JPS6253989A - Phthalocyanine compound - Google Patents

Abstract

PURPOSE:A compound shown by the formula I(PC is phthalocyanine residue; L is alkylene; n is >=1 integer). EXAMPLE:A compound shown by the formula II[central atom is Co(II)]. USE:An intermediate for synthesizing in high yield a polymerizable or cross linkable phthalocyanine compound useful as a sensitized material for electropho tography, etc., having high solubility and compatibility. PREPARATION:For example, a carboxyl group-containing phthalocyanine such as Co(II) phthalocyaninetetracarboxylate, etc., as a starting raw material is reacted with an extremely excess amount of a dihydric alcohol shown by the formula HO-L-OH such as ethylene glycol, etc. in the presence of an acid catalyst such as benzenesulfonic acid, etc., at 150-250 deg.C for 1-7 days and esterified through dehydrochlorination.

Description

[Detailed description of the invention] Background of the invention Technical field The present invention relates to phthalocyanine compounds.

Prior art and its problems Metal phthalocyanines contain metal ions in a large π-electron conjugated system, so they have attracted attention as materials for light absorption, conduction, photoelectric grooves, energy conversion, electrodes, catalysts, etc., and various studies have been conducted on them. It is being said.

However, phthalocyanine has low solubility in solvents and low compatibility with high molecular weight polymers, making it difficult to mold into films and the like, and also having poor stability after molding.

Therefore, the present inventors proposed various polymers having phthalocyanine in the main chain or in the side chain (Makromol
, Chew, 3014801981. Same ±207
3, 1979, etc.) found that it can be easily formed into films, etc., and can be made into a material with advanced functions.

Japanese Patent Application No. 59-39997 discloses phthalocyanine as a monomer which itself has high solubility and compatibility and can be polymerized or crosslinked by electron beams, ultraviolet rays, etc.

That is, a phthalocyanine having a carboxyl group synthesized by a known method is converted into an acid chloride using thionyl chloride, and (here, L represents an alkylene group and R represents hydrogen or a lower alkyl group) is added to the acid chloride, followed by heating. The reaction is carried out by

However, the yield of this method is still not sufficient and some improvement is required.

II. OBJECTS OF THE INVENTION The object of the present invention is to be able to synthesize a phthalocyanine compound in a high yield, which itself has high solubility and compatibility, and which can be polymerized or crosslinked by electron beams, ultraviolet rays, etc. The purpose of this invention is to provide a good phthalocyanine compound.

■Disclosure of invention These objects are achieved by the invention described below.

That is, the present invention is a phthalocyanine compound characterized by being represented by the following formula.

formula %formula%) (In the above formula, Pc represents a phthalocyanine residue, L represents an alkylene group.

n is an integer of 1 or more. ) (1) Specific Structure of the Invention The specific structure of the present invention will be explained in detail below.The 2-talocyanine compound of the present invention is represented by the following formula.

Formula % Formula %) In the above formula, L represents an alkylene group, but the alkylene group may be linear or branched, and there is no particular restriction on the number of carbon atoms.
It may be about 30 or less, but usually 1 to 5. In particular, it is about 2 to 3.

Further, n is an integer of 1 or more, and may generally be any integer from 1 to 8, but is usually 2.4 or 8, particularly 2 or 4.

On the other hand, Pc represents a monovalent or higher valence residue of phthalocyanine, and the group represented by -Coo-L-0) is bonded to the benzene ring forming the phthalocyanine ring.

In this case, the above group is bonded to any position of the benzene ring of the phthalocyanine, but is usually bonded to the 3-position or 4-position.

Therefore, the bonding position of the above group is 3.3' when n=2
- is the main one, but others are 3゜4'-13, 3"-13
,4"- or 4°A'-ps*Z Also, when n=4, 3.3', 3", 3"- are the main ones, and when n=8, 3, 4.3', 4'.

Mainly 3", 4", 3", 4"-.

Furthermore, the central atom of phthalocyanine is not particularly limited, and in addition to Fe, Cu, Co, Ni, etc., V, Pb, St
, Ge, Sn, Ai.

In addition to Ru, 'Ti, Zn, Mg, Mn, VO, etc., H2 is also possible.

