound to a polymer such as polysilane or polydisilanilenephenylene, which can be expected to exhibit functionalities due to δ-conjugation and δ-π conjugation.

Therefore, development of phthalocyanine ring-containing compounds having excellent compatibility with various substances and various functions has been desired.

[0005]

Means for Solving the Problems and Actions The present inventor has conducted intensive studies to meet the above-mentioned demands. As a result, dihalogeno (phthalocyanino) silicon having the following structural formula (1) and organic silicon having the following structural formula (2) have been obtained. By reacting a silicon compound and, if necessary, an organosilicon compound of the following structural formula (3) in the presence of a compound selected from an alkali metal and an alkaline earth metal and a complex salt thereof, and contacting with oxygen if necessary. It has been found that a phthalocyanine ring-containing compound represented by the general formula (4) can be obtained.

[0006]

Embedded image (In the above formula, X is a halogen atom, R is a hydrogen atom or a monovalent organic group having 1 to 14 carbon atoms, and each R may be the same or different from each other. A and B may be the same or different from each other. A different divalent organic group having 1 to 10 carbon atoms or -O- or PC is a phthalocyanine ring-containing group represented by the following formula (5) or (6), and n, m, k and s are each n> 0. , 0.5 ≧ m ≧
0, 0.4 ≧ k ≧ 0.002, n + m + k = 1, 250
0 ≧ s ≧ 5 is a positive number. )

[0007]

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The phthalocyanine ring-containing compound of the above formula (4) has a remarkably improved compatibility with various resins and solvents as compared with a simple phthalocyanine, and has a specific light in the ultraviolet and visible regions. It has absorption and the main chain skeleton is a silicon-containing group, so it exhibits electrical conductivity and has good film-forming properties. Therefore, it can be used as a colorant, and it can be used as a photosensitizer and a photoresponsive material. The present invention has been found to be effective as a functional material such as an electric conductive material and a photoelectric conversion material, and has led to the present invention.

Hereinafter, the present invention will be described in more detail. In the method for producing a phthalocyanine ring-containing compound of the present invention,
The starting materials are the compounds of the following structural formulas (1) and (2) and optionally the compound of the formula (3).

[0010]

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In the above formula, X is a halogen atom such as fluorine, chlorine and bromine, and usually chlorine is used.

R is the same or different monovalent organic group having 1 to 14 carbon atoms, such as a methyl group, an ethyl group, a pentyl group,
Alkyl group such as hexyl group, phenyl group, tolyl group,
Aryl groups such as xylyl group, benzyl group, phenethyl group, aralkyl group such as 4-biphenylethyl group, other hydrocarbon groups such as alkenyl group such as vinyl group, dihydropyranyl group, oxygen-containing group such as anisyl group, Examples include nitrogen-containing groups such as a 4- (dimethylamino) phenyl group and 3- (N-pyroyl) ethyl group, and silicon-containing groups such as a trimethylsilyl group, a phenyldimethylsilyl group, and a pentamethyldisilanyl group. .

A and B each represent a divalent organic group having 1 to 10 carbon atoms or -O-, and the divalent organic group includes a methylene group, an ethylene group, a phenylene group, a naphthylene group, an ethenylene group, an ethynylene group, Examples thereof include a thienylene group and a pyridinylene group.

Here, the compound of the formula (1) is, for example, Ma
cromolecules 1978, 1,186-1
91, and the compounds of formulas (2) and (3) can be prepared, for example, by the method of Orga
nometallics 1987, 6,1673-1
679 can be produced by a known method.

In the present invention, the above formulas (1) and (2)
Is reacted with a compound of the formula (3) if necessary in the presence of a compound selected from alkali metals, alkaline earth metals and complex salts thereof.

The alkali metals used in this case include metal sodium, metal lithium, metal potassium,
Examples thereof include magnesium (I) iodine, magnesium (I) bromide, and sodium naphthalenide. Among them, sodium metal and sodium naphthalenide are preferred from the viewpoint of reaction activity and ease of handling.

The amounts of these substances used are determined by the formulas (1) to (4).
The amount is preferably equivalent to or more than the total halogen amount of the compound (3), and about 1.1 to 2.5 times in the actual reaction.

