JPH04352786A - Naphthalocyanine derivative containing perfluoroalkyl group - Google Patents

Abstract

PURPOSE:To provide the subject new compound useful as a polymeric materials such as optical information recording medium, photoelectric conversion medium, photosensitive material for electrophotography, high-performance film and thin film. CONSTITUTION:The compound of formula I (R is 1-10C alkyl; RF is 1-6C perfluoroalkyl), e.g. perfluoropropyl-bis(trihexylsiloxy)-silicon naphthalocyanine. The compound of formula I can be produced by reacting a diperfluoroalkanoyl peroxide of formula II with a naphthalocyanine compound of formula III preferably at 0-100 deg.C for 0.5-20hr.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to novel perfluoroalkyl group-containing naphthalocyanine derivatives.

0002

BACKGROUND OF THE INVENTION Conventionally, cyanine compounds have been known as near-infrared and infrared absorbers, but the cyanine compounds are generally unstable to light and heat. On the other hand, naphthalocyanine compounds are very stable against light, heat, humidity, etc., have excellent fastness, and have a strong color tone, so they can be used as various dyes, pigments, optical information recording media, photoelectric conversion media, etc. It is attracting attention as a polymer material for electrophotographic photoreceptors and highly functional films or thin films obtained by blending with polymers.

However, naphthalocyanine compounds generally have very poor solubility in organic solvents, so
The reality is that it is difficult to form a film by film-forming processing, and therefore there is a strong desire to develop a compound that has the excellent properties of naphthalocyanine and can be processed into a film-forming process.

0004

[Problems to be Solved by the Invention] An object of the present invention is to provide a novel perfluoroalkyl group-containing naphthalocyanine derivative that has excellent weather resistance, extremely high solubility in various organic solvents, and can be processed into a film. Our goal is to provide the following.

[0005]

[Means for Solving the Problems] According to the present invention, the following general formula 2 (wherein R represents an alkyl group having 1 to 10 carbon atoms, and RF represents a perfluoroalkyl group having 1 to 6 carbon atoms) ) A perfluoroalkyl group-containing naphthalocyanine derivative (hereinafter referred to as naphthalocyanine derivative A) is provided.

[0006]

[Chemical 2]

The present invention will be explained in more detail below.

The perfluoroalkyl group-containing naphthalocyanine derivative of the present invention is the naphthalocyanine derivative A represented by the general formula 2, and in this case, when R is an alkyl group of 11 or more, it is difficult to manufacture. .

Specific examples of the naphthalocyanine derivative A represented by the general formula 2 include perfluoromethyl-bis(trihexylsiloxy)silicon naphthalocyanine, perfluoroethyl-bis(trihexylsiloxy)silicon naphthalocyanine, and perfluoroethyl-bis(trihexylsiloxy)silicon naphthalocyanine. Propyl-bis(trihexylsiloxy) silicon naphthalocyanine, Perfluorobutyl-bis(trihexylsiloxy) silicon naphthalocyanine, Perfluoropentyl-bis(trihexylsiloxy) silicon naphthalocyanine, Perfluorohexyl-bis(trihexylsiloxy) silicon naphthalocyanine etc. can be preferably mentioned.

Further, in order to prepare the naphthalocyanine derivative A of the present invention, for example, a diperfluoroalkanoyl peroxide represented by the following general formula 3 is reacted with a naphthalocyanine represented by the following general formula 4. can be obtained easily.

[0011]

[C3]

0012

[C4]

Specific examples of diperfluoroalkanoyl peroxides represented by the general formula 3 include bis(perfluoroacetyl) peroxide, bis(perfluoropropionyl) peroxide, bis(perfluorobutyryl) peroxide, and bis(perfluoropentanoyl) peroxide. , bis(perfluorohexanoyl) peroxide, bis(perfluoroheptanoyl)
It is a peroxide.

[0014] The reaction between the diperfluoroalkanoyl peroxide and the naphthalocyanine can be carried out at normal pressure, preferably at a reaction temperature of 0 to 100°C.
By reacting for 0.5 to 20 hours, the naphthalocyanine derivative A of the present invention can be obtained. When the reaction temperature is less than 0°C, the reaction takes a long time and
If the temperature exceeds 0°C, the pressure during the reaction becomes high and the reaction operation becomes difficult, which is not preferable.

[0015] When the diperfluoroalkanoyl peroxide and the naphthalocyanine are reacted, the reaction is carried out in the presence of a solvent such as a halogenated aliphatic compound in order to facilitate the handling of the diperfluoroalkanoyl peroxide. can be done. As the halogenated aliphatic solvent, 1,1,2-trichloro-1,2,2-trifluoroethane and the like are industrially most preferred.

The reaction product obtained by the above reaction can be purified by known methods such as recrystallization and column chromatography.

[0017]

Effects of the Invention The perfluoroalkyl group-containing naphthalocyanine derivative of the present invention is a new substance and is soluble in various organic solvents, so it can be used in optical information recording media, photoelectric conversion media, electrophotographic photoreceptors, and photoreceptors. It is useful as a polymeric material such as a highly functional film or thin film obtained by blending with molecules.

[0018]

EXAMPLES The present invention will be explained in more detail below with reference to Examples and Test Examples, but the present invention is not limited thereto.

[0019]

[Example 1] 0.5 g (0.37 mmol) of bis(trihexylsiloxy) silicon naphthalocyanine was added to 20 ml of chloroform and mixed, and 1,1 containing 0.16 g (0.37 mmol) of bis(perfluorobutyryl) peroxide was added. , 3.2 g of 2-trichloro-1,2,2-trifluoroethane solution was added and heated at a temperature of 40° C.
A time reaction was performed. After the reaction is complete, the reaction mixture is reduced to 0.5
It was washed with a wt % aqueous sodium hydroxide solution and a saturated saline solution. Next, the obtained chloroform layer was dried using magnesium sulfate, the product was purified by column chromatography, and further recrystallized using a hexane-ethanol mixed solution. As a result, the following structural formula 5
Perfluoropropyl-bis(trihexylsiloxy)silicon naphthalocyanine represented by was obtained in a yield of 43%.

[0020]

[C5]

[0021] The number of perfluoroalkyl groups introduced in the above naphthalocyanine was determined using o-chlorobenzotrifluoride as an internal standard solution.
- It was determined by NMR that there was only one. UV (measurement solvent:
chloroform), IR, 1H-NMR, 19F-NMR
, the melting point is shown below. UV (nm) 781,766 IR (cm￣1) 1350 (CF3), 1225 (
CF2) 1H-NMR (CDCl3) δ 10.55-9.95 (m, 7H) 9.15-8
．． 45 (m, 8H), 7.95 (b, 8H) 1.00 to 0.00 (m, 54H), -0.95 (b,
12H) -1.90 to -2.25 (m, 12H) 19F-NMR
(CDCl3, external standard CF3CO2H) δ -2.
8 (CF3), -18.0 (CF2), -45.7 (C
F2) Melting point (℃) 226-228

[0022]

[Test Example] Perfluoropropyl obtained in Example 1
Bis(trihexylsiloxy)silicon naphthalocyanine was dissolved in various solvents shown in Table 1, and its solubility was investigated. Furthermore, as a comparative example, the solubility of metal-free naphthalocyanine was also investigated. The results are shown in Table 1.

[0023]

[Table 1]

Claims (1)

[Claims] [Claim 1] The following general formula 1 (in the formula, R is 1 carbon number
~10 alkyl group, RF represents a perfluoroalkyl group having 1 to 6 carbon atoms) A naphthalocyanine derivative containing a perfluoroalkyl group. [Chemical formula 1]