However, among these, Fe, Ni, and C.

Or Cu is suitable.

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

Note that other substituents are not usually bonded to the phthalocyanine residue, but the benzene ring of Pc in particular has a carboxy group,
A substituent such as a sulfo group or an amino group may be bonded.

Such a phthalocyanine compound is synthesized as follows.

First, a phthalocyanine having n, usually 2.4 to 8 carboxyl groups in the benzene ring is usually synthesized.

These synthesis methods are known; for example, when n=2, P2O3, n
=4 is Makromol, Chers.

U mouth = 571 (1980), 1 bid, , ±242
9-2438 (1981), n=8, Makromol, Chew, 181
．． 5E15 (1980).

The following route is followed to synthesize the phthalocyanine compound of the present invention from this phthalocyanine having a carboxy group, which is schematically shown below.

As a first route, a phthalocyanine having a carboxyl group and a large excess of HO-L-OH (e.g., ethylene glycol, propylene glycol, butylene glycol, etc.) are combined with an acid catalyst (e.g., p-toluenesulfonic acid, benzenesulfonic acid, etc.). phenolsulfonic acid, etc.) to perform dehydration and esterification. In this case, the reaction is carried out at a temperature of 150 to 250°C for about 1 to 7 days.

As a second route, a phthalocyanine having a carboxy group is converted into an acid chloride using thionyl chloride. Then, dehydrochlorination and esterification are performed with dehydrated 0H-L-OH. In this case, the reaction temperature is 150 to 250.
It is carried out for 1 to 7 days at ℃.

The above reaction product is generally prepared using acetone to obtain a precipitate, which is filtered, dried, and then dissolved in DMF, THF, benzene, etc., and then re-dissolved in acetone, ethyl acetate, methanol, etc.
Obtain crystals generated using water or the like.

The reaction product thus obtained has a yield of 70-1
As high as 00%.

In addition, in the infrared absorption spectrum, 3400 to 3450
c "νOH of 1 and ν of 2925 to 2940 cm-'
and OH2 νc=o from 1710 to 1720 cm-1 appears.

As for the melting point, it generally thermally decomposes at around 400°C.

It also has good solubility in organic solvents, and if it itself has poor solubility, it is also possible to change the terminal group =CH to a group with good solubility, such as a vinyl group.

In order to introduce a vinyl group, it is sufficient to react with CH2=CHRCOCI, which gives a phthalocyanine polymer by using an electron beam, ultraviolet rays, or a polymerization initiator.

■ Specific effects of the invention The phthalocyanine compound of the present invention can be synthesized in good yield using a known phthalocyanine having a carboxy group as a starting material, and has high solubility, so it itself has high solubility and compatibility. It is expected to be used as an intermediate in the synthesis of phthalocyanine as a heptamer that can be polymerized or crosslinked by electron beams, ultraviolet rays, etc. Using the phthalocyanine compound of the present invention as an intermediate, the above-mentioned phthalocyanine having a vinyl group can be synthesized in a high yield, resulting in the realization of high-performance materials that have a wide range of uses, such as photosensitive materials for electrophotography and optical recording materials. becomes possible.

■ Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and Example 1 will explain the present invention in further detail.
o+1oll:hem,.

1111, 571 (1980)].
) 7 Talocyanine tetracarboxylic acid was synthesized. Purified ethylene glycol 30mJ for 1.0g of this compound
1 and P-1 luenesulfonic acid were added in catalytic amounts, and the mixture was reacted at 150°C for 24 hours. The reaction product was precipitated using acetone, filtered and dried to obtain PC(-COOCH2CH2
0H)4 [Central atom; 11.3 g of Co(II) was obtained.

Yield 100% Infrared absorption spectrum: H3450cm-'.

shico22930ca+-1゜ν(H,01?20c+++”Electronic spectrum 867ns(loge=
4.75) (DMF solution) 628n
m sh * (4,70) 325n Peng (4,85) (This sh shows an absorption shoulder) Thermal decomposition temperature 393°C Example 2 Synthesis of Fe(m) phthalocyanine tetracarboxylic acid according to the literature (Example 1) did. 1.0 g of this compound was made into an acid chloride using thionyl chloride, and the mixture was reacted with dehydrated ethylene glycol 30IllI at 200°C. Ethylene gelicol was removed from the reaction solution by distillation, and acetone was poured into it, filtered, dried, and P c (-COO
CH2CH20H) [center atom; Fe(m)] was obtained.