It is recommended to carry out the above reaction in a solvent. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as octane, isooctane and decane, diethyl ether, tetrahydrofuran, and the like.
Ether solvents such as 1,2-dimethoxyethane, diethylene glycol dimethyl ether and tetraethylene glycol diethyl ether are generally used.

In this case, it is recommended to first react the compounds of the formulas (2) and (3) with an excess of an alkali metal and then add the compound of the formula (1) to carry out the reaction.

The reaction temperature is 0 to 200 ° C., especially 20 to 18 ° C.
0 ° C., and the reaction time is usually 0.1
~ 20 hours.

The above reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon, and more preferably in a substantially anhydrous state, whereby PC represented by the following formula (4) is obtained. Although a compound represented by the following formula (5) is obtained, silicon in the phthalocyanine ring is in a highly coordinated state and its radical is easily generated stably. And a siloxy group of the following formula (6).

[0022]

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[0023]

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Further, according to the production method of the present invention, it is possible to obtain a compound having a wide range of molecular weights from low to high molecular weight. However, if the phthalocyanine ring is too large, the compatibility is deteriorated. Does not appear. Therefore, in order to increase the compatibility with various substances and to exert the effect of the phthalocyanine ring, in the above formula (4), 0.4 ≧
k ≧ 0.002, more preferably 0.2 ≧ k ≧ 0.00
5 and 2500 ≧ s ≧ 5, more preferably 200
≧ s ≧ 10. Further, when the number of polyfunctional groups increases, three-dimensionalization proceeds, and the molecular weight and the yield are reduced. Therefore, 0.5 ≧ m ≧ 0. Therefore, the raw materials (1), (2) ) And (3) are preferably used in the above-mentioned ratio for the reaction. In addition, the control of the molecular weight is as follows.
At a desired time, triorganohalogenosilane such as phenyldimethylchlorosilane and trimethylchlorosilane may be added to capture the active terminal and block it.

After the above reaction, post-treatment purification can be carried out according to a conventional method. The yield is usually 25 to 75%.

According to the present invention, as described above, a phthalocyanine ring-containing compound represented by the following general formula (4) is obtained.

[0027]

Embedded image (Wherein, R, A, and B have the same meanings as above, PC is a phthalocyanine ring-containing group represented by the following formula (5) or (6), n, m, k, and s are each n> 0, 0.5 ≧ m ≧
0, 0.4 ≧ k ≧ 0.002, n + m + k = 1, 250
0 ≧ s ≧ 5 is a positive number. )

[0028]

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This compound (4) has absorption bands in the ultraviolet region and the visible region, respectively. This is because the compound (4) contains a phthalocyanine ring and the interaction of the δ-π electron system derived from the disilanilene site.
The compound (4) may be used not only in the solvent used in the above-mentioned reaction, but also in methyl ethyl ketone, ethyl acetate and various other solvents, as well as vinyl polymers such as polyvinyl chloride, polyvinyl acetate and polymethyl methacrylate. -Compatible with polyamides such as nylon, polyesters such as polyethylene terephthalate, and other various polymers and plastics.

[0030]

According to the present invention, the compatibility is dramatically improved as compared with a single phthalocyanine, the application as a colorant is widened, and the phthalocyanine has a specific light absorption band in the ultraviolet and visible regions. Since the main chain skeleton is a silicon-containing group, electric conductivity is exhibited by doping, and further excellent film-forming property is obtained. Therefore, a photosensitizer, a photoresponsive material, an electroconductive material, A phthalocyanine ring-containing compound of the above formula (4) useful as a conversion material or the like can be easily and reliably synthesized.

[0031]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Example] 3 replaced with an argon atmosphere
In a 00 ml flask, 0.61 g of sodium (27
mmol) and 50 ml of dry THF were added, and 3.7 g (29 mmol) of naphthalene was added with stirring at room temperature, followed by stirring for 5 hours. Under ice cooling, 3.1 g (8.0 mmol) of 1,4-bis (chloromethylphenylsilyl) benzene
l) and 25 ml of a THF solution of 0.61 g (2.0 mmol) of 1,4-bis (dichloromethylsilyl) benzene were added dropwise, followed by stirring at room temperature for 15 hours. Thereafter, 0.61 g (1.0 mm) of dichloro (phthalocyanino) silicon
ol) in 25 ml of a THF suspension and stirring was continued for 20 hours. Then, phenyldimethylchlorosilane 0.6
g was added to capture the active end and destroy excess sodium. Finally, hydrolysis, liquid separation, washing and filtration were carried out by a conventional method, and then reprecipitation from methanol gave 2.1 g of a green solid. From a nuclear magnetic resonance spectrum, an infrared absorption spectrum, a gel permeation chromatograph and the like, it was confirmed to be a compound of the following formula (I).

