JPH0378871B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to novel phthalocyanine compounds. Prior art and its problems Metal phthalocyanine has metal ions in a large π-electron conjugated system, so it has properties such as light absorption, conduction, and
It has attracted attention as a material for photovoltaics, energy conversion, electrodes, catalysts, etc., and various research is being conducted on it. 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.Chem. 30 1480 1981, 180 2073).
(1979, etc.) and found that it can be easily molded into films and can be made into a material with advanced functions. However, if phthalocyanine itself is provided as a monomer that has high solubility and compatibility and can be polymerized or crosslinked by electron beams, ultraviolet rays, etc.
It is believed that high-performance materials with even wider applications will be realized. OBJECTS OF THE INVENTION An object of the present invention is to provide a phthalocyanine compound which itself has high solubility and compatibility and can be polymerized or crosslinked by electron beams, ultraviolet rays, etc. 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 {In the above formula, Pc represents a phthalocyanine residue, L represents an alkylene group, R represents hydrogen or a lower alkyl group, and n is an integer of 1 or more. } Specific Structure of the Invention The specific structure of the present invention will be described in detail below. In the above formula, L represents an alkylene group, and the alkylene group may be linear or branched. The number of carbon atoms is not particularly limited and may be about 30 or less, but is usually about 1 to 5, particularly about 2 to 3. R is also hydrogen or a lower alkyl group, especially hydrogen or a methyl group. And n is an integer of 1 or more, and generally 1 to
It can be any integer of 8, but is usually 2, 4 or 8, especially 2 or 4. On the other hand, Pc represents a monovalent or higher valence residue of phthalocyanine, and the above

The vinyl-containing group represented by the formula is bonded to the benzene ring forming the phthalocyanine ring. In this case, the vinyl-containing group is bonded to any position on the benzene ring of the phthalocyanine, but usually 3
It is bonded at the - to 4-positions. Therefore, when n=2, the bonding positions of the vinyl-containing group are 3,3'-3,4'-3,3''-, 3,4''-, 4,
4′- and is a mixture of these isomers. In addition, when n = 4, 3, 3', 3'', 3- are mainly used, and when n = 8, 3, 4, 3', 4', 3'', 4'', 3,
Mainly 4. Furthermore, there is no particular restriction on the central atom of phthalocyanine, and in addition to Fe, Cu, Co, Ni, etc., V,
Pb, Si, Ge, Sn, Al, Ru, Ti, Zn, Mg,
In addition to Mn, VO, etc., _H2 is also possible. In this case, one or two other ligands may be further coordinated above and below the phthalocyanine ring. However, among these, Fe, Ni, Co or
Cu is preferred. Although other substituents are not usually bonded to the Pc phthalocyanine residue, substituents such as a carboxy group, a sulfo group, and an amino group may be bonded to the benzene ring of Pc in particular. 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, n=2
Proceedings of the Society of Polymer Science, Vol. 32 (1983) No. 3, P505,
n=4 is Makromol.Chem. 182 2429-2438
(1981), n = 8, Makromol.Chem. 181 565
(1980). Next, thionyl chloride was added to this and refluxed,
The precipitate is filtered and washed with petroleum ether to obtain acid chloride. to this,

[Formula] (L and R are the same as above) is added and heated to carry out the reaction. After the reaction, centrifuge, add water to the supernatant,
A precipitate is obtained, filtered, dried, dissolved in acetone, concentrated, and then purified. The phthalocyanine compound thus obtained has almost the same electronic spectrum as phthalocyanine itself. Further, the infrared absorption spectrum has ν _C =0 around 1720 cm ⁻¹ and 〓C=C around 1610 to 1650 cm ⁻¹ . As for the melting point, it generally decomposes thermally at about 170 to 200°C. Specific effects of the invention The phthalocyanine compound of the present invention has high solubility in solvents, and has high solubility in organic solvents such as chloroform, benzene, toluene, dioxane, dimethylformamide, and methyl ethyl ketone.
Dissolves very well. Furthermore, it has extremely high compatibility with resins such as epoxy resins, vinyl chloride-vinyl acetate copolymers, polyurethanes, and the like. Since it has vinyl content, especially acryloyl group or methacryloyl group, electron beam,
It can be easily polymerized or crosslinked by ultraviolet rays, X-rays, etc. Therefore, after being formed into a coating film, it can be polymerized or crosslinked to form a recording film or the like for an optical recording medium, which is extremely useful in practice. Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail. Example 1 Co-3, 3′, 3″,
3-tetracarboxyphthalocyanine was obtained. Thionyl chloride SOCl ₂ was added to this, and the mixture was refluxed for 10 hours. The precipitate was filtered and washed with petroleum ether.
-3,3',3'',3-tetrachlorinated carbonyl phthalocyanine was obtained. Yield: 96% To 0.5 g of this acid chloride, 20 ml of 2-hydroxystyl methacrylate was added and reacted at 60°C for 5 days. After the reaction, This was centrifuged and water was added to the supernatant to obtain a precipitate. The precipitate was filtered, dried and dissolved in acetone. This acetone solution was concentrated and Wacogen C-
200 was used as a solvent for development. The developed and separated acetone solution was concentrated and dried to obtain 0.14 g _of blue-green Co-Pc [ _{-COOCH2CH2OCOC} ( _CH3 )= _CH2 ] ₄ . Yield 17.5% Elemental analysis (%) C H N Found 57.18 4.07 8.62 Calc. 60.26 4.02 9.37 λmax 613-618nm (ε=10000) Shoulder 670nm (ε=9000) ν _C=0 1725cm ^-1 ν _C=C 1640cm ^{- 1} Example of thermal decomposition at 170°C 2 Similar synthesis was carried out in Example 1 using Fe-3,3',3'',3-tetracarboxyphthalocyanine as a raw material. Yield 12.7% Elemental analysis (%) C H N Found 59.97 6.77 8.92 Calc. 60.41 4.03 9.40 λmax 644nm (ε=11200) Shoulder 680nm (ε=7600) ν _C=0 1720cm ^-1 ν _C=C 1640cm ^-1 Pyrolysis at 170℃. Yield 12.7% Example 3 In Example 1, the phthalocyanine raw materials were Co-3,3',3'',3-tetracarboxyphthalocyanine, Ni-3,3',3'',3-tetracarboxyphthalocyanine, Cu-3,3' , 3″, 3-tetracarboxyphthalocyanine, Co-dicarboxyphthalocyanine, and the vinyl group-containing raw material was replaced with 2-hydroxyethyl acrylate, 2-hydroxy-1-propyl methacrylate to produce the compounds shown in Table 1 below. I got it. The elemental analysis values of each compound are also listed in Table 1. In this case, the values in brackets are calculated values. The infrared spectrum was almost the same as above, and the visible absorption spectrum was almost the same as each raw material phthalocyanine. Furthermore, as a result of analysis using a differential thermometer for each of these compounds, thermal decomposition started at 170 to 200°C.

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Claims (1)

[Claims] 1. A phthalocyanine compound represented by the following formula. formula {In the above formula, Pc represents a phthalocyanine residue, L represents an alkylene group, R represents hydrogen or a lower alkyl group, and n is an integer of 1 or more. }