Yield 80% Infrared absorption spectrum νon 3400cm-'
.

shiCH22925c+s-1+ shic,,o 1720cm-”Electronic spectrum 833nm (Ioge=
4.74) (D) IF warm solution 580
n+s sh (4,35) 332 nm (4,74) Thermal decomposition temperature 338°C Example 3 The central atom Fe (m) (7
)Pc+cOOcH2CH20H)4 was synthesized.

Yield 60% Example 4 The central atom C was prepared in the same manner as in Example 2.

(II) (7) Pc(7COOCH2CH20H)4 was synthesized.

Yield 64% Example 5 By the same method as in Example 1, the central atom was N1(II).
P C+ C00CH2CH20H) was synthesized.

Yield 20% Infrared absorption spectrum ν□ H3400c tm −
'.

CH22940cm-'.

Sh c,, o 1710 cm-' Electronic spectrum 870 nm sh (log e
(DMF solution) = 4
．． 09) E107nm (4,34) 338nm (4,34) Thermal decomposition temperature 290nm sh (4,58)
370°C Example 6 By the same method as in Example 1, the central atom Cu(II)
Pc+COOCH2CH20H)4 was synthesized.

Yield 18% Infrared absorption spectrum νOH3400cm-'.

CH22940cm-' * νc, o 1710cm-' Electronic spectrum 871nm (logε=4
．． 15) (DMF solution) 804nm
(4,49)333r++s (4,52) Thermal decomposition temperature 383°C Example 7 Co(II) phthalocyanine tetracarboxylic acid and propylene glycol were reacted in the same manner as in Example 1,
It was purified in the same way.

Yield 60% Infrared absorption spectrum ν□H3400cm-' + cH22940cm-'.

νc=o 1720cm-' Electronic spectrum 888nrrr (logε=
4.82) (DMF solution) f33
or+m sh(4,ftO)323nm (4,7
1) Thermal decomposition temperature 388°C Experimental Example 1 The sample of Example 1.2 was reacted with methacryloyl chloride.

That is, methacryloyl chloride is P c (-C00C
Pc+COOCH2C was reacted with H2CH20H)4 in the presence of a polymerization inhibitor hydroquinone in a benzene solution.
H20COCCH3=CH2)4 was obtained.

Detailed experimental conditions, yield, etc. are shown in Table 1.

Note that the reaction product is Compound A depending on the sample used.
, B.

In addition, the yield is P c (-COOCH2CH20H)
It is from 4.

For comparison, Table 1 shows Japanese Patent Application No. 59-39997.
The yield obtained by the method described in the above is also listed (compounds synthesized by this method are designated as C and D).

Table 1 A Example I Co 60 2 97
B Example 2 Fe 80 2 82
C comparison Co --17,50
Comparison Fe--12, 7 From the results in Table 1, it was found that according to the present invention, vinyl group-introduced phthalocyanine can be obtained using phthalocyanine tetracarboxylic acid as a starting material in a much higher yield than conventional methods. Recognize.

Experimental example 2 Using compounds A and B obtained in Experimental Example 1.

4-vinylpyridine (4-VP) and 2-hydroxyethyl methacrylate (2-HEMA) and azobisisobutyronitrile (AIB) in a nitrogen stream or atmosphere.
A solution was prepared using N) as an initiator to obtain a polymer.

Table 2 shows the experimental conditions, yield, etc.

The molar ratio of phthalocyanine was determined by metal atomic absorption spectroscopy.

Table 2 From the results in Table 2, it can be seen that the vinyl group-containing phthalocyanine compound derived from the present invention undergoes addition polymerization with a vinyl monomer to obtain a polymer having phthalocyanine in the main chain.

Claims (1)

[Claims] A phthalocyanine compound represented by the following formula. Formula Pc-(COO-L-OH)_n {In the above formula, Pc represents a phthalocyanine residue, L represents an alkylene group, and n is an integer of 1 or more. }