[0033]

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Comparative Example A reaction was carried out in the same manner as in Example 1 except that dichloro (phthalocyanino) silicon was not used and phenyldimethylchlorosilane was 1.16 g, but the same amount of raw material was used. 2.5 g were obtained.
This compound was confirmed to be a compound of the following formula (II) from a nuclear magnetic resonance spectrum, an infrared absorption spectrum, a gel permeation chromatograph and the like.

[0035]

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Next, the absorption spectrum, ionization potential and electric conductivity of the compound I obtained in the example and the compound II obtained in the comparative example were measured. Figure 1 shows the results
And Table 1.

The method for measuring the ionization potential is described in Surface Analysis System Model AC- manufactured by Riken Keiki Co., Ltd.
This was performed using No. 1. For the sample, a film was formed by coating a polymer dissolved in toluene on a glass substrate, and the film was measured and measured as a work function in the air under normal temperature and normal pressure.

The method for measuring the conductivity is as follows. A film-like coating film of a sample is formed on a glass substrate on which four linear metal thin films are vacuum-deposited, a constant voltage is applied, and the sample is brought into contact with a dopant vapor. This was performed by a method of measuring the current flowing through. The dopants used were acceptor-type iodine and ferric chloride. For iodine doping, the measurement sample was brought into contact with iodine vapor in a light-shielded and sealed state, the time-dependent change of the direct current was tracked, and the conductivity was determined from the current value at which the state became stable. In the case of ferric chloride having a low vapor pressure, the heating was performed under reduced pressure and heating. First, the container containing the solid ferric chloride and the sample film for measurement is connected to a vacuum pump, the pressure is reduced to 4 mmHg, and the ferric chloride at the bottom is heated by a mantle heater to perform doping. The heating was stopped as it was, and the electrical conductivity was determined from the current value when allowed to cool to room temperature.

[0039]

[Table 1]

As shown in Table 1, Compound I and Compound II
Have almost the same molecular weight, but differ greatly in photoelectron properties. Compound I is in the visible region (320-460 nm, 600
It has a characteristic absorption band at ７720 nm), the ionization potential is lower than that of Compound II, and the conductivity is greatly improved as compared with Compound II having no phthalocyanine ring.

[Brief description of the drawings]

FIG. 1 is an ultraviolet absorption spectrum of the compounds obtained in Examples and Comparative Examples.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 77/60 C08G 77/48

Claims (1)

(57) [Claims] 1. The following structural formula (1):(Wherein, X represents a halogen atom.)
Geno (phthalocyanino) silicon and the following structural formula (2) XR_TwoSi-A-SiR_TwoX (2) (wherein, R is a hydrogen atom or a monovalent group having 1 to 14 carbon atoms)
In the formula, each R may be the same or different from each other. A is
X is a divalent organic group having 1 to 10 carbon atoms or -O-, and X is
Means the same as above. ) Organic silicon compound represented by
And, if necessary, the following structural formula (3) X_TwoR Si-B-SiR X_Two ... (3) (wherein, B is a divalent organic group having 1 to 10 carbon atoms or -O-
And R and X have the same meaning as described above. )
Organic silicon compounds to be used
In the presence of compounds selected from the class of metals and their complex salts
And represented by the following general formula (4).
For producing a phthalocyanine ring-containing compound. Embedded image(Where R, A, and B have the same meanings as above, and PC is
Including a phthalocyanine ring represented by the following formula (5) or (6)
N, m, k, and s are respectively n> 0, 0.5 ≧ m ≧
0, 0.4 ≧ k ≧ 0.002, n + m + k = 1, 250
0 ≧ s ≧ 5 is a positive